Si-SUBSTITUTED LITHIUM THIOBORATE MATERIAL WITH HIGH LITHIUM ION CONDUCTIVITY FOR USE AS SOLID-STATE ELECTROLYTE AND ELECTRODE ADDITIVE

Information

  • Patent Application
  • 20240322226
  • Publication Number
    20240322226
  • Date Filed
    May 31, 2024
    6 months ago
  • Date Published
    September 26, 2024
    3 months ago
Abstract
Aspects disclosed herein include materials comprising: a lithium thioborate composition characterized by formula FX1: Li3−z[B+Q]1[S+G]3 (FX1); wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B; wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S; wherein z is a number greater than 0 and less than or equal to 0.40, optionally less than or equal to 0.05; and wherein the composition comprises only the first dopant, only the second dopant, or both the first dopant and the second dopant.
Description
BACKGROUND OF INVENTION

Solid state ion conducting materials have a number of useful applications, including as materials in a Li-ion all-solid-state battery (ASSB). To commercialize Li-ion ASSBs, a suitable Li-ion conducting solid-state electrolyte is required. A solid-state electrolyte should exhibit a wide electrochemical stability window and ionic conductivity near that of traditional liquid electrolytes. Three compounds with near-liquid-electrolyte conductivity (˜10−2 S cm−1) have been reported: Li10GeP2S12 (LGPS), Li6PS5Br argyrodite, and a Li7P3S11 glass ceramic. Unfortunately, all three discovered electrolytes exhibit electrochemical instability against the Li anode, limiting application in commercial products. Some materials are known or are predicted to have a wide electrochemical stability window, sufficient for resisting electron injection from the Li anode, but suffer from prohibitively low ionic conductivity in their pure or intrinsic form. Accordingly, there is a need for ion conducting solid state materials suitable as solid state electrolytes for battery technologies.


SUMMARY OF THE INVENTION

Aspects disclosed herein include materials comprising: a lithium thioborate composition characterized by formula FX1: Li3−z[B+Q]1[S+G]3 (FX1); wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B; wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S; wherein z is 0 or a number greater than 0 and less than or equal to 0.40, optionally less than or equal to 0.05; and wherein the composition comprises only the first dopant, only the second dopant, or both the first dopant and the second dopant.


Aspects disclosed herein include solid state electrolytes comprising: a lithium solid state electrolyte comprising Li, one or more principal elements, and at least one dopant; wherein the dopant substitutes for a portion of the one of the one or more principal elements of the lithium solid state electrolyte and is aliovalent with the respective substituted principal elements; wherein the ionic conductivity of the lithium solid state electrolyte is greater than or equal to 1·10−5 S/cm at 25° C.


Aspects disclosed herein include doped lithium solid state electrolytes comprising: a doped inorganic composition having at least one dopant; wherein the doped composition has up to 20 at. % of one or more principal elements substituted with the at least one dopant relative to a reference composition of a reference lithium solid state electrolyte; wherein each dopant is one or more elements each aliovalent with the respective substituted principal element; wherein the presence of the one or more dopants provides for an ionic conductivity greater than or equal to 1·10−5 S/cm at 25° C.


Aspects disclosed herein include methods for increasing an ionic conductivity of a reference lithium solid state electrolyte, the method comprising: forming a doped lithium solid state electrolyte having a doped composition; wherein the reference lithium solid state electrolyte has a reference composition, and wherein the doped composition has up to 20 at. % of one or more principal elements substituted with at least one dopant relative to the reference composition; wherein each element of the at least one dopant is aliovalent with respect to the respective substituted principal element; and wherein the doped lithium solid state electrolyte has a greater ionic conductivity than the reference lithium solid state electrolyte by a factor of at least 10.


Without wishing to be bound by any particular theory, there may be discussion herein of beliefs or understandings of underlying principles relating to the devices and methods disclosed herein. It is recognized that regardless of the ultimate correctness of any mechanistic explanation or hypothesis, an embodiment of the invention can nonetheless be operative and useful.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1: Schematic of the semi-supervised machine learning approach. Li-containing structures are aggregated from the ICSD and MP database. Each input structure is simplified and transformed to yield a unique descriptor representation. The descriptor representations are clustered with hierarchical agglomerative clustering. Each cluster is then labeled with experimental σ25° C. data and the intracluster conductivity variance is calculated. Comparison of the composite intracluster conductivity variance (intracluster conductivity variance summed across all clusters) enables identification of descriptors that are well correlated with ionic conductivity.



FIG. 2: The composite intracluster conductivity variance (Wσ) for the first 50 clusters generated using each descriptor. Half-violin plots show the raw Wσ score for each cluster as symbols next to the violin distribution. Simplification-descriptor combinations are sorted in order of ascending mean. The control is a random assignment of clusters, with Wσ values averaged over 100 randomly assigned sets. The smooth overlap of atomic positions (SOAP) descriptor outperforms all other descriptors. Although not shown here, SOAP continues to outperform for all depths of clustering through 300.



FIG. 3: Agglomerative clustering dendrogram for the 2nd-order SOAP descriptor. The hierarchical clustering representation is shown for the first 241 clusters. An arbitrary variance cutoff is placed such that 9 large clusters are produced to facilitate analysis. The violin plots show the σ25° C. distribution for the labels within the 9 large clusters. Three outlier clusters are grouped into two additional clusters and are hereafter ignored. The density (per 241 clusters) of low Ea (<0.6 eV) and high conductivity (σ25° C.>10−5 cm−1) labels is shown underneath the agglomerative dendrogram. The results illustrate that agglomerative clustering on the 2nd-order SOAP descriptor results in favorable aggregation of most high-conductivity labels.



FIG. 4: Wσ vs. cluster number for three different SOAP-CAN models compared with the best-performing models for density-CAN, mXRD-A40, orbital field matrix, and structure heterogeneity-A40. The three SOAP-CAN models are those with the lowest Wσ mean for the clustering ranges: 2-100, 101-200, and 201-300. Almost all SOAP-CAN models outperformed the best non-SOAP models, irrespective of the specific combination of rcut, nmax, and Imax hyperparameters.



FIG. 5: The WEa for the first 50 clusters generated using each descriptor. Half-violin plots show the raw WEa score for each cluster as symbols next to the violin distribution. Simplification-descriptor combinations are sorted in order of ascending mean. The control is a random assignment of clusters, with WEa values averaged over 100 randomly assigned sets.



FIG. 6: The best performing 2nd order descriptor: SOAP-CAN mixed with the sine Coulomb descriptor. The clustering performance is shown for the full label set of 219. Since the mXRD—A40 representation is also compatible with the full label set, it is shown for reference. The 2nd order descriptor outperforms the 1st order SOAP-CAN descriptor at most depths of clustering.



FIG. 7: The partial agglomerative dendrogram generated for the 2nd-order SOAP-CAN descriptor-simplification. The area shown is the 2nd mega cluster taken from FIG. 3 of the main text. At a clustering depth of 241, the 21 high-conductivity labels are sorted into 5 clusters which account for 2.2% of the input structures.



FIG. 8: The 2×2×2 supercell of Li3VS4 used for the CI-NEB calculation of Li migration energy. Blue atoms represent the Li position from the CI-NEB output images.



FIG. 9: The primitive cell of Na3Li3Al2F12 used for the CI-NEB calculation of Li migration energy. Blue atoms represent the Li position from the CI-NEB output images.



FIG. 10: The 2×2×2 supercell of Li2Te used for the CI-NEB calculation of Li migration energy. Blue atoms represent the Li position from the CI-NEB output images.



FIG. 11: The 2×2×1 supercell of LiAlTe2 used for the CI-NEB calculation of Li migration energy. Blue atoms represent the Li position from the CI-NEB output images.



FIG. 12: The 2×2×1 supercell of LiInTe2 used for the CI-NEB calculation of Li migration energy. Blue atoms represent the Li position from the CI-NEB output images.



FIG. 13: The 2×2×2 supercell of Li6MnS4 used for the CI-NEB calculation of Li migration energy. Blue atoms represent the Li position from the CI-NEB output images.



FIG. 14: The 2×2×1 supercell of LiGaTe2 used for the CI-NEB calculation of Li migration energy. Blue atoms represent the Li position from the CI-NEB output images.



FIG. 15: The 2×1×2 supercell of Li3BS3 used for the CI-NEB calculation of Li migration energy. Blue, green, and orange atoms represent the Li position from the CI-NEB output images.



FIG. 16: The 2×2×2 supercell of KLi6TaO6 used for the CI-NEB calculation of Li migration energy. Blue and orange atoms represent the Li position from the CI-NEB output images.



FIG. 17: The 2×1×2 supercell of Li3CuS2 used for the CI-NEB calculation of Li migration energy. Blue atoms represent the Li position from the CI-NEB output images.



FIG. 18: Nyquist data for a-Li2.95B0.95Si0.05S3 near room temperature. The partially resolved semi-circular features suggests the presence of at least two RC circuit elements.



FIG. 19: The 31 promising structures that are predicted to be stable and to exhibit Li-hopping activation energy below 600 meV.



FIG. 20A: Explored for use as both an anode340 and a cathode341. NEB has been employed to predict an activation energy of 95 meV.342 All Li occupies tetrahedral sites that are edge sharing with adjacent V tetrahedra.



FIG. 20B: The structure appears to be unexplored. Discussion of structural motifs by Geller et al.343 All Li atoms are in a tetrahedral bonding environment.



FIG. 20C: A screening approach using bond valence site energy calculations identified the oxide as a promising structure: Li2Te2O5.344 All Li are in tetrahedral bonding environment.



FIG. 20D: All Li are in a tetrahedral environment with corner sharing. The structure hasn't been examined as an ionic conductor—ongoing research is focused on optoelectronic properties.345



FIG. 20E: All Li are in a tetrahedral environment with corner sharing. The structure hasn't been examined as an ionic conductor—ongoing research is focused on optoelectronic properties.346



FIG. 20F: All Li are in an edge-sharing tetrahedral bonding environment. Augustine et al. posit that the structure could be a viable cathode material. They performed ab-initio calculations to measure the enthalpy of formation and have concluded that the structure should be stable.347



FIG. 20G: All Li are in a tetrahedral environment with corner sharing. The structure hasn't been examined as an ionic conductor—ongoing research is focused on optoelectronic properties.348 Isaenko et al. report an experimental band gap of 2.41 eV.



FIG. 20H: All Li are in a tetrahedral bonding environment. Recent NEB work suggests an activation barrier of 250 meV.349



FIG. 20I: All Li are in a tetrahedral bonding environment with edge or corner sharing. Recent electrochemical characterization by Suzuki et al. found an ionic conductivity near 10−5 S cm−1 with aliovalent substitution of Sn.350



FIG. 20J: All Li are in an edge-sharing tetrahedral bonding environment. Explored for use as a cathode by Kawasaki et al. in 2021.351 They found an initial charge-discharge capacity of 380 mAh g−1 with average voltage of 2.1 V vs. L/Li+.



FIG. 20K: All Li are in an edge-sharing tetrahedral bonding environment. Never explored for battery purposes. Synthesis by Huang et al.352



FIG. 20L: All Li sits in four- and five-coordinate environments. Kahle et al. previously screened ˜1400 Li-containing compounds and identified Li4Re6S11 as a potentially promising SSE using molecular dynamics simulation.353 Their simulations failed to resolve RT diffusion but found promising diffusivity at elevated temperatures.



FIG. 20M: All Li are in a tetrahedral bonding environment.



FIG. 20N: All Li are in an octahedral bonding environment. Muy et al. identify Li3ErBr6 as one of eighteen promising compounds using a phonon-band descriptor approach.354 They synthesize the Cl analogue and report an experimental conductivity of 0.05-0.3 mS cm−1. The material also mentioned briefly in perspective by Li et al.355



FIG. 20O: All Li are in a tetrahedral bonding environment.



FIG. 20P: All Li are in a tetrahedral bonding environment. Sendek et al. identified Li2HIO as promising using a combined ML and DFT approach.356 They predicted a RT diffusion barrier of 350 meV.



FIG. 20Q: All Li are in an edge-sharing tetrahedral bonding environment. Synthesis via Huang et al.352



FIG. 20R: Li ions are in a distorted octahedral and some 5-coordinate bonding environments.



FIG. 20S: All Li are in an octahedral bonding environment. Mentioned briefly in perspective by Li et al.355



FIG. 20T: All Li are in an octahedral bonding environment. Discussed briefly in perspective by Li et al.355 Predicted by Kahle et al. to be a fast ionic conductor using molecular dynamics simulations.353 They predict an activation energy of 350 meV.



FIG. 20U: All Li are in a tetrahedral bonding environments.



FIG. 20V: All Li are in a three coordinate bonding environment.



FIG. 20W: All Li are in a tetrahedral bonding environment. Optical properties and air-stability have been briefly discussed by Kim et al.357



FIG. 20X: All Li are in an edge-sharing tetrahedral bonding environment. Synthetic accounts appear to exist in some books.



FIG. 20Y: Li are all in an edge-sharing tetrahedral bonding environment. Wang et al. predicted that this might be a high-conductivity structure by using a “structure matching” algodithm.358



FIG. 20Z: All Li are in a 5-coordinate bonding environment. A hydrothermal synthetic method has been described by Li et al.359



FIG. 20AA: All Li are in 3-coordinate or 2-coordinate bonding environments. Identified by Snydacker et al. as a suitable coating for Li anode passivation via convex hull calculations.360



FIG. 20AB: All Li are in octahedral or tetrahedral bonding environments. The tetrahedra sit between the octahedral layers. Amorphous Li4TiS4 is thought to form upon discharge of TiS4-based cathodes.361



FIG. 20AC: All Li are in a tetrahedral bonding environment. Wang et al. predicted that LiGaS2 might be a high-conductivity structure by using a “structure matching” algorithm.358 Separately, He et al. used ab initio calculation to predict the same.362



FIG. 20AD: All Li are in a corner-sharing tetrahedral bonding environments.



FIG. 20AE: Li are mostly in tetrahedral bonding environments, although some 5-coordinate environments exist. Kahle et al. identified Li10B14Cl2O2s as a potentially promising SSE material using a “pinball” model.353



FIG. 21: The 21 promising structures that are predicted to be within 15 meV of Ehull and to exhibit Li-hopping activation energy below 600 meV.



FIG. 22A: Li are in 8-coordinate sites surrounded by oxygens.



FIG. 22B: All Li are in tetrahedral bonding environments—corner sharing with Zn and P tetrahedra. Richard's et al. used NEB to predict that Li10Zn7P8S32 has a 252 meV activation energy for Li diffusion.363 They also predict a RT conductivity of 3.44 mS cm−1.



FIG. 22C: All Li are in tetrahedral bonding environments—corner sharing with Zn and P tetrahedra. Richard's et al. used NEB to predict that Li6Zn3P4S16 has a 181 meV activation energy for Li diffusion.363 They also predict a RT conductivity of 27.7 mS cm−1.



FIG. 22D: All Li are in tetrahedral bonding environments.



FIG. 22E: All Li are in tetrahedral bonding environments.



FIG. 22F: All Li are in tetrahedral bonding environment.



FIG. 22G: Octahedral Li layers with Li tetrahedra interspersed between.



FIG. 22H: All Li are in tetrahedral bonding environments.



FIG. 221: All Li are in edge-sharing tetrahedral bonding environments. Previously examined as a cathode material by Chen et al.364



FIG. 22J: All Li are in tetrahedral bonding environments.



FIG. 22K: All Li are in tetrahedral bonding environments.



FIG. 22L: All Li are in tetrahedral bonding environments.



FIG. 22M: All Li are in tetrahedral bonding environments. Devlin et al. have previously published a synthetic method for Li2MnSnS4.365



FIG. 22N: All Li are in edge-sharing tetrahedral bonding environments.



FIG. 22O: All Li are in edge-sharing octahedral bonding environments. A synthetic method has been published by Steiner et al.366



FIG. 22P: All Li are in tetrahedral bonding environments.



FIG. 22Q: All Li are in corner-sharing tetrahedral bonding environments. Li1OSi3P3S23Cl was theoretically studied by Rao et al.367 They used it is a model system for a neural-network molecular dynamics pipeline.



FIG. 22R: All Li are in tetrahedral or octahedral bonding environments.



FIG. 22S: All Li are in octahedral bonding environments. Muy et al. examined LiSnCl3 using a phonon-band descriptor approach.354 Despite a promising band-center value, they suggest it has a low stability window. Körbel et al. identify it as a promising piezoelectric material.368



FIG. 22T: All Li are in tetrahedral bonding environments.



FIG. 22U: All Li are in distorted tetrahedral bonding environments.



FIG. 23: The six promising structures that lack Materials Project data but are predicted to exhibit Li-hopping activation energy below 600 meV.



FIG. 24A: All Li are in tetrahedral bonding environments. Synthetic method by Prömper et al.369



FIG. 24B: All Li are in 5-coordinate bonding environments. Previously studied by Abdel-Khalek et al. in a glass ceramic.370 Discussed in some detail by Rousse et al.371



FIG. 24C: All Li are in octahedral bonding environments.



FIG. 24D: All Li are in tetrahedral bonding environments. Synthetic method by Branford et al.372



FIG. 24E: All Li are in tetrahedral bonding environments. A melt flux synthesis has been developed by Li et al—they examined the material for second-harmonic generation response.373



FIG. 24F: Most Li are in tetrahedral bonding environments, with some partial substitution onto the octahedral Ti sites.



FIG. 25: Steady-state current of Au/a-Li2.95B0.95Si0.05S3/Au cell for different voltage polarizations. Measurements were done at 25° C. with applied voltages of 0.125 V, 0.25 V, 0.375 V, 0.5 V and 1.0 V.



FIGS. 26A-26G: Characterization of Li3BS3 with vacancy engineering. FIG. 26A: XRD patterns for Li3BS3, 2.5% Si substituted Li3BS3 (Li2.975B0.975Si0.025S3), 5% Si substituted Li3BS3 (Li2.95B0.95Si0.05S3), and amorphized 5% Si substituted Li3BS3 (a-Li2.95B0.95Si0.05S3). No impurities are observed in any pattern. FIG. 26B: Arrhenius fits for Li3BS3. FIG. 26C: Lattice parameter comparison for Li3BS3, Li2.975B0.975Si0.025S3, and Li2.95B0.95B0.05S3. FIG. 26D: Arrhenius fits for Li2.95B0.95Si0.05S3, and a-Li2.95B0.95Si0.05S3. FIG. 26E: Electrochemical impedance spectroscopy for the a-Li2.95B0.95Si0.05S3 at various temperatures. FIG. 26F: 7Li NMR and (FIG. 26G)11B NMR of the Li3BS3, Li2.95B0.95Si0.05S3, and a-Li2.95B0.95Si0.05S3. Results show that combined aliovalent substitution and amorphization can improve the ionic conductivity of Li3BS3 by over four orders of magnitude.



FIGS. 27A-27B: Experimentally measured (FIG. 27A) powder X-ray diffraction patterns and (FIG. 27B) Raman spectra of Li3−xBS3−xClx compositions (0≤x≤0.4). Downward arrows indicate the presence of LiCl impurity.



FIG. 28: Experimentally measured powder X-ray diffraction patterns of Li3−x−yB1−ySiyS3−xClx.



FIGS. 29A-29B: Experimentally obtained (FIG. 29A) Arrhenius plots and (FIG. 29B) room-temperature ionic conductivity values and activation energies for Li3−xBS3−xClx, plotted from electrochemical impedance spectroscopy data.



FIG. 30: Experimentally obtained room-temperature ionic conductivity values and activation energies for Li3−x−yB1−ySiyS3−xClx, plotted from electrochemical impedance spectroscopy data.



FIG. 31: Arrhenius plots, room-temperature ionic conductivity values and activation energies for a-Li2.95B0.95Si0.05S3, Li2.95B0.95Si0.05S3, and Li3BS3.



FIG. 32A: Arrhenius plots and room-temperature ionic conductivity values for Li2.9B0.95Si0.05S2.95Cl0.05, Li2.95B0.95Si0.05S3, Li2.95BS2.95Cl0.05, and Li3BS3.



FIG. 32B shows Arrhenius plots and room-temperature ionic conductivity values for Li3BS3, Li2.95 B0.95 Si0.05 S3, a-Li2.95B0.95Si0.05S3, Li2.95BS2.95Cl0.05 and Li2.9BS2.9Cl0.1.



FIG. 33: Room-temperature ionic conductivity values and activation energies for Li3BS3, Li2.95BS2.95Cl0.05, Li2.9BS2.9Cl0.1, Li2.8BS2.8Cl0.2, Li2.95B0.95Si0.05S3, and Li2.9B0.95Si0.05S2.95Cl0.05.



FIG. 34: Room-temperature ionic conductivity values for Li3BS3, Li2.95BS2.95Cl0.05, Li2.9BS2.9Cl0.1, Li2.8BS2.8Cl0.2, Li2.95B0.95Si0.05S3, Li2.9B0.95Si0.05S2.95Cl0.05, a-Li2.95B0.95Si0.05S3, Li2.85B0.85Si0.15S3, Li2.85B0.9Si0.1S2.95Cl0.05, and Li2.6BS2.6Cl0.4.



FIG. 35: provides XRD patterns for Li3BS3, Li2.95 BS2.95 Cl0.05 and Li2.9BS2.9Cl0.1. The patterns do not appear to show any impurities.





STATEMENTS REGARDING CHEMICAL COMPOUNDS AND NOMENCLATURE

In general, the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The following definitions are provided to clarify their specific use in the context of the invention.


The term “dopant” is used herein broadly to refer to one or more elements intentionally provided in a material's composition to improve or enhance one or more properties or functionalities of the resulting doped material to compared to the undoped reference form of the material, which is typically intrinsic and stoichiometric. A doped composition is optionally referred to as an extrinsic composition, whereas the undoped composition is optionally referred to as the intrinsic or reference composition. As used herein, the term dopant is used broadly to include low concentration impurities or low concentration additive element(s), such that providing said dopant may be referred to as doping and/or alloying as these terms are known in the art. As used herein, a dopant is a substitute for another or principal element, where the dopant replaces or substitutes for a portion of the amount or concentration of the principal element relative to the amount or concentration the principal element in the undoped composition. For clarity and as a convenient handle, each element of a reference undoped composition may be referred to as a “principal element”. Generally, a principal element is an element identified (or which would be identified by one of skill in a relevant art) in a chemical formula of a composition and is exclusive of impurity elements present in the composition at less than 0.05 at. %, less than 0.05 mol. %, and/or less than 0.05 wt. % (optionally less than 0.04 at. %, less than 0.04 mol. %, and/or less than 0.04 wt. %; optionally less than 0.03 at. %, less than 0.03 mol. %, and/or less than 0.03 wt. %; optionally less than 0.02 at. %, less than 0.02 mol. %, and/or less than 0.02 wt. %; optionally less than 0.01 at. %, less than 0.01 mol. %, and/or less than 0.01 wt. %). Therefore, for example: Li, B, and S are principal elements of the composition Li3BS3; Li, V, and S are the principal elements of the composition Li3VS4; Na, Li, Al, and F are the principal elements of the composition Na3Li3Al2F12; Li and Te are the principal elements of the composition Li2Te; Li, Al, and Te are the principal elements of the composition LiAlTe2; Li, In, and Te are the principal elements of the composition LiInTe2; Li, Mn, and S are the principal elements of the composition Li6MnS4; Li, Ga, and Te are the principal elements of the composition LiGaTe2; K, Li, Ta, and O are the principal elements of the composition KLi6TaO6; Li, Cu, and S are the principal elements of the composition Li3CuS2; etc. Generally, materials disclosed herein comprise one or more dopants that are substitutes for one or more principal elements (optionally, non-Li principal elements) of a composition (i.e., a principal element other than Li of a composition, such as any of those listed in the prior sentence; e.g., a dopant may be a substitute for B or S in Li3BS3, where the B and S are principal elements (optionally, non-Li principal elements) of the composition Li3BS3). As used herein, a dopant is optionally one element being substitute for a principal element of a composition (e.g., Si being a dopant for B in Li3BS3). As used herein, a dopant is optionally two elements being substitutes for a principal element of a composition (e.g., Si and Ge together being a dopant for B in Li3BS3). As used herein, a dopant is optionally three or more elements being substitutes for a principal element of a composition. Herein, the terms “doped” and “substituted” are generally used interchangeably when referring to a material or composition having one or more dopants, as disclosed herein, substituting one or more principal elements, such as one or more principal elements (optionally, non-Li principal elements). A doped composition may have one dopant or more than one dopants. For example, a doped composition may have a first dopant (or, first type of dopant) being a dopant or substitute for a first principal element (optionally, a non-Li principal element) of a composition (e.g., B of Li3BS3) and the same doped composition may have a second dopant (or, second type of dopant) being a dopant or substitute for a second principal element (optionally, a non-Li principal element) of a composition (e.g., S of Li3BS3). As used herein, a dopant element may be present in the structure of the doped composition substitutionally (as a substitutional dopant element), interstitially (as an interstitial dopant element), or both substitutionally and interstitially. As used herein, a dopant element is preferably aliovalent with respect to the principal element it replaces or for which it is a substitute. For example, a dopant element for B (e.g., in Li3BS3) is preferably aliovalent with respect to B, such that said dopant element is a member of an element Group other than Group 13 of the Periodic Table of Elements (e.g., Si, being a member of Group 14). For example, a dopant element for S (e.g., in Li3BS3) is preferably aliovalent with respect to S, such that said dopant element is a member of an element Group other than Group 16 of the Periodic Table of Elements (e.g., Cl, being a member of Group 17). In some aspects, the material or composition thereof having the one or more dopants is characterized as a solid solution. In some aspects, the introduction of one or more dopants to a material or composition thereof obeys Vegard's law where the one or more dopants incorporate into the material's lattice or structure as a solid solution.


The term “amorphizing” refers to a process that reduces grain sizes (average, median, and/or bounds of a 95% confidence interval) of a material (or composition thereof), reduces crystallite sizes (average, median, and/or bounds of a 95% confidence interval) of a material (or composition thereof), increasing amorphous content of a material (or composition thereof), decreasing total crystallinity of a material (or composition thereof), and/or increasing an amount or concentration of defects in a material (or composition thereof). A defect generally refers to a crystallographic defect. As recognized by those skilled in the relevant art such as materials science or crystallography in particular, a defect may be a point defect, a line defect, a planar defect, and/or a bulk defect. A vacancy (or, “vacancy defect”), such as a vacancy of a principal element such as B in Li3BS3, is an example of a defect. A broken or dangling bond, which is optionally but not necessarily a result of a vacancy defect, is another example of a defect. Generally, but not necessarily, amorphizing refers to a process performed on a material after said material is formed or made. Thus, generally but not necessarily, amorphizing does not refer to the process of doping or making a doped composition (although doping may introduce defects such as interstitial defects), but rather to a separate or subsequent processing step performed on a material that has been formed. An example of an amorphizing process is ball milling, or any similar processes. In some aspects, the term amorphizing refers to a process that necessarily increases amorphous content of a material (or composition thereof) and decreases total crystallinity of the material (or composition thereof), while also optionally reducing grain sizes (average, median, and/or bounds of a 95% confidence interval) of the material (or composition thereof), optionally reducing crystallite sizes (average, median, and/or bounds of a 95% confidence interval) of the material (or composition thereof), and/or optionally increasing an amount or concentration of defects in the material (or composition thereof).


The term “ionic conductivity” is intended to be consistent with the term as it is readily known by one skilled in relevant arts, particularly in the art of semiconductors and/or solid state electrolytes, and refers the property of ionic conductivity as it would relate to the performance of a material or composition thereof as an ionically conductive solid state electrolyte in an electrochemical cell such as a battery. In some aspects, ionic conductivity particularly refers to ionic conductivity of Li+ ions in a material or a composition thereof. As used herein, unless explicitly otherwise stated, ionic conductivity of a material (or composition thereof) refers to ionic conductivity within or through the material, such as through a thickness or lateral dimension of the material (e.g., through the thickness of a thin film), instead of a surface ionic conductivity along a film's surface longitudinally. Unless otherwise explicitly stated, the term ionic conductivity refers to a combination of grain boundary transport of ions and bulk ionic conductivity. Preferably, but not necessarily, an ionic conductivity claimed herein is an average ionic conductivity, being an average of at least three repeated measurements. Further to the descriptions in Examples 1A-3 provided herein, useful techniques, assumptions, parameters, calculations, etc., for measuring ionic conductivity in materials disclosed herein is found in P. Vadhva, et al. (“Electrochemical Impedance Spectroscopy for All-Solid-State Batteries: Theory, Methods and Future Outlook”, first published in ChemElectroChem; Volume 8; Issue 11; 2021; Pages 1930-1947; DOI: 10.1002/celc.202100108), which is incorporated herein in its entirety.


The term “electronic conductivity” is intended to be consistent with the term as it is readily known by one skilled in relevant arts, particularly in the art of semiconductors and/or solid state electrolytes, and refers the property of electronic conductivity (conductivity or transport of electrons) as it would relate to the performance of a material or composition thereof as an ionically conductive (and preferably electronically insulating) solid state electrolyte in an electrochemical cell such as a battery. For clarity, electronic conductivity does not refer to nor include ionic conductivity. As used herein, unless explicitly otherwise stated, electronic conductivity of a material (or composition thereof) refers to electronic conductivity within or through the material, such as through a thickness or lateral dimension of the material (e.g., through the thickness of a thin film), instead of a surface electronic conductivity along a film's surface longitudinally. Unless otherwise explicitly stated, the term electronic conductivity may be inclusive of any and all possible mechanisms of electronic transport (i.e., transport/conductivity of electrons; e.g., including Poole-Frenkel emission, hopping conduction, ohmic conduction, space-charge-limited conduction, and/or grain-boundary-limited conduction). Further to the descriptions in Examples 1A-3 provided herein, useful techniques, assumptions, parameters, calculations, etc., for measuring electronic conductivity in materials disclosed herein is found in P. Vadhva, et al. (“Electrochemical Impedance Spectroscopy for All-Solid-State Batteries: Theory, Methods and Future Outlook”, published in ChemElectroChem; Volume 8; Issue 11; 2021; Pages 1930-1947; DOI: 10.1002/celc.202100108), which is incorporated herein in its entirety.


The term “electrochemical cell” refers to devices and/or device components that convert chemical energy into electrical energy or electrical energy into chemical energy. Electrochemical cells have two or more electrodes (e.g., positive and negative electrodes) and one or more electrolytes. For example, an electrolyte may be a fluid electrolyte or a solid electrolyte. In aspects disclosed herein, electrochemical cells comprise at least one solid state electrolyte (optionally but not necessarily also having a fluid electrolyte), the solid state electrolyte comprising a material or composition disclosed herein. The solid state electrolyte is an ionically conductive (e.g., for Li+ ions), and preferably electronically insulating to prevent electrical/electronic shorting between oppositely-charged electrodes within the electrochemical cell or battery. Reactions occurring at the electrode, such as sorption and desorption of a chemical species or such as an oxidation or reduction reaction, contribute to charge transfer processes in the electrochemical cell. Electrochemical cells include, but are not limited to, primary (non-rechargeable) batteries and secondary (rechargeable) batteries. In certain aspects, the term electrochemical cell includes metal hydride batteries, metal-air batteries, fuel cells, supercapacitors, capacitors, flow batteries, solid-state batteries, and catalysis or electrocatalytic cells (e.g., those utilizing an alkaline aqueous electrolyte). In some aspects, an electrochemical cell is a Li-ion or Li-ion based battery.


The term “gravimetric capacity”, consistent with the term as used in the art, particularly in the art of battery devices and electrochemistry, refers to amount of charge that can be stored per unit mass. The units are typically mAh/g or C/g. Generally, in the art, gravimetric capacity is normalized by the mass of active material in a cathode or anode, with the balance-of-plant ignored (carbon, binder, etc.) to allow for comparison between active materials. With respect to a battery, the capacity of the battery is normalized to the entire cell which includes all the “inactive” components like carbons, the current collectors, electrolyte, etc. Solid state electrolytes are normally reported as a way to enable Li metal anodes, which have a much higher gravimetric capacity than commercialized graphite anodes. For example, even though solid-state electrolytes are heavier/denser than liquid electrolytes, a solid-state battery could have higher capacity if the solid-state electrolyte is paired with a Li metal anode.


The term “stability”, as used herein in reference to a solid state electrolyte or a material, or composition thereof, that is a candidate solid state electrolyte generally refers to chemical and electrochemical stability (thermodynamic and kinetic) of the electrolyte or material, or composition thereof, with respect to reduction by a Li metal anode at voltages relevant to the operation of a battery having said electrolyte or material. Further to the descriptions in Examples 1A-3 provided herein, useful background, description, techniques, assumptions, parameters, calculations, etc., for determining stability of solid state electrolytes and materials that are candidate solid state electrolytes is found in H. Park, et al. (“Predicting Charge Transfer Stability between Sulfide Solid Electrolytes and Li Metal Anodes”, ACS Energy Lett. 2021, 6, 1, 150-157; DOI: 10.1021/acsenergylett.0c02372), which is incorporated herein in its entirety.


As used herein, total crystallinity refers to the sum of the wt. % of all crystal phases present in the material or a composition thereof. Optionally in any aspect disclosed herein, a material disclosed herein is characterized by a total crystallinity equal to or less than about 25% by weight (wt. %), optionally equal to or less than about 20 wt. %, optionally equal to or less than about 15 wt. %, optionally equal to or less than about 10 wt. %, optionally equal to or less than about 8 wt. %, optionally equal to or less than about 5 wt. %, optionally equal to or less than about 4 wt. %, optionally equal to or less than about 3 wt. %, optionally equal to or less than about 2 wt. %, optionally equal to or less than about 1 wt. %, optionally equal to or less than about 0.8 wt. %, optionally equal to or less than about 0.5 wt. %, optionally equal to or less than about 0.2 wt. %, optionally equal to or less than about 0.1 wt. %, optionally equal to or less than about 0.08 wt. %, optionally equal to or less than about 0.05 wt. %, optionally equal to or less than about 0.01 wt. %. The total crystallinity of a material or composition thereof can be determined through Rietveld quantitative analysis of X-ray diffraction (XRD) data measured from the material or a representative sample thereof. For example, the XRD may be measured using a sheet, film, pellet, powder, or such, of the material, for example. Optionally, XRD data is collected using a powder x-ray diffraction technique with a scan from 5 to 80 degrees, unless otherwise specified. For example, the Rietveld quantitative analysis method may employ a least squares method to model the XRD data and then determine the concentration of crystal phase(s) in the sample based on known lattice(s) and scale factor(s)s for the identified phase(s). However, it is understood that different methods and instrumentation for determining total crystallinity can also be employed.


In an embodiment, a composition or compound of the invention, such as an alloy or precursor to an alloy, is isolated or substantially purified. In an embodiment, an isolated or purified compound is at least partially isolated or substantially purified as would be understood in the art. In an embodiment, a substantially purified composition, compound or formulation of the invention has a chemical purity of 95%, optionally for some applications 99%, optionally for some applications 99.9%, optionally for some applications 99.99%, and optionally for some applications 99.999% pure.


DETAILED DESCRIPTION OF THE INVENTION

In the following description, numerous specific details of the devices, device components and methods of the present invention are set forth in order to provide a thorough explanation of the precise nature of the invention. It will be apparent, however, to those of skill in the art that the invention can be practiced without these specific details.


The Li-ion all-solid-state battery (ASSB) is a promising template for next-generation energy storage. To commercialize Li-ion ASSBs, a suitable solid-state electrolyte is required. A solid-state electrolyte must exhibit a wide electrochemical stability window and ionic conductivity near that of traditional liquid electrolytes. Three compounds with near-liquid-electrolyte conductivity (˜10−2 S cm−1) have been discovered: Li10GeP2S12 (LGPS), Li6PS5Br argyrodite, and a Li7P3S11 glass ceramic. All three discovered electrolytes exhibit electrochemical instability against the Li anode, limiting application in commercial products. Li3BS3 is predicted to have a wide electrochemical stability window, sufficient for resisting electron injection from the Li anode.1 However, the ionic conductivity of pure or intrinsic Li3BS3 is prohibitively low (10−7-10−6 S cm−1).


In aspects herein, we present a method to significantly enhance the ionic conductivity of materials such as Li3BS3, which are candidates for solid state lithium ion conductivity electrolytes, through incorporation of Si and subsequent amorphization. Also disclosed here are ionically conductive materials, such as doped or substituted Li3BS3. For example, by substituting up to 5%, for example, of the B sites with Si, Li3−xB1-xSixS3 achieves an ionic conductivity surpassing 10−5 S cm−1 at room temperature. When the doped product is further amorphized, for example through continuous ball milling, the ionic conductivity is further enhanced to above 10−3 S cm−1 at room temperature.


Pure or intrinsic Li3BS3 has been studied and characterized in the past. The pure structure exhibits an ionic conductivity in the range of 10−7-10−6 S cm−1, which is unfavorably low for the material to be useful as a solid state lithium ion conductor. Ionic conductivity of pure/intrinsic Li3BS3 can be enhanced via extended ball milling to near 10−4 S cm−1.2 aspects disclosed herein include materials and associated methods demonstrating further significant enhancement in ionic conductivity of materials that are candidates for solid state lithium ion conductors (e.g., for use in a solid state electrolyte), such as Li3BS3.


In aspects, substitution of a principal element such as B, S, or both B and S in Li3BS3 with an aliovalent dopant element also reduces the amount of Li in the composition relative to the undoped composition. For example, in aspects, the relative amount of Li is reduced according to formula FX2: Li3−x−yB1−x[Q]xS3−y[G]y, where Q (“first dopant”) is one or more (“first”) dopant elements aliovalent with respect to B, G (“second dopant”) is one or more (“second”) dopant elements each aliovalent with respect to S, x is a number (e.g., selected from range of 0.005 to 0.20) corresponding to the relative amount of substitution of B, and y is a number (e.g., selected from range of 0.005 to 0.20) corresponding to the relative amount of substitution of S. Generally, this reduction in Li occurs to maintain overall charge neutrality of the structure assuming formal oxidation states.


For example, aliovalent substitution of Si into the Li3BS3 lattice may introduce vacancies which can act as charge carrying defects. Aliovalent substitution for 5% of the B, for example, results in Li2.95B0.95Si0.05S6 which exhibits a room temperature ionic conductivity of 1.82·10−5 S cm−1. In aspects, extended amorphization of the Li2.95B0.95Si0.05S3 further improves the ionic conductivity to between 1·10−3 and 3·10−3 S cm−1. Thus, through aliovalent substitution and amorphization, in aspects, the ionic conductivity of Li3BS3 is improved to near that of conventional liquid electrolytes.


In aspects, doped materials and compositions thereof disclosed herein, such as amorphous Li2.95B0.95Si0.055S (a-Li2.95B0.95Si0.05S3), offer many unique advantages over most solid-state electrolyte candidates. The synthesis occurs at a relatively low temperature (˜800° C.) and pelletization can occur at room temperature. In some aspects, unlike most oxide candidates, doped materials and compositions thereof disclosed herein, such as a-Li2.95B0.95Si0.05S3, exhibit superb inter-grain conductivity without the need for a high-temperature grain-boundary sintering step. The precursor materials are also relatively inexpensive. For example, in comparing to LGPS, the a-Li2.95B0.95Si0.05S3 swaps Ge (˜$2400/kg) and P (˜$5/kg) for B (˜200/kg) and Si ($1/kg). Additionally, all four constituent elements have a low atomic mass, which is conducive to making ASSBs with high gravimetric capacity.


In some aspects, materials disclosed herein may be useful in a variety of aspects and applications beyond solid-state electrolytes. For example, the doped or substituted materials and compositions thereof disclosed herein, such as Li2.95B0.95Si0.05S3, may be employed as an artificial interphase on the Li anode surface. In such an application, doped materials and compositions thereof, such as Li2.95B0.95Si0.05S3, may facilitate ionic conduction while preventing the Li anode from reducing an adjacent SSE.


In some aspects, materials disclosed herein may also be employed as an additive for electrodes. In some aspects, materials disclosed herein may also be employed in glass electrolyte mixtures. In such applications, for example, doped materials and compositions thereof, such as Li2.95B0.95Si0.05S3, may serve either or both of the following roles: (1) improving electrochemical stability of the electrode/electrolyte and (2) improving ionic conductivity of the electrode/electrolyte.


In aspects herein, we present first materials comprising: a lithium trioborate composition characterized by formula FX4: Li3−yBS3−yGy (FX4); wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S; wherein y is a number greater than 0 and less than or equal to 0.40; and wherein G is one or more Group 17 (halogen) elements.


In aspects herein, we present second materials comprising: a lithium thioborate composition characterized by formula FX2: Li3−x−yB1−xQxS3−yGy (FX2); wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B; wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S; wherein x is a number greater than 0 and less than or equal to 0.10; wherein y is a number greater than 0 and less than or equal to 0.40; and wherein G is one or more Group 17 (halogen) elements.


Aspects disclosed herein include first devices comprising: a material, the material comprising: a lithium thioborate composition characterized by formula FX4: Li3−zB1S3−yGy (FX4); wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S; wherein y is a number greater than 0 and less than or equal to 0.40; and wherein G is one or more Group 17 (halogen) elements.


Aspects disclosed herein include second devices comprising: a material, the material comprising: a lithium thioborate composition characterized by formula FX2: Li3−zB1−xQxS3−yGy (FX2); wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B; wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S; wherein x is a number greater than 0 and less than or equal to 0.10; wherein y is a number greater than 0 and less than or equal to 0.40; and wherein G is one or more Group 17 (halogen) elements.


In one embodiment of the first or second devices, the device is an electrochemical cell. In some embodiments, the electrochemical cell comprises a solid state electrolyte having the material.


In one embodiment of the first or second devices, the device is a rechargeable lithium battery.


Aspects disclosed herein include solid state electrolytes comprising: a lithium thioborate composition characterized by formula FX4: Li3−zB1S3−yGy (FX4); wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S; wherein y is a number greater than 0 and less than or equal to 0.40; and wherein G is one or more Group 17 (halogen) elements.


Aspects disclosed herein include solid state electrolytes comprising: a lithium thioborate composition characterized by formula FX2: Li3−x−yB1−xQxS3−yGy (FX2); wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B; wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S; wherein x is a number greater than 0 and less than or equal to 0.10; wherein y is a number greater than 0 and less than or equal to 0.40; and wherein G is one or more Group 17 (halogen) elements.


Aspects disclosed herein include methods of making a material, the method comprising: combining a plurality of precursors comprising lithium, boron, sulfur, and a dopant; and heating the combined plurality of precursors to form the material having a lithium thioborate composition; wherein the lithium thioborate composition is characterized by formula FX4: Li3−zB1S3−yGy (FX4); wherein G is the dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S; wherein z is a number greater than 0 and less than or equal to 0.40; and wherein G is one or more Group 17 (halogen) elements.


Aspects disclosed herein include methods of making a material, the method comprising: combining a plurality of precursors comprising lithium, boron, sulfur, a first dopant, and a second dopant; and heating the combined plurality of precursors to form the material having a lithium thioborate composition; wherein the lithium thioborate composition is characterized by formula FX2: Li3−x−yB1−xQxS3−yGy (FX2); wherein Q is the first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B; wherein G is the second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S; wherein x is a number greater than 0 and less than or equal to 0.10; wherein y is a number greater than 0 and less than or equal to 0.40; and wherein G is one or more Group 17 (halogen) elements.


References cited above:

  • 1. Park, H., Yu, S. & Siegel, D. J. Predicting Charge Transfer Stability between Sulfide Solid Electrolytes and Li Metal Anodes. ACS Energy Lett. 6, 150-157 (2021).
  • 2. Kimura, T. et al. Characteristics of a Li3BS3 Thioborate Glass Electrolyte Obtained via a Mechanochemical Process. ACS Appl. Energy Mater. 5, 1421-1426 (2022).


The substituted or doped compositions disclosed herein generally have a low concentration or a low relative amount of one or more dopants. Preferably, a total dopant concentration (concentration of the one or more dopants in a composition) in a material or composition thereof is less than or equal to 30 at. %, optionally less than or equal to 28 at. %, optionally less than or equal to 25 at. %, optionally less than or equal to 22 at. %, optionally less than or equal to 21 at. %, optionally less than or equal to 20 at. %, optionally less than or equal to 19 at. %, optionally less than or equal to 18 at. %, optionally less than or equal to 17 at. %, optionally less than or equal to 16 at. %, optionally less than or equal to 15 at. %, optionally less than or equal to 14 at. %, optionally less than or equal to 13 at. %, optionally less than or equal to 12 at. %, optionally less than or equal to 11 at. %, optionally less than or equal to 10 at. %, optionally less than or equal to 9 at. %, optionally less than or equal to 8 at. %, optionally less than or equal to 7 at. %, optionally less than or equal to 6 at. %, optionally less than or equal to 5.0 at. %, optionally less than or equal to 4.5 at. %, optionally less than or equal to 4.0 at. %, optionally less than or equal to 3.5 at. %, optionally less than or equal to 3.0 at. %, optionally less than or equal to 2.7 at. %, optionally less than or equal to 2.5 at. %, optionally less than or equal to 2.3 at. %, optionally less than or equal to 2.1 at. %, optionally less than or equal to 2.0 at. %, optionally less than or equal to 1.9 at. %, optionally less than or equal to 1.7 at. %, optionally less than or equal to 1.5 at. %, optionally less than or equal to 1.3 at. %, optionally less than or equal to 1.0 at. %, optionally less than or equal to 0.8 at. %, optionally less than or equal to 0.7 at. %, optionally less than or equal to 0.6 at. %, optionally less than or equal to 0.5 at. %, optionally less than or equal to 0.4 at. %, optionally less than or equal to 0.3 at. %, optionally less than or equal to 0.2 at. %. Preferably, a total dopant concentration (concentration of the one or more dopants in a composition) in a material or composition thereof is greater than or equal to 0.1 at. % (optionally greater than or equal to 0.12%, optionally greater than or equal to 0.14%, optionally greater than or equal to 0.15%, optionally greater than or equal to 0.16%, optionally greater than or equal to 0.17%, optionally greater than or equal to 0.19%, optionally greater than or equal to 0.20%, optionally greater than or equal to 0.21%, optionally greater than or equal to 0.22%, optionally greater than or equal to 0.23%, optionally greater than or equal to 0.25%, optionally greater than or equal to 0.27%, optionally greater than or equal to 0.29%, optionally greater than or equal to 0.30%, optionally greater than or equal to 0.35%, optionally greater than or equal to 0.40%, optionally greater than or equal to 0.45%, optionally greater than or equal to 0.50%, optionally greater than or equal to 0.55%, optionally greater than or equal to 0.65%, optionally greater than or equal to 0.70%, optionally greater than or equal to 0.75%, optionally greater than or equal to 0.80%, optionally greater than or equal to 0.85%, optionally greater than or equal to 0.95%, optionally greater than or equal to 1.0%, optionally greater than or equal to 1.2%, optionally greater than or equal to 1.5%, optionally greater than or equal to 1.7%, optionally greater than or equal to 2.0%, optionally greater than or equal to 2.2%, optionally greater than or equal to 2.5%) and less than or equal to 30 at. % (optionally less than or equal to 28 at. %, optionally less than or equal to 25 at. %, optionally less than or equal to 22 at. %, optionally less than or equal to 21 at. %, optionally less than or equal to 20 at. %, optionally less than or equal to 19 at. %, optionally less than or equal to 18 at. %, optionally less than or equal to 17 at. %, optionally less than or equal to 16 at. %, optionally less than or equal to 15 at. %, optionally less than or equal to 14 at. %, optionally less than or equal to 13 at. %, optionally less than or equal to 12 at. %, optionally less than or equal to 11 at. %, optionally less than or equal to 10 at. %, optionally less than or equal to 9 at. %, optionally less than or equal to 8 at. %, optionally less than or equal to 7 at. %, optionally less than or equal to 6 at. %, optionally less than or equal to 5.0 at. %, optionally less than or equal to 4.5 at. %, optionally less than or equal to 4.0 at. %, optionally less than or equal to 3.5 at. %, optionally less than or equal to 3.0 at. %, optionally less than or equal to 2.7 at. %, optionally less than or equal to 2.5 at. %, optionally less than or equal to 2.3 at. %, optionally less than or equal to 2.1 at. %, optionally less than or equal to 2.0 at. %, optionally less than or equal to 1.9 at. %, optionally less than or equal to 1.7 at. %, optionally less than or equal to 1.5 at. %, optionally less than or equal to 1.3 at. %, optionally less than or equal to 1.0 at. %, optionally less than or equal to 0.8 at. %, optionally less than or equal to 0.7 at. %, optionally less than or equal to 0.6 at. %, optionally less than or equal to 0.5 at. %, optionally less than or equal to 0.4 at. %, optionally less than or equal to 0.3 at. %, optionally less than or equal to 0.2 at. %). Any value and range of total dopant concentration (concentration of the one or more dopants in a composition) between 0.1 at. % and 30 at. % is explicitly contemplated and disclosed herein. For example, optionally a total dopant concentration (concentration of the one or more dopants in a composition) in a material or composition thereof is selected from the range of 0.1 at. % to 20 at. %, optionally selected from the range of 0.1 at. % to 15 at. %, optionally selected from the range of 0.1 at. % to 10 at. %, optionally selected from the range of 0.1 at. % to 5 at. %, optionally selected from the range of 0.1 at. % to 4.0 at. %, optionally selected from the range of 0.1 at. % to 3.0 at. %, optionally selected from the range of 0.1 at. % to 2.5 at. %, optionally selected from the range of 0.1 at. % to 2.0 at. %, optionally selected from the range of 0.1 at. % to 1.5 at. %, optionally selected from the range of 0.1 at. % to 1.0 at. %, optionally selected from the range of 0.1 at. % to 0.95 at. %.


Preferably for some aspects or applications, a total dopant concentration (concentration of the one or more dopants in a composition) in a material or composition thereof is less than or equal to 30 mol. %, optionally less than or equal to 28 mol. %, optionally less than or equal to 25 mol. %, optionally less than or equal to 22 mol. %, optionally less than or equal to 21 mol. %, optionally less than or equal to 20 mol. %, optionally less than or equal to 19 mol. %, optionally less than or equal to 18 mol. %, optionally less than or equal to 17 mol. %, optionally less than or equal to 16 mol. %, optionally less than or equal to 15 mol. %, optionally less than or equal to 14 mol. %, optionally less than or equal to 13 mol. %, optionally less than or equal to 12 mol. %, optionally less than or equal to 11 mol. %, optionally less than or equal to 10 mol. %, optionally less than or equal to 9 mol. %, optionally less than or equal to 8 mol. %, optionally less than or equal to 7 mol. %, optionally less than or equal to 6 mol. %, optionally less than or equal to 5.0 mol. %, optionally less than or equal to 4.5 mol. %, optionally less than or equal to 4.0 mol. %, optionally less than or equal to 3.5 mol. %, optionally less than or equal to 3.0 mol. %, optionally less than or equal to 2.7 mol. %, optionally less than or equal to 2.5 mol. %, optionally less than or equal to 2.3 mol. %, optionally less than or equal to 2.1 mol. %, optionally less than or equal to 2.0 mol. %, optionally less than or equal to 1.9 mol. %, optionally less than or equal to 1.7 mol. %, optionally less than or equal to 1.5 mol. %, optionally less than or equal to 1.3 mol. %, optionally less than or equal to 1.0 mol. %, optionally less than or equal to 0.8 mol. %, optionally less than or equal to 0.7 mol. %, optionally less than or equal to 0.6 mol. %, optionally less than or equal to 0.5 mol. %, optionally less than or equal to 0.4 mol. %, optionally less than or equal to 0.3 mol. %, optionally less than or equal to 0.2 mol. %. Preferably, a total dopant concentration (concentration of the one or more dopants in a composition) in a material or composition thereof is greater than or equal to 0.1 mol. % (optionally greater than or equal to 0.12%, optionally greater than or equal to 0.14%, optionally greater than or equal to 0.15%, optionally greater than or equal to 0.16%, optionally greater than or equal to 0.17%, optionally greater than or equal to 0.19%, optionally greater than or equal to 0.20%, optionally greater than or equal to 0.21%, optionally greater than or equal to 0.22%, optionally greater than or equal to 0.23%, optionally greater than or equal to 0.25%, optionally greater than or equal to 0.27%, optionally greater than or equal to 0.29%, optionally greater than or equal to 0.30%, optionally greater than or equal to 0.35%, optionally greater than or equal to 0.40%, optionally greater than or equal to 0.45%, optionally greater than or equal to 0.50%, optionally greater than or equal to 0.55%, optionally greater than or equal to 0.65%, optionally greater than or equal to 0.70%, optionally greater than or equal to 0.75%, optionally greater than or equal to 0.80%, optionally greater than or equal to 0.85%, optionally greater than or equal to 0.95%, optionally greater than or equal to 1.0%, optionally greater than or equal to 1.2%, optionally greater than or equal to 1.5%, optionally greater than or equal to 1.7%, optionally greater than or equal to 2.0%, optionally greater than or equal to 2.2%, optionally greater than or equal to 2.5%) and less than or equal to 30 mol. % (optionally less than or equal to 28 mol. %, optionally less than or equal to 25 mol. %, optionally less than or equal to 22 mol. %, optionally less than or equal to 21 mol. %, optionally less than or equal to 20 mol. %, optionally less than or equal to 19 mol. %, optionally less than or equal to 18 mol. %, optionally less than or equal to 17 mol. %, optionally less than or equal to 16 mol. %, optionally less than or equal to 15 mol. %, optionally less than or equal to 14 mol. %, optionally less than or equal to 13 mol. %, optionally less than or equal to 12 mol. %, optionally less than or equal to 11 mol. %, optionally less than or equal to 10 mol. %, optionally less than or equal to 9 mol. %, optionally less than or equal to 8 mol. %, optionally less than or equal to 7 mol. %, optionally less than or equal to 6 mol. %, optionally less than or equal to 5.0 mol. %, optionally less than or equal to 4.5 mol. %, optionally less than or equal to 4.0 mol. %, optionally less than or equal to 3.5 mol. %, optionally less than or equal to 3.0 mol. %, optionally less than or equal to 2.7 mol. %, optionally less than or equal to 2.5 mol. %, optionally less than or equal to 2.3 mol. %, optionally less than or equal to 2.1 mol. %, optionally less than or equal to 2.0 mol. %, optionally less than or equal to 1.9 mol. %, optionally less than or equal to 1.7 mol. %, optionally less than or equal to 1.5 mol. %, optionally less than or equal to 1.3 mol. %, optionally less than or equal to 1.0 mol. %, optionally less than or equal to 0.8 mol. %, optionally less than or equal to 0.7 mol. %, optionally less than or equal to 0.6 mol. %, optionally less than or equal to 0.5 mol. %, optionally less than or equal to 0.4 mol. %, optionally less than or equal to 0.3 mol. %, optionally less than or equal to 0.2 mol. %). Any value and range of total dopant concentration (concentration of the one or more dopants in a composition) between 0.1 mol. % and 30 mol. % is explicitly contemplated and disclosed herein. For example, optionally a total dopant concentration (concentration of the one or more dopants in a composition) in a material or composition thereof is selected from the range of 0.1 mol. % to 20 mol. %, optionally selected from the range of 0.1 mol. % to 15 mol. %, optionally selected from the range of 0.1 mol. % to 10 mol. %, optionally selected from the range of 0.1 mol. % to 5 mol. %, optionally selected from the range of 0.1 mol. % to 4.0 mol. %, optionally selected from the range of 0.1 mol. % to 3.0 mol. %, optionally selected from the range of 0.1 mol. % to 2.5 mol. %, optionally selected from the range of 0.1 mol. % to 2.0 mol. %, optionally selected from the range of 0.1 mol. % to 1.5 mol. %, optionally selected from the range of 0.1 mol. % to 1.0 mol. %, optionally selected from the range of 0.1 mol. % to 0.95 mol. %.


Preferably for some aspects or applications, a total dopant concentration (concentration of the one or more dopants in a composition) in a material or composition thereof is less than or equal to 30 wt. %, optionally less than or equal to 28 wt. %, optionally less than or equal to 25 wt. %, optionally less than or equal to 22 wt. %, optionally less than or equal to 21 wt. %, optionally less than or equal to 20 wt. %, optionally less than or equal to 19 wt. %, optionally less than or equal to 18 wt. %, optionally less than or equal to 17 wt. %, optionally less than or equal to 16 wt. %, optionally less than or equal to 15 wt. %, optionally less than or equal to 14 wt. %, optionally less than or equal to 13 wt. %, optionally less than or equal to 12 wt. %, optionally less than or equal to 11 wt. %, optionally less than or equal to 10 wt. %, optionally less than or equal to 9 wt. %, optionally less than or equal to 8 wt. %, optionally less than or equal to 7 wt. %, optionally less than or equal to 6 wt. %, optionally less than or equal to 5.0 wt. %, optionally less than or equal to 4.5 wt. %, optionally less than or equal to 4.0 wt. %, optionally less than or equal to 3.5 wt. %, optionally less than or equal to 3.0 wt. %, optionally less than or equal to 2.7 wt. %, optionally less than or equal to 2.5 wt. %, optionally less than or equal to 2.3 wt. %, optionally less than or equal to 2.1 wt. %, optionally less than or equal to 2.0 wt. %, optionally less than or equal to 1.9 wt. %, optionally less than or equal to 1.7 wt. %, optionally less than or equal to 1.5 wt. %, optionally less than or equal to 1.3 wt. %, optionally less than or equal to 1.0 wt. %, optionally less than or equal to 0.8 wt. %, optionally less than or equal to 0.7 wt. %, optionally less than or equal to 0.6 wt. %, optionally less than or equal to 0.5 wt. %, optionally less than or equal to 0.4 wt. %, optionally less than or equal to 0.3 wt. %, optionally less than or equal to 0.2 wt. %. Preferably, a total dopant concentration (concentration of the one or more dopants in a composition) in a material or composition thereof is greater than or equal to 0.1 wt. % (optionally greater than or equal to 0.12%, optionally greater than or equal to 0.14%, optionally greater than or equal to 0.15%, optionally greater than or equal to 0.16%, optionally greater than or equal to 0.17%, optionally greater than or equal to 0.19%, optionally greater than or equal to 0.20%, optionally greater than or equal to 0.21%, optionally greater than or equal to 0.22%, optionally greater than or equal to 0.23%, optionally greater than or equal to 0.25%, optionally greater than or equal to 0.27%, optionally greater than or equal to 0.29%, optionally greater than or equal to 0.30%, optionally greater than or equal to 0.35%, optionally greater than or equal to 0.40%, optionally greater than or equal to 0.45%, optionally greater than or equal to 0.50%, optionally greater than or equal to 0.55%, optionally greater than or equal to 0.65%, optionally greater than or equal to 0.70%, optionally greater than or equal to 0.75%, optionally greater than or equal to 0.80%, optionally greater than or equal to 0.85%, optionally greater than or equal to 0.95%, optionally greater than or equal to 1.0%, optionally greater than or equal to 1.2%, optionally greater than or equal to 1.5%, optionally greater than or equal to 1.7%, optionally greater than or equal to 2.0%, optionally greater than or equal to 2.2%, optionally greater than or equal to 2.5%) and less than or equal to 30 wt. % (optionally less than or equal to 28 wt. %, optionally less than or equal to 25 wt. %, optionally less than or equal to 22 wt. %, optionally less than or equal to 21 wt. %, optionally less than or equal to 20 wt. %, optionally less than or equal to 19 wt. %, optionally less than or equal to 18 wt. %, optionally less than or equal to 17 wt. %, optionally less than or equal to 16 wt. %, optionally less than or equal to 15 wt. %, optionally less than or equal to 14 wt. %, optionally less than or equal to 13 wt. %, optionally less than or equal to 12 wt. %, optionally less than or equal to 11 wt. %, optionally less than or equal to 10 wt. %, optionally less than or equal to 9 wt. %, optionally less than or equal to 8 wt. %, optionally less than or equal to 7 wt. %, optionally less than or equal to 6 wt. %, optionally less than or equal to 5.0 wt. %, optionally less than or equal to 4.5 wt. %, optionally less than or equal to 4.0 wt. %, optionally less than or equal to 3.5 wt. %, optionally less than or equal to 3.0 wt. %, optionally less than or equal to 2.7 wt. %, optionally less than or equal to 2.5 wt. %, optionally less than or equal to 2.3 wt. %, optionally less than or equal to 2.1 wt. %, optionally less than or equal to 2.0 wt. %, optionally less than or equal to 1.9 wt. %, optionally less than or equal to 1.7 wt. %, optionally less than or equal to 1.5 wt. %, optionally less than or equal to 1.3 wt. %, optionally less than or equal to 1.0 wt. %, optionally less than or equal to 0.8 wt. %, optionally less than or equal to 0.7 wt. %, optionally less than or equal to 0.6 wt. %, optionally less than or equal to 0.5 wt. %, optionally less than or equal to 0.4 wt. %, optionally less than or equal to 0.3 wt. %, optionally less than or equal to 0.2 wt. %). Any value and range of total dopant concentration (concentration of the one or more dopants in a composition) between 0.1 wt. % and 30 wt. % is explicitly contemplated and disclosed herein. For example, optionally a total dopant concentration (concentration of the one or more dopants in a composition) in a material or composition thereof is selected from the range of 0.1 wt. % to 20 wt. %, optionally selected from the range of 0.1 wt. % to 15 wt. %, optionally selected from the range of 0.1 wt. % to 10 wt. %, optionally selected from the range of 0.1 wt. % to 5 wt. %, optionally selected from the range of 0.1 wt. % to 4.0 wt. %, optionally selected from the range of 0.1 wt. % to 3.0 wt. %, optionally selected from the range of 0.1 wt. % to 2.5 wt. %, optionally selected from the range of 0.1 wt. % to 2.0 wt. %, optionally selected from the range of 0.1 wt. % to 1.5 wt. %, optionally selected from the range of 0.1 wt. % to 1.0 wt. %, optionally selected from the range of 0.1 wt. % to 0.95 wt. %.


The substituted or doped compositions disclosed herein generally have only a small amount of a principal element substituted for or replaced with a dopant (the dopant being one or more elements aliovalent with respect to the substituted or replaced principal element). Optionally, the relative amount of any principal element of a composition that is substituted with a dopant is less than or equal to 20 at. %, optionally less than or equal to 19 at. %, optionally less than or equal to 18 at. %, optionally less than or equal to 17 at. %, optionally less than or equal to 16 at. %, optionally less than or equal to 15 at. %, optionally less than or equal to 14 at. %, optionally less than or equal to 13 at. %, optionally less than or equal to 12 at. %, optionally less than or equal to 11 at. %, optionally less than or equal to 10 at. %, optionally less than or equal to 9 at. %, optionally less than or equal to 8 at. %, optionally less than or equal to 7 at. %, optionally less than or equal to 6 at. %, optionally less than or equal to 5.0 at. %, optionally less than or equal to 4.5 at. %, optionally less than or equal to 4.0 at. %, optionally less than or equal to 3.5 at. %, optionally less than or equal to 3.0 at. %, optionally less than or equal to 2.7 at. %, optionally less than or equal to 2.5 at. %, optionally less than or equal to 2.3 at. %, optionally less than or equal to 2.1 at. %, optionally less than or equal to 2.0 at. %, optionally less than or equal to 1.9 at. %, optionally less than or equal to 1.7 at. %, optionally less than or equal to 1.5 at. %, optionally less than or equal to 1.3 at. %, optionally less than or equal to 1.0 at. %, optionally less than or equal to 0.8 at. %, optionally less than or equal to 0.7 at. %, optionally less than or equal to 0.6 at. %, optionally less than or equal to 0.5 at. %, optionally less than or equal to 0.4 at. %, optionally less than or equal to 0.3 at. %, optionally less than or equal to 0.2 at. %. Optionally, the relative amount of any principal element of a composition that is substituted with a dopant is greater than or equal to 0.1 at. % (optionally greater than or equal to 0.12%, optionally greater than or equal to 0.14%, optionally greater than or equal to 0.15%, optionally greater than or equal to 0.16%, optionally greater than or equal to 0.17%, optionally greater than or equal to 0.19%, optionally greater than or equal to 0.20%, optionally greater than or equal to 0.21%, optionally greater than or equal to 0.22%, optionally greater than or equal to 0.23%, optionally greater than or equal to 0.25%, optionally greater than or equal to 0.27%, optionally greater than or equal to 0.29%, optionally greater than or equal to 0.30%, optionally greater than or equal to 0.35%, optionally greater than or equal to 0.40%, optionally greater than or equal to 0.45%, optionally greater than or equal to 0.50%, optionally greater than or equal to 0.55%, optionally greater than or equal to 0.65%, optionally greater than or equal to 0.70%, optionally greater than or equal to 0.75%, optionally greater than or equal to 0.80%, optionally greater than or equal to 0.85%, optionally greater than or equal to 0.95%, optionally greater than or equal to 1.0%, optionally greater than or equal to 1.2%, optionally greater than or equal to 1.5%, optionally greater than or equal to 1.7%, optionally greater than or equal to 2.0%, optionally greater than or equal to 2.2%, optionally greater than or equal to 2.5%) and less than or equal to 20 at. % (optionally less than or equal to 19 at. %, optionally less than or equal to 18 at. %, optionally less than or equal to 17 at. %, optionally less than or equal to 16 at. %, optionally less than or equal to 15 at. %, optionally less than or equal to 14 at. %, optionally less than or equal to 13 at. %, optionally less than or equal to 12 at. %, optionally less than or equal to 11 at. %, optionally less than or equal to 10 at. %, optionally less than or equal to 9 at. %, optionally less than or equal to 8 at. %, optionally less than or equal to 7 at. %, optionally less than or equal to 6 at. %, optionally less than or equal to 5.0 at. %, optionally less than or equal to 4.5 at. %, optionally less than or equal to 4.0 at. %, optionally less than or equal to 3.5 at. %, optionally less than or equal to 3.0 at. %, optionally less than or equal to 2.7 at. %, optionally less than or equal to 2.5 at. %, optionally less than or equal to 2.3 at. %, optionally less than or equal to 2.1 at. %, optionally less than or equal to 2.0 at. %, optionally less than or equal to 1.9 at. %, optionally less than or equal to 1.7 at. %, optionally less than or equal to 1.5 at. %, optionally less than or equal to 1.3 at. %, optionally less than or equal to 1.0 at. %, optionally less than or equal to 0.8 at. %, optionally less than or equal to 0.7 at. %, optionally less than or equal to 0.6 at. %, optionally less than or equal to 0.5 at. %, optionally less than or equal to 0.4 at. %, optionally less than or equal to 0.3 at. %, optionally less than or equal to 0.2 at. %). Any value and range of the relative amount, of any principal element of a composition that is substituted with a dopant, between 0.1 at. % and 20 at. % is explicitly contemplated and disclosed herein. For example, optionally, the relative amount of any principal element of a composition that is substituted with a dopant is selected from the range of 0.1 at. % to 20 at. %, optionally selected from the range of 0.1 at. % to 15 at. %, optionally selected from the range of 0.1 at. % to 10 at. %, optionally selected from the range of 0.1 at. % to 5 at. %, optionally selected from the range of 0.1 at. % to 4.0 at. %, optionally selected from the range of 0.1 at. % to 3.0 at. %, optionally selected from the range of 0.1 at. % to 2.5 at. %, optionally selected from the range of 0.1 at. % to 2.0 at. %, optionally selected from the range of 0.1 at. % to 1.5 at. %, optionally selected from the range of 0.1 at. % to 1.0 at. %, optionally selected from the range of 0.1 at. % to 0.95 at. %.


Optionally, the relative amount of any principal element of a composition that is substituted with a dopant is less than or equal to 20 mol. %, optionally less than or equal to 19 mol. %, optionally less than or equal to 18 mol. %, optionally less than or equal to 17 mol. %, optionally less than or equal to 16 mol. %, optionally less than or equal to 15 mol. %, optionally less than or equal to 14 mol. %, optionally less than or equal to 13 mol. %, optionally less than or equal to 12 mol. %, optionally less than or equal to 11 mol. %, optionally less than or equal to 10 mol. %, optionally less than or equal to 9 mol. %, optionally less than or equal to 8 mol. %, optionally less than or equal to 7 mol. %, optionally less than or equal to 6 mol. %, optionally less than or equal to 5.0 mol. %, optionally less than or equal to 4.5 mol. %, optionally less than or equal to 4.0 mol. %, optionally less than or equal to 3.5 mol. %, optionally less than or equal to 3.0 mol. %, optionally less than or equal to 2.7 mol. %, optionally less than or equal to 2.5 mol. %, optionally less than or equal to 2.3 mol. %, optionally less than or equal to 2.1 mol. %, optionally less than or equal to 2.0 mol. %, optionally less than or equal to 1.9 mol. %, optionally less than or equal to 1.7 mol. %, optionally less than or equal to 1.5 mol. %, optionally less than or equal to 1.3 mol. %, optionally less than or equal to 1.0 mol. %, optionally less than or equal to 0.8 mol. %, optionally less than or equal to 0.7 mol. %, optionally less than or equal to 0.6 mol. %, optionally less than or equal to 0.5 mol. %, optionally less than or equal to 0.4 mol. %, optionally less than or equal to 0.3 mol. %, optionally less than or equal to 0.2 mol. %. Optionally, the relative amount of any principal element of a composition that is substituted with a dopant is greater than or equal to 0.1 mol. % (optionally greater than or equal to 0.12%, optionally greater than or equal to 0.14%, optionally greater than or equal to 0.15%, optionally greater than or equal to 0.16%, optionally greater than or equal to 0.17%, optionally greater than or equal to 0.19%, optionally greater than or equal to 0.20%, optionally greater than or equal to 0.21%, optionally greater than or equal to 0.22%, optionally greater than or equal to 0.23%, optionally greater than or equal to 0.25%, optionally greater than or equal to 0.27%, optionally greater than or equal to 0.29%, optionally greater than or equal to 0.30%, optionally greater than or equal to 0.35%, optionally greater than or equal to 0.40%, optionally greater than or equal to 0.45%, optionally greater than or equal to 0.50%, optionally greater than or equal to 0.55%, optionally greater than or equal to 0.65%, optionally greater than or equal to 0.70%, optionally greater than or equal to 0.75%, optionally greater than or equal to 0.80%, optionally greater than or equal to 0.85%, optionally greater than or equal to 0.95%, optionally greater than or equal to 1.0%, optionally greater than or equal to 1.2%, optionally greater than or equal to 1.5%, optionally greater than or equal to 1.7%, optionally greater than or equal to 2.0%, optionally greater than or equal to 2.2%, optionally greater than or equal to 2.5%) and less than or equal to 20 mol. % (optionally less than or equal to 19 mol. %, optionally less than or equal to 18 mol. %, optionally less than or equal to 17 mol. %, optionally less than or equal to 16 mol. %, optionally less than or equal to 15 mol. %, optionally less than or equal to 14 mol. %, optionally less than or equal to 13 mol. %, optionally less than or equal to 12 mol. %, optionally less than or equal to 11 mol. %, optionally less than or equal to 10 mol. %, optionally less than or equal to 9 mol. %, optionally less than or equal to 8 mol. %, optionally less than or equal to 7 mol. %, optionally less than or equal to 6 mol. %, optionally less than or equal to 5.0 mol. %, optionally less than or equal to 4.5 mol. %, optionally less than or equal to 4.0 mol. %, optionally less than or equal to 3.5 mol. %, optionally less than or equal to 3.0 mol. %, optionally less than or equal to 2.7 mol. %, optionally less than or equal to 2.5 mol. %, optionally less than or equal to 2.3 mol. %, optionally less than or equal to 2.1 mol. %, optionally less than or equal to 2.0 mol. %, optionally less than or equal to 1.9 mol. %, optionally less than or equal to 1.7 mol. %, optionally less than or equal to 1.5 mol. %, optionally less than or equal to 1.3 mol. %, optionally less than or equal to 1.0 mol. %, optionally less than or equal to 0.8 mol. %, optionally less than or equal to 0.7 mol. %, optionally less than or equal to 0.6 mol. %, optionally less than or equal to 0.5 mol. %, optionally less than or equal to 0.4 mol. %, optionally less than or equal to 0.3 mol. %, optionally less than or equal to 0.2 mol. %). Any value and range of the relative amount, of any principal element of a composition that is substituted with a dopant, between 0.1 mol. % and 20 mol. % is explicitly contemplated and disclosed herein. For example, optionally, the relative amount of any principal element of a composition that is substituted with a dopant is selected from the range of 0.1 mol. % to 20 mol. %, optionally selected from the range of 0.1 mol. % to 15 mol. %, optionally selected from the range of 0.1 mol. % to 10 mol. %, optionally selected from the range of 0.1 mol. % to 5 mol. %, optionally selected from the range of 0.1 mol. % to 4.0 mol. %, optionally selected from the range of 0.1 mol. % to 3.0 mol. %, optionally selected from the range of 0.1 mol. % to 2.5 mol. %, optionally selected from the range of 0.1 mol. % to 2.0 mol. %, optionally selected from the range of 0.1 mol. % to 1.5 mol. %, optionally selected from the range of 0.1 mol. % to 1.0 mol. %, optionally selected from the range of 0.1 mol. % to 0.95 mol. %.


Optionally, the relative amount of any principal element of a composition that is substituted with a dopant is less than or equal to 20 wt. %, optionally less than or equal to 19 wt. %, optionally less than or equal to 18 wt. %, optionally less than or equal to 17 wt. %, optionally less than or equal to 16 wt. %, optionally less than or equal to 15 wt. %, optionally less than or equal to 14 wt. %, optionally less than or equal to 13 wt. %, optionally less than or equal to 12 wt. %, optionally less than or equal to 11 wt. %, optionally less than or equal to 10 wt. %, optionally less than or equal to 9 wt. %, optionally less than or equal to 8 wt. %, optionally less than or equal to 7 wt. %, optionally less than or equal to 6 wt. %, optionally less than or equal to 5.0 wt. %, optionally less than or equal to 4.5 wt. %, optionally less than or equal to 4.0 wt. %, optionally less than or equal to 3.5 wt. %, optionally less than or equal to 3.0 wt. %, optionally less than or equal to 2.7 wt. %, optionally less than or equal to 2.5 wt. %, optionally less than or equal to 2.3 wt. %, optionally less than or equal to 2.1 wt. %, optionally less than or equal to 2.0 wt. %, optionally less than or equal to 1.9 wt. %, optionally less than or equal to 1.7 wt. %, optionally less than or equal to 1.5 wt. %, optionally less than or equal to 1.3 wt. %, optionally less than or equal to 1.0 wt. %, optionally less than or equal to 0.8 wt. %, optionally less than or equal to 0.7 wt. %, optionally less than or equal to 0.6 wt. %, optionally less than or equal to 0.5 wt. %, optionally less than or equal to 0.4 wt. %, optionally less than or equal to 0.3 wt. %, optionally less than or equal to 0.2 wt. %. Optionally, the relative amount of any principal element of a composition that is substituted with a dopant is greater than or equal to 0.1 wt. % (optionally greater than or equal to 0.12%, optionally greater than or equal to 0.14%, optionally greater than or equal to 0.15%, optionally greater than or equal to 0.16%, optionally greater than or equal to 0.17%, optionally greater than or equal to 0.19%, optionally greater than or equal to 0.20%, optionally greater than or equal to 0.21%, optionally greater than or equal to 0.22%, optionally greater than or equal to 0.23%, optionally greater than or equal to 0.25%, optionally greater than or equal to 0.27%, optionally greater than or equal to 0.29%, optionally greater than or equal to 0.30%, optionally greater than or equal to 0.35%, optionally greater than or equal to 0.40%, optionally greater than or equal to 0.45%, optionally greater than or equal to 0.50%, optionally greater than or equal to 0.55%, optionally greater than or equal to 0.65%, optionally greater than or equal to 0.70%, optionally greater than or equal to 0.75%, optionally greater than or equal to 0.80%, optionally greater than or equal to 0.85%, optionally greater than or equal to 0.95%, optionally greater than or equal to 1.0%, optionally greater than or equal to 1.2%, optionally greater than or equal to 1.5%, optionally greater than or equal to 1.7%, optionally greater than or equal to 2.0%, optionally greater than or equal to 2.2%, optionally greater than or equal to 2.5%) and less than or equal to 20 wt. % (optionally less than or equal to 19 wt. %, optionally less than or equal to 18 wt. %, optionally less than or equal to 17 wt. %, optionally less than or equal to 16 wt. %, optionally less than or equal to 15 wt. %, optionally less than or equal to 14 wt. %, optionally less than or equal to 13 wt. %, optionally less than or equal to 12 wt. %, optionally less than or equal to 11 wt. %, optionally less than or equal to 10 wt. %, optionally less than or equal to 9 wt. %, optionally less than or equal to 8 wt. %, optionally less than or equal to 7 wt. %, optionally less than or equal to 6 wt. %, optionally less than or equal to 5.0 wt. %, optionally less than or equal to 4.5 wt. %, optionally less than or equal to 4.0 wt. %, optionally less than or equal to 3.5 wt. %, optionally less than or equal to 3.0 wt. %, optionally less than or equal to 2.7 wt. %, optionally less than or equal to 2.5 wt. %, optionally less than or equal to 2.3 wt. %, optionally less than or equal to 2.1 wt. %, optionally less than or equal to 2.0 wt. %, optionally less than or equal to 1.9 wt. %, optionally less than or equal to 1.7 wt. %, optionally less than or equal to 1.5 wt. %, optionally less than or equal to 1.3 wt. %, optionally less than or equal to 1.0 wt. %, optionally less than or equal to 0.8 wt. %, optionally less than or equal to 0.7 wt. %, optionally less than or equal to 0.6 wt. %, optionally less than or equal to 0.5 wt. %, optionally less than or equal to 0.4 wt. %, optionally less than or equal to 0.3 wt. %, optionally less than or equal to 0.2 wt. %). Any value and range of the relative amount, of any principal element of a composition that is substituted with a dopant, between 0.1 wt. % and 20 wt. % is explicitly contemplated and disclosed herein. For example, optionally, the relative amount of any principal element of a composition that is substituted with a dopant is selected from the range of 0.1 wt. % to 20 wt. %, optionally selected from the range of 0.1 wt. % to 15 wt. %, optionally selected from the range of 0.1 wt. % to 10 wt. %, optionally selected from the range of 0.1 wt. % to 5 wt. %, optionally selected from the range of 0.1 wt. % to 4.0 wt. %, optionally selected from the range of 0.1 wt. % to 3.0 wt. %, optionally selected from the range of 0.1 wt. % to 2.5 wt. %, optionally selected from the range of 0.1 wt. % to 2.0 wt. %, optionally selected from the range of 0.1 wt. % to 1.5 wt. %, optionally selected from the range of 0.1 wt. % to 1.0 wt. %, optionally selected from the range of 0.1 wt. % to 0.95 wt. %.


Certain Aspects And Embodiments

Various aspects are contemplated and disclosed herein, several of which are set forth in the paragraphs below. It is explicitly contemplated and disclosed that any aspect or portion thereof can be combined to form an aspect. In addition, it is explicitly contemplated and disclosed that: any reference to Aspect 1 includes reference to Aspects 1a, 1b, 1c, 1d, 1e, 1f, 1g, 1h, 1i, 1j, 1k, and/or 1l, and any combination thereof; any reference to Aspect 3 includes reference to Aspects 3a, 3b, and/or 3c; and so on (i.e., any reference to an aspect includes reference to that aspect's lettered versions). Moreover, the terms “any preceding aspect” and “any one of the preceding aspects” means any aspect that appears prior to the aspect that contains such phrase (for example, the sentence “Aspect 15: The material, device, electrolyte, or method of any preceding Aspect . . . ” means that any Aspect prior to Aspect 15 is referenced, including letter versions, including aspects 1a through 14b). For example, it is contemplated and disclosed that, optionally, any composition, method, or formulation of any the below aspects may be useful with or combined with any other aspect provided below. Further, for example, it is contemplated and disclosed that any embodiment or aspect described above may, optionally, be combined with any of the below listed aspects.


Aspect 1a: A material comprising:

    • a lithium thioborate composition characterized by formula FX1:





Li3−z[B+Q]1[S+G]3  (FX1);

    • wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein z is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein the composition comprises only the first dopant, only the second dopant, or both the first dopant and the second dopant.


Aspect 1b: A device comprising:

    • a material, the material comprising:
    • a lithium thioborate composition characterized by formula FX1:





Li3−z[B+Q]1[S+G]3  (FX1);

    • wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein z is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein the composition comprises only the first dopant, only the second dopant, or both the first dopant and the second dopant.


Aspect 1c: A solid state electrolyte comprising:

    • a lithium thioborate composition characterized by formula FX1:





Li3−z[B+Q]1[S+G]3  (FX1);

    • wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein z is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein the composition comprises only the first dopant, only the second dopant, or both the first dopant and the second dopant.


Aspect 1d: A method of making a material, the method comprising:

    • combining a plurality of precursors comprising lithium, boron, sulfur, and at least one of a first dopant and a second dopant; and
    • heating the combined plurality of precursors to form the material having a lithium thioborate composition;
    • wherein the lithium thioborate composition is characterized by formula FX1:





Li3−z[B+Q]1[S+G]3  (FX1);

    • wherein Q is the first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is the second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein z is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein the composition comprises only the first dopant, only the second dopant, or both the first dopant and the second dopant.


Aspect 1e: An electrolyte comprising:

    • a lithium solid state electrolyte comprising Li, one or more principal elements (optionally, non-Li principal elements), and at least one dopant;
    • wherein the dopant substitutes for a portion of the one of the one or more principal elements (optionally, non-Li principal elements) of the lithium solid state electrolyte and is aliovalent with the respective substituted principal elements (optionally, non-Li principal elements);
    • wherein the ionic conductivity of the lithium solid state electrolyte is greater than or equal to 1·10−5 S/cm at 25° C.


Aspect 1f: A doped lithium solid state electrolyte comprising:

    • a doped inorganic composition having at least one dopant;
    • wherein the doped composition has up to 20 at. % (optionally up to 15 at. %, optionally up to 12 at. %, optionally up to 10 at. %, optionally up to 8 at. %, optionally up to 5 at. %, optionally up to 3 at. %, optionally up to 2 at. %, optionally up to 1 at. %, optionally up to 0.9 at. %, optionally up to 0.8 at. %, optionally up to 0.7 at. %, optionally up to 0.5 at. %) of one or more principal elements (optionally, non-Li principal elements) substituted with the at least one dopant relative to a reference composition of a reference lithium solid state electrolyte;
    • wherein each dopant is one or more elements each aliovalent with the respective substituted principal element (optionally, a non-Li principal element);
    • wherein the presence of the one or more dopants provides for an ionic conductivity greater than or equal to 1·10−5 S/cm at 25° C.


Aspect 1g: A method for increasing an ionic conductivity of a reference lithium solid state electrolyte, the method comprising:

    • forming a doped lithium solid state electrolyte having a doped composition;
    • wherein the reference lithium solid state electrolyte has a reference composition, and wherein the doped composition has up to 20 at. % (optionally up to 15 at. %, optionally up to 12 at. %, optionally up to 10 at. %, optionally up to 8 at. %, optionally up to 5 at. %, optionally up to 3 at. %, optionally up to 2 at. %, optionally up to 1 at. %, optionally up to 0.9 at. %, optionally up to 0.8 at. %, optionally up to 0.7 at. %, optionally up to 0.5 at. %) of one or more principal elements (optionally, non-Li principal elements) substituted with at least one dopant relative to the reference composition;
    • wherein each element of the at least one dopant is aliovalent with respect to the respective substituted principal element (optionally, a non-Li principal element); and
    • wherein the doped lithium solid state electrolyte has a greater ionic conductivity than the reference lithium solid state electrolyte by a factor of at least 2 (optionally at least 3, optionally at least 4, optionally at least 5, optionally at least 6, optionally at least 7, optionally at least 8, optionally at least 9, optionally at least 10, optionally at least 11, optionally at least 12, optionally at least 13, optionally at least 14, optionally at least 15, optionally at least 18, optionally at least 20, optionally at least 21, optionally at least 22, optionally at least 23, optionally at least 24, optionally at least 25, optionally at least 50, optionally at least 75, optionally at least 100, optionally at least 125, optionally at least 150, optionally at least 175, optionally at least 200, optionally at least 300, optionally at least 400, optionally at least 500, optionally at least 600, optionally at least 700, optionally at least 800, optionally at least 900, optionally at least 1000, optionally at least 1100, optionally at least 1200, optionally at least 1300, optionally at least 1400).


Aspect 1h: The material, device, electrolyte, or method of Aspect 1, wherein z is greater than 0 and less than 1 (optionally less than or equal to 0.50, optionally less than or equal to 0.45, optionally less than or equal to 0.40, optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025).


The material, device, electrolyte, or method of Aspect 1, wherein z is greater than 0 and less than 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025).


Aspect 1j: The material, device, electrolyte, or method of Aspect 1, wherein the material or the composition thereof is a solid solution.


Aspect 1k: Any material or composition disclosed herein, such as any of those disclosed in Examples 1A and 1B, optionally further doped/substituted and/or optionally amorphized.


Aspect 1l: The material, device, electrolyte, or method of Aspect 1, wherein z is greater than 0 and less than 0.15.


Aspect 2a: A material comprising:

    • a lithium thioborate composition characterized by formula FX2:





Li3−x−yB1−xQxS3−yGy  (FX2);

    • wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein x is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025);
    • wherein y is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 2b: A device comprising:

    • a material, the material comprising:
    • a lithium thioborate composition characterized by formula FX2:





Li3−x−yB1−xQxS3−yGy  (FX2);

    • wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein x is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025);
    • wherein y is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 2c: A solid state electrolyte comprising:

    • a lithium thioborate composition characterized by formula FX2:





Li3−x−yB1−xQxS3−yGy  (FX2);

    • wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein x is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025);
    • wherein y is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 2d: A method of making a material, the method comprising:

    • combining a plurality of precursors comprising lithium, boron, sulfur, a first dopant, and a second dopant; and
    • heating the combined plurality of precursors to form the material having a lithium thioborate composition;
    • wherein the lithium thioborate composition is characterized by formula FX2:





Li3−x−yB1−xQxS3−yGy  (FX4);

    • wherein Q is the first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is the second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein x is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025);
    • wherein y is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 2e: An electrolyte comprising:

    • a lithium solid state electrolyte comprising Li, one or more principal elements (optionally, non-Li principal elements), and at least one dopant;
    • wherein the dopant substitutes for a portion of the one of the one or more principal elements (optionally, non-Li principal elements) of the lithium solid state electrolyte and is aliovalent with the respective substituted principal elements (optionally, non-Li principal elements);
    • wherein the ionic conductivity of the lithium solid state electrolyte is greater than or equal to 1·10−5 S/cm at 25° C.


Aspect 2f: A doped lithium solid state electrolyte comprising:

    • a doped inorganic composition having at least one dopant;
    • wherein the doped composition has up to 20 at. % (optionally up to 15 at. %, optionally up to 12 at. %, optionally up to 10 at. %, optionally up to 8 at. %, optionally up to 5 at. %, optionally up to 3 at. %, optionally up to 2 at. %, optionally up to 1 at. %, optionally up to 0.9 at. %, optionally up to 0.8 at. %, optionally up to 0.7 at. %, optionally up to 0.5 at. %) of one or more principal elements (optionally, non-Li principal elements) substituted with the at least one dopant relative to a reference composition of a reference lithium solid state electrolyte;
    • wherein each dopant is one or more elements each aliovalent with the respective substituted principal element (optionally, a non-Li principal element);
    • wherein the presence of the one or more dopants provides for an ionic conductivity greater than or equal to 1·10−5 S/cm at 25° C.


Aspect 2g: A method for increasing an ionic conductivity of a reference lithium solid state electrolyte, the method comprising:

    • forming a doped lithium solid state electrolyte having a doped composition;
    • wherein the reference lithium solid state electrolyte has a reference composition, and wherein the doped composition has up to 20 at. % (optionally up to 15 at. %, optionally up to 12 at. %, optionally up to 10 at. %, optionally up to 8 at. %, optionally up to 5 at. %, optionally up to 3 at. %, optionally up to 2 at. %, optionally up to 1 at. %, optionally up to 0.9 at. %, optionally up to 0.8 at. %, optionally up to 0.7 at. %, optionally up to 0.5 at. %) of one or more principal elements (optionally, non-Li principal elements) substituted with at least one dopant relative to the reference composition;
    • wherein each element of the at least one dopant is aliovalent with respect to the respective substituted principal element (optionally, a non-Li principal element); and
    • wherein the doped lithium solid state electrolyte has a greater ionic conductivity than the reference lithium solid state electrolyte by a factor of at least 2 (optionally at least 3, optionally at least 4, optionally at least 5, optionally at least 6, optionally at least 7, optionally at least 8, optionally at least 9, optionally at least 10, optionally at least 11, optionally at least 12, optionally at least 13, optionally at least 14, optionally at least 15, optionally at least 18, optionally at least 20, optionally at least 21, optionally at least 22, optionally at least 23, optionally at least 24, optionally at least 25, optionally at least 50, optionally at least 75, optionally at least 100, optionally at least 125, optionally at least 150, optionally at least 175, optionally at least 200, optionally at least 300, optionally at least 400, optionally at least 500, optionally at least 600, optionally at least 700, optionally at least 800, optionally at least 900, optionally at least 1000, optionally at least 1100, optionally at least 1200, optionally at least 1300, optionally at least 1400).


Aspect 2h: The material, device, electrolyte, or method of Aspect 2, wherein y is greater than 0 and less than 1 (optionally less than or equal to 0.50, optionally less than or equal to 0.45, optionally less than or equal to 0.40, optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025).


Aspect 2i: The material, device, electrolyte, or method of Aspect 2, wherein x is greater than 0 and less than 1 (optionally less than or equal to 0.50, optionally less than or equal to 0.45, optionally less than or equal to 0.40, optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025).


Aspect 2j: The material, device, electrolyte, or method of Aspect 2, wherein y is greater than 0 and less than 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025).


Aspect 2k: The material, device, electrolyte, or method of Aspect 2, wherein x is greater than 0 and less than 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025).


Aspect 2l: The material, device, electrolyte, or method of Aspect 2, wherein the material or the composition thereof is a solid solution.


Aspect 2m: Any material or composition disclosed herein, such as any of those disclosed in Examples 1A and 1B, optionally further doped/substituted and/or optionally amorphized.


Aspect 2n: The material, device, electrolyte, or method of Aspect 2, wherein y is greater than 0 and less than 0.15.


Aspect 2o: The material, device, electrolyte, or method of Aspect 2, wherein y is greater than 0 and less than 0.15.


Aspect 3a: A material comprising:

    • a lithium thioborate composition characterized by formula FX4:





Li3−yBS3−yGy  (FX4);

    • wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein y is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 3b: A device comprising:

    • a material, the material comprising:
    • a lithium thioborate composition characterized by formula FX4:





Li3−yBS3−yGy  (FX4);

    • wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein y is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 3c: A solid state electrolyte comprising:

    • a lithium thioborate composition characterized by formula FX4:





Li3−yBS3−yGy  (FX4);

    • wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein y is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 3d: A method of making a material, the method comprising:

    • combining a plurality of precursors comprising lithium, boron, sulfur, and a dopant; and
    • heating the combined plurality of precursors to form the material having a lithium thioborate composition;
    • wherein the lithium thioborate composition is characterized by formula FX4:





Li3−yBS3−yGy  (FX4);

    • wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein y is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 3e: An electrolyte comprising:

    • a lithium solid state electrolyte comprising Li, one or more principal elements (optionally, non-Li principal elements), and at least one dopant;
    • wherein the dopant substitutes for a portion of the one of the one or more principal elements (optionally, non-Li principal elements) of the lithium solid state electrolyte and is aliovalent with the respective substituted principal elements (optionally, non-Li principal elements);
    • wherein the ionic conductivity of the lithium solid state electrolyte is greater than or equal to 1·10−5 S/cm at 25° C.


Aspect 3f: A doped lithium solid state electrolyte comprising:

    • a doped inorganic composition having at least one dopant;
    • wherein the doped composition has up to 20 at. % (optionally up to 15 at. %, optionally up to 12 at. %, optionally up to 10 at. %, optionally up to 8 at. %, optionally up to 5 at. %, optionally up to 3 at. %, optionally up to 2 at. %, optionally up to 1 at. %, optionally up to 0.9 at. %, optionally up to 0.8 at. %, optionally up to 0.7 at. %, optionally up to 0.5 at. %) of one or more principal elements (optionally, non-Li principal elements) substituted with the at least one dopant relative to a reference composition of a reference lithium solid state electrolyte;
    • wherein each dopant is one or more elements each aliovalent with the respective substituted principal element (optionally, a non-Li principal element);
    • wherein the presence of the one or more dopants provides for an ionic conductivity greater than or equal to 1·10−5 S/cm at 25° C.


Aspect 3g: A method for increasing an ionic conductivity of a reference lithium solid state electrolyte, the method comprising:

    • forming a doped lithium solid state electrolyte having a doped composition;
    • wherein the reference lithium solid state electrolyte has a reference composition, and wherein the doped composition has up to 20 at. % (optionally up to 15 at. %, optionally up to 12 at. %, optionally up to 10 at. %, optionally up to 8 at. %, optionally up to 5 at. %, optionally up to 3 at. %, optionally up to 2 at. %, optionally up to 1 at. %, optionally up to 0.9 at. %, optionally up to 0.8 at. %, optionally up to 0.7 at. %, optionally up to 0.5 at. %) of one or more principal elements (optionally, non-Li principal elements) substituted with at least one dopant relative to the reference composition;
    • wherein each element of the at least one dopant is aliovalent with respect to the respective substituted principal element (optionally, a non-Li principal element); and
    • wherein the doped lithium solid state electrolyte has a greater ionic conductivity than the reference lithium solid state electrolyte by a factor of at least 2 (optionally at least 3, optionally at least 4, optionally at least 5, optionally at least 6, optionally at least 7, optionally at least 8, optionally at least 9, optionally at least 10, optionally at least 11, optionally at least 12, optionally at least 13, optionally at least 14, optionally at least 15, optionally at least 18, optionally at least 20, optionally at least 21, optionally at least 22, optionally at least 23, optionally at least 24, optionally at least 25, optionally at least 50, optionally at least 75, optionally at least 100, optionally at least 125, optionally at least 150, optionally at least 175, optionally at least 200, optionally at least 300, optionally at least 400, optionally at least 500, optionally at least 600, optionally at least 700, optionally at least 800, optionally at least 900, optionally at least 1000, optionally at least 1100, optionally at least 1200, optionally at least 1300, optionally at least 1400).


Aspect 3h: The material, device, electrolyte, or method of Aspect 3, wherein y is greater than 0 and less than 1 (optionally less than or equal to 0.50, optionally less than or equal to 0.45, optionally less than or equal to 0.40, optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025).


Aspect 3i: The material, device, electrolyte, or method of Aspect 3, wherein y is greater than 0 and less than 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025).


Aspect 3j: The material, device, electrolyte, or method of Aspect 3, wherein the material or the composition thereof is a solid solution.


Aspect 3k: Any material or composition disclosed herein, such as any of those disclosed in Examples 1A and 1B, optionally further doped/substituted and/or optionally amorphized.


Aspect 3l: The material, device, electrolyte, or method of Aspect 3, wherein y is greater than 0 and less than 0.15.


Aspect 4: The material, device, electrolyte, or method of any preceding Aspect, having a greater ionic conductivity than that of an undoped stoichiometric Li3BS3 material by a factor of at least 2 (optionally at least 3, optionally at least 4, optionally at least 5, optionally at least 6, optionally at least 7, optionally at least 8, optionally at least 9, optionally at least 10, optionally at least 11, optionally at least 12, optionally at least 13, optionally at least 14, optionally at least 15, optionally at least 18, optionally at least 20, optionally at least 21, optionally at least 22, optionally at least 23, optionally at least 24, optionally at least 25, optionally at least 50, optionally at least 75, optionally at least 100, optionally at least 125, optionally at least 150, optionally at least 175, optionally at least 200, optionally at least 300, optionally at least 400, optionally at least 500, optionally at least 600, optionally at least 700, optionally at least 800, optionally at least 900, optionally at least 1000, optionally at least 1100, optionally at least 1200, optionally at least 1300, optionally at least 1400) at 25° C., wherein the undoped stoichiometric Li3BS3 material is free of Q and G.


Aspect 5a: The material, device, electrolyte, or method of any preceding Aspect being characterized by an ionic conductivity (such as average ionic conductivity) greater than 6·10−6 S/cm (optionally greater than or equal to 7·10−6 S/cm, optionally greater than or equal to 8·10−6 S/cm, optionally greater than or equal to 9·10−6 S/cm, optionally greater than or equal to 1.0·10−5 S/cm, optionally greater than or equal to 1.2·10−5 S/cm, optionally greater than or equal to 1.4·10−5 S/cm, optionally greater than or equal to 1.5·10−5 S/cm, optionally greater than or equal to 1.6·10−5 S/cm, optionally greater than or equal to 1.9·10−5 S/cm, optionally greater than or equal to 2.0·10−5 S/cm, optionally greater than or equal to 2.5·10−5 S/cm, optionally greater than or equal to 3.0·10−5 S/cm, optionally greater than or equal to 3.5·10−5 S/cm, optionally greater than or equal to 4.0·10−5 S/cm, optionally greater than or equal to 4.5·10−5 S/cm, optionally greater than or equal to 5.0·10−5 S/cm, optionally greater than or equal to 5.5·10−5 S/cm, optionally greater than or equal to 6.0·10−5 S/cm, optionally greater than or equal to 6.5·10−5 S/cm, optionally greater than or equal to 7.0·10−5 S/cm, optionally greater than or equal to 7.5·10−5 S/cm, optionally greater than or equal to 8.0·10−5 S/cm, optionally greater than or equal to 8.5·10−5 S/cm, optionally greater than or equal to 9.0·10−5 S/cm, optionally greater than or equal to 9.5·10−5 S/cm, optionally greater than or equal to 1.0·10−4 S/cm, optionally greater than or equal to 1.2·10−4 S/cm, optionally greater than or equal to 1.5·10−4 S/cm, optionally greater than or equal to 1.7·10−4 S/cm, optionally greater than or equal to 1.9·10−4 S/cm, optionally greater than or equal to 2.0·10−4 S/cm, optionally greater than or equal to 2.5·10−4 S/cm, optionally greater than or equal to 3.0·10−4 S/cm, optionally greater than or equal to 3.5·10−4 S/cm, optionally greater than or equal to 4.0·10−4 S/cm, optionally greater than or equal to 4.5·10−4 S/cm, optionally greater than or equal to 5.0·10−4 S/cm, optionally greater than or equal to 5.5·10−4 S/cm, optionally greater than or equal to 6.0·10−4 S/cm, optionally greater than or equal to 6.5·10−4 S/cm, optionally greater than or equal to 7.0·10−4 S/cm, optionally greater than or equal to 7.5·10−4 S/cm, optionally greater than or equal to 8.0·10−4 S/cm, optionally greater than or equal to 8.5·10−4 S/cm, optionally greater than or equal to 9.0·10−4 S/cm, optionally greater than or equal to 9.3·10−4 S/cm, optionally greater than or equal to 9.5·10−4 S/cm, optionally greater than or equal to 9.7·10−4 S/cm, optionally greater than or equal to 1.0·10−3 S/cm, optionally greater than or equal to 1.1·10−3 S/cm, optionally greater than or equal to 1.2·10−3 S/cm, optionally greater than or equal to 1.5·10−3 S/cm, optionally greater than or equal to 1.6·10−3 S/cm, optionally greater than or equal to 1.7·10−3 S/cm, optionally greater than or equal to 1.8·10−3 S/cm, optionally greater than or equal to 1.9·10−3 S/cm, optionally greater than or equal to 2.0·10−3 S/cm, optionally greater than or equal to 2.1·10−3 S/cm, optionally greater than or equal to 2.2·10−3 S/cm, optionally greater than or equal to 2.5·10−3 S/cm, optionally greater than or equal to 2.7·10−3 S/cm, optionally greater than or equal to 2.9·10−3 S/cm, optionally greater than or equal to 3.0·10−3 S/cm, optionally greater than or equal to 3.1·10−3 S/cm) at 25° C. Aspect 5b: The material, device, electrolyte, or method of any preceding Aspect being characterized by an ionic conductivity (such as average ionic conductivity) selected from the range of 6·10−6 S/cm to 5·10−2 S/cm, and wherein any value and range of ionic conductivity therebetween is explicitly contemplated and disclosed herein. Aspect 5c: The material, device, electrolyte, or method of any preceding Aspect being characterized by an ionic conductivity (such as average ionic conductivity) selected from the range of 6·10−6 S/cm to 1·10−2 S/cm, optionally selected from the range of 1·10−4 S/cm to 1·10−2 S/cm, optionally selected from the range of 5·10−4 S/cm to 1·10−2 S/cm, optionally selected from the range of 1·10−3 S/cm to 1·10−2 S/cm.


Aspect 6a: The material, device, electrolyte, or method of any preceding Aspect, except Aspect 3, wherein the composition is characterized by the ratio Q/(B+Q) being greater than 0.001 and less than 0.20, and wherein any value and range therebetween is explicitly contemplated and disclosed herein. Aspect 6b: The material, device, electrolyte, or method of any preceding Aspect, except Aspect 3, wherein the composition is characterized by the ratio Q/(B+Q) being selected from the range of 0.01 to 0.20, optionally selected from the range of 0.02 to 0.20, optionally selected from the range of 0.01 to 0.15, optionally selected from the range of 0.01 to 0.12, optionally selected from the range of 0.02 to 0.10.


Aspect 8: The material, device, electrolyte, or method of any preceding Aspect, except Aspect 3, wherein the composition is characterized by the ratio Q/(B+Q) being greater than 0.020 and less than 0.075.


Aspect 9a: The material, device, electrolyte, or method of any preceding Aspect, except Aspect 3, wherein Q is one or more Group 14 elements and/or one or more metal elements such as transition metal elements. Aspect 9b: The material, device, electrolyte, or method of any preceding Aspect, except Aspect 3, wherein Q is one or more Group 14 elements. Aspect 9c: The material, device, electrolyte, or method of any preceding Aspect, except Aspect 3, wherein Q is one Group 14 element. Aspect 9d: The material, device, electrolyte, or method of any preceding Aspect, wherein Q is one or more metal elements, such as one or more transition metal elements.


Aspect 10a: The material, device, electrolyte, or method of any preceding Aspect, except Aspect 3, wherein Q is Si, Ge, Sn, and/or Zr. Aspect 10b: The material, device, electrolyte, or method of any preceding Aspect, except Aspect 3, wherein Q is Si and/or Ge. Aspect 10c: The material, device, electrolyte, or method of any preceding Aspect, except Aspect 3, wherein Q comprises Si. Aspect 10d: The material, device, electrolyte, or method of any preceding Aspect, except Aspect 3, wherein Q is Si.


Aspect 11a: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition is characterized by the ratio G/(S+G) being greater than 0.001 and less than 0.20, and wherein any value and range therebetween is explicitly contemplated and disclosed herein. Aspect 11b: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition is characterized by the ratio Q/(B+Q) being selected from the range of 0.01 to 0.20, optionally selected from the range of 0.02 to 0.20, optionally selected from the range of 0.01 to 0.15, optionally selected from the range of 0.01 to 0.12, optionally selected from the range of 0.02 to 0.10.


Aspect 12: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition is characterized by the ratio G/(S+G) being greater than 0.020 and less than 0.2, and wherein any value and range therebetween is explicitly contemplated and disclosed herein.


Aspect 13a: The material, device, electrolyte, or method of any preceding Aspect, wherein G is one or more Group 17 (halogen) elements. Aspect 13b: The material, device, electrolyte, or method of any preceding Aspect, wherein G is one Group 17 (halogen) element.


Aspect 14a: The material, device, electrolyte, or method of any preceding Aspect, wherein G is Cl and/or Br. Aspect 14b: The material, device, electrolyte, or method of any preceding Aspect, wherein G comprises Cl. Aspect 14c: The material, device, electrolyte, or method of any preceding Aspect, wherein G is Cl.


Aspect 15a: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition is characterized by formula FX2, FX3, or FX4:





Li3−x−yB1−x[Q]xS3−y[G]y  (FX2);





Li3−xB1−x[Q]xS3  (FX3);





Li3−yB1S3−y[G]y; wherein:  (FX4)

    • x is selected from the range of 0.005 (optionally 0.007, optionally 0.009, optionally 0.01, optionally 0.015, optionally 0.02, optionally 0.025, optionally 0.03, optionally 0.035, optionally 0.04, optionally 0.045, optionally 0.05, optionally 0.055, optionally 0.06) to 0.20 (optionally 0.19, optionally 0.18, optionally 0.17, optionally 0.16, optionally 0.15, optionally 0.14, optionally 0.13, optionally 0.12, optionally 0.11, optionally 0.10, optionally 0.09, optionally 0.08, optionally 0.07, optionally 0.06); and
    • y is selected from the range of 0.005 (optionally 0.007, optionally 0.009, optionally 0.01, optionally 0.015, optionally 0.02, optionally 0.025, optionally 0.03, optionally 0.035, optionally 0.04, optionally 0.045, optionally 0.05, optionally 0.055, optionally 0.06) to 0.20 (optionally 0.19, optionally 0.18, optionally 0.17, optionally 0.16, optionally 0.15, optionally 0.14, optionally 0.13, optionally 0.12, optionally 0.11, optionally 0.10, optionally 0.09, optionally 0.08, optionally 0.07, optionally 0.06). Therefore, in Aspect 12, the variable z of claim 1 is equal to or approximately equal to x (in FX3), y (in FX4), or x+y (in FX2).


Aspect 15b: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition is characterized by formula FX3; and wherein x is greater than 0 and less than or equal to 0.05, y is 0, and z is equal to or approximately equal to x.


Aspect 16a: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition is characterized by formula FX3; and wherein x is greater than 0.025 (optionally greater than 0.03, optionally greater than 0.04) and less than or equal to 0.05 (optionally less than or equal to 0.06), y is 0, and z is equal to or approximately equal to x. Aspect 16b: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition is characterized by formula FX3; and wherein x is about 0.05, y is 0, and z is equal to or approximately equal to x.


Aspect 17a: The material, device, electrolyte, or method of any preceding Aspect, wherein the material or the composition thereof is amorphous or substantially amorphous. Aspect 17b: The material, device, electrolyte, or method of any preceding Aspect, wherein the material or the composition thereof is has a total crystallinity less than 50 wt. %. Aspect 17c: The material, device, electrolyte, or method of any preceding Aspect, wherein the material or the composition thereof is has a total crystallinity less than or equal to about 35 wt. %, optionally less than or equal to about 30 wt. %, optionally less than or equal to about 25 wt. %, optionally less than or equal to about 20 wt. %, optionally less than or equal to about 15 wt. %, optionally equal to or less than about 10 wt. %, optionally equal to or less than about 8 wt. %, optionally equal to or less than about 5 wt. %, optionally equal to or less than about 4 wt. %, optionally equal to or less than about 3 wt. %, optionally equal to or less than about 2 wt. %, optionally equal to or less than about 1 wt. %, optionally equal to or less than about 0.8 wt. %, optionally equal to or less than about 0.5 wt. %, optionally equal to or less than about 0.2 wt. %, optionally equal to or less than about 0.1 wt. %, optionally equal to or less than about 0.08 wt. %, optionally equal to or less than about 0.05 wt. %, optionally equal to or less than about 0.01 wt. %.


Aspect 18: The material, device, electrolyte, or method of any preceding Aspect, being characterized by an ionic conductivity greater than or equal to 1·10−5 S/cm at 25° C.


Aspect 19: The material, device, electrolyte, or method of any preceding Aspect, being characterized by an ionic conductivity greater than or equal to 1·10−3 S/cm at 25° C.


Aspect 20: The material, device, electrolyte, or method of any preceding Aspect, being characterized by an ionic conductivity selected from the range of 1·10−5 S/cm to 1·10−2 at 25° C.


Aspect 21: The material, device, electrolyte, or method of any preceding Aspect, being characterized by an electronic conductivity less than 5·10−10 S/cm (optionally less than or equal to about 4.8·10−10 S/cm, optionally less than or equal to about 4.5·10−10 S/cm, optionally less than or equal to about 4.3·10−10 S/cm, optionally less than or equal to about 4.1·10−10 S/cm, optionally less than or equal to about 4.0·10−10 S/cm, optionally less than or equal to about 3.8·10−10 S/cm, optionally less than or equal to about 3.5·10−10 S/cm, optionally less than or equal to about 3.2·10−10 S/cm, optionally less than or equal to about 3.0·10−10 S/cm, optionally less than or equal to about 2.0·10−10 S/cm, optionally less than or equal to about 1.0·10−10 S/cm) at 25° C.


Aspect 22: The material, device, electrolyte, or method of any preceding Aspect, being characterized by an activation energy (Ea) for an ionic conductivity of less than or equal to about 500 meV (optionally less than or equal to about 475 meV, optionally less than or equal to about 450 meV, optionally less than or equal to about 425 meV, optionally less than or equal to about 400 meV, optionally less than or equal to about 375 meV, optionally less than or equal to about 350 meV, optionally less than or equal to about 325 meV, optionally less than or equal to about 300 meV, optionally less than or equal to about 275 meV, optionally less than or equal to about 250 meV, optionally less than or equal to about 225 meV, optionally less than or equal to about 200 meV, optionally less than or equal to about 175 meV) when its temperature-dependent ionic conductivity is fit to equation EQ1:










σ
=



σ
0

T



e


-

E
a




k
B


T





;




(
EQ1
)







wherein:

    • σ is the ionic conductivity;
    • σ0 is a conductivity prefactor;
    • T is temperature;
    • kB is the Boltzmann's constant; and
    • Ea is the activation energy for ionic conductivity.


Aspect 23: The material, device, electrolyte, or method of any preceding Aspect, wherein charge carriers of the material are monovalent.


Aspect 24: A device comprising the material of any of the preceding Aspects.


Aspect 25: The device of Aspect 24 being an electrochemical cell.


Aspect 26: The device of Aspect 25, being a rechargeable lithium battery.


Aspect 27: The device of Aspect 25 or 26 having a solid state electrolyte comprising the material of any one of the preceding claims.


Aspect 28: The device of Aspect 25, 26, or 27 having a coating on a Li anode, the coating comprising the material of any one of the preceding claims.


Aspect 29: A device comprising:

    • a material, the material comprising:
    • a lithium thioborate composition characterized by formula FX1:





Li3−z[B+Q]1[S+G]3  (FX1);

    • wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein z is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein the composition comprises only the first dopant, only the second dopant, or both the first dopant and the second dopant.


Aspect 26: A device comprising:

    • a material, the material comprising:
    • a lithium thioborate composition characterized by formula FX2:





Li3−x−yB1−xQxS3−yGy  (FX2);

    • wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein x is a number greater than 0 and less than or equal to 0.10 (optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025);
    • wherein y is a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 27: A device comprising:

    • a material, the material comprising:
    • a lithium thioborate composition characterized by formula FX4:





Li3−yBS3−yGy  (FX4);

    • wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein y is a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 28: The device of Aspect 25, 26, or 27 being an electrochemical cell.


Aspect 29: The device of Aspect 28, wherein the electrochemical cell comprises a solid state electrolyte having the material.


Aspect 30: The device of Aspect 28 or 29, being a rechargeable lithium battery.


Aspect 31: A solid state electrolyte comprising:

    • a lithium thioborate composition characterized by formula FX1:





Li3−z[B+Q]1[S+G]3  (FX1);

    • wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein z is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein the composition comprises only the first dopant, only the second dopant, or both the first dopant and the second dopant.


Aspect 32: A solid state electrolyte comprising:

    • a lithium thioborate composition characterized by formula FX2:





Li3−x−yB1−xQxS3−yGy  (FX2);

    • wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein x is a number greater than 0 and less than or equal to 0.10 (optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025);
    • wherein y is a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 33: A solid state electrolyte comprising:

    • a lithium thioborate composition characterized by formula FX4:





Li3−yBS3−yGy  (FX4);

    • wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein y is a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 34: A method of making a material, the method comprising:

    • combining a plurality of precursors comprising lithium, boron, sulfur, and at least one of a first dopant and a second dopant; and
    • heating the combined plurality of precursors to form the material having a lithium thioborate composition;
    • wherein the lithium thioborate composition is characterized by formula FX1:





Li3−z[B+Q]1[S+G]3  (FX1);

    • wherein Q is the first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is the second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein z is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein the composition comprises only the first dopant, only the second dopant, or both the first dopant and the second dopant.


Aspect 35: A method of making a material, the method comprising:

    • combining a plurality of precursors comprising lithium, boron, sulfur, a first dopant, and a second dopant; and
    • heating the combined plurality of precursors to form the material having a lithium thioborate composition;
    • wherein the lithium thioborate composition is characterized by formula FX2:





Li3−x−yB1−xQxS3−yGy  (FX2);

    • wherein Q is the first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;
    • wherein G is the second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein x is a number greater than 0 and less than or equal to 0.10 (optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025);
    • wherein y is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements.


Aspect 36: A method of making a material, the method comprising:

    • combining a plurality of precursors comprising lithium, boron, sulfur, a first dopant, and a second dopant; and
    • heating the combined plurality of precursors to form the material having a lithium thioborate composition;
    • wherein the lithium thioborate composition is characterized by formula FX4:





Li3−yBS3−yGy  (FX4);

    • wherein G is the second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;
    • wherein y is 0 or a number greater than 0 and less than or equal to 0.40 (optionally less than or equal to 0.35, optionally less than or equal to 0.30, optionally less than or equal to 0.25, optionally less than or equal to 0.20, optionally less than or equal to 0.18, optionally less than or equal to 0.16, optionally less than or equal to 0.15, optionally less than or equal to 0.13, optionally less than or equal to 0.11, optionally less than or equal to 0.10, optionally less than or equal to 0.09, optionally less than or equal to 0.08, optionally less than or equal to 0.07, optionally less than or equal to 0.06, optionally less than or equal to 0.05, optionally less than or equal to 0.04, optionally less than or equal to 0.03, optionally less than or equal to 0.025); and
    • wherein G is one or more Group 17 (halogen) elements


Aspect 37: The method of Aspect 34, 35 or 36 further comprising amorphizing the material to increase its ionic conductivity.


Aspect 38a: The method of Aspect 37, wherein the step of amorphizing comprises reducing grain sizes of the lithium thioborate composition, increasing amorphous content of the lithium thioborate composition, decreasing a total crystallinity of the lithium thioborate composition, and/or increasing a concentration of defects in the lithium thioborate composition. Aspect 38b: The method of Aspect 37, wherein the step of amorphizing comprises increasing amorphous content of the lithium thioborate composition and decreasing a total crystallinity of the lithium thioborate composition.


Aspect 39: The method of any of Aspects 34-38, wherein the plurality of precursors comprises a lithium-containing precursor, a boron-containing precursor, and a sulfur-containing precursor.


Aspect 40: The method of any of Aspects 34-39, wherein the step of combining comprises mixing and/or milling.


Aspect 41: The method of any of Aspects 34-40, wherein the step of heating comprises melting the plurality of precursors at a temperature less than 1500° C. (optionally less than or equal to 1400° C., optionally less than or equal to 1300° C., optionally less than or equal to 1200° C., optionally less than or equal to 1100° C., optionally less than or equal to 1000° C., optionally less than or equal to 975° C., optionally less than or equal to 950° C., optionally less than or equal to 900° C., optionally less than or equal to 875° C., optionally less than or equal to 850° C., optionally less than or equal to 825° C., optionally less than or equal to 800° C.) to form a melt comprising lithium, boron, sulfur, and at least of the first dopant and the second dopant.


Aspect 42: The method of Aspect 41, wherein the step of heating further comprises cooling the melt thereby forming the material as a solid.


Aspect 43: An electrolyte comprising:

    • a lithium solid state electrolyte comprising Li, one or more principal elements (optionally, non-Li principal elements), and at least one dopant;
    • wherein the dopant substitutes for a portion of the one of the one or more principal elements (optionally, non-Li principal elements) of the lithium solid state electrolyte and is aliovalent with the respective substituted principal elements (optionally, non-Li principal elements);
    • wherein the ionic conductivity of the lithium solid state electrolyte is greater than or equal to 1·10−5 S/cm (optionally selected from the range of 1·10−5 S/cm to 5·10−2 S/cm) at 25° C.


Aspect 44: The electrolyte of Aspect 37, wherein the lithium solid state electrolyte is obtained from doping (or forming a doped or substituted variation of) a material characterized by formula FX5, FX6, FX7, FX8, FX9, FX10, FX11, FX12, or FX13:





Li3VS4  (FX5);





Na3Li3Al2F12  (FX6);





Li2Te  (FX7);





LiAlTe2  (FX8);





LiInTe2  (FX9);





Li6MnS4  (FX10);





LiGaTe2  (FX11);





KLi6TaO6; or  (FX12)





Li3CuS2  (FX13).


Aspect 45: A doped lithium solid state electrolyte comprising:

    • a doped inorganic composition having at least one dopant;
    • wherein the doped composition has up to 20 at. % (optionally up to 15 at. %, optionally up to 12 at. %, optionally up to 10 at. %, optionally up to 8 at. %, optionally up to 5 at. %, optionally up to 3 at. %, optionally up to 2 at. %, optionally up to 1 at. %, optionally up to 0.9 at. %, optionally up to 0.8 at. %, optionally up to 0.7 at. %, optionally up to 0.5 at. %) of one or more principal elements (optionally, non-Li principal elements) substituted with the at least one dopant relative to a reference composition of a reference lithium solid state electrolyte;
    • wherein each dopant is one or more elements each aliovalent with the respective substituted principal element (optionally, a non-Li principal element);
    • wherein the presence of the one or more dopants provides for an ionic conductivity greater than or equal to 11-1 S/cm at 25° C.


Aspect 46: The material of Aspect 45, wherein the doped inorganic composition has up to 10 at. % of each of the one or more principal element (optionally, a non-Li principal element) substituted with a respective dopant.


Aspect 47: The method of Aspect 45 or 46, wherein the doped composition has up to 10 at. % of a cationic principal element, such as B, (optionally, a non-Li principal element) substituted with a first dopant, the first dopant being one or more elements each aliovalent with respect to said cationic principal element (optionally, a non-Li principal element).


Aspect 48: The method of any of Aspects 45-47, wherein the doped composition has up to 10 at. % of an anionic principal element, such as S, (optionally, a non-Li principal element) substituted with a second dopant, the second dopant being one or more elements each aliovalent with respect to said anionic principal element (optionally, a non-Li principal element).


Aspect 49: The material of any of Aspects 45-48, wherein the presence of the one or more dopants provides for the doped lithium solid state electrolyte having an ionic conductivity greater than that of the reference lithium solid state electrolyte by a factor of at least 2 (optionally at least 3, optionally at least 4, optionally at least 5, optionally at least 6, optionally at least 7, optionally at least 8, optionally at least 9, optionally at least 10, optionally at least 11, optionally at least 12, optionally at least 13, optionally at least 14, optionally at least 15, optionally at least 18, optionally at least 20, optionally at least 21, optionally at least 22, optionally at least 23, optionally at least 24, optionally at least 25, optionally at least 50, optionally at least 75, optionally at least 100, optionally at least 125, optionally at least 150, optionally at least 175, optionally at least 200, optionally at least 300, optionally at least 400, optionally at least 500, optionally at least 600, optionally at least 700, optionally at least 800, optionally at least 900, optionally at least 1000, optionally at least 1100, optionally at least 1200, optionally at least 1300, optionally at least 1400).


Aspect 50: The material of any of Aspects 45-49, wherein the reference composition is characterized by formula FX5, FX6, FX7, FX8, FX9, FX10, FX11, FX12, or FX13:





Li3VS4  (FX5);





Na3Li3Al2F12  (FX6);





Li2Te  (FX7);





LiAlTe2  (FX8);





LiInTe2  (FX9);





Li6MnS4  (FX10);





LiGaTe2  (FX11);





KLi6TaO6  (FX12); or





Li3CuS2  (FX13).


Aspect 51: A method for increasing an ionic conductivity of a reference lithium solid state electrolyte, the method comprising:

    • forming a doped lithium solid state electrolyte having a doped composition;
    • wherein the reference lithium solid state electrolyte has a reference composition, and wherein the doped composition has up to 20 at. % (optionally up to 15 at. %, optionally up to 12 at. %, optionally up to 10 at. %, optionally up to 8 at. %, optionally up to 5 at. %, optionally up to 3 at. %, optionally up to 2 at. %, optionally up to 1 at. %, optionally up to 0.9 at. %, optionally up to 0.8 at. %, optionally up to 0.7 at. %, optionally up to 0.5 at. %) of one or more principal elements (optionally, non-Li principal elements) substituted with at least one dopant relative to the reference composition;
    • wherein each element of the at least one dopant is aliovalent with respect to the respective substituted principal element (optionally, a non-Li principal element); and
    • wherein the doped lithium solid state electrolyte has a greater ionic conductivity than the reference lithium solid state electrolyte by a factor of at least 2 (optionally at least 3, optionally at least 4, optionally at least 5, optionally at least 6, optionally at least 7, optionally at least 8, optionally at least 9, optionally at least 10, optionally at least 11, optionally at least 12, optionally at least 13, optionally at least 14, optionally at least 15, optionally at least 18, optionally at least 20, optionally at least 21, optionally at least 22, optionally at least 23, optionally at least 24, optionally at least 25, optionally at least 50, optionally at least 75, optionally at least 100, optionally at least 125, optionally at least 150, optionally at least 175, optionally at least 200, optionally at least 300, optionally at least 400, optionally at least 500, optionally at least 600, optionally at least 700, optionally at least 800, optionally at least 900, optionally at least 1000, optionally at least 1100, optionally at least 1200, optionally at least 1300, optionally at least 1400).


Aspect 52: The method of Aspect 51, wherein the doped composition has up to 10 at. % of a cationic principal element (optionally, a non-Li principal element) substituted with a first dopant, the first dopant being one or more elements each aliovalent with respect to said cationic principal element (optionally, a non-Li principal element).


Aspect 53: The method of Aspect 51 or 52, wherein the doped composition has up to 10 at. % of an anionic principal element (optionally, a non-Li principal element) substituted with a second dopant, the second dopant being one or more elements each aliovalent with respect to said anionic principal element (optionally, a non-Li principal element).


Aspect 54: The method of any of Aspects 51-53, wherein the step of forming comprises amorphizing the material to increase its ionic conductivity.


Aspect 55a: The method of Aspect 54, wherein the step of amorphizing comprises reducing grain sizes of the lithium thioborate composition, increasing amorphous content of the lithium thioborate composition, and/or increasing a concentration of defects in the lithium thioborate composition. Aspect 55b: The method of Aspect 54, wherein the step of amorphizing comprises increasing amorphous content of the lithium thioborate composition and decreasing a total crystallinity of the lithium thioborate composition.


Aspect 56: The method of any of Aspects 51-55, wherein the reference lithium solid state electrolyte and the doped lithium solid state electrolyte are inorganic materials.


Aspect 57a: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition is further doped with the O (oxygen) such that the lithium borate composition further comprises O. Aspect 57b: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition is further doped with the O (oxygen) such that the lithium borate composition further comprises O being greater than 0 at. % but less than 0.3 at. % O, optionally less than 0.2 at. % O, optionally less than or equal to 0.1 at. % O, optionally less than or equal to 0.08 at. % O, optionally less than or equal to 0.06 at. % O, optionally less than or equal to 0.05 at. % O, optionally less than or equal to 0.03 at. % O, optionally less than or equal to 0.02 at. % O, optionally less than or equal to 0.01 at. % O).


Aspect 58a: The material, device, electrolyte, or method of any preceding Aspect other than Aspect 57, wherein the composition is free of O (oxygen) such that the content of O is less than that measurable (e.g., below noise/background level) by techniques known in the art. Aspect 58b: The material, device, electrolyte, or method of any preceding Aspect other than Aspect 57, wherein the composition is free of O (oxygen) or the content of O is less than 0.01 at. %, optionally less than 0.009 at. %.


Aspect 59: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition comprises both ionic and covalent bonding. Optionally, for example, assuming the Li—S correlations are ionic and the B-S correlations are covalent, the composition may have about 80% ionic bonding and about 20% covalent bonding.


Aspect 60: The material, device, electrolyte, or method of any preceding Aspect, wherein the composition comprises a vacancy defect concentration about equal to z (where z is approximately x+y).


The invention can be further understood by the following non-limiting examples.


Overview of Examples 1-3: Despite ongoing efforts to identify high-performance electrolytes for solid-state Li-ion batteries, thousands of prospective Li-containing structures remain unexplored. Here, we employ a semi-supervised learning approach to expedite identification of superionic conductors. We screen 180 unique descriptor representations and use agglomerative clustering to cluster ˜26,000 Li-containing structures. The clusters are then labeled with experimental ionic conductivity data to assess the fitness of the descriptors. By inspecting clusters containing the highest conductivity labels, we identify 212 promising structures that are further screened using bond valence site energy and nudged elastic band calculations. Li3BS3 is identified as a potential high-conductivity material and selected for experimental characterization. With sufficient defect engineering, we show that Li3BS3 is a superionic conductor with room temperature ionic conductivity greater than 1 mS cm−1. While the semi-supervised method shows promise for identification of superionic conductors, the results illustrate a continued need for descriptors that explicitly encode for defects.


Example 1A: Semi-Supervised Machine Learning Approach for Identification of Candidate Solid State Li-Ion Conductors or Lithium Solid State Electrolytes

Identifying new materials that could improve solid-state ion battery prospects is an ongoing challenge. The search for an ideal solid-state Li electrolyte is a prime example. Research has focused on eight classes of materials: LISICON-type structures, argyrodites, garnets, NASICON-type structures, Li-nitrides, Li-hydrides, perovskites, and Li-halides1. However, only three compounds with near-liquid-electrolyte conductivity (˜10−2 S cm−1) have been discovered: Li10GeP2S12 (LGPS)2, Li6PS5Br argyrodite3, and Li7P3S11 ceramic-glassi,4. Although promising discoveries, all three high-conductivity structures are unstable against the Li anode5-10. While investigations to limit instability are ongoing11,12, identification of additional superionic structures is desirable. Discovery of new structures that support superionic conductivity improves the odds of identifying or engineering a stable electrode|SSE interface. For example, engineering solutions that fail to stabilize the Li|argyrodite interface may prove more successful when applied to not-yet-discovered superionic conductors. Discovery of new superionic conductors may also enable stable architectures via multi-electrolyte approaches which have been proposed as more promising than single-electrolyte architectures for achieving stability against Li metal and cathode materials13. High-performing structures that enable new battery chemistries may exist outside of the eight classes. However, exploration under the traditional Edisonian approach prioritizes small perturbations to well-known variable spaces.


Machine learning (ML) is a promising tool for expediting the discovery of useful solid-state materials. By describing prospective materials with physically meaningful descriptors, ML models can identify high-dimensional patterns in large datasets that are not readily apparent14-20. Ongoing descriptor engineering21-26 has enabled discovery of battery components27,28, electrocatalysts15,29, photovoltaic components16,30, piezoelectrics31, new metallic glasses14 and new alloys32. However, application of ML for discovery of SSEs and other emerging technologies can be challenging. Supervised ML approaches require empirical data for use as “labels”. For example, graph neural network (GNN) approaches have been successful in many domains but generally require thousands to tens of thousands of labels to avoid overfitting33. By contrast, relatively few SSEs have been experimentally characterized compared to the ˜26,000 known Li-containing structures19,34-36. Characterized materials often exhibit ill-defined properties owing to the variety of synthetic approaches and non-standardized testing methods37. Well-performing materials often contain charge-carrying defects that are not explicitly characterized or reporteda38. Negative examples, i.e. materials with undesirable properties, are useful for ML models but are seldom reported.


Semi-supervised ML can guide synthetic prioritization of SSEs by overcoming the issues associated with label scarcity. Supervised ML requires labels because it infers correlation functions by mapping the input descriptors to the labels39. Semi-supervised ML prioritizes comparison of descriptors to identify relationships between the descriptors in a dataset36,39. The input compositions are clustered (or grouped) by comparison of descriptors using a similarity metric. The clustering process does not consider labels, and thus circumvents the need for abundant labels. The resultant clusters can be labeled ex post facto to examine correlation between the descriptor and a physical property of interest. For semi-supervised ML, ideal descriptors result in a set of clusters where each cluster has similar labels and thus the label variance is minimized. Promising synthetic targets may then be identified by their membership in clusters that contain desirable labels.


A key insight of this work is that semi-supervised ML can be used to rank descriptors in terms of their correlation to physical properties of interest. Descriptors are representations of the input materials that encode the chemistry, composition, structure, and/or other system properties. An ideal descriptor should be a unique representation, a continuous function of the structure, exhibit rotational/translational invariance, and be readily comparable across all structures in the dataset24-26. Recently, Zhang et al. demonstrated that a modified X-Ray diffraction (mXRD) descriptor lead to favorable clustering for Li SSEs34. By labeling the resultant clusters with experimental room-temperature Li-ion conductivities, they identified 16 prospective fast-ion conductors. However, an ideal descriptor is not known a priori, and no comprehensive descriptor screening has yet been pursued for correlation with SSE properties. Descriptor screening is desirable for both experimentalists and computationalists. For experimentalists, ranking of descriptors affords insight into what aspects of materials are most correlated with target properties. For computationalists, descriptors rankings enable improved regression and supervised learning models by guiding the selection of input representation(s). Descriptor transformations for inorganic structures have been curated in a variety of software packages, including: Matminer24, Dscribe25, SchNet40, and Aenet41.


Herein, we employ hierarchical agglomerative clustering to screen many descriptors, without assuming correlation to ionic conductivity. The performance of 20 descriptors is assessed for semi-supervised identification of Li SSEs. Each descriptor is paired with 9 structural simplification strategies, yielding a total of 180 unique representations per input structure. The approach is applied to a dataset of ˜26,000 Li-containing phases, encompassing all Li-containing structures contained in the Inorganic Crystal Structure Database (ICSD—v.4.4.0) and the Materials Project (MP—v.2020.09.08) database (FIG. 1). A set of 220 experimental room temperature ionic conductivities (σ25° C.) are aggregated from literature reports and used as labels. Experimental labels are selected because they may bias models towards identifying structures that are synthetically tractable and processable. Descriptors that encode the spatial environment are found to be most correlated with the ionic conductivity labels. Whereas descriptors that encode the electronic, compositional, or bonding environment have less predictive power. For the structural descriptors, simplifications that neglect the mobile ion perform best. The descriptor screening results suggest that ionic conductivity is most sensitive to the spatial environment of the framework lattice.


Using the descriptors, the semi-supervised approach can identify potential fast solid-state Li-ion conductors. By selecting structures in clusters containing high conductivity labels, the ˜26,000 input structures are down selected to just 212 promising structures. Practical considerations, a semi-empirical bond valence site energy (BVSE) method,42 and the Nudged Elastic Band (NEB) method are employed to rank the structures. From the ten highest ranking structures, Li3BS3 is selected for model validation. Synthesis of pure Li3BS3 yields a poor conductor. However, by employing defect engineering strategies we demonstrate that Li3BS3 is a superionic conductor with an ionic conductivity greater than 10−3 S cm−1.


Screening Simplification-Descriptor Combinations:

A set of 20 descriptors is selected for screening the semi-supervised learning approach (Table 1). The descriptors generally encode four types of information: the spatial environment, the chemical bonding environment, the electronic environment, and composition. All descriptors are implemented in Python using the Matminer24 or Dscribe25 libraries. The code is published to a github repository and is available for download (https://github.com/FALL-ML/materials-discovery). Zhang et al. illustrated that structure simplification prior to learning can produce lower variance outcomes34. Their mXRD descriptor was found to work best with removal of all cations, all the anions replaced by a single representative anion, and the structure volume scaled to 40 Å3 per anion. Inspired by the previous success in using structure simplification, we screen eight structure simplifications in addition to the unperturbed structure. For simplifications the following categories of atoms are replaced with a representative specie: (1) Cations are represented as Al, (2) Anions are represented as S, (3) Mobile ions are represented as Li, and (4) Neutral atoms are represented as Mg. Categories of atom are removed as to yield the four simplifications: CAMN (all atoms retained), CAN (mobile ions removed), AM (cations and neutral atoms removed), and A (only anions retained). Four additional simplifications are formed by scaling each lattice volume to 40 Å3 per anion: CAMN-40, CAN-40, AM-40, and A-40.









TABLE 1







The descriptors used for agglomerative clustering. Descriptor vectors are attained


by simplifying the input structures and then applying the descriptor transformation.


In total, 180 unique descriptor vectors are screened for each structure.









Descriptor
Descriptor Description
Refs





Bond Fraction
“Bag of bonds” approach described in Hansen et. al. wherein
43



pairwise nuclear charges and distances are encoded.



Band Center
Estimation of band center from constituent atoms'
44



electronegativity values described by Butler et al.



Crystal Structure Analysis by
Calculation of the largest sphere that can pass through the
45


Voronoi Decomposition
lattice-sans-mobile-ion using Voronoi decomposition of



(CAVD)
structures.



Chemical Ordering
Warren-Cowley-like ordering method to determine how different
46



the structure's ordering is from random.



Density Features
Calculates density, volume per atom, and the packing fraction.
47


Electronegativity Difference
Composition weighted calculation of the electronegativity
48



difference between cations and anions.



Ewald Energy
Sum of coulomb interaction energies across all lattice sites
49



described by Ewald et al.



Global Instability Index
Averaged square root of the sum of squared differences over




the bond valence sums.



Jarvis
Diverse set of descriptors from the Jarvis-ML library.
50


Maximum Packing Efficiency
A measure of the void space within the unit cell.
46


Meredig
Composite descriptor from Meredig et al.
51


Modified XRD (mXRD)
Powder diffraction pattern calculated using Bragg's law.
47


Orbital Field Matrix
Descriptor that encodes the distribution of valence shell
52



electrons for each input structure.



Oxidation States
Concentration weighted oxidation state statistics.
48


Radial Distribution Function
Radial distribution function for each structure.
47


Sine Coulomb Matrix
Coulomb matrix for periodic lattices, developed by Faber et al.
53,54


Smooth Overlap of Atomic
Geometric encoder that is rotationally/transitionally invariant
25


Positions (SOAP)
through use of spherical harmonics and radial basis functions.




Atoms are represented by a smeared gaussian.



Structural Complexity
The Shannon information entropy for a given structure.
55


Structure Variance
Bond length and atomic volume variance for each structure.
46


Valence Orbital
Structure averaged number of valence electrons in each orbital.
48,56


Control
A control descriptor is not explicitly used. Instead, clustering




outcomes are randomly assigned. For composite intracluster




variance calculations, 100 control iterations are averaged.









Agglomerative clustering is performed on all Li-containing structures from the ICSD and MP repositories. Agglomerative clustering is a “bottom-up” approach to clustering where each structure starts in its own cluster of one. Clusters are merged according to Ward's Minimum Variance criterion in Euclidean space, which minimizes the global descriptor variance57:






W
=




k
=
1


n
C






i


C
k





[


d
i

-


d
_

k


]

2









    • where nc is the number of clusters in a set, Ck is cluster k, di is a descriptor representation for structure i, and dk is the average descriptor representation in cluster k. Each cluster merger results in the lowest variance set of clusters, relative to all other possible mergers. Other common linkage criteria (average, complete, and single linkages) and metrics (I1, I2, manhatten, cosine) were screened but are found to result in clustering outcomes with larger W. For each simplification-descriptor combination, all clustering sets from 2-300 are computed. Physically relevant labels are applied to the resultant clustering sets to assess how well each simplification-descriptor combination performs. To compare between the 180 different simplification-descriptions combinations, the data is labeled with 155 experimental room temperature conductivity (σRT) values aggregated from the literature reports (see Example 1B: sections I-IV). A secondary label set is also screened, comprised of 6845 activation energies (Ea) computationally generated using a bond valence energy approach (see Example 1B: section V).





An ideal simplification-descriptor combination results in clustering where each cluster contains labels with similar σRT values. Ward's minimum variance method is applied to the conductivity labels as a measure of clustering efficacy:34







W
σ

=




k
=
1


n
c






i


C
k





[



log

(

σ
RT

)

i

-



log


(

σ
RT

)


_

k


]

2









    • where nc is the number of clusters in a set, Ck is cluster k, and log(σRT)k denotes the mean for all labels in cluster k. Since clusters containing only one label effectively drop out of the Wσ calculation, a frozen-state strategy is employed when needed (see Example 1B: section IV). Each descriptor's Wσ results are shown in FIG. 2 for the first 50 clustering outcomes (i.e. the Wσ is shown for each set of 2, 3, . . . , 49, and 50 clusters). For simplicity, only the best-performing simplification-descriptor combination is shown for each descriptor.





Using σ25° C. labels, the best semi-supervised ML performance is attained when using the SOAP descriptor. SOAP is a spatial descriptor that employs smeared gaussians to represent atomic positions for each crystal structure25. Predictions using the SOAP descriptor have exhibited similar performance to state-of-the-art graph neural networks (GCNs) on a variety of materials science datasets58. Optimization of SOAP hyper-parameters (radial cutoff, number of radial basis functions, degree of spherical harmonics) is explored in section VI of the supplemental information. SOAP is found to perform best when combined with the CAN structure simplification. That is, the simplification where the mobile Li atoms are removed, and the remaining atoms are simplified into three representative species: cations, anions, and neutral atoms. SOAP outperforms all other descriptors for all depths of clustering. The SOAP descriptor can be modestly improved (2-3% decrease in Wσ) by mixing with other descriptors to make a 2nd order SOAP descriptor (see Example 1B: section VI).


Semi-Supervised Identification of Prospective Li-Ion Conductors:

Agglomerative clustering with the 2nd order SOAP descriptor is used to identify prospective ionic conductors. Wσ minimization is prioritized over WEa minimization because Ea alone is not necessarily a good predictor of conductivity; σ25° C. may be affected by properties including the ionic carrier concentration, hopping attempt frequency, and the presence of concerted migration modes59. The agglomerative dendrogram for the 2nd order SOAP is shown in FIG. 3, with the label densities plotted below. The agglomerative dendrogram is depicted to 241 clusters, after which the Wσ does not appreciably decrease. To facilitate discussion, an arbitrary cutoff is placed to yield 9 large clusters. The results show that although cluster #2 contains only 15% of the input structures, it accounts for over half of the high-conductivity (σ25° C.>10−5 S cm−1) labels. By the 17th clustering step, the densest cluster accounts for 6.2% of the structures while containing over half (52%) of the high-conductivity labels.


Candidates for next-generation SSEs can be identified by evaluating clusters that either contain or are near high conductivity labels. Clusters #2, #4, and #7 are promising because they account for 85% of the high σ25° C. labels. However, targeting these clusters would necessitate screening thousands of structures. Instead, we search from the 241st cluster depth, targeting all clusters that contain or are directly adjacent (i.e. the nearest cluster in the Euclidean feature space) to high σ25° C. labels. The promising structures are further screened using calculated stability (E vs. Ehull) and band gap (Eg) properties from the Materials Project, and the BVSE Ea values. We select the structures that have (1) an Ehull of 70 meV or lower,60 (2) an Eg of at least 1 eV, and (3) a BVSE-calculated Ea below a conservative 0.6 eV. We note that while a true Eg value of 1 eV would be problematic for an SSE, the bandgaps reported on Materials Project are typically underestimated by about 40%61. The approach identifies 212 structures as prospective ionic conductors. Climbing image nudged elastic band (CI-NEB) is employed to calculate the Ea for Li-ion hopping on the ten materials with the lowest BVSE-calculated Ea and an Ehull of 0 eV. The CI-NEB functionals and parameters can be found in the supporting information section VII. The top 10 prospective structures are tabulated in Table 2.









TABLE 2







The top 10 prospective structures from the semi-supervised learning model as


ranked by BVSE−calculated Ea. Structures in or directly adjacent to high-


conductivity clusters were identified as promising. The list of promising structures was then


further simplified by removing structures with Materials Project reported Ehull values greater


than 0 V and Eg values less than 1 eV. To rank the remaining structures, the Ea


was calculated using BVSE and NEB approaches.











E vs. Ehull
Eg
Ea_calc (meV)














compound
space group
MP_ID
ICSD_ID
(eV/atom)
(eV)
BVSE
NEB

















Li3VS4
P43m (#215)
mp-760375

0
1.88
160
390


Na3Li3Al2F12
Ia3d (#230)
mp-6711
9923
0
7.85
230
340


Li2Te
Fm3m (#225)
mp-2530
60434
0
2.49
260
320


LiAlTe2
I42d (#122)
mp-4586
280226
0
2.46
260
310


LiInTe2
I42d (#122)
mp-20782
658016
0
1.49
270
450


Li6MnS4
P42/nmc (#137)
mp-756490

0
1.55
270
466


LiGaTe2
I42d (#122)
mp-5048
162555
0
1.59
270
340


Li3BS3
Pnma (#62)
mp-5614
380104
0
2.89
280
260


KLi6TaO6
R3m (#166)
mp-9059
73159
0
4.27
300
404


Li3CuS2
Ibam (#72)
mp-1177695

0
2.03
310
440









The CI-NEB calculations generally agree with the BVSE calculated Ea values, suggesting favorable activation energies (<500 meV). Discrepancies between the two values may arise because BVSE does not allow framework ions to relax during Li+ migration and does not account for repulsive interactions between atoms of the mobile ion species. BVSE also does not capture cooperative conduction mechanisms or those involving the so-called paddlewheel effect. Despite these limitations, we note that the model identifies numerous diverse structures beyond those routinely explored. Table 1 includes four tellurides, a vanadium sulfide, and multiple transition-metal-containing structures. Of the structures in Table 1, 70% avoid the space groups for the best-performing SSEs discovered to date: LPS (62), LGPS (137), the argyrodites (216), and LLZO (230).


Data Processing and Semi-Supervised Learning:

The ˜26,000 input compositions are exported from the Inorganic Crystalline Structure Database (ICSD v. 4.4.0) and Material's Project (MP—v.2020.09.08) as crystallographic information files (.cif). All structures containing Li are imported. Although transition metals could produce undesirable redox activity, transition metal containing structures are not screened out. Some of the best-performing SSEs contain transition metals (e.g. LLZO and LLTO). Entries that existed in both ICSD and MP are merged. Data manipulations and structure simplifications are performed using the Python libraries NumPy (v1.19.1), Pandas (v1.0.5), ASE (v3.19.1), and Pymatgen (v2020.8.3). Descriptor transformations are performed using the Python libraries Pymatgen (v2020.8.3), Matminer (v0.6.3), and Dscribe. Agglomerative hierarchical clustering is performed using the Python library scipy (v1.5.0). All code has been successfully executed on a custom-built CPU with an AMD Ryzen Threadripper 3990x Processor and 256 GB of RAM, in Ubuntu 20.04 running on Windows Subsystem for Linux 2. All code is made available on the github (https://github.com/FALL-ML/materials-discovery).


CI-NEB:

Migration barriers for Li ion hopping are evaluated with the Climbing Image-Nudged Elastic Band (CI-NEB) method as implemented in the QuantumESPRESSO PWheb software package81-84. Density-functional theory (DFT) calculations are performed using the Perdew-Burke-Emzerfof (PBE) generalized gradient approximation functional and projector-augmented wave (PAW) sets85,86. Convergence testing for the kinetic-energy cutoff of the plane-wave basis and the k-point sampling is performed for each structure to ensure an accuracy of 1 meV per atom. The lattice parameters and atomic positions of the as-retrieved structure are optimized. Supercells are created for each structure that are a minimum of 10 Å in each lattice direction to minimize interactions between periodic images of the mobile ion. To study the migration barrier in the dilute limit, a single Li vacancy is created in the boundary endpoint structures of each studied pathway. A uniform background charge is used to balance excess charge. Each boundary configuration is relaxed until the force on each atom is less than 3×10−4 eV/Å. Images are created by linearly interpolating framework atomic positions between the initial and final boundary configurations. The initial pathway for the mobile ion is generated from the BVSE output minimum energy pathway to promote faster convergence of the NEB calculation. An NEB force convergence threshold of 0.05 eV/Å is used. The calculation is first converged using the default NEB algorithm and then restarted with the Cl scheme to allow for the maximum energy of the pathway to be determined.


Example 1B: Additional Aspects and Details for Semi-Supervised Machine Learning Approach for Identification of Candidate Solid State Li-Ion Conductors or Lithium Solid State Electrolytes
Section I. Digitized Labels for Lithium-Ion Conductors: RT Conductivity, Activation Energy, and Corresponding ICSD Identifier

Data labels for the semi-supervised learning approach were ultimately digitized from over 300 literature publications. Many more publications were initially examined. The stepwise decision chart below was used as a guide for deciding what data to digitize. Room temperature conductivity data was only digitized if it originated from an equivalent circuit fit (where a blocking feature was clearly present) or if calculated from NMR. DC techniques were categorically discounted because they cannot differentiate between electronic and ionic conductivity.


All of the digitized data is presented in the subsequent tableI. Activation energies were also digitized when available. The activation energies were not used in the manuscript but are still presented here to aid future machine learning endeavors. The digitized data was manually matched with the appropriate ICSD ID, so that the crystallographic information file (.cif) can be downloaded.




















σ25° C.
Ea
Space
Space
Other




Compound
(S cm−1)
(eV)
Group
Group #
names
ICSD
Citation






















LiAlSi3O8
 1.30E−10

C1
2

81980
1


LiSn2(PO4)3
2.04E−9

P1
2

83832
2


Li7BiO6
 8.80E−07
0.58
P1
2

155950
3


Li7SbO6
 6.70E−08
0.7
P1
2

413370
3


Li7P3S11
 1.70E−02
0.17
P1
2

157654
4


Li7P3S11
 3.2E−3
0.124
P1
2

157654
5


LiV(PO4)F
 8.1E−7
0.23
P1
2

183876
6


Li2B3PO8
 5.80E−15
0.76
P1
2

248343
7


Li3BP2O8
 9.60E−12
0.62
P1
2

248343
7


Li2NaBP2O8
 4.40E−18
1.21
P1
2

291512
7


Li4P2O7
<1E−10
1.617
P1
2

248414
8


LiMgSO4F
 5.40E−08
0.54
P1
2

281119
9


Li6CuB4O10
 1.00E−13
0.92
P1
2
β-Li6CuB4O10
4819
10


Li0.91Hf2.022(PO4)3
<1E−10
0.47
C1
2


11


Li7P3S11
 8.6E−3
0.29
P1
2


12


Li2ZnGeO4
 1.00E−07
0.4
Pc
7

34362
13


Li3.8Ge0.8P0.2S4
1.78E−6
0.47
P21/m
11


14


Li3.6Ge0.6P0.4S4
1.75E−4
0.34
P21/m
11


14


Li3.4Ge0.4P0.6S4
6.54E−4
0.28
P21/m
11


14


Li3.35Ge0.35P0.65S4
1.54E−3
0.23
P21/m
11


14


Li3.3Ge0.3P0.7S4
1.74E−3
0.22
P21/m
11


14


Li3.25Ge0.25P0.75S4
 2.2E−03
0.207
P21/m
11


14


Li3.2Ge0.2P0.8S4
5.55E−4
0.27
P21/m
11


14


Li4SiS4
 5.00E−08
0.56
P21/m
11

59708
15


Li7.22Si1.5P0.5O8
1.64E−7
0.48
P21/m
11

238602
16


Li4SiO4
 5.00E−10
0.55
P21/m
11

238603
17


Li4SiS4
1.59E−8
0.56
P21/m
11


18


Li3.8Si0.8P0.2S4
8.11E−7
0.37
P21/m
11


18


Li3.6Si0.6P0.4S4
7.19E−5
0.34
P21/m
11


18


Li3.5Si0.5P0.5S4
1.66E−4
0.34
P21/m
11


18


Li3.4Si0.4P0.6S4
6.62E−4
0.29
P21/m
11


18


Li3.3Si0.3P0.7S4
1.02E−5
0.36
P21/m
11


18


Li3.2Si0.2P0.8S4
3.20E−6
0.37
P21/m
11


18


Li4SiS4
1.62E−8
0.56
P21/m
11


18


Li3.8Si0.8P0.2S4
8.07E−7
0.37
P21/m
11


18


Li3.6Si0.6P0.4S4
7.11E−5
0.34
P21/m
11


18


Li3.5Si0.5P0.5S4
1.61E−4
0.34
P21/m
11


18


Li3.4Si0.4P0.6S4
6.49E−4
0.29
P21/m
11


18


Li3.3Si0.3P0.7S4
9.84E−6
0.36
P21/m
11


18


Li3.2Si0.2P0.8S4
3.05E−6
0.37
P21/m
11


18


Li3.1P0.9Si0.1O4
7.47E−8

P21/m
11


19


Li3.5P0.5Si0.5O4
2.89E−6

P21/m
11


19


Li3.9P0.1Si0.9O4
1.99E−8

P21/m
11


19


Li3.7P0.3Si0.7O4
3.84E−7

P21/m
11

35168
19


Li3InCl6
2.04E−3
0.35
C2/m
12

89617
20


Li2P2S6
 7.80E−11
0.48
C2/m
12

253894
21


Li0.6[Li0.2Sn0.8S2]
 1.2E−4
0.17
C2/m
12


22


Li3(Mo8S8O8(OH)8(HWO5(H2O)))*(H2O)18
 3.8E−7
0.62
C2/m
12

412011
23


Li17Sb13S28
1.05E−9
0.4
C2/m
12

429902
24


Li3InBr6
9.04E−4

C2/m
12


25


Li3YBr6
1.92E−3
0.37
C2/m
12


26


Li0.84Sn0.79S2
 1.2E−4
0.17
C2/m
12


27


LiAlSi4O10
 1.01E−10

P2/c
13

194284
1


LiPO3
 1.00E−09

P2/c
13

51630
28


LiGaBr4
7.00E−6
0.54
P21/c
14

61337
25


Li2SO4
 1.40E−14
1.1
P21/c
14

2512
29


Li3BO3
 7.40E−11
0.63
P21/c
14

9105
30


Li6Ge2O7
 8.50E−07
0.43
P21/c
14

31050
31


LiAlCl4
 1.00E−06
0.47
P21/c
14

35275
32


LiYO2
 1.80E−08
0.72
P21/c
14

45511
33


LiBO2
 1.00E−08
0.71
P21/c
14

200891
34


LiClC3H7NO
 1.6E−4
0.881
P21/c
14

238683
35


LaLiO2
<1E−10
0.92
P21/c
14

239278
36


(La0.9Sr0.1)LiO2
 6.29E−10
0.62
P21/c
14

239279
36


La(Li0.76Mg0.08)O2
 7.27E−10
0.66
P21/c
14

239280
36


Li2.5V2(PO4)3
 1.9E−7

P21/c
14

240269
37


Li4Zn(PO4)2
<1E−10
1.3
P21/c
14
α-Li4Zn(PO4)2
255464
38


LiSbO2
<1E−10
0.88
P21/c
14

262075
39


Li2Sr2Al(PO4)3
<1E−10
1.02
P21/c
14

431319
40


Li2ZrO3
 6.10E−10
0.78
C2/c
15

94894
33


Li6Zr2O7
 5.20E−10
0.68
C2/c
15

73835
41


Li3AlF6
 5.00E−07
0.54
C2/c
15

85171
42


Li2SnS3
 1.50E−05
0.59
C2/c
15

251656
43


LiTa2PO8
 1.6E−3
0.32
C2/c
15

267438
44


LiBaP2O7
 1.00E−10

C2/c
15

280927
45


Li3Na5(TiS4)2
 8.80E−06
0.4
C2/c
15

391258
46


LiGd(PO3)4
<1E−10
1.7
C2/c
15

416442
47


LiVO3
2.048E−9 

C2/c
15

51443
48


Li2CrCl4
<1E−10
1.22
C2/c
15

202627
49


Li3ErI6
9.92E−5
0.37
C2/c
15


50


Li3.7Zn0.7Ga0.3(PO4)2
<1E−10
0.91
P212121
19
β′-
255466
38







Li3.7Zn0.7Ga0.3(PO4)2




Li3SbS4
 1.5E−6
0.518
Pmn21
31

8407
51


Li3PS4
 2.60E−07
0.49
Pmn21
31
γ-Li3PS4
180318
52


LiGaO2
 2.40E−14
0.86
Pna21
33

18152
53


LiB6OgF
 5.40E−24
1.38
Pna21
33

420286
54


Li3SbS3
 1.00E−07
0.4
Pna21
33

424834
55


LiSi2N3
 6.17E−08
0.64
Cmc21
36

34118
56


Li2(PO2N)
<1E−10
0.57
Cmc21
36

188493
57


LiGa2GeS6
 3.80E−08
0.47
Fdd2
43

254406
58


La0.64Li0.08TiO3
3.35E−4

Pmmm
47

92228
59


La0.62Li0.14TiO3
4.42E−4

Pmmm
47

92231
59


La0.595Li0.215TiO3
8.53E−4

Pmmm
47

92234
59


Li0.4Na0.1La0.5Nb2O6
9.92E−6

Pmmm
47

180629
60


Li0.3Na0.2La0.5Nb2O6
1.11E−5

Pmmm
47

180630
60


Li0.2Na0.3La0.5Nb2O6
1.18E−5

Pmmm
47

180631
60


Li0.1Na0.4La0.5Nb2O6
1.21E−5

Pmmm
47

180632
60


Li0.07Na0.43La0.5Nb2O6
1.23E−5

Pmmm
47

180633
60


Li0.04Na0.46La0.5Nb2O6
5.91E−6

Pmmm
47

180634
60


Li0.02Na0.48La0.5Nb2O6
3.99E−6

Pmmm
47

180635
60


(Ag0.33Li0.67)0.27La0.57TiO3
  1E−4
0.30
Pmmm
47


61


(Ag0.5Li0.5)0.27La0.57TiO3
 2.3E−5
0.28
Pmmm
47


61


(Ag0.67Li0.33)0.27La0.57TiO3
  2E−7
0.37
Pmmm
47


61


Pr0.56Li0.34TiO3.01
  1E−6
0.47
Pmmm
47


62


Nd0.55Li0.34TiO3
  8E−7
0.53
Pmmm
47


62


Li0.09La0.77TiO3
1.23E−4

Pmmm
47


63


Li0.15La0.72TiO3
4.14E−4

Pmmm
47


63


Li0.24La0.65TiO3
5.77E−4

Pmmm
47


63


Li0.12La0.75TiO3
2.38E−4

Pmmm
47


63


Li0.16La0.7TiO3
5.21E−4

Pmmm
47


63


Li0.23La0.7TiO3
5.26E−4

Pmmm
47


63


Li5AlO4
 5.00E−10
0.99
Pmmn
59

16229
64


Li14Nd5(Si11N19O5)O2F2
 1.7E−10
0.69
Pmmn
59

262923
65


Li5GaO4
 5.00E−09
0.71
Pbca
61
α-Li5GaO4
9082
64


Li2SiN2
 1.60E−07

Pbca
61

420126
66


Li6.5O8P1.5Si0.5
 4.49E−07
0.44
Pnma
62

238600
16


Li3.4Si0.7S0.3O4
4.21E−7

Pnma
62

47145
67


Li3.2Si0.6S0.4O4
1.32E−6

Pnma
62


67


Li3.1Si0.55S0.45O4
3.14E−7

Pnma
62


67


Li6.6SiPO8
1.48E−7
0.49
Pnma
62

238601
16


Li4.2Si0.8Al0.2S4
2.40E−8
0.53
Pnma
62


18


Li4.4Si0.6Al0.4S4
3.04E−8
0.52
Pnma
62


18


Li4.6Si0.4Al0.6S4
1.45E−8
0.52
Pnma
62


18


Li4.8Si0.2Al0.8S4
2.25E−7
0.52
Pnma
62


18


Li3.8Si0.8Al0.2S4
2.38E−8
0.53
Pnma
62


18


Li3.6Si0.6Al0.4S4
3.06E−8
0.52
Pnma
62


18


Li3.4Si0.4Al0.6S4
1.45E−8
0.52
Pnma
62


18


Li3.2Si0.2Al0.8S4
2.28E−7
0.52
Pnma
62


18


Li4Zn(PO4)2
<1E−10
1.1
Pnma
62
β-Li4Zn(PO4)2
255465
38


Li3.5Zn0.5Ga0.5(PO4)2
<1E−10
1.02
Pnma
62
β-Li3.5Zn0.5Ga0.5(PO4)2
255468
38


Li3PS4
 1.60E−04
0.36
Pnma
62
β-Li3PS4
180319
52


Li3PO4
<1E−10
1.14
Pnma
62
γ-Li3PO4
20208
68


Li3PS4
3.00E−7

Pnma
62
γ-Li3PS4
35018
69


Li2.88PO3.73N0.14
 1.4E−13
0.97
Pnma
62

79426
70


Li3PO4
 4.2E−18
1.24
Pnma
62
γ-Li3PO4
79427
70


Li4GeS4
  2E−7
0.53
Pnma
62

92200
71


Li14Zn(GeO4)4
 1.00E−06
0.24
Pnma
62

100169
72


Li3.75Ge0.75V0.25O4
5.66E−6

Pnma
62

150918
73


Li3.70Ge0.85W0.15O4
3.80E−5

Pnma
62

150920
73


Li0.2Ca0.4TaO3
3.53E−9
0.54
Pnma
62

151936
74


Li0.2(Ca0.36Sr0.04)TaO3
 9.2E−9

Pnma
62

151937
74


Li2Mg2(MoO4)3
<1E−10
0.71
Pnma
62

170956
75


Li4SnSe4
  2E−5
0.45
Pnma
62

193768
76


Li(BH4)
  1E−8

Pnma
62

239763
77


LiZnSO4F
 2.80E−05
0.2455
Pnma
62

261343
78


Li4GeS4
 2.00E−07
0.53
Pnma
62

290831
79


Li4SnS4
 7.0E−5
0.29
Pnma
62

290832
80


Li2ZnI4
 4.00E−08
0.58
Pnma
62

402062
81


Pr0.53Li0.41TiO3
0.84E−7
0.462
Pnma
62


82


Pr0.54Li0.38TiO3
1.18E−6
0.452
Pnma
62


82


Pr0.55Li0.35TiO3
1.51E−6
0.441
Pnma
62


82


Pr0.56Li0.32TiO3
1.91E−6
0.437
Pnma
62


82


Pr0.57Li0.29TiO3
2.86E−6
0.429
Pnma
62


82


Pr0.58Li0.26TiO3
3.87E−6
0.421
Pnma
62


82


Pr0.59Li0.23TiO3
3.40E−6
0.425
Pnma
62


82


Li2.5Y0.5Zr0.5Cl6
 1.4E−3
0.33
Pnma
62


83


Li2.633Er0.633Zr0.367Cl6
 1.1E−3
0.35
Pnma
62


83


Li3.33Ge0.33V0.67O4
6.94E−6

Pnma
62


84


Li3.6Ge0.6V0.4O4
1.97E−5
0.44
Pnma
62


84


Li3.75Ge0.75V0.25O4
1.08E−5

Pnma
62


84


Li3.5Ge0.5V0.5O4
1.77E−5

Pnma
62

66576
84


Li3.87Sn0.87As0.13S4
1.48E−5
0.39
Pnma
62


85


Li3.855Sn0.855As0.145S4
1.31E−4
0.35
Pnma
62


85


Li3.85Sn0.85As0.15S4
2.08E−4
0.31
Pnma
62


85


Li3.84Sn0.84As0.16S4
5.85E−4
0.29
Pnma
62


85


Li3.83Sn0.83As0.17S4
1.39E−3
0.21
Pnma
62


85


Li3.825Sn0.825As0.175S4
5.18E−4
0.27
Pnma
62


85


Li3.82Sn0.82As0.18S4
2.83E−4
0.35
Pnma
62


85


Li3.8Sn0.8As0.2S4
1.06E−4
0.4
Pnma
62


85


Li3.75Sn0.75As0.25S4
3.69E−6
0.48
Pnma
62


85


Nd0.54Li0.36TiO3
3.42E−8
0.50
Pnma
62

81047
86


Pr0.51Li0.39TiO2.96
5.34E−7
0.44
Pnma
62

81048
86


Sm0.52Li0.38TiO2.97
  2E−7
0.64
Pnma
62


62


Li4GeO4
 2.80E−10
0.73
Cmcm
63

18096
87


LiCl*H2O
  1E−8
0.777
Cmcm
63

281198
88


Li2MgBr4
 7.80E−10
0.77
Cmmm
65

73276
89


Li0.22La0.60TiO3
 4.8E−4
0.391
Cmmm
65


90


Li0.18La0.61TiO3
 2.0E−4
0.432
Cmmm
65

99398
90


LiBiO2
 3.80E−08
0.1
Ibam
72

46022
30


Li2.5Zn0.25PS4
8.40E−4

I4
82


69


LiZnPS4
 5.4E−8

I4
82

95785
69


Li2Zn0.5PS4
1.30E−4
0.22
I4
82

264462
69


(Li1.69Zn0.66)PS4
1.30E−4
0.181
I4
82

264462
69


Li1.5Zn0.75PS4
1.65E−5
0.25
I4
82

264463
69


(Li1.19Zn0.9)PS4
0.65E−5
0.25
I4
82

264463
69


(Li0.5Ce0.5)(MoO4)
 1.3E−8
0.4
I41/a
88

186450
91


(Li0.5Ce0.25Pr0.25)(MoO4)
  1E−9
0.5
I41/a
88

186451
91


(Li0.5Ce0.25Sm0.25)(MoO4)
 1.8E−10
0.5
I41/a
88

186452
91


Li2TeO4
<1E−10
1.129
P4122
91

1485
92


Li3BN2
 1.60E−10
0.67
P42212
94
α-Li3BN2
655673
93


Li2B4O7
 1.00E−10

I41cd
110

65930
94


LiY(BH4)4
1.26E−6

P42c
112

239762
77


LiPN2
 1.6E−7
0.40
I42d
122

66007
95


La0.565Li0.305TiO3
9.57E−4

P4/mmm
123

92235
59


La0.5Li0.5TiO3
9.25E−4
0.39
P4/mmm
123

92236
59


Li0.33La0.5TiO3
  1E−3
0.15
P4/mmm
123

82671
96


Li0.27La0.57TiO3
 3.4E−4
0.38
P4/mmm
123


61


La0.61Li0.18TiO3
4.12e-4

P4/mmm
123


97


La0.55Li0.36TiO3
6.88E−4
0.35
P4/mmm
123


97


La0.54Li0.39TiO3
6.51E−4

P4/mmm
123


97


La0.52Li0.45TiO3
5.01E−4

P4/mmm
123

50434
97


La0.58Li0.27TiO3
5.99E−4

P4/mmm
123

82672
97


La0.56Li0.33TiO3
6.68E−4

P4/mmm
123

504435
97


Li0.31La0.63TiO3
4.11E−4

P4/mmm
123


63


Li0.39La0.59TiO3
8.83E−4

P4/mmm
123


63


Li0.49La0.55TiO3
9.39E−4

P4/mmm
123


63


Li0.68La0.49TiO3
1.03E−3

P4/mmm
123


63


Li0.24La0.65TiO3
9.57E−4

P4/mmm
123


63


Li0.33La0.58TiO3
8.93E−4

P4/mmm
123


63


Li0.36La0.55TiO3
9.34E−4

P4/mmm
123


63


Li0.42La0.52TiO3
8.47E−4

P4/mmm
123


63


Li0.29La0.57TiO3
 4.4E−5
0.453
P4/mmm
123


90


La0.56Li0.33TiO3
1.65E−4
0.41
P4/mmm
123


98


La0.56Li0.33TiO3-5 wt % Al2O3
1.66E−4
0.24
P4/mmm
123


98


La0.56Li0.33TiO3-10 wt % Al2O3
9.33E−4
0.17
P4/mmm
123


98


La0.56Li0.33TiO3-15 wt % Al2O3
9.56E−5
0.50
P4/mmm
123


98


Li(LaTiO4)
<1E−10
0.83
P4/nmm Z
129

91843
99


Li(NdTiO4)
<1E−10
0.87
P4/nmm Z
129

91844
99


La0.65Li0.05(Mg0.5W0.5)O3
 1.8E−7
0.46
P4/nmm
129

151900
100


La0.63Li0.11(Mg0.5W0.5)O3
 6.8E−6
0.38
P4/nmm
129

151901
100


La0.62Li0.14(Mg0.5W0.5)O3
 1.2E−5
0.37
P4/nmm
129

151902
100


Li4PS4I
 1.2E−4
0.37
P4/nmm Z
129

432169
101


Li9.75Sn0.75P2.25S12
3.57E−3

P42/nmc S
137





Li6ZnO4
 9.40E−09
0.61
P42/nmc
137

62137
64


Li9.42Si1.02P2.1S9.96O2.04
 1.1E−4
0.238
P42/nmc
137


102


Li9.54Si1.74P1.44S11.7Cl0.3
2.53E−2
0.238
P42/nmc
137


102


Li10GeP2S11.7O0.3
1.15E−2
0.155
P42/nmc
137


102


Li10(Si0.5Sn0.5)P2S12
4.28E−3
0.29
P42/nmc
137


102


Li9P3S9O3
4.27E−5
0.311
P42/nmc
137


103


Li10.05Ge1.05P1.95S12
1.22E−2
0.28
P42/nmc4
137


104


Li10.2Ge1.2P1.8S12
1.32E−2

P42/nmc4
137


104


Li10.5Ge1.5P1.5S12
1.10E−2

P42/nmc4
137


104


Li10GePS12
1.21E−2

P42/nmc
137

188887
104


Li10.35Ge1.35P1.65S12
1.44E−2
0.269
P42/nmc S
137

193947
104


Li3.475Si0.475P0.525S4
5.27E−3

P42/nmc
137


105


Li3.45Si0.45P0.55S4
6.73E−3
0.27
P42/nmc
137


105


Li3.425Si0.425P0.575S4
5.65E−3

P42/nmc
137


105


Li3.4Si0.4P0.6S4
4.21E−3

P42/nmc
137


105


Li3.335Sn0.33P0.67S4
3.73E−3

P42/nmc
137


105


Li3.3Sn0.3P0.7S4
3.65E−3

P42/nmc
137


105


Li3.285Sn0.28P0.72S4
4.36E−3

P42/nmc
137


105


Li3.27Sn0.27P0.73S4
4.96E−3

P42/nmc
137


105


Li3.26Sn0.26P0.74S4
4.53E−3

P42/nmc
137


105


Li3.25Sn0.25P0.75S4
 3.6E−3

P42/nmc
137


105


Li10SiP2S12
 2.3E−3
0.196
P42/nmc
137


106


Li10SnP2S12
  7E−3
0.27
P42/nmc C
137

193755
107


Li10GeP2S12
2.46E−2
0.274
P42/nmc
137

241439
108


Li10(Ge0.776Sn0.224)P2S12
1.41E−2
0.276
P42/nmc
137

255748
108


Li10SnP2S12
3.98E−3
0.305
P42/nmc
137

255750
108


Li10(Ge0.416Sn0.584)P2S12
7.43E−3
0.285
P42/nmc
137

255757
108


Li10.35Si1.35P1.65S12
 6.5E−3

P42/nmc S
137

252037
109


Li9.81Sn0.81P2.19S12
 5.5E−3

P42/nmc
137

252040
109


Li10GeP2S12
 1.20E−02
0.25
P42/nmc
137

255749
110


Li10.2Si1.2P1.8S12
4.16E−3

P42/nmc S
137


111


Li10.275Si1.275P1.725S12
5.61E−3

P42/nmc S
137


111


Li10.35Si1.35P1.65S12
6.68E−3

P42/nmc S
137


111


Li10.425Si1.425P1.575S12
5.22E−3

P42/nmc S
137


111


Li10GeP2S12
1.21E−2

P42/nmc S
137


111


Li10.05Ge1.05P1.95S12
1.25E−2

P42/nmc S
137


111


Li10.2Ge1.2P1.8S12
1.36E−2

P42/nmc S
137


111


Li10.35Ge1.35P1.65S12
1.41E−2

P42/nmc S
137


111


Li10.5Ge1.5P1.5S12
1.09E−2

P42/nmc S
137


111


Li9.79Sn0.79P2.21S12
4.56E−3

P42/nmc S
137


111


Li9.81Sn0.81P2.19S12
4.98E−3

P42/nmc S
137


111


Li9.87Sn0.87P2.13S12
4.32E−3

P42/nmc S
137


111


Li9.9Sn0.9P2.1S12
3.66E−3

P42/nmc S
137


111


Li10SnP2S12
3.65E−3

P42/nmc S
137


111


Li10.2(Sn0.2Si0.8)1.2P1.8S12
7.82E−3

P42/nmc S
137

5667
111


Li10.5(Sn0.2Si0.8)1.5P1.5S12
8.79E−3

P42/nmc S
137

5668
111


Li10.35(Sn0.2Si0.8)1.35P1.65S12
1.08E−2

P42/nmc S
137

5669
111


Li10.35(Sn0.27Si1.08)P1.65S12
 1.1E−3
0.197
P42/nmc S
137

257946
111


Li10.2(Sn0.2Si0.8)1.2P1.8S12
2.69E−3

P42/nmc S
137

257948
111


Li10GeP2S12
1.43E−3
0.24
P42/nmc S
137


112


Li9.8Ba0.1GeP2S12
5.61E−4

P42/nmc S
137


112


Li9.6Ba0.2GeP2S12
5.72E−4

P42/nmc S
137


112


Li9.4Ba0.3GeP2S12
7.07E−4
0.29
P42/nmc S
137


112


Li9.2Ba0.4GeP2S12
3.16E−4

P42/nmc S
137


112


Li9Ba0.5GeP2S12
9.98E−5

P42/nmc S
137


112


Li10GeP2S12
 5.0E−3
0.35
P42/nmc
137


113


LiIaNb2O7

<1E−8


I4/mmm
139

72566
114


Li4Sr3Nb5.77Fe0.23O19.77
<1E−10

I4/mmm
139

87823
115


Li4Sr3Nb6O20
<1E−10

I4/mmm
139

87824
115


Li4Sr3.056Nb6O20
<1E−10
0.74
I4/mmm
139

109168
115


LiScO2
 1.00E−12
0.87
I41/amd
141

36124
33


r-LiAlO2
 1.10E−12
0.97
I41/amd
141

99517
33


Li3BN2
 8.70E−08
0.55
I41/amd
141
β-Li3BN2
155126
93


Li4SrN2
 2.30E−13
0.9
I41/amd
141

87413
116


LiScO2
<1E−10
1.047
I41/amd
141

257819
117


Li0.9SC0.9Zr0.1O2
<1E−10
0.912
I41/amd
141

257820
117


Li7La3HfO12
9.85E−7
0.53
I41/acdZ
142
“tetragonal-LLHO”
174202
118


Li7LasZr2O12
1.63E−6
0.54
I41/acdZ
142
“tetraganol-LLZO”
183684
119


Li7La3Zr2O12
  5E−7
0.59
I41/acdZ
142


120


Li7La3Zr2O12
 9.9E−6
0.43
I41/acdZ
142

238687
121


LiGaSiO4
 3.00E−16
0.9
R3H
146

65125
122


LiGa0.5Al0.5GeO4
<1E−10
1.06
R3H
146

257740
123


LiAlGeO4
<1E−10
0.97
R3H
146

257741
123


LiGaGeO4
<1E−10
1.12
R3
148

257739
123


LiTi2(PO4)3
1.61E−4
0.21
R3
148


124


Li1.2Ti1.8Al0.2(PO4)3
4.82E−3
0.18
R3
148


124


LiNaSO4
 8.80E−10

P31c
159

14364
125


Li3.333Mg0.333P2S6
8.20E−8
0.517
P31m
162

95606
126


Li2.667Mg0.667P2S6
 4.00E−06
0.46
P31m
162

95607
126


Li4P2S6
 2.38E−07
0.29
P31m
162

242170
127


Li4P2S6
 1.6E−10
0.48
P31m
162


128


Li3YCl6
5.39E−4
0.40
P3m1
164


26


Li3ErCl6
 3.3E−4
0.41
P3m1
164

50151
129


Li4.4Al0.4Ge0.6S4
4.33E−5
0.38
P3m1
164

235201
130


Li4.4Al0.4Sn0.6S4
 3.6E−6
0.15
P3m1
164

235207
130


Li5NCl2
 1.20E−06
0.5
R3m
166

84763
131


LiHf2(PO4)3
2.833E−7 

R3cH
167


2


LiZr2(PO4)3
 2.96E−10

R3cH
167

201935
2


LiGe2(PO4)3
3.33E−7

R3cH
167

263767
2


Li1.1Ti1.9Sc0.1(PO4)3
3.89E−4
0.3
R3cH
167


132


Li1.2Ti1.8Sc0.2(PO4)3
2.51E−3
0.25
R3cH
167


132


Li1.3Ti1.7Sc0.3(PO4)3
7.91E−4
0.28
R3cH
167


132


Li1.4Ti1.6Sc0.4(PO4)3
1.99E−4
0.31
R3cH
167


132


Li1.5Ti1.5Sc0.5(PO4)3
9.74E−5
0.32
R3cH
167


132


LiTi2(PO4)3
7.61E−6
0.38
R3cH
167

95979
132


LiGe2(PO4)3
4.83E−9
0.654
R3cH
167

69763
133


Li1.2Al0.2Ge1.8(PO4)3
4.83E−5
0.387
R3cH
167

263760
133


Li1.4A10.4Ge1.6(PO4)3
1.88E−4
0.407
R3cH
167

263762
133


Li1.5A10.5Ge1.5(PO4)3
3.36E−4
0.426
R3cH
167

263763
133


Li1.7Al0.7Ge1.3(PO4)3
2.64E−4
0.450
R3cH
167

263765
133


Li1.8Al0.8Ge1.2(PO4)3
1.37E−4
0.429
R3cH
167

263766
133


LiTi2(PO4)3
 1.0E−4

R3cH
167


134


Li1.2Ti2Si0.2P2.8O12
 8.6E−5

R3cH
167


134


Li1.3Ti2Si0.3P2.7O12
 3.2E−4

R3cH
167


134


Li1.4Ti2Si0.4P2.6O12
 1.5E−4

R3cH
167


134


Li1.5Ti2Si0.5P2.5O12
 9.6E−5

R3cH
167


134


Li1.3Al0.3Ti1.7(PO4)3
  3E−3

R3cH
167


134


Li1.4Al0.4Ti1.6(PO4)3
3.88E−4

R3cH
167


134


Li1.5Al0.5Ti1.5(PO4)3
2.48E−4

R3cH
167


134


Li1.2Cr0.2Ti1.8(PO4)3
1.82E−5

R3cH
167


134


Li1.3Cr0.3Ti1.7(PO4)3
3.51E−5

R3cH
167


134


Li1.4Cr0.4Ti1.6(PO4)3
1.49E−4

R3cH
167


134


Li1.5Cr0.5Ti1.5(PO4)3
3.86E−4

R3cH
167


134


Li1.6Cr0.6Ti1.4(PO4)3
1.26E−4

R3cH
167


134


Li1.7Cr0.7Ti1.3(PO4)3
8.05E−6

R3cH
167


134


Li1.2Ga0.2Ti1.8(PO4)3
1.62E−4

R3cH
167


134


Li1.3Ga0.3Ti1.7(PO4)3
2.61E−4

R3cH
167


134


Li1.4Ga0.4Ti1.6(PO4)3
1.28E−4

R3cH
167


134


Li1.5Ga0.5Ti1.5(PO4)3
1.22E−4

R3cH
167


134


Li1.2Fe0.2Ti1.8(PO4)3
1.80E−4

R3cH
167


134


Li1.3Fe0.3Ti1.7(PO4)3
2.46E−4

R3cH
167


134


Li1.4Fe0.4Ti1.6(PO4)3
3.92E−4

R3cH
167


134


Li1.2Sc0.2Ti1.8(PO4)3
6.90E−4

R3cH
167


134


Li1.3Sc0.3Ti1.7(PO4)3
7.03E−4

R3cH
167


134


Li1.4Sc0.4Ti1.6(PO4)3
5.15E−4

R3cH
167


134


Li1.5Sc0.5Ti1.5(PO4)3
2.53E−4

R3cH
167


134


Li1.2In0.2Ti1.8(PO4)3
3.90E−4

R3cH
167


134


Li1.3In0.3Ti1.7(PO4)3
3.93E−4

R3cH
167


134


Li1.4In0.4Ti1.6(PO4)3
3.02E−4

R3cH
167


134


Li1.5In0.5Ti1.5(PO4)3
2.04E−4

R3cH
167


134


Li1.2La0.2Ti1.8(PO4)3
8.00E−5

R3cH
167


134


Li1.3La0.3Ti1.7(PO4)3
5.23E−4

R3cH
167


134


Li1.4La0.4Ti1.6(PO4)3
4.98E−4

R3cH
167


134


Li1.5La0.5Ti1.5(PO4)3
2.81E−4

R3cH
167


134


Li1.5Fe0.5Ti1.5(PO4)3
1.74E−4

R3cH
167

55751
134


Li0.87Hf2.032P3O12
 1.29E−05
0.33
R3cH
167

83501
134


Li1.2Al0.2Ti1.8(PO4)3
5.95E−4

R3cH
167

427621
134


Li(Ti1.4Sn0.6)(PO4)3
2.28E−5
0.32
R3cH
167

183672
135


Li(Ti0.6Sn1.4)(PO4)3
9.42E−6

R3cH
167

183676
135


Li(Ti0.4Sn1.6)(PO4)3
3.15E−6

R3cH
167

183677
135


Li1.15Y0.15Zr1.85(PO4)3
 1.4E−4
0.39
R3cH
167

191891
136


LiZr2(PO4)3
  1E−9
0.76
R3cH
167

201935
137


Li1.3(Al0.3Ti1.7)(PO4)3
8.02E−7

R3cH
167

253240
138


Li1.3(Al0.23Ga0.07Ti1.7)(PO4)3
4.46E−6

R3cH
167

253241
138


Li1.3(Al0.23Sc0.07Ti1.7)(PO4)3
1.94E−7

R3cH
167

253242
138


Li1.3(Al0.23Y0.07Ti1.7)(PO4)3
3.84E−8

R3cH
167

253243
138


Li1.3Al0.3Ti1.7(PO4)3
  7E−4

R3cH
167

257190
139


LiZr2(PO4)3
 8.5E−5

R3cH
167


140


Li1.025Y0.025Zr1.975(PO4)3
1.28E−4

R3cH
167


140


Li1.05Y0.05Zr1.95(PO4)3
 1.3E−4

R3cH
167


140


Li1.1Y0.1Zr1.9(PO4)3
 1.0E−4

R3cH
167


140


Li1.1Al0.1Ge1.9(PO4)3
1.29E−5

R3cH
167


140


Li1.2Al0.2Ge1.8(PO4)3
1.89E−5
0.46
R3cH
167


140


Li1.3Al0.3Ge1.7(PO4)3
1.91E−4

R3cH
167


140


Li1.4Al0.4Ge1.6(PO4)3
3.17E−4
0.37
R3cH
167


140


Li1.5Al0.5Ge1.5(PO4)3
3.45E−4

R3cH
167


140


Li1.6Al0.6Ge1.4(PO4)3
3.94E−4
0.37
R3cH
167


140


Li1.7Al0.7Ge1.3(PO4)3
2.75E−4

R3cH
167


140


Li1.8Al0.8Ge1.2(PO4)3
1.23E−4
0.43
R3cH
167


140


LiGe2(PO4)3
3.12E−9
0.60
R3cH
167


141


Li0.86Hf2.035(PO4)3
 9.2E−8
0.48
R3cH
167


11


Li1.7Al0.3Ti1.6(PO4)3
  5E−5

R3cH
167


142


Li1.2In0.2Ti1.8(PO4)3
8.22E−5
0.32
R3cH
167


143


Li1.3Al0.2Sc0.1Ti1.7(PO4)3
9.72E−4
0.25
R3cH
167


144


Li1.3Al0.15Sc0.15Ti1.7(PO4)3
1.24E−3
0.23
R3cH
167


144


Li1.3Al0.1Sc0.2Ti1.7(PO4)3
4.29E−4
0.26
R3cH
167


144


Li1.3Sc0.3Ti1.7(PO4)3
4.52E−4
0.25
R3cH
167


144


Li1.3Al0.3Ti1.7(PO4)3
1.13E−3
0.23
R3cH
167

257190
144


LiTi(PO4)3
  6E−5
0.33
R3c
167


145


Li1.05Al0.05Ti0.95(PO4)3
 1.1E−3
0.31
R3c
167


145


Li1.1Al0.1Ti0.9(PO4)3
 6.7E−4
0.32
R3c
167


145


Li1.2Al0.2Ti0.8(PO4)3
 4.0E−3
0.31
R3c
167


145


Li1.3Al0.3Ti0.7(PO4)3
 6.2E−3
0.30
R3c
167


145


Li1.4Al0.4Ti0.6(PO4)3
 3.3E−3
0.29
R3c
167


145


Li1.05Cr0.05Ti0.95(PO4)3
 1.8E−4
0.33
R3c
167


145


Li1.1Cr0.1Ti0.9(PO4)3
 2.6E−4
0.32
R3c
167


145


Li1.2Cr0.2Ti0.8(PO4)3
 4.3E−4
0.31
R3c
167


145


Li1.3Cr0.3Ti0.7(PO4)3
 2.9E−4
0.32
R3c
167


145


Li1.05Fe0.05Ti0.95(PO4)3
 1.3E−4
0.34
R3c
167


145


Li1.1Fe0.1Ti0.9(PO4)3
 6.3E−4
0.34
R3c
167


145


Li1.2Fe0.2Ti0.8(PO4)3
 1.4E−3
0.32
R3c
167


145


Li1.3Fe0.3Ti0.7(PO4)3
 2.3E−3
0.31
R3c
167


145


Li1.5Fe0.5Ti0.5(PO4)3
 2.7E−4
0.32
R3c
167


145


LiGe2(PO4)3
3.37E−7
0.38
R3c
167


146


Li1.3Al0.3Ge1.7(PO4)3
1.42E−4
0.37
R3c
167


146


Li1.7Al0.7Ge1.3(PO4)3
2.04E−4

R3c
167


146


Li1.3Cr0.3Ge1.7(PO4)3
8.87E−5
0.39
R3c
167


146


Li1.5Cr0.5Ge1.5(PO4)3
1.21E−4
0.37
R3c
167


146


Li1.7Cr0.7Ge1.3(PO4)3
2.46E−5

R3c
167


146


Li1.3Ga0.3Ge1.7(PO4)3
4.47E−5
0.38
R3c
167


146


Li1.5Ga0.5Ge1.5(PO4)3
2.01E−5

R3c
167


146


Li1.3Fe0.3Ge1.7(PO4)3
2.99E−5
0.39
R3c
167


146


Li1.5Fe0.5Ge1.5(PO4)3
2.56E−5

R3c
167


146


Li1.3Sc0.3Ge1.7(PO4)3
5.59E−5

R3c
167


146


Li1.3In0.3Ge1.7(PO4)3
9.22E−6

R3c
167


146


Li1.5In0.5Ge1.5(PO4)3
5.81E−6

R3c
167


146


Li1.5Al0.5Ge1.5(PO4)3
2.86E−4
0.38
R3c
167

263764
146


LiIO3
 1.90E−07

P63
173

35473
147


Li9Mg3(PO4)4F3
<1E−10
0.835
P63
173

426103
148


Pb6.12Ca1.9Li1.96(PO4)6
<1E−10
1.05
P63/m
176

59615
149


LiNdSiO4
<1E−10

P63/m
176


150


LiDySiO4
<1E−10

P63/m
176


150


Li2La8Si6O25
<1E−10

P63/m
176


150


Li3La7Si6O24
<1E−10

P63/m
176


150


Li0.284Sm4.512Si3O12.91
<1E−10

P63/m
176

83279
150


LiLa9Si6O26
<1E−10

P63/m
176

291218
150


LiEu9Si6O26
<1E−10

P63/m
176

291220
150


LiAlSiO4
 2.00E−09
0.68
P6422
181

55665
151


Li3(NH2)2I
  1E−5
0.58
P63mc
186

167528
152


Ba3LiTa5ZrSi4O26
<1E−10
0.79
P62m
189

239277
153


Li3N
 1.2E−3
0.25
P6/mmm
191

26540
154


Li3N
 3.00E−04
0.26
P6/mmm
191

156894
155


Fe2Na2K(Li3Si12O30)
<1E−10
1.22
P6/mcc
192

235750
156


Li3P
7.03E−4
0.18
P63/mmc
194

642223
157


Li5.5K0.25La2.75Nb2O12
3.19E−3
0.49
I213
199


158


Li5.5La3Nb1.75In0.25O12
8.07E−3
0.49
I213
199


158


Li6BaLa2Nb2O12
  6E−6
0.44
I213
199


159


Li5La3Nb2O12
  8E−6
0.43
I213
199

54865
159


(K0.1Li0.9)(SbO3)
1.36E−8

Pn3Z
201

200984
160


Li8GeP4
 1.8E−5
0.435
Pa3
205
α-Li8GeP4
235184
161


Li8SiP4
 4.5E−5
0.404
Pa3
205

235186
161


Li3AlN2
 5.00E−08
0.45
Ia3
206

257464
162


Li2MgTi3O8
<1E−10
0.71
P4332
212

86165
163


Li2CoTi3O8
<1E−10
1.33
P4332
212

86166
163


Li2CoGe3O8
<1E−10
1.49
P4332
212

86167
163


Li2ZnGe3O8
<1E−10
2.14
P4332
212

86169
163


(Li0.61Mg0.39)(Li0.46Mg0.005Ti0.035)Ti1.5O4
 6.56E−10
0.685
P4332
212

168144
164


(Li0.55Mg0.45)(Li0.445Mg0.055)Ti1.5O4
 1.53E−11
0.786
P4332
212

168145
164


Li5NI2
4.00E−6

F43m
216

16800
165


Li2VCl4
6.95E−6

F43m
216

74959
166


Li6PS5Cl0.25Br0.75
1.86E−3
0.328
F43m
216


167


Li6PS5Cl
2.05E−3
0.452
F43m
216

259200
167


Li6PS5Cl0.5Br0.5
3.33E−3
0.367
F43m
216

259201
167


Li6PS5Br
1.15E−3
0.303
F43m
216

259202
167


Li6PS5Br0.5I0.5
2.62E−5
0.312
F43m
216

259203
167


Li6PS5I
 1.3E−6
0.383
F43m
216

259204
167


Li6PS5Cl0.75Br0.25
2.26E−3
0.408
F43m
216

259206
167


Li6PS5Br0.75I0.25
1.12E−4
0.321
F43m
216

259209
167


Li6PS5Br0.25I0.75
4.72E−6
0.351
F43m
216

259211
167


Li6PS5Br
7.01E−4
0.194
F43m
216

234584
168


Li6.025P0.975Si0.025S5Br
8.78E−4
0.196
F43m
216

234585
168


Li6.05P0.95Si0.05S5Br
4.37E−4
0.173
F43m
216

234586
168


Li6.075P0.925Si0.075S5Br
8.73E−4
0.178
F43m
216

234587
168


Li6.1P0.95Si0.1S5Br
7.99E−4
0.22
F43m
216

234588
168


Li6.125P0.875Si0.125S5Br
9.02E−4
0.189
F43m
216

234589
168


Li6.175P0.825Si0.175S5Br
9.31E−4
0.142
F43m
216

234591
168


Li6.2P0.8Si0.2S5Br
1.69E−3
0.25
F43m
216

234592
168


Li6.225P0.775Si0.225S5Br
1.08E−3
0.248
F43m
216

234593
168


Li6.25P0.75Si0.25S5Br
1.41E−3
0.223
F43m
216

234594
168


Li6.3P0.7Si0.3S5Br
1.65E−3
0.236
F43m
216

234595
168


Li6.35P0.65Si0.35S5Br
2.34E−3
0.142
F43m
216

234596
168


Li6.5P0.5Si0.5S5Br
2.19E−3
0.27
F43m
216

234597
168


Li7Ge3PS12
 1.1E−4
0.259
F43m
216

258187
169


Li6B0.9PH3.6S4.9
 1.8E−3
0.166
F43m
216

264526
170


Li6PS5Cl
 1.30E−03
0.33
F43m
216


171


Li6PS5Br
2.77E−3
0.31
F43m
216

267193
172


Li6P(S4.9Se0.1)Br
3.20E−3
0.33
F43m
216

267194
172


Li6P(S4.8Se0.2)Br
3.92E−3
0.34
F43m
216

267195
172


Li6P(S4.7Se0.3)Br
3.62E−3
0.33
F43m
216

267196
172


Li6P(S4.6Se0.4)Br
3.64E−3
0.33
F43m
216

267197
172


Li6P(S4.5Se0.5)Br
2.68E−3
0.34
F43m
216

267198
172


Li6P(S4.4Se0.6)Br
2.78E−3
0.34
F43m
216

267199
172


Li6P(S4.3Se0.7)Br
3.01E−3
0.35
F43m
216

267200
172


Li6P(S4.2Se0.8)Br
3.48E−3
0.34
F43m
216

267201
172


Li6P(S4.1Se0.9)Br
3.82E−3
0.34
F43m
216

267202
172


Li6P(S4Se)Br
3.61E−3
0.34
F43m
216

267203
172


Li6PO5Cl
 5.54E−10
0.66
F43m
216

421479
173


Li6PS5Br
 3.2E−5
0.32
F43m
216

234598
174


Li6PS5Cl
 3.3E−5
0.38
F43m
216

259205
174


Li6PS5I
 2.2E−4
0.26
F43m
216

259212
174


Li6PS5I
1.26E−6
0.38
F43m
216


175


Li6P0.92Ge0.08S5I
9.02E−6
0.39
F43m
216


175


Li6P0.85Ge0.15S5I
3.99E−5
0.36
F43m
216


175


Li6P0.75Ge0.25S5I
3.26E−5
0.36
F43m
216


175


Li6P0.74Ge0.26S5I
1.51E−4
0.30
F43m
216


175


Li6P0.64Ge0.36S5I
6.58E−4
0.24
F43m
216


175


Li6P0.53Ge0.47S5I
1.52E−3
0.24
F43m
216


175


Li6P0.48Ge0.52S5I
1.83E−3
0.23
F43m
216


175


Li6P0.31Ge0.69S5I
5.16E−3
0.24
F43m
216


175


Li6P0.21Ge0.79S5I
5.41E−3
0.25
F43m
216


175


Li6PS5Cl
1.31E−6
0.38
F43m
216


176


Li6PS5Br
2.41E−5
0.16
F43m
216

259208
176


Li6PS5I
 4.1E−7
0.32
F43m
216

418489
176


Li6PS5I
9.24E−5

F43m
216


177


Li6.1P0.9Sn0.1S5I
1.61E−4

F43m
216


177


Li6.2P0.8Sn0.2S5I
2.32E−4

F43m
216


177


Li6.25P0.75Sn0.25S5I
2.92E−4

F43m
216


177


Li6.3P0.7Sn0.3S5I
3.06E−4

F43m
216


177


Li6.5P0.5Sn0.5S5I
2.35E−4

F43m
216


177


Li6.4P0.6Ge0.4S5I
2.51E−4

F43m
216


177


Li6.45P0.55Ge0.45S5I
3.65E−4

F43m
216


177


Li6.5P0.5Ge0.5S5I
5.42E−4

F43m
216


177


Li6.55P0.45Ge0.55S5I
4.11E−4

F43m
216


177


Li6.6P0.4Ge0.6S5I
2.74E−4

F43m
216


177


Li6.8P0.2Ge0.8S5I
5.21E−5

F43m
216


177


LiCe(BH4)3Cl
1.03E−4

I43m
217

185218
178


Li7PN4
 1.60E−07
0.4
P43n
218

69017
95


β-Li8GeP4
 8.6E−5
0.394
P43n
218
β-Li8GeP4
235185
161


Li4B7O12Cl
 2.4E−5

F43c
219

1125
179


Fe0.16La2.95Li5.68Zr2O12
9.35E−4
0.29
I43d
220

431391
180


Fe0.19La2.95Li5.57Zr2O12
1.38E−3
0.28
I43d
220

431392
180


Li3ClO
 2.5E−2

Pm3m
221


181


Li2.99Ba0.005Cl0.5I0.5
 2.5E−3
0.06
Pm3m
221


181


Li0.31La0.63((Ti0.9Co0.1)O3
2.60E−4

Pm3m
221

151533
182


(La0.49Li0.461Sr0.049)(TiO3)
7.09E−4
0.33
Pm3m
221

190825
183


(La0.46Li0.429Sr0.111)(TiO3)
1.97E−4
0.33
Pm3m
221

190826
183


(La0.402Li0.368Sr0.230)(TiO3)
2.87E−5
0.36
Pm3m
221

190827
183


Li2(OH)0.9F0.1Cl
3.86E−5
0.52
Pm3m
221


184


Li2(OH)Br
1.20E−6
0.75
Pm3m
221

200874
184


Li9NS3
 8.30E−07
0.52
Pm3m
221

240749
185


(La0.55Li0.45)(Ti0.9Al0.1)O3
1.51E−3

Pm3m
221

254045
186


(La0.6Li0.4)(Ti0.8Al0.2)O3
5.68E−4

Pm3m
221

254046
186


(La0.65Li0.35)(Ti0.7Al0.3)O3
1.61E−4

Pm3m
221

254047
186


(La0.7Li0.3)(Ti0.6Al0.4)O3
1.04E−7

Pm3m
221

254048
186


(Li0.16Sr0.69)(Ga0.25Ta0.75)O3
3.69E−6
0.359
Pm3m
221

291520
187


Li0.375Sr0.4375Zr0.25Ta0.75O3
 2.0E−4
0.26
Pm3m
221


188


Li0.25Sr0.625Ta0.5Zr0.5O3
3.34E−7
0.42
Pm3m
221


188


Li0.375Sr0.4375Hf0.25Ta0.75O3
 3.8E−4
0.36
Pm3m
221


189


Li0.375Sr0.4375Zr0.25Nb0.75O3
2.00E−5
0.26
Pm3m
221


190


Li0.25Sr0.625Zr0.5Nb0.5O3
2.75E−7
0.36
Pm3m
221


190


Li2.99Ba0.005ClO
 2.5E−2
0.13
Pm3m
221


191


Li2.99Ba0.005Cl0.5I0.5O
3.37E−3

Pm3m
221


191


Sm0.5Li0.42TiO2.96
 3.93E−10
0.58
Pm3m
221


86


La0.52Li0.35TiO2.96
9.11E−4
0.32
Pm3m
221


86


La0.61Li0.15TiO3
2.06E−4

Pm3m
221


192


La0.58Li0.24TiO3
7.22E−4

Pm3m
221


192


La0.55Li0.33TiO3
1.58E−3

Pm3m
221


192


La0.54Li0.36TiO3
9.79E−3

Pm3m
221


192


La0.52Li0.42TiO3
7.21E−4

Pm3m
221


192


La0.5Sr0.06Li0.06TiO3
1.13E−5
0.37
Pm3m
221


193


La0.56Sr0.1Li0.1TiO3
1.37E−5
0.37
Pm3m
221


193


La0.51Sr0.15Li0.15TiO3
 5.3E−5
0.38
Pm3m
221


193


La0.41Sr0.25Li0.25TiO3
7.64E−5
0.35
Pm3m
221


193


La0.385Sr0.275Li0.275TiO3
6.04E−5
0.37
Pm3m
221


193


La0.36Sr0.3Li0.3TiO3
1.92E−5
0.35
Pm3m
221


193


La0.61Li0.18TiO3
2.09E−4

Pm3m
221


97


La0.58Li0.27TiO3
8.32E−4

Pm3m
221


97


La0.56Li0.33TiO3
1.30E−3

Pm3m
221


97


La0.55Li0.36TiO3
1.54E−3
0.33
Pm3m
221


97


La0.54Li0.39TiO3
1.25E−3

Pm3m
221


97


La0.52Li0.45TiO3
7.85E−4

Pm3m
221


97


La0.51Li0.34TiO2.94
  7E−5
0.36
Pm3m
221


62


Li3OBr
 1.10E−06
0.74
Pm3m
221

67265
194, 195


Li7.2N1.6Cl2.4
 8.4E−7
0.49
Fm3m
225

49646
131


Li6NI3
 3.70E−06

Fm3m
225

83380
165


Li0.19La0.67(Ti0.9Co0.1)O3
1.08E−4

Fm3m
225

151535
182


Li6NBr3
 1.00E−08
0.69
Fm3m
225

84091
196


LiI
  1E−7

Fm3m
225

414244
197


Li(Li0.34Ti1.66)O4
6.03E−8
0.506
Fd3m
227

168137
164


(Li0.916Mg0.084)(Li0.352Mg0.016Ti1.634)O4
1.73E−8
0.564
Fd3m
227

168139
164


(Li0.826Mg0.174)(Li0.374Mg0.026Ti1.60)O4
4.24E−9
0.615
Fd3m
227

168141
164


(Li0.74Mg0.26)(Li0.40Mg0.04Ti1.56)O4
1.51E−9
0.639
Fd3m
227

168142
164


Li2MnCl4
4.79E−6

Fd3m
227

69678
166


Li2MgCl4
6.24E−7

Fd3m
227

74957
166


Li1.9Mn0.9Ga0.1Cl4
2.37E−7

Fd3m
227

50305
198


Li1.65Mn0.65In0.35Cl4
 9.9E−8

Fd3m
227

50306
198


LiCdCl4
 5.80E−07
0.44
Fd3m
227

74958
199


LiSrNb2O6F
<1E−10
0.604
Fd3m
227

236009
200


LiSrTa2O6F
<1E−10
0.604
Fd3m
227

236010
200


LiSr0.9Nb2O6F0.8
<1E−10
0.709
Fd3m
227

236011
200


LiSr0.9Ta2O6F0.8
<1E−10
0.76
Fd3m
227

236012
200


Li1.1SrNb1.9Zr0.1O6F
<1E−10
0.622
Fd3m
227

236013
200


Li1.1SrTa1.9Zr0.1O6F
<1E−10
0.693
Fd3m
227

236014
200


Li6SrLa2Nb2O12
 4.2E−6
0.5
Ia3d
230

157628
159


Li6CaLa2Nb2O12
 1.6E−6
0.55
Ia3d
230

161386
159


Li5.25Ba0.25La2.75Ta2O12
6.03E−6
0.479
Ia3d
230


201


Li5.5Ba0.5La2.5Ta2O12
1.35E−5
0.455
Ia3d
230


201


Li6.25Ba1.25La1.75Ta2O12
5.05E−5
0.395
Ia3d
230


201


Li6.5Ba1.5La1.5Ta2O12
 3.2E−5
0.402
Ia3d
230


201


Li6.75Ba1.75La1.25Ta2O12
1.25E−5
0.418
Ia3d
230


201


Li7Ba2LaTa2O12
3.00E−6
0.442
Ia3d
230


201


Li5La3Ta2O12
4.33E−6
0.50
Ia3d
230

154400
201


Li6BaLa2Ta2O12
3.02E−5
0.419
Ia3d
230

237201
201


Li7La3Zr1.89Al0.15O12
 3.4E−4
0.334
Ia3d
230


202


Li7.06La3Y0.06Zr1.94O12
9.56E−4
0.26
Ia3d
230


203


Li6.25La3Zr2Ga0.25O12
 3.5E−4

Ia3d
230


204


Li7La3Zr2O12
 1.2E−4

Ia3d
230


205


Li6.8La3Zr1.8Ta0.2O12
 2.8E−4

Ia3d
230


205


Li6.6La3Zr1.6Ta0.4O12
 7.3E−4

Ia3d
230


205


Li6.5La3Zr1.5Ta0.5O12
 9.2E−4

Ia3d
230


205


Li6.4La3Zr1.4Ta0.6O12
 1.0E−3
0.35
Ia3d
230


205


Li6.2La3Zr1.2Ta0.8O12
 3.2E−4

Ia3d
230


205


Li6La3ZrTaO12
 1.6E−4

Ia3d
230


205


Li7La3Zr2O12
 1.2E−4

Ia3d
230


205


Li6.8La3Zr1.8Ta0.2O12
 2.8E−4

Ia3d
230


205


Li6.6La3Zr1.6Ta0.4O12
 7.3E−4

Ia3d
230


205


Li6.5La3Zr1.5Ta0.5O12
 9.2E−4

Ia3d
230


205


Li6.4La3Zr1.4Ta0.6O12
  1E−3
0.35
Ia3d
230


205


Li6.2La3Zr1.2Ta0.8O12
 3.2E−4

Ia3d
230


205


Li6La3ZrTaO12
 1.6E−4

Ia3d
230


205


Li6.8LasZr1.8Ta0.2O12
 7.8E−4

Ia3d
230


206


Li6.75La3Zr1.75Ta0.25O12
 8.8E−4

Ia3d
230


206


Li6.65La3Zr1.65Ta0.35O12
 7.7E−4

Ia3d
230


206


Li6.6La3Zr1.6Ta0.4O12
 7.2E−4

Ia3d
230


206


Li6.55La3Zr1.55Ta0.45O12
 6.9E−4

Ia3d
230


206


Li6La3ZrTaO12
 4.4E−4

Ia3d
230


206


Li5La3Ta2O12
 1.6E−4

Ia3d
230


206


Li6.7La3Zr1.7Ta0.3O12
 9.6E−4
0.37
Ia3d
230


206


Li6.5La3Zr1.5Ta0.5O12
 6.7E−4

Ia3d
230

183686
206


Li6.05Ga0.25La3Zr2O11.8F0.2
1.28E−3
0.28
Ia3d
230


207


Li5.72Al0.26La3Zr1.5W0.25O12
 4.9E−4
0.35
Ia3d
230


208


Li6.8La3Zr1.9Mo0.1O12
8.00E−5
0.46
Ia3d
230


209


Li6.6La3Zr1.8Mo0.2O12
3.11E−4
0.48
Ia3d
230


209


Li6.4La3Zr1.7Mo0.3O12
3.69E−4
0.49
Ia3d
230


209


Li6.2La3Zr1.6Mo0.4O12
3.40E−4
0.48
Ia3d
230


209


Li6.5La3Zr1.75Mo0.25O12
3.33E−4
0.39
Ia3d
230

239128
209


Li6.75La3Zr1.875Te0.125O12
3.30E−4
0.41
Ia3d
230


210


Li6.5La3Zr1.75Te0.25O12
1.02E−3
0.38
Ia3d
230


210


Li6.375La3Zr1.375Nb0.625O12
1.37E−3
0.25
Ia3d
230


211


Li5La3Ta2O12
 1.2E−6
0.56
Ia3d
230

154400
212


Li5La3Nb2O12
  1E−5
0.43
Ia3d
230

171171
212


Li5La3Bi2O12
 4.00E−05
0.47
Ia3d
230

158372
213


Li6La2SrBi2O12
 5.20E−05
0.43
Ia3d
230

158373
213


Li5Nd3Sb2O12
 1.3E−7
0.67
Ia3d
230

159426
214


Li4Nd3TeSbO12
1.96E−6
0.64
Ia3d
230

159732
215


Li5La3Sb2O12
 8.2E−6
0.51
Ia3d
230

161342
216


Li6SrLa2Sb2O12
 6.6E−6
0.54
Ia3d
230

161343
216


Li6(La2Ca)(NbO6)2
1.33E−6

Ia3d
230

161386
217


Li6(La2Sr)(NbO6)2
3.69E−6

Ia3d
230

161387
217


Li6CaLa2Ta2O12
 2.2E−6
0.5
Ia3d
230

163860
218


Li6BaLa2Ta2O12
 1.3E−5
0.44
Ia3d
230

163861
218


Li6.15La3Zr1.75Ta0.25Ga0.2O12
 4.1E−4
0.27
Ia3d
230


219


Li6.15La3Zr1.75Ta0.25Al0.2O12
 3.7E−4
0.30
Ia3d
230


219


Li6.75La3Zr1.75Ta0.25O12
 8.7E−4
0.22
Ia3d
230

183873
219


Li6.16Al0.28La3Zr2O12
 6.1E−4
0.34
Ia3d
230

185539
220


Li7La3Zr2O12
1.97E−6
0.49
Ia3d
230


221


Li7La3Zr2O12-0.5 wt % Al
1.58E−4

Ia3d
230


221


Li7La3Zr2O12-0.9 wt % Al
 3.2E−4
0.34
Ia3d
230


221


Li6.06Al0.2LasZr2O12
  4E−4
0.34
Ia3d
230

185539
221


Li6BaLa2Ta2O12
2.45E−5
0.40
Ia3d
230

185602
222


Nd3Zr2Al0.5Li5.5O12
 3.9E−5
0.56
Ia3d
230

189530
223


(Li6.26Al0.24)La3Zr2O12
 3.1E−4
0.33
Ia3d
230

195182
224


Li6La3Nb1.5Y0.5O12
1.88E−4

Ia3d
230

237141
225


Li5.2La3Nb1.9Y0.1O12
6.39E−5

Ia3d
230

237143
225


Li5.4La3Nb1.8Y0.2O12
6.74E−5

Ia3d
230

237144
225


Li6.5La3Nb1.75Y0.25O12
9.18E−5

Ia3d
230

237145
225


Li6.5La3Nb1.25Y0.75O12
3.43E−4

Ia3d
230

237146
225


Li6Ba0.5Sr0.5La2Ta2O12
 7.1E−6
0.45
Ia3d
230

237199
226


Li6SrLa2Ta2O12
 5.4E−6
0.45
Ia3d
230

237200
226


Li6BaLa2Ta2O12
 1.5E−5
0.47
Ia3d
230

237201
226


Li6CaLa2Ta2O12
 2.2E−6
0.47
Ia3d
230

237202
226


Li6BaLa2Ta2O12
  4E−5
0.4
Ia3d
230


227


Li6SrLa2Ta2O12
  7E−6
0.5
Ia3d
230


227


Li6SrLa2Ta2O12
  7E−6
0.5
Ia3d
230

237200
227


Li6BaLa2Ta2O12
  4E−5
0.4
Ia3d
230

237201
227


Li5.74La3Zr1.5Ta0.5O12
9.03E−4
0.435
Ia3d
230

239663
228


La3Li5.08Ta1.51Zr0.39O12
1.03E−4
0.536
Ia3d
230

239664
228


Li51.2Al1.6La24Zr16O96
2.54E−4
0.36
Ia3d
230

241475
229


Li49.6Al1.6La24Zr14.4Ta1.6O96
6.14E−4
0.29
Ia3d
230

241476
229


Li6.5La3Hf1.5Ta0.5O12
 4.0E−4
0.40
Ia3d
230

258921
230


Li6.5La3Sn1.5Ta0.5O12
 1.9E−4
0.45
Ia3d
230

258922
230


Li5La3Ta2O12
1.59E−5

Ia3d
230

259164
231


Li5.3La3Ta1.85Sm0.15O12
7.11E−6

Ia3d
230

259165
231


Li5.5La3Ta1.75Sm0.25O12
5.17E−6

Ia3d
230

259166
231


Li5.70La3Ta1.65Sm0.35O12
2.15E−5

Ia3d
230

259167
231


Li5.90La3Ta1.55Sm0.45O12
1.18E−5

Ia3d
230

259168
231


Li6.10La3Ta1.45Sm0.55O12
1.40E−5

Ia3d
230

259169
231


Li7La3Zr2O12
 5.69E−04
0.36
Ia3d
230
“cubic LLZO”
422259
232


Li5La3Nb2O12
4.99e-6

Ia3d
230


233


Li5La3Nb1.95Y0.05O12
1.32E−5

Ia3d
230


233


Li5La3Nb1.9Y0.1O12
1.43E−5

Ia3d
230


233


Li5La3Nb1.85Y0.15O12
5.85E−6

Ia3d
230


233


Li5La3Nb1.8Y0.2O12
9.05E−6

Ia3d
230


233


Li5La3Nb1.75Y0.25O12
9.42E−6

Ia3d
230


233


Li6.24La3Zr2Al0.24O11.98
 4.0E−4
0.26
Ia3d
230


234


Li7La3Zr2O12—0.3Ga
 3.8E−5
0.37
Ia3d
230


235


Li7La3Zr2O12—0.4Ga
 4.4E−5
0.36
Ia3d
230


235


Li7La3Zr2O12—0.5Ga
 8.9E−5
0.36
Ia3d
230


235


Li7La3Zr2O12—Ga
 5.4E−4
0.32
Ia3d
230


235


La3Zr2Ga0.5Li5.5O12
  1E−4

Ia3d
230


236


Li6.8La3Zr1.8Sb0.2O12
 5.9E−5
0.39
Ia3d
230


237


Li6.6La3Zr1.6Sb0.4O12
 7.7E−4
0.34
Ia3d
230


237


Li6.4La3Zr1.4Sb0.6O12
 6.6E−4
0.36
Ia3d
230


237


Li6.2La3Zr1.2Sb0.8O12
 4.5E−4
0.37
Ia3d
230


237


Li6La3ZrSbO12
 2.6E−4
0.38
Ia3d
230


237


Li6.5La3Zr1.75Te0.25O12—0.07Al
  4E−4
0.33
Ia3d
230


238


Li6.65La2.75Ba0.25Zr1.4Ta0.5Nb0.1O12
5.27E−4
0.26
Ia3d
230


239


Li6.4La3Zr1.4Ta0.6O12
7.24E−4
0.24
Ia3d
230


239


Li6.4La3Zr1.4Ta0.5Nb0.1O12
4.44E−4
0.27
Ia3d
230


239


Li6.4La3Zr1.4Ta0.4Nb0.2O12
4.55E−4
0.28
Ia3d
230


239


Li6.4La3Zr1.4Ta0.3Nb0.3O12
6.06E−4
0.26
Ia3d
230


239


Li7La3Zr2O12
1.74E−4
0.26
Ia3d
230


239


Li3Nd3Te2O12
<1E−10
1.22
Ia3d
230


240


Li7.131La3Zr2O12Al0.244
7.73E−5

Ia3d
230


241


Li6.949La3Zr2O12Al0.262
2.25E−4

Ia3d
230


241


Li6.835La3Zr2O12Al0.231
2.20E−4

Ia3d
230


241


Li6.660La3Zr2O12Al0.258
1.51E−4

Ia3d
230


241


Li6.75La3Zr1.75Ta0.25O12
 4.1E−4
0.42
Ia3d
230


121


Li6.5La3Zr1.5Ta0.5O12
 6.1E−4
0.4
Ia3d
230


121


Li6La3ZrTaO12
 2.1E−4
0.42
Ia3d
230


121


Li3Gd3Te2O12
<1E−10

Ia3d
230


242


Li3Tb3Te2O12
<1E−10

Ia3d
230


242


Li3Er3Te2O12
<1E−10

Ia3d
230


242


Li3Lu3Te2O12
<1E10

Ia3d
230


242


Li2S*P2S5
 3.2E−03





4


0.7Li2S—0.3P2S5
 5.4E−5





4


Li3.8Ge0.8P0.2S4
1.75E−6
0.466




14


Li3.6Ge0.6P0.4S4
1.74E−4
0.339




14


Li3.4Ge0.4P0.6S4
6.53E−4
0.275




14


Li3.35Ge0.35P0.65S4
1.53E−3
0.229




14


Li3.3Ge0.3P0.7S4
1.76E−3
0.221




14


Li3.2Ge0.2P0.8S4
5.57E−4
0.275




14


Li2.9Ca0.05InBr6
2.16E−4





25


Li2.86Ca0.07InBr6
4.04E−4





25


Li2.8Ca0.1InBr6
3.00E−4





25


Li2.7Ca0.15InBr6
6.97E−5





25


Li3.9Zn0.05GeS4
2.72E−7
0.517




71


Li3.8Zn0.1GeS4
9.95E−8
0.545




71


Li3.6Zn0.2GeS4
5.90E−8
0.539




71


Li7GeS3
 9.7E−9





71


Li7ZnGeS4
 1.4E−9





71


Li9.6P3S12
 1.2E−3
0.259




102


Li1.3Al0.3Ge1.7(PO4)3
8.24E−5
0.386




133


Li1.6Al0.6Ge1.4(PO4)3
2.84E−4
0.430




133


LiTi2(PO4)3—0.2Li2O
 2.4E−4





134


LiTi2(PO4)3—0.3Li2O
 1.5E−3





134


LiTi2(PO4)3—0.4Li2O
 1.3E−4





134


Li1.3Al0.3Ti1.7(PO4)3—0.3Li2O
 3.5E−4





134


LiTi2(PO4)30.1Li4P2O7
 1.6E−4





134


Li1.4Al0.4Ti1.6(PO4)3
3.38E−3
0.30


LATP

243


Li1.2Ge0.2Ti1.8(PO4)3
7.94E−5
0.27


LAGP

243


Li1.5Ge0.5Ti1.5(PO4)3
1.90E−4
0.33


LAGP

243


Li1.2Al0.2Ti1.8(PO4)3
3.38E−3
0.28


LATP
427619
243


Li3ClO
0.85E−3
0.26




194


Li3C10.5Br0.50
1.94E−3
0.18




194


Li3OCl
1.47E−4
0.26




194


Li3OCl0.5Br0.5
9.49E−4
0.18




194


Li6.6La2.6Ce0.4Zr2O12
1.44E−5
0.48




244


Li1.4Al0.4Ti1.6(PO4)3
 1.1E−03





245


80Li2S * 20P2S5
 7.2E−04





246


0.8Li2S—0.2P2S5
 7.2E−4





246


0.75Li2S—0.25P2S5
 2.8E−4





246


Li2S*P2S5*P2S3
 5.4E−03





247


Li7S*P2S5*Li3N
 1.4E−03





248


Li7La3Nb1.9Y0.1O12
1.44E−5
0.55




233


Li7La3Zr2O12
2.35E−4
0.339




249


Li6.88La3Zr1.88Nb0.12O12
5.99E−4
0.319




249


Li6.75La3Zr1.75Nb0.25O12
7.71E−4
0.3




249


Li6.62La3Zr1.62Nb0.38O12
4.41E−4
0.31




249


Li6.5La3Zr1.5Nb0.5O12
2.98E−4
0.319




249


Li6La3ZrNbO12
1.50E−4
0.42




249


Li5La3Nb2O12
  3E−5
0.44




249


Li7La3Hf2O12
 2.4E−4
0.29




250


Li7GePS8
  7E−3
0.22




251


Li10(Ge0.95Si0.05)P2S12
8.63E−3
0.251




252


Li10(Ge0.9Si0.1)P2S12
8.07E−3
0.26




252


Li10(Ge0.8Si0.2)P2S12
7.28E−3
0.261




252


Li10(Ge0.7Si0.3)P2S12
5.82E−3
0.265




252


Li10(Ge0.6Si0.4)P2S12
5.24E−3
0.28




252


Li10(Ge0.5Si0.5)P2S12
 4.2E−3
0.284




252


Li10(Ge0.2Si0.8)P2S12
4.81E−3
0.269




252


Li10(Ge0.95Sn0.05)P2S12
 7.8E−3
0.254




252


Li10(Ge0.9Sn0.1)P2S12
7.53E−3
0.256




252


Li10(Ge0.8Sn0.2)P2S12
7.06E−3
0.252




252


Li10(Ge0.7Sn0.3)P2S12
6.49E−3
0.254




252


Li10(Ge0.5Sn0.5)P2S12
6.17E−3
0.249




252


Li10(Ge0.4Sn0.6)P2S12
5.76E−3
0.265




252


Li10(Ge0.3Sn0.7)P2S12
5.56E−3
0.261




252


Li10(Ge0.2Sn0.8)P2S12
4.77E−3
0.269




252


0.5(Li2O) * 0.5(P2O5)
 1.1E−9
0.71




253


0.58(Li2O) * 0.5(P2O5)
  2E−8
0.60




253


0.6(Li2O) * 0.5(P2O5)
  3E−8
0.61




253


0.63(Li2O) * 0.5(P2O5)
 1.3E−7
0.56




253


0.66(Li2O) * 0.5(P2O5)
 2.3E−7
0.55




253


0.7(Li2O) * 0.5(P2O5)
  3E−7
0.57




253


0.2(Li2S) 0.8(GeS2)
 1.1E−7
0.52




253


0.3(Li2S) 0.7(GeS2)
 9.3E−7
0.48




253


0.4(Li2S) 0.6(GeS2)
 2.9E−6
0.42




253


0.5(Li2S) 0.5(GeS2)
 3.3E−5
0.35




253


0.6(Li2S) 0.4(GeS2)
 9.2E−5
0.32




253


0.63(Li2S) 0.37(GeS2)
 1.5E−4
0.34




253


0.66(Li2S) 0.34(GeS2)
 1.0E−4
0.37




253


0.7(Li2S) 0.3(GeS2)
 1.2E−4
0.34




253


Li2O—P2O5
 1.1E−9
0.71




253


0.58Li2O—0.42P2O5
 2.0E−8
0.60




253


0.6Li2O—0.4P2O5
 3.0E−8
0.61




253


0.63Li2O—0.37P2O5
 1.3E−7
0.56




253


0.66Li2O—0.34P2O5
 2.3E−7
0.55




253


0.7Li2O—0.3P2O5
 3.0E−7
0.57




253


0.2Li2S—0.8GeS2
 1.1E−7
0.52




253


0.3Li2S—0.7GeS2
 9.3E−7
0.48




253


0.4Li2S—0.6GeS2
 2.9E−6
0.42




253


0.5Li2S—0.5GeS2
 3.3E−5
0.35




253


0.6Li2S—0.4GeS2
 9.2E−5
0.32




253


0.63Li2S—0.37GeS2
 1.5E−4
0.34




253


0.66Li2S—0.34GeS2
 1.0E−4
0.37




253


0.7Li2S—0.3GeS2
 1.2E−4
0.34




253


Li6.55La3Zr2Ga0.15O12
 1.3E−3
0.3




254


Li6.40La3Zr2Ga0.2O12
  9E−4
0.3




254


Li6.10La3Zr2Ga0.25O12
  7E−5
0.3




254


Li6.8La3Zr1.8Sb0.2O12
 5.9E−5
0.39




255


Li6.6La3Zr1.6Sb0.4O12
 7.7E−4
0.34




255


Li6.4La3Zr1.4Sb0.6O12
 6.6E−4
0.36




255


Li6.2La3Zr1.2Sb0.8O12
 4.5E−4
0.37




255


Li6La3ZrSbO12
 2.6E−4
0.38




255


Li(In0.62Li1.38)Br3.92
 4.9E−6
0.58




256


Li3InBr6
1.77E−4





257


Li3InBr4Cl2
7.58E−6





257


Li3InBr3Cl3
1.14E−4





257


Li3InBr2.5Cl3.5
3.60E−6





257


Li3InBr2Cl4
6.89E−8





257


Li1.8Mg1.1Cl4
1.52E−6





258


Li1.6Mg1.2Cl4
3.07E−6





258


Li1.34Mg1.33Cl4
3.07E−6





258


Li1.9Mn1.05Cl4
4.61E−6





258


Li1.72Mn1.14Cl4
3.62E−6





258


Li1.6Mn1.2Cl4
1.45E−5





258


Li1.52Mn1.24Cl4
1.85E−5





258


Li1.34Mn1.33Cl4
9.57E−6





258


Li1.94Cl1.03Cl4
2.56E−6





258


Li1.90Cd1.05Cl4
3.50E−6





258


Li2OHBrF
7.10E−7





259


Li2OHBr0.99F0.01
9.16E−7





259


Li2OHBr0.98F0.02
1.11E−6





259


Li2OHBr0.95F0.05
6.75E−7





259


Li2OHBr0.9F0.1
6.80E−7





259


Li2OHBr0.8F0.2
5.44E−7





259


Li3(OH)2Cl
2.72E−8
0.88




260


Li5(OH)3Cl2
2.52E−8
0.75




260


Li2OHCl
4.28E−8
0.56




260


Li5(OH)2Cl3
1.48E−7
0.49




260


Li3OHCl2
8.92E−8
0.67




260


Li3.7Zn0.15GeO4
4.63E−7





261


Li3.5Zn0.25GeO4
2.42E−7





261


Li3.1Zn0.45GeO4
9.89E−8





261


Li2.8Zn0.6GeO4
1.27E−7





261


Li2.6Zn0.7GeO4
5.79E−8





261


Li2.3Zn0.85GeO4
4.23E−9





261


Li7La2.75Ca0.25Zr1.75Nb0.25O12
 2.2E−4
0.35




262


Li1.5Cr0.5Ti1.5(PO4)3
1.98E−4
0.29




263


Li3V2(PO4)3
2.09E−7





263


Li3V1.8Al0.2(PO4)3
1.88E−6





263


Li3V1.6Al0.4(PO4)3
6.21E−6





263


Li3V1.4Al0.6(PO4)3
9.34E−7





263


Li7P2.9Mn0.1S10.7I0.3
 5.6E−3
0.22




264


0.3 Li2S * 0.7 SiS2
 1.6E−6
0.46




265


0.4 Li2S * 0.6 SiS2
 2.8E−5
0.38




265


0.5 Li2S * 0.5 SiS2
 1.0E−4
0.32




265


0.6 Li2S * 0.4 SiS2
 5.0E−4
0.25




265


(2Li2S—P2S5)
1.12E−4





266


(2Li2S—P2S5)0.85(LiI)0.15
2.35E−4





266


(2Li2S—P2S5)0.75(LiI)0.25
3.96E−4





266


(2Li2S—P2S5)0.60(LiI)0.40
7.60E−4





266


(2Li2S—P2S5)0.55(LiI)0.45
1.12E−3





266


0.14SiS2—0.09P2S5—0.47Li2S—0.30LiI
1.32E−3
0.34




267


0.26B2S3—0.3Li2S—0.44LiI
1.57E−3
0.3




268


0.26B2S3—0.31Li2S—0.43LiI
7.99E−4
0.33




268


0.27B2S3—0.32Li2S—0.41LiI
4.25E−4
0.35




268


0.5SiS2—0.5Li2S
 1.5E−4
0.34




269


0.1LiBr—0.45SiS2—0.45Li2S
 1.9E−4
0.30




269


0.2LiBr—0.4SiS2—0.4Li2S
 2.1E−4
0.33




269


0.25LiBr—0.38SiS2—0.38Li2S
 2.4E−4
0.31




269


0.3LiBr—0.3SiS2—0.35Li2S
 3.2E−4
0.33




269


0.35LiBr—0.33SiS2—0.33Li2S
 2.3E−4
0.38




269


0.4LiBr—0.3SiS2—0.3Li2S
 1.1E−4
0.42




269


SiS2—Li2S
1.20E−4
0.35




270


0.9(SiS2—Li2S)—0.1LiCl
1.84E−4
0.34




270


0.8(SiS2—Li2S)—0.2LiCl
2.35E−4
0.33




270


0.75(SiS2—Li2S)—0.25LiCl
2.66E−4
0.35




270


0.7(SiS2—Li2S)—0.3LiCl
2.33E−4
0.35




270


0.65(SiS2—Li2S)—0.35LiCl
1.78E−4
0.36




270


0.6(SiS2—Li2S)—0.4LiCl
0.93E−4
0.34




270


(0.4SiS2—0.6Li2S)
 5.3E−4
0.33




271


0.9(0.4SiS2—0.6Li2S)—0.1LiI
 6.5E−4
0.31




271


0.8(0.4SiS2—0.6Li2S)—0.2LiI
 7.7E−4
0.30




271


0.7(0.4SiS2—0.6Li2S)—0.3LiI
1.15E−3
0.29




271


0.6(0.4SiS2—0.6Li2S)—0.4LiI
1.78E−3
0.28




271


0.55(0.4SiS2—0.6Li2S)—0.45LiI
1.41E−3
0.29




271


0.24SiS2—0.36Li2S—0.4LiI
 1.8E−3
0.28




272


0.28SiS2—0.42Li2S—0.30LiI
 1.8E−3
0.31




273


0.14SiS2—0.09P2S5—0.47Li2S—0.30LiI
 2.1E−3
0.34




273


0.27SiS2—0.03Al2S3—0.30Li2S—0.40LiI
 1.2E−3
0.34




273


0.21SiS2—0.09B2S3—0.30Li2S—0.40LiI
 1.7E−3
0.30




273


0.30Li2S—0.7GeS2
 4.4E−7
0.63




274


0.40Li2S—0.60GeS2
 3.2E−6
0.52




274


0.50Li2S—0.50GeS2
 4.0E−5
0.51




274


0.3Li2S—0.7P2S5
 1.7E−2
0.18




275


0.7Li2S—0.3P2S5
 3.2E−3
0.12




276


0.6Li2S—0.4P2S5
 1.5E−4
0.31




277


0.95(0.6Li2S—0.4SiS2)—0.05Li4SiO4
1.58E−3
0.34




278


0.9(0.6Li2S—0.4SiS2)—0.1Li4SiO4
4.34E−4
0.37




278


0.8(0.6Li2S—0.4SiS2)—0.2Li4SiO4
1.59E−4
0.43




278


0.95(0.6Li2S—0.4SiS2)—0.05Li3PO4
8.68E−4
0.35




278


0.7(0.6Li2S—0.4SiS2)—0.3Li3PO4
2.08E−5
0.46




278


0.6(0.6Li2S—0.4SiS2)—0.4Li3PO4
5.33E−6
0.51




278


0.95(0.6Li2S—0.4SiS2)—0.05Li4GeO4
1.19E−3
0.28




278


0.9(0.6Li2S—0.4SiS2)—0.1Li4GeO4
3.18E−4
0.35




278


0.85(0.6Li2S—0.4SiS2)—0.15Li4GeO4
1.14E−4
0.40




278


0.95(0.6Li2S—0.4SiS2)—0.05Li3BO3
1.44E−3
0.33




278


0.93(0.6Li2S—0.4SiS2)—0.07Li3BO3
3.84E−4
0.35




278


0.85(0.6Li2S—0.4SiS2)—0.15Li3BO3
3.42E−4
0.36




278


0.75(0.6Li2S—0.4SiS2)—0.25Li3BO3
7.06E−5
0.38




278


0.95(0.6Li2S—0.4SiS2)—0.05Li3AlO3
1.31E−3
0.31




278


0.94(0.6Li2S—0.4SiS2)—0.06Li3AlO3
6.83E−4
0.34




278


0.92(0.6Li2S—0.4SiS2)—0.08Li3AlO3
4.04E−4
0.34




278


0.825(0.6Li2S—0.4SiS2)—0.175Li3AlO3
1.31E−4
0.36




278


0.975(0.6Li2S—0.4SiS2)—0.025Li3GaO3
6.82E−4
0.31




278


0.95(0.6Li2S—0.4SiS2)—0.05Li3GaO3
3.25E−4
0.32




278


0.92(0.6Li2S—0.4SiS2)—0.08Li3GaO3
3.03E−4
0.35




278


0.89(0.6Li2S—0.4SiS2)—0.11Li3GaO3
1.13E−4
0.38




278


0.97(0.6Li2S—0.4SiS2)—0.03Li3InO3
3.09E−4
0.34




278


0.95(0.6Li2S—0.4SiS2)—0.05Li3InO3
3.25E−4
0.35




278


0.9(0.6Li2S—0.4SiS2)—0.1Li3InO3
6.84E−5
0.40




278


0.95(0.6Li2S—0.4SiS2)—0.05Li4SiO4
1.54E−3
0.38




279


0.9(0.6Li2S—0.4SiS2)—0.1Li4SiO4
4.39E−4
0.40




279


0.95(0.6Li2S—0.4SiS2)—0.05Li2SO4
4.53E−4
0.41




279


0.9(0.6Li2S—0.4SiS2)—0.1Li2SO4
4.70E−5
0.45




279


0.5Li2O—0.1TiO2—0.4P2O5
5.67E−8
0.56




280


0.5025Li2O—0.0025Al2O3—0.095TiO2—0.4P2O5
1.56E−8
0.55




280


0.505Li2O—0.005Al2O3—0.09TiO2—0.4P2O5
1.78E−7
0.50




280


0.5075Li2O—0.0075Al2O3—0.085TiO2—0.4P2O5
2.51E−7
0.57




280


0.51Li2O—0.01Al2O3—0.08TiO2—0.4P2O5
1.58E−7
0.55




280


0.515Li2O—0.015Al2O3—0.07TiO2—0.4P2O5
1.25E−7
0.56




280


0.525Li2O—0.025Al2O3—0.05TiO2—0.4P2O5
2.17E−7
0.56




280


0.53Li2O—0.03Al2O3—0.04TiO2—0.4P2O5
2.72E−7
0.54




280


0.54Li2O—0.04Al2O3—0.02TiO2—0.4P2O5
1.97E−7
0.55




280


0.545Li2O—0.045Al2O3—0.01TiO2—0.4P2O5
7.14E−8
0.56




280


0.95(0.6Li2S—0.4SiS2)—0.05Li4SiO4
1.51E−3
0.34




281


0.90(0.6Li2S—0.4SiS2)—0.1Li4SiO4
4.34E−4
0.37




281


0.8(0.6Li2S—0.4SiS2)—0.2Li4SiO4
1.63E−4
0.43




281


0.95(0.6Li2S—0.4SiS2)—0.05Li3PO4
9.32E−4
0.35




281


0.9(0.6Li2S—0.4SiS2)—0.1Li3PO4
4.55E−4
0.37




281


0.7(0.6Li2S—0.4SiS2)—0.3Li3PO4
2.08E−5
0.46




281


0.6(0.6Li2S—0.4SiS2)—0.4Li3PO4
5.33E−6
0.51




281


0.95(0.6Li2S—0.4SiS2)—0.05Li4GeO4
1.21E−3
0.28




281


0.9(0.6Li2S—0.4SiS2)—0.1Li4GeO4
3.18E−4
0.34




281


0.85(0.6Li2S—0.4SiS2)—0.15Li4GeO4
1.14E−4
0.41




281


Li7PS6
 8.0E−5





282


0.7Li2S—0.3P2S5
 3.2E−3
0.12




283


0.95(0.6Li2S—0.4SiS2)—0.05Li3BO3
1.40E−3





284


0.93(0.6Li2S—0.4SiS2)—0.07Li3BO3
3.71E−4





284


0.85(0.6Li2S—0.4SiS2)—0.15Li3BO3
3.39E−4





284


0.75(0.6Li2S—0.4SiS2)—0.25Li3BO3
7.15E−5





284


0.95(0.6Li2S—0.4SiS2)—0.05Li3AlO3
1.22E−3





284


0.94(0.6Li2S—0.4SiS2)—0.06Li3AlO3
6.67E−4





284


0.92(0.6Li2S—0.4SiS2)—0.08Li3AlO3
3.94E−4





284


0.825(0.6Li2S—0.4SiS2)—0.175Li3AlO3
1.25E−4





284


0.975(0.6Li2S—0.4SiS2)—0.025Li3GaO3
7.05E−4





284


0.95(0.6Li2S—0.4SiS2)—0.05Li3GaO3
3.36E−4





284


0.92(0.6Li2S—0.4SiS2)—0.08Li3GaO3
3.06E−4





284


0.89(0.6Li2S—0.4SiS2)—0.11Li3GaO3
1.20E−4





284


0.97(0.6Li2S—0.4SiS2)—0.03Li3InO3
3.11E−4





284


0.95(0.6Li2S—0.4SiS2)—0.05Li3InO3
2.99E−4





284


0.90(0.6Li2S—0.4SiS2)—0.10Li3InO3
6.81E−5





284


(0.67Li2S—0.33SiS2)—(0.75Li2S—0.25P2S5)
 1.2E−3
0.28




285


0.2Li3N—0.8SiS2
1.46E−6
0.45




286


0.3Li3N—0.7SiS2
2.97E−5
0.36




286


0.4Li3N—0.6SiS2
2.74E−4
0.30




286


0.5Li3N—0.5SiS2
4.47E−5
0.34




286


0.6Li3N—0.4SiS2
2.25E−8
0.63




286


0.6Li2S—0.4P2S3
5.70E−6





287


0.63Li2S—0.37P2S3
2.55E−5





287


0.667Li2S—0.333P2S3
 1.1E−4
0.40




287


0.7Li2S—0.3P2S3
7.90E−5





287


0.75Li2S—0.25P2S3
5.08E−5





287


0.6Li2S—0.4SiS2
 5.1E−4
0.33




288


0.555Li2S—0.4SiS2—0.045Li3N
 1.5E−3
0.28




288


0.525Li2S—0.4SiS2—0.075Li3N
 9.6E−4
0.29




288


0.1Li2O—0.1LiCl—0.65B2O3—0.1SiO2—0.05Al2O3
 1.9E−4
0.427




289


0.75Li2O—0.25P2S5
1.80E−5
0.48




290


0.75(0.7Li2O—0.3Li2S)—0.25P2S5
2.42E−5
0.48




290


0.75(0.5Li2O—0.5Li2S)—0.25P2S5
2.83E−5
0.46




290


0.75(0.4Li2O—0.6Li2S)—0.25P2S5
4.99E−5
0.44




290


0.75(0.3Li2O—0.7Li2S)—0.25P2S5
8.89E−5
0.40




290


0.75(0.2Li2O—0.8Li2S)—0.25P2S5
1.63E−4
0.38




290


0.75(0.1Li2O—0.9Li2S)—0.25P2S5
2.27E−4
0.36




290


0.75Li2S—0.25P2S5
1.80E−4
0.41




290


0.45Li2—0.55SiS2
1.08E−4
0.40




291


0.5Li2—0.5SiS2
3.36E−4
0.32




291


0.55Li2—0.45SiS2
6.53E−4
0.30




291


0.60Li2—0.4SiS2
1.19E−3
0.29




291


0.63Li2—0.37SiS2
1.05E−3
0.30




291


0.65Li2—0.35SiS2
7.41E−4
0.33




291


0.95(0.5Li2—0.5SiS2)—0.05(0.5Li2O—0.5P2O5)
4.27E−4
0.38




291


0.95(0.53Li2—0.47SiS2)—0.05(0.53Li2O—0.47P2O5)
5.91E−4
0.33




291


0.95(0.55Li2—0.45SiS2)—0.05(0.55Li2O—0.45P2O5)
1.01E−3
0.34




291


0.95(0.58Li2—0.42SiS2)—0.05(0.58Li2O—0.42P2O5)
1.06E−3
0.34




291


0.95(0.6Li2—0.4SiS2)—0.05(0.6Li2O—0.4P2O5)
1.01E−3
0.27




291


0.95(0.63Li2—0.37SiS2)—0.05(0.63Li2O—0.37P2O5)
8.71E−4
0.33




291


0.95(0.65Li2—0.35SiS2)—0.05(0.65Li2O—0.35P2O5)
5.34E−4
0.32




291


0.95(0.67Li2—0.33SiS2)—0.05(0.67Li2O—0.33P2O5)
1.99E−4
0.37




291


0.8(0.55Li2—0.45SiS2)—0.2(0.55Li2O—0.45P2O5)
7.88E−5
0.41




291


0.8(0.6Li2—0.4SiS2)—0.2(0.6Li2O—0.4P2O5)
7.69E−5
0.41




291


0.8(0.65Li2—0.35SiS2)—0.2(0.65Li2O—0.35P2O5)
5.21E−5
0.42




291


0.65Li2S—0.35P2S5
4.14E−5





292


0.675Li2S—0.325P2S5
7.84E−5





292


0.7Li2S—0.3P2S5
1.58E−3
0.39




292


0.725Li2S—0.275P2S5
4.51E−4





292


0.75Li2S—0.25P2S5
3.67E−4





292


0.6Li2S—0.4SiS2
1.69E−4





293


0.1LiI—0.9(0.6Li2S—0.4SiS2)
2.35E−4





293


0.2LiI—0.8(0.6Li2S—0.4SiS2)
3.52E−4





293


0.3LiI—0.7(0.6Li2S—0.4SiS2)
7.42E−4





293


0.5Li2S—0.5SiS2
1.58E−6





293


0.1LiI—0.9(0.5Li2S—0.5SiS2)
3.99E−5





293


0.2LiI—0.8(0.6Li2S—0.4SiS2)
1.23E−4





293


0.3LiI—0.7(0.6Li2S—0.4SiS2)
3.62E−4





293


Li6Si2S7
4.11E−4
0.37




294


0.95Li6Si2S7—0.05Li6B4O9
4.11E−4
0.35




294


0.9Li6Si2S7—0.1Li6B4O9
3.76E−4
0.39




294


0.875Li6Si2S7—0.125Li6B4O9
2.77E−4
0.39




294


0.75Li6Si2S7—0.25Li6B4O9
1.42E−4
0.40




294


0.95Li6Si2S7—0.05Li6B4S9
4.90E−4
0.37




294


0.925Li6Si2S7—0.075Li6B4S9
3.65E−4
0.38




294


0.9Li6Si2S7—0.1Li6B4S9
4.73E−4
0.38




294


0.875Li6Si2S7—0.125Li6B4S9
4.40E−4
0.37




294


0.75Li6Si2S7—0.25Li6B4S9
5.02E−4
0.36




294


0.63Li6Si2S7—0.37Li6B4S9
4.39E−4
0.39




294


(Li2S)60(SiS2)28(P2S5)12
1.23E−3
0.34




295


Li7La3Zr2O12-5 wt % LiPO3
 2.5E−6
0.51




120


Li7La3Zr2O12-3 wt %
 1.5E−5
0.44




120


65Li2O•27B2O3•8SiO2









Li7La3Zr2O12-5 wt %
 2.5E−5
0.39




120


40.2Li2O•5.7Y2O3•54.1SiO2









0.6Li2S—0.4P2S5
3.32E−6
0.52




296


0.667Li2S—0.333P2S5
3.836E−5 
0.44




296


0.7Li2S—0.3P2S5
3.77E−5
0.45




296


0.75Li2S—0.25P2S5
2.79E−4
0.40




296


0.8Li2S—0.2P2S5
1.32E−4
0.44




296


(0.75Li2S—0.25P2S5)
2.68E−4
0.26




297


0.95(0.75Li2S—0.25P2S5)—0.05LiBH4
3.98E−4
0.25




297


0.89(0.75Li2S—0.25P2S5)—0.11LiBH4
6.18E−4
0.26




297


0.67(0.75Li2S—0.25P2S5)—0.33LiBH4
1.13E−3
0.21




297


Li7P2.9S10.85Mo0.01
 4.8E−3
0.24




298


Li7P3S11
 2.6E−3
0.29




298


Li7P2.9Mn0.1S10.7I0.3
 5.6E−3
0.22




299


Li11AlP2S12
8.02E−4
0.26




300


Li3PS4
1.78E−4
0.33




301


Li3PS4 - 2 wt % Al2O3
2.27E−4
0.35




301


Li3PS4 - 5 wt % Al2O3
1.96E−4
0.35




301


Li3PS4 - 8 wt % Al2O3
1.60E−4
0.36




301


Li3PS4 - 10 wt % Al2O3
1.50E−4
0.36




301


Li3PS4 - 30 wt % Al2O3
9.96E−5
0.36




301


Li3PS4 - 50 wt % Al2O3
9.38E−7
0.44




301


Li3PS4 - 70 wt % Al2O3
3.92E−8
0.60




301


Li3PS4 - 90 wt % Al2O3
1.54E−9
0.79




301


Li3PS4 - 2 wt % SiO2
2.28E−4
0.32




301


Li3PS4 - 5 wt % SiO2
1.96E−4
0.33




301


Li3PS4 - 8 wt % SiO2
1.60E−4
0.33




301


Li3PS4 - 10 wt % SiO2
1.50E−4
0.33




301


Li3PS4 - 30 wt % SiO2
1.00E−4
0.35




301


Li3PS4 - 50 wt % SiO2
3.80E−5
0.36




301


Li3PS4 - 70 wt % SiO2
5.92E−6
0.38




301


Li3PS4 - 90 wt % SiO2
8.53E−9
0.41




301


Li3PS4 - 5 wt % Li6ZnNb4O14
2.28E−4
0.29




301


Li3PS4 - 10 wt % Li6ZnNb4O14
2.43E−4
0.31




301


Li3PS4 - 15 wt % Li6ZnNb4O14
2.41E−4
0.32




301


Li3PS4 - 20 wt % Li6ZnNb4O14
2.22E−4
0.33




301


Li3PS4 - 30 wt % Li6ZnNb4O14
1.87E−4
0.34




301


Li3PS4 - 50 wt % Li6ZnNb4O14
1.42E−4
0.36




301


Li3PS4 - 70 wt % Li6ZnNb4O14
7.23E−5
0.38




301


Li3PS4 - 90 wt % Li6ZnNb4O14
2.99E−7
0.40




301


Li3PS4
1.46E−4
0.38




302


Li3PS4 - 10 wt % Li7La3Zr2O12
2.96E−4
0.36




302


Li3PS4 - 20 wt % Li7La3Zr2O12
3.70E−4
0.35




302


Li3PS4 - 25 wt % Li7La3Zr2O12
4.10E−4
0.35




302


Li3PS4 - 30 wt % Li7La3Zr2O12
5.38E−4
0.36




302


Li3PS4 - 35 wt % Li7La3Zr2O12
4.00E−4
0.36




302


Li3PS4 - 40 wt % Li7La3Zr2O12
3.33E−4
0.36




302


Li3PS4 - 60 wt % Li7La3Zr2O12
2.19E−4
0.40




302


Li3PS4 - 70 wt % Li7La3Zr2O12
1.26E−5
0.43




302


Li3PS4 - 90 wt % Li7La3Zr2O12
6.04E−6
0.44




302


Li7La3Zr2O12
5.20E−8
0.47




302


Li3.45Ge0.45P0.55S3.1Se0.9
 9.8E−4





303


Li3.4Ge0.4P0.6S3.2Se0.8
1.17E−3





303


Li3.35Ge0.35P0.65S3.3Se0.7
1.20E−3





303


Li3.3Ge0.3P0.7S3.4Se0.6
1.33E−3





303


Li3.25Ge0.25P0.75S3.5Se0.5
5.03E−4





303


Li3.20Ge0.20P0.8S3.6Se0.4
1.08E−3





303


Li3.15Ge0.15P0.85S3.7Se0.3
8.16E−4





303


Li3.1Ge0.1P0.9S3.8Se0.2
1.13E−3





303


Li3.05Ge0.05P0.95S3.9Se0.1
1.41E−3





303


Li3PS4
9.35E−4





303


0.8Li20—0.2P2S5
1.54E−5





304


0.05Li2S—0.75Li2O—0.2P2S5
1.39E−5





304


0.1Li2S—0.7Li2O—0.2P2S5
1.59E−5





304


0.15Li2S—0.65Li2O—0.2P2S5
2.32E−5





304


0.2Li2S—0.6Li2O—0.2P2S5
2.89E−5





304


0.25Li2S—0.55Li2O—0.2P2S5
3.80E−5





304


0.3Li2S—0.5Li2O—0.2P2S5
4.35E−5





304


0.35Li2S—0.45Li2O—0.2P2S5
5.26E−5





304


0.4Li2S—0.4Li2O—0.2P2S5
4.45E−5





304


0.45Li2S—0.35Li2O—0.2P2S5
6.35E−5





304


0.5Li2S—0.3Li2O—0.2P2S5
8.11E−5





304


0.55Li2S—0.25Li2O—0.2P2S5
1.12E−4





304


0.6Li2S—0.2Li2O—0.2P2S5
1.12E−4





304


0.65Li2S—0.15Li2O—0.2P2S5
1.13E−4





304


0.7Li2S—0.1Li2O—0.2P2S5
1.09E−4





304


0.75Li2S—0.05Li2O—0.2P2S5
1.43E−4





304


0.8Li2S—0.2P2S5
2.99E−4





304


0.75Li2O—0.25P2S5
1.55E−5





304


0.05Li2S—0.7Li2O—0.25P2S5
1.42E−5





304


0.1Li2S—0.65Li2O—0.25P2S5
2.52E−5





304


0.15Li2S—0.6Li2O—0.25P2S5
2.67E−5





304


0.2Li2S—0.55Li2O—0.25P2S5
2.74E−5





304


0.25Li2S—0.5Li2O—0.25P2S5
3.80E−5





304


0.3Li2S—0.45Li2O—0.25P2S5
5.88E−5





304


0.35Li2S—0.4Li2O—0.25P2S5
1.33E−5





304


0.4Li2S—0.35Li2O—0.25P2S5
2.44E−5





304


0.45Li2S—0.3Li2O—0.25P2S5
2.30E−5





304


0.5Li2S—0.25Li2O—0.25P2S5
9.56E−6





304


0.55Li2S—0.2Li2O—0.25P2S5
7.06E−5





304


0.6Li2S—0.15Li2O—0.25P2S5
9.27E−5





304


0.65Li2S—0.1Li2O—0.25P2S5
1.15E−4





304


0.7Li2S—0.05Li2O—0.25P2S5
9.76E−5





304


0.75Li2S—0.25P2S5
1.60E−4





304


0.7Li20—0.3P2S5
 5.78E−11





304


0.05Li2S—0.65Li2O—0.3P2S5
1.51E−8





304


0.1Li2S—0.6Li2O—0.3P2S5
7.78E−8





304


0.15Li2S—0.55Li2O—0.3P2S5
2.90E−7





304


0.2Li2S—0.5Li2O—0.3P2S5
1.67E−5





304


0.25Li2S—0.45Li2O—0.3P2S5
8.64E−7





304


0.3Li2S—0.4Li2O—0.3P2S5
1.62E−6





304


0.35Li2S—0.35Li2O—0.3P2S5
3.68E−6





304


0.4Li2S—0.3Li2O—0.3P2S5
5.86E−6





304


0.45Li2S—0.25Li2O—0.3P2S5
5.10E−6





304


0.5Li2S—0.2Li2O—0.3P2S5
8.33E−6





304


0.55Li2S—0.15Li2O—0.3P2S5
1.01E−5





304


0.6Li2S—0.1Li2O—0.3P2S5
2.29E−5





304


0.65Li2S—0.05Li2O—0.3P2S5
2.48E−5





304


0.7Li2S—0.3P2S5
5.34E−5





304


0.9Li3PS4•10ZnO
 2.9E−4





305


0.7Li2S—0.3P2S5
7.10E−4
0.23




306


0.7Li2S—0.29P2S5—0.01Li3PO4
1.83E−3
0.19




306


0.7Li2S—0.28P2S5—0.02Li3PO4
9.89E−4
0.21




306


0.7Li2S—0.27P2S5—0.03Li3PO4
4.40E−4
0.25




306


0.7Li2S—0.25P2S5—0.05Li3PO4
2.67E−4
0.29




306


0.7Li2S—0.3P2S5
1.67E−3
0.23




307


0.99(0.7Li2S—0.3P2S5)—0.01Li2ZrO3
2.86E−3
0.18




307


0.98(0.7Li2S—0.3P2S5)—0.02Li2ZrO3
1.22E−3
0.25




307


0.95(0.7Li2S—0.3P2S5)—0.05Li2ZrO3
7.42E−4
0.29




307


Li2.7PO3.9
  7E−8
0.68




308


Li3.6(Si0.19P0.82)O4.2
 2.0E−7
0.57




308


Li3.1PO3.8N0.16
2.00E−6
0.57




308


Li3.3PO3.8N0.22
2.40E−6
0.56




308


Li2.9PO3.3N0.46
3.30E−6
0.54




308


Li4.4PO4.3
9.39E−7
0.64




309


Li4.0PO3.9N0.4
1.70E−6
0.62




309


Li3.7PO3.4N0.7
2.36E−6
0.60




309


Li3.5PO3.2N0.8
2.59E−6
0.59




309


Li3.4PO3.1N0.9
2.81E−6
0.58




309


Li3.2PO3.0N
2.99E−6
0.57




309


Li2.9PO2.6N0.91
 2.1E−6
0.52




310


Li1.8PO1.2N1.5
 1.7E−6
0.49




310


Li3.3PO2.9N0.83
 3.1E−6
0.47




310


0.45B2S3—0.55Li2S
8.19E−5
0.23




311


0.815(0.45B2S3—0.55Li2S)—0.185LiI
3.08E−4
0.20




311


0.69(0.45B2S3—0.55Li2S)—0.31LiI
7.58E−4
0.23




311


0.33B2S3—0.67Li2S
2.26E−4
0.31




311


0.95(0.33B2S3—0.67Li2S)—0.05LiI
4.37E−4
0.29




311


0.9(0.33B2S3—0.67Li2S)—0.1LiI
4.81E−4
0.28




311


0.85(0.33B2S3—0.67Li2S)—0.15LiI
4.92E−4
0.28




311


0.75(0.33B2S3—0.67Li2S)—0.25LiI
6.10E−4
0.27




311


0.66(0.33B2S3—0.67Li2S)—0.34LiI
5.22E−4
0.32




311


0.6(0.33B2S3—0.67Li2S)—0.4LiI
4.89E−4
0.35




311


0.29B2S3—0.71Li2S
2.71E−4
0.32




311


0.95(0.29B2S3—0.71Li2S)—0.05LiI
3.72E−4
0.31




311


0.875(0.29B2S3—0.71Li2S)—0.125LiI
6.27E−4
0.29




311


0.78(0.29B2S3—0.71Li2S)—0.22LiI
6.56E−4
0.29




311


0.64(0.29B2S3—0.71Li2S)—0.36LiI
8.10E−4
0.36




311



3.03E−4
0.36




311


0.92(0.25B2S3—0.75Li2S)—0.08LiI
3.83E−4
0.30




311


0.89(0.25B2S3—0.75Li2S)—0.11LiI
3.48E−4
0.33




311


0.5Li2S—0.5SiS2
4.80E−5





312


0.985(0.5Li2S—0.5SiS2)—0.015Li3PO4
6.28E−5





312


0.975(0.5Li2S—0.5SiS2)—0.025Li3PO4
8.76E−5





312


0.95(0.5Li2S—0.5SiS2)—0.05Li3PO4
8.68E−5





312


0.9(0.5Li2S—0.5SiS2)—0.1Li3PO4
6.76E−5





312



1.85E−4





312


0.99(0.6Li2S—0.4SiS2)—0.01Li3PO4
2.53E−4





312


0.97(0.6Li2S—0.4SiS2)—0.03Li3PO4
3.97E−4





312


0.95(0.6Li2S—0.4SiS2)—0.05Li3PO4
2.03E−4





312


0.9(0.6Li2S—0.4SiS2)—0.1Li3PO4
5.20E−5





312


0.61Li2S—0.39SiS2
5.24E−4





312


0.99(0.61Li2S—0.39SiS2)—0.01Li3PO4
5.05E−4





312


0.985(0.61Li2S—0.39SiS2)—0.015Li3PO4
5.96E−4





312


0.98(0.61Li2S—0.39SiS2)—0.02Li3PO4
7.69E−4





312


0.975(0.61Li2S—0.39SiS2)—0.025Li3PO4
6.36E−4





312


0.97(0.61Li2S—0.39SiS2)—0.03Li3PO4
5.83E−4





312


0.95(0.61Li2S—0.39SiS2)—0.05Li3PO4
4.68E−4





312


0.9(0.61Li2S—0.39SiS2)—0.1Li3PO4
1.28E−4





312


0.99(0.65Li2S—0.35SiS2)—0.01Li3PO4
3.60E−4





312


0.97(0.65Li2S—0.35SiS2)—0.03Li3PO4
2.62E−4





312


0.95(0.65Li2S—0.35SiS2)—0.05Li3PO4
1.81E−4





312


0.9(0.65Li2S—0.35SiS2)—0.1Li3PO4
7.13E−5





312


0.7Li2S—0.3P2S5
 5.2E−3





313


LiI
3.07E−7





314


0.998LiI—0.002CaI2
9.80E−7





314


0.99LiI—0.01CaI2
5.54E−6
0.43




314


LiI
2.74E−8
0.43




315


0.8LiI—0.2Al2O3
6.84E−6
0.35




315


0.7LiI—0.3Al2O3
2.07E−5
0.33




315


0.6LiI—0.4Al2O3
3.94E−5
0.33




315


0.5LiI—0.5Al2O3
2.58E−5
0.33




315


0.4LiI—0.6Al2O3
6.76E−6
0.37




315


Li3.5P0.5Si0.5O4
4.27E−7
0.57




19


Li3.5P0.5Ge0.5O4
7.89E−6
0.56




19


Li3.5As0.5Si0.5O4
4.05E−6
0.55




19


Li3.5V0.5Si0.5O4
1.20E−5
0.53




19


Li3.5As0.5Ge0.5O4
2.83E−5
0.51




19


Li3.5V0.5Ge0.5O4
3.00E−5





19


Li3.5As0.5Ti0.5O4
3.22E−5
0.52




19


Li3.5As0.5V0.5O4
4.01E−5
0.49




19


LiHf2(PO4)3—0.1Li2O
1.12E−4





19


LiHf2(PO4)3—0.2Li2O
2.78E−5





19


LiHf2(PO4)3—0.3Li2O
2.58E−5





19


LiHf2(PO4)3—0.4Li2O
3.40E−5





19


LiTi2(PO4)3
1.69E−6
0.30




316


0.95LiTi2(PO4)3—0.05Li3PO4
5.52E−5
0.29




316


0.9LiTi2(PO4)3—0.1Li3PO4
1.38E−4
0.28




316


0.8LiTi2(PO4)3—0.2Li3PO4
1.93E−4
0.31




316


0.7LiTi2(PO4)3—0.3Li3PO4
2.45E−4
0.30




316


0.95LiTi2(PO4)3—0.05Li3BO3
3.59E−5
0.30




316


0.9LiTi2(PO4)3—0.1Li3BO3
2.54E−4
0.30




316


0.8LiTi2(PO4)3—0.2Li3BO3
2.97E−4
0.30




316


0.7LiTi2(PO4)3—0.3Li3BO3
2.45E−4
0.29




316


0.5LiTi2(PO4)3—0.5Li3BO3
2.73E−5
0.31




316


LiTi2(PO4)3
1.00E−4





317


LiTi2(PO4)3—0.15LiPO4
6.00E−4





317


LiTi2(PO4)3—0.3LiPO4
9.92E−4





317


LiTi2(PO4)3—0.6LiPO4
1.23E−3





317


LiTi2(PO4)3—0.9LiPO4
1.10E−3





317


LiTi2(PO4)3—0.15LiBO3
4.80E−4





317


LiTi2(PO4)3—0.3LiBO3
1.66E−3





317


LiTi2(PO4)3—0.6LiBO3
1.12E−3





317


LiTi2(PO4)3—0.9LiBO3
8.91E−4





317


LiTi2(PO4)3—1.5LiBO3
6.48E−4





317


LiTi2(PO4)3—0.2Li2SO4
8.35E−4





317


LiTi2(PO4)3—0.4Li2SO4
1.66E−3





317


LiTi2(PO4)3—0.6Li2SO4
5.67E−4





317


LiTi2(PO4)3—0.4LiCl
6.45E−4





317


LiTi2(PO4)3—0.8LiCl
1.28E−3





317


LiTi2(PO4)3—1.2LiCl
1.02E−3





317


LiTi2(PO4)3—0.4LiNO3
1.18E−3





317


LiTi2(PO4)3—0.8LiNO3
1.49E−3





317


LiTi2(PO4)3—1.2LiNO3
9.95E−4





317


Li0.39La0.54TiO3
1.08E−3
0.316




318


(Li0.39La0.54)1.006Al0.006Ti0.994O3
1.13E−3
0.308




318


(Li0.39La0.54)1.01Al0.02Ti0.98O3
1.58E−3
0.278




318


(Li0.39La0.54)1.03Al0.06Ti0.94O3
1.39E−3
0.290




318


(Li0.39La0.54)1.005Cr0.01Ti0.99O3
9.52E−4
0.300




318



1.01E−3
0.315




318


(Li0.39La0.54)1.025Cr0.05Ti0.95O3
1.04E−3
0.298




318


La0.51Li0.34TiO2.94
  1E−3
0.38




319


La0.57Li0.26TiO2.99
  1E−3
0.34




319


La0.6Li0.16TiO3.01
 6.3E−4
0.33




319


La0.64Li0.067TiO3
 7.9E−5
0.36




319


(La0.5Li0.5)0.95Sr0.05TiO3
1.49E−3





319


(La0.5Li0.5)0.9Sr0.1TiO3
1.30E−3





319


(La0.5Li0.5)0.75Sr0.25TiO3
8.99E−5





319


(La0.5Li0.5)0.95Ba0.05TiO3
7.61E−4





319


La0.63Li0.1Mg0.5W0.5O3
1.69E−6
0.39




319


Li0.5La0.5TiO3
8.67E−4
0.28




320


Li0.5La0.5Ti0.98Sn0.02O3
4.86E−4





320


Li0.5La0.5Ti0.96Sn0.04O3
3.89E−4





320


Li0.5La0.5Ti0.94Sn0.06O3
3.52E−4
0.294




320


Li0.5La0.5Ti0.9Sn0.1O3
2.60E−4





320


Li0.5La0.5Ti0.98Zr0.02O3
4.16E−4





320


Li0.5La0.5Ti0.96Zr0.04O3
2.86E−4





320


Li0.5La0.5Ti0.94Zr0.06O3
2.23E−4





320


Li0.5La0.5Ti0.9Zr0.1O3
7.05E−5





320


Li0.5La0.5Ti0.998Mn0.002O3
9.12E−4





320


Li0.5La0.5Ti0.996Mn0.004O3
9.64E−4





320


Li0.5La0.5Ti0.994Mn0.006O3
1.08E−3





320


Li0.5La0.5Ti0.992Mn0.008O3
1.13E−3





320


Li0.5La0.5Ti0.99Mn0.01O3
1.13E−3





320


Li0.5La0.5Ti0.998Ge0.002O3
9.12E−4





320


Li0.5La0.5Ti0.996Ge0.004O3
9.64E−4





320


Li0.5La0.5Ti0.994Ge0.006O3
1.08E−3





320


Li0.5La0.5Ti0.992Ge0.008O3
1.13E−3
0.265




320


Li0.5La0.5Ti0.99Ge0.01O3
1.13E−3





320


La0.58Li0.36Ti0.95Mg0.05O3
 2.1E−4
0.29




321


La0.56Li0.36Ti0.95Al0.05O3
 6.4E−4
0.26




321


La0.55Li0.36Ti0.95Mn0.05O3
 1.9E−4
0.29




321


La0.55Li0.36Ti0.95Ge0.05O3
 3.6E−4
0.29




321


La0.55Li0.36Ti0.95Ru0.05O3
 5.2E−5
0.28




321


La0.51Li0.36Ti0.95W0.05O3
 7.3E−4
0.27




321


La0.55Li0.36Ti0.9W0.1O3
 4.4E−4
0.27




321


La0.55Li0.36Ti0.995Al0.005O3
 1.1E−3
0.28




321


La0.55Li0.36Ti0.992Al0.008O3
 6.5E−4
0.29




321


La0.54Li0.36Ti0.995W0.005O3
 2.6E−4
0.30




321


La0.54Li0.36TiO3
 8.9E−4
0.29




321


La0.606Li0.06Ti0.94Al0.06O3
1.68E−6
0.36




322


La0.566Li0.1Ti0.9Al0.1O3
7.34E−6
0.35




322


La0.516Li0.15Ti0.85Al0.15O3
9.66E−6
0.36




322


La0.466Li0.2Ti0.8Al0.2O3
4.28E−5
0.33




322


La0.416Li0.25Ti0.75Al0.25O3
7.66E−5
0.35




322


La0.366Li0.3Ti0.7Al0.3O3
1.72E−5
0.33




322


Li0.12La0.63TiO3
2.00E−4





323


Li0.18La0.61TiO3
4.43E−4





323


Li0.24La0.59TiO3
9.93E−4





323


Li0.3La0.57TiO3
1.10E−3





323


Li0.39La0.54TiO3
1.02E−3





323


Li0.45La0.52TiO3
9.05E−4





323


LiZr2(PO4)3
4.77E−7





324


Li1.05Al0.05Zr1.9(PO4)3
5.79E−7





324


Li1.1Al0.1Zr1.8(PO4)3
6.35E−7





324


Li1.2Al0.2Zr1.6(PO4)3
1.90E−6
0.48




324


Li1.225Al0.225Zr1.55(PO4)3
2.13E−6
0.48




324


Li1.25Al0.25Zr1.5(PO4)3
2.06E−6
0.48




324


Li1.275Al0.275Zr1.45(PO4)3
3.05E−6
0.48




324


Li1.3Al0.3Zr1.4(PO4)3
1.91E−6
0.48




324


LiHf2(PO4)3
3.42E−6





325


LiHfTi(PO4)3
5.63E−7





325


Li0.1Zr1.1Nb0.9P3O12
  6E−6





325


LiTi2(PO4)3
1.04E−7





326


Li1.1Sc0.1Ti1.9(PO4)3
1.75E−5





326


Li1.2Sc0.2Ti1.8(PO4)3
4.11E−5
0.34




326


Li1.3Sc0.3Ti1.7(PO4)3
4.06E−5





326


Li1.4Sc0.4Ti1.6(PO4)3
9.43E−6





326


Li1.5Sc0.5Ti1.5(PO4)3
5.42E−7





326


Li1.1Y0.1Ti1.9(PO4)3
2.94E−7





326


Li1.2Y0.2Ti1.8(PO4)3
7.95E−7





326


Li1.3Y0.3Ti1.7(PO4)3
1.01E−6
0.40




326


Li1.4Y0.4Ti1.6(PO4)3
2.97E−7





326


LiTi2(PO4)3—0.5LiF
2.318E−4 
0.28




327


LiTi2(PO4)3
7.181E−6 
0.48




327


14Li2O—9Al2O3—38TiO2—39P2O5
 1.3E−3
0.33




328


Li6.6La3Zr1.6Ta0.4O12
3.13E−4
0.38




329


Li6.6La2.875Y0.125Zr1.6Ta0.4O12
3.17E−4
0.35




329


Li6.6La2.75Y0.25Zr1.6Ta0.4O12
4.36E−4
0.34




329


Li6.6La2.5Y0.5Zr1.6Ta0.4O12
2.26E−4
0.39




329


Li2ZrS3
 7.3E−6





330


Li2.2Zn0.1Zr0.9S3
 1.2E−4





330


0.7Li2S—0.3P2S5
 8.1E−5
0.425




12


Li7PS6
1.61E−6
0.16




176









Section II. Labels for Comparing all Descriptors-Simplification Combinations

A subset of the digitized labels was used for comparing between the different semi-supervised learning models. In total, the label subset is comprised of 155 structures. The subset is required because not all structures are compatible with all the descriptor transformations. Some descriptor-structure combinations produce coding errors, imaginary values, or infinite values. To directly compare all the descriptors, its necessary to have a common set of labels. The 155 labels that worked for all descriptors is listed in the subsequent table:




















σ25° C.
Ea
Space
Space
Other




Compound
(S cm−1)
(eV)
Group
Group #
names
ICSD
Citation






















Li4P2O7

<1E−10

1.617
P1
2

248414
8


Li7P3S11
3.2E−3
0.124
P1
2

157654
5


Li7BiO6
8.80E−07
0.58
P1
2

155950
3


Li7SbO6
6.70E−08
0.7
P1
2

413370
3


Li6CuB4O10
1.00E−13
0.92
P1
2
β-Li6CuB4O10
4819
10


LiAlSi3O8
1.30E−10

C1
2

81980
1


Li3BP2O8
9.60E−12
0.62
P1
2

248343
7


LiSn2(PO4)3
2.04E−9 

P1
2

83832
2


LiV(PO4)F
8.1E−7
0.23
P1
2

183876
6


Li2NaBP2O8
4.40E−18
1.21
P1
2

291512
7


LiMgSO4F
5.40E−08
0.54
P1
2

281119
9


Li2ZnGeO4
1.00E−07
0.4
Pc
7

34362
13


Li4SiO4
5.00E−10
0.55
P21/m
11

238603
17


Li3.7P0.3Si0.7O4
3.84E−7 

P21/m
11

35168
19


Li7.22Si1.5P0.5O8
1.64E−7 
0.48
P21/m
11

238602
16


Li3InCl6
2.04E−3 
0.35
C2/m
12

89617
20


Li2P2S6
7.80E−11
0.48
C2/m
12

253894
21


LiPO3
1.00E−09

P2/c
13

51630
28


LiAlSi4O10
1.01E−10

P2/c
13

194284
1


LaLiO2

<1E−10

0.92
P21/C
14

239278
36


LiBO2
1.00E−08
0.71
P21/C
14

200891
34


LiSbO2

<1E−10

0.88
P21/C
14

262075
39


LiYO2
1.80E−08
0.72
P21/C
14

45511
33


LiAlCl4
1.00E−06
0.47
P21/C
14

35275
32


Li3BO3
7.40E−11
0.63
P21/C
14

9105
30


Li2SO4
1.40E−14
1.1
P21/C
14

2512
29


Li6Ge2O7
8.50E−07
0.43
P21/C
14

31050
31


LiGaBr4
7.00E−6 
0.54
P21/C
14

61337
25


Li4Zn(PO4)2

<1E−10

1.3
P21/C
14
α-Li4Zn(PO4)2
255464
38


La(Li0.76Mg0.08)O2
7.27E−10
0.66
P21/C
14

239280
36


(La0.9Sr0.1)LiO2
6.29E−10
0.62
P21/C
14

239279
36


Li2Sr2Al(PO4)3

<1E−10

1.02
P21/C
14

431319
40


Li2.5V2(PO4)3
1.9E−7

P21/C
14

240269
37


Li2SnS3
1.50E−05
0.59
C2/c
15

251656
43


LiVO3
2.048E−9 

C2/c
15

51443
48


Li6Zr2O7
5.20E−10
0.68
C2/c
15

73835
41


Li3AlF6
5.00E−07
0.54
C2/c
15

85171
42


LiTa2PO8
1.6E−3
0.32
C2/c
15

267438
44


LiBaP2O7
1.00E−10

C2/c
15

280927
45


Li3Na5(TiS4)2
8.80E−06
0.4
C2/c
15

391258
46


LiGd(PO3)4

<1E−10

1.7
C2/c
15

416442
47


Li3.7Zn0.7Ga0.3(PO4)2

<1E−10

0.91
P212121
19
β′-
255466
38







Li3.7Zn0.7Ga0.3(PO4)2




Li3SbS4
1.5E−6
0.518
Pmn21
31

8407
51


Li3PS4
2.60E−07
0.49
Pmn21
31
γ-Li3PS4
180318
52


Li3SbS3
1.00E−07
0.4
Pna21
33

424834
55


LiGaO2
2.40E−14
0.86
Pna21
33

18152
53


LiB6OgF
5.40E−24
1.38
Pna21
33

420286
54


LiSi2N3
6.17E−08
0.64
Cmc21
36

34118
56


Li2(PO2N)

<1E−10

0.57
Cmc21
36

188493
57


LiGa2GeS6
3.80E−08
0.47
Fdd2
43

254406
58


Li3AlO4
5.00E−10
0.99
Pmmn
59

16229
64


Li14Nd5(Si11N19O5)O2F2
 1.7E−10
0.69
Pmmn
59

262923
65


Li2SiN2
1.60E−07

Pbca
61

420126
66


Li5GaO4
5.00E−09
0.71
Pbca
61
α-Li5GaO4
9082
64


Li3PS4
1.60E−04
0.36
Pnma
62
β-Li3PS4
180319
52


Li3PO4
 4.2E−18
1.24
Pnma
62
γ-Li3PO4
79427
70


Li3PO4

<1E−10

1.14
Pnma
62
γ-Li3PO4
20208
68


Li4SnS4
7.0E−5
0.29
Pnma
62

290832
80


Li4SnSe4

2E−5

0.45
Pnma
62

193768
76


Li4GeS4
2.00E−07
0.53
Pnma
62

290831
79


Li4GeS4

2E−7

0.53
Pnma
62

92200
71


Li2ZnI4
4.00E−08
0.58
Pnma
62

402062
81


Li3.5Ge0.5V0.5O4
1.77E−5 

Pnma
62

66576
84


Li6.6SiPO8
1.48E−7 
0.49
Pnma
62

238601
16


Li3.75Ge0.75V0.25O4
5.66E−6 

Pnma
62

150918
73


Li4Zn(PO4)2

<1E−10

1.1
Pnma
62
β-
255465
38







Li4Zn(PO4)2




Li2.88PO3.73N0.14
 1.4E−13
0.97
Pnma
62

79426
70


Li2Mg2(MoO4)3

<1E−10

0.71
Pnma
62

170956
75


Li3.70Ge0.85W0.15O4
3.80E−5 

Pnma
62

150920
73


Li14Zn(GeO4)4
1.00E−06
0.24
Pnma
62

100169
72


Nd0.54Li0.36TiO3
3.42E−8 
0.50
Pnma
62

81047
86


Li6.5O8P1.5Si0.5
4.49E−07
0.44
Pnma
62

238600
16


Pr0.51Li0.39TiO2.96
5.34E−7 
0.44
Pnma
62

81048
86


LiZnSO4F
2.80E−05
0.2455
Pnma
62

261343
78


Li3.5Zn0.5Ga0.5(PO4)2

<1E−10

1.02
Pnma
62
β-
255468
38







Li3.5Zn0.5Ga0.5(PO4)2




Li4H8C14O4

1E−8

0.777
Cmcm
63
LiCl*H2O
281198
88


Li2MgBr4
7.80E−10
0.77
Cmmm
65

73276
89


Li0.18La0.61TiO3
2.0E−4
0.432
Cmmm
65

99398
90


LiBiO2
3.80E−08
0.1
Ibam
72

46022
30


LiZnPS4
5.4E−8

I4
82

95785
69


(Li1.19Zn0.9)PS4
0.65E−5 
0.25
I4
82

264463
69


(Li1.69Zn0.66)PS4
1.30E−4 
0.181
I4
82

264462
69


(Li0.5Ce0.5)(MoO4)
1.3E−8
0.4
I41/a
88

186450
91


(Li0.5Ce0.25Sm0.25)(MoO4)
 1.8E−10
0.5
I41/a
88

186452
91


(Li0.5Ce0.25Pr0.25)(MoO4)

1E−9

0.5
I41/a
88

186451
91


Li2TeO4

<1E−10

1.129
P4122
91

1485
92


Li3BN2
1.60E−10
0.67
P42212
94
α-Li3BN2
655673
93


Li2B4O7
1.00E−10

I41cd
110

65930
94


La0.52Li0.45TiO3
5.01E−4 

P4/mmm
123

50434
97


Li(NdTiO4)

<1E−10

0.87
P4/nmmZ
129

91844
99


Li4PS4I
1.2E−4
0.37
P4/nmmZ
129

432169
101


Li(LaTiO4)

<1E−10

0.83
P4/nmmZ
129

91843
99


La0.62Li0.14(Mg0.5W0.5)O3
1.2E−5
0.37
P4/nmm
129

151902
100


Li6ZnO4
9.40E−09
0.61
P42/nmc
137

62137
64


Li10SnP2S12

7E−3

0.27
P42/nmc C
137

193755
107


Li10SnP2S12
3.98E−3 
0.305
P42/nmc
137

255750
108


Li10GePS12
1.21E−2 

P42/nmc
137

188887
104


Li10GeP2S12
2.46E−2 
0.274
P42/nmc
137

241439
108


Li10GeP2S12
1.20E−02
0.25
P42/nmc
137

255749
110


Li10.35Ge1.35P1.65S12
1.44E−2 
0.269
P42/nmc S
137

193947
104


Li10.35Si1.35P1.65S12
6.5E−3

P42/nmcS
137

252037
109


Li9.81Sn0.81P2.19S12
5.5E−3

P42/nmc
137

252040
109


Li10.2(Sn0.2Si0.8)1.2P1.8S12
7.82E−3 

P42/nmcS
137

5667
111


Li10.2(Sn0.2Si0.8)1.2P1.8S12
2.69E−3 

P42/nmcS
137

257948
111


Li10.5(Sn0.2Si0.8)1.5P1.5S12
8.79E−3 

P42/nmcS
137

5668
111


Li10(Ge0.776Sn0.224)P2S12
1.41E−2 
0.276
P42/nmc
137

255748
108


LiLaNb2O7
 <1E−8

I4/mmm
139

72566
114


Li4Sr3Nb6O20

<1E−10


I4/mmm
139

87824
115


Li4Sr3.056Nb6O20

<1E−10

0.74
I4/mmm
139

109168
115


Li4Sr3Nb5.77Fe0.23O19.77

<1E−10


I4/mmm
139

87823
115


Li4SrN2
2.30E−13
0.9
I41/amd
141

87413
116


LiAlO2
1.10E−12
0.97
I41/amd
141
r-LiAlO2
99517
33


LiSCO2

<1E−10

1.047
I41/amd
141

257819
117


LiSCO2
1.00E−12
0.87
I41/amd
141

36124
33


Li0.9Sc0.9Zr0.1O2

<1E−10

0.912
I41/amd
141

257820
117


Li7La3Zr2O12
1.63E−6 
0.54
I41/acdZ
142
“tetraganol-LLZO”
183684
119


LiAlGeO4

<1E−10

0.97
R3H
146

257741
123


LiGaSiO4
3.00E−16
0.9
R3H
146

65125
122


LiGa0.5Al0.5GeO4

<1E−10

1.06
R3H
146

257740
123


LiNaSO4
8.80E−10

P31c
159

14364
125


Li5NCl2
1.20E−06
0.5
R3m
166

84763
131


LiGe2(PO4)3
4.83E−9 
0.654
R3cH
167

69763
133


LiZr2(PO4)3
2.96E−10

R3cH
167

201935
2


LiTi2(PO4)3
7.61E−6 
0.38
R3cH
167

95979
132


LiGe2(PO4)3
3.33E−7 

R3cH
167

263767
2


Li1.3(Al0.23Y0.07Ti1.7)(PO4)3
3.84E−8 

R3cH
167

253243
138


Li9Mg3(PO4)4F3

<1E−10

0.835
P63
173

426103
148


LiLa9Si6O26

<1E−10


P63/m
176

291218
150


Li0.284Sm4.512Si3O12.91

<1E−10


P63/m
176

83279
150


Pb6.12Ca1.9Li1.96(PO4)6

<1E−10

1.05
P63/m
176

59615
149


Li5La3Nb2O12

8E−6

0.43
I213
199

54865
159


(K0.1Li0.9)(SbO3)
1.36E−8 

Pn3Z
201

200984
160


Li2CoTi3O8

<1E−10

1.33
P4332
212

86166
163


Li2ZnGe3O8

<1E−10

2.14
P4332
212

86169
163


Li2MgTi3O8

<1E−10

0.71
P4332
212

86165
163


(Li0.55Mg0.45)(Li0.445Mg0.055)Ti1.504
1.53E−11
0.786
P4332
212

168145
164


(Li0.61Mg0.39)(Li0.46Mg0.005Ti0.035)Ti1.504
6.56E−10
0.685
P4332
212

168144
164


Li2VCl4
6.95E−6 

F43m
216

74959
166


Li5NI2
4.00E−6 

F43m
216

16800
165


Li6PO5Cl
5.54E−10
0.66
F43m
216

421479
173


Li7PN4
1.60E−07
0.4
P43n
218

69017
95


Li9NS3
8.30E−07
0.52
Pm3m
221

240749
185


Li3OBr
1.10E−06
0.74
Pm3m
221

67265
194,195


Li2(OH)Br
1.20E−6 
0.75
Pm3m
221

200874
184


LiI

1E−7


Fm3m
225

414244
197


Li7.2N1.6Cl2.4
8.4E−7
0.49
Fm3m
225

49646
131


Li0.19La0.67(Ti0.9Co0.1)O3
1.08E−4 

Fm3m
225

151535
182


LiCdCl4
5.80E−07
0.44
Fd3m
227

74958
199


Li2MnCl4
4.79E−6 

Fd3m
227

69678
166


Li2MgCl4
6.24E−7 

Fd3m
227

74957
166


LiSrTa2O6F

<1E−10

0.604
Fd3m
227

236010
200


Li1.9Mn0.9Ga0.1Cl4
2.37E−7 

Fd3m
227

50305
198


Li(Li0.34Ti1.66)O4
6.03E−8 
0.506
Fd3m
227

168137
164


(Li0.74Mg0.26)(Li0.40Mg0.04Ti1.56)O4
1.51E−9 
0.639
Fd3m
227

168142
164


(Li0.826Mg0.174)(Li0.374Mg0.026Ti1.60)O4
4.24E−9 
0.615
Fd3m
227

168141
164









Section III. Labels Used for the Final SOAP Model

Once the best-performing descriptor-simplification is identified, an expanded set of labels can be employed. The mathematical transformation for the SOAP descriptor is compatible with most of the ˜26,000 structures. In addition to the 155 labels used for descriptor comparisons, 64 labels were added. The full list of labels is included in the table below:




















σ25° C.
Ea
Space
Space
Other




Compound
(S cm−1)
(eV)
Group
Group #
names
ICSD
Citation






















Li4P2O71

<1E−10

1.617
P1
2

248414
8


Li7P3S11
3.2E−3
0.124
P1
2

157654
5


Li7BiO6
8.80E−07
0.58
P1
2

155950
3


Li7SbO6
6.70E−08
0.7
P1
2

413370
3


Li6CuB4O10
1.00E−13
0.92
P1
2
β-Li6CuB4O10
4819
10


LiAlSi3O8
1.30E−10

C1
2

81980
1


Li3BP2O8
9.60E−12
0.62
P1
2

248343
7


LiSn2(PO4)3
2.04E−9 

P1
2

83832
2


LiV(PO4)F
8.1E−7
0.23
P1
2

183876
6


LiMgSO4F
5.40E−08
0.54
P1
2

281119
9


Li2NaBP2O8
4.40E−18
1.21
P1
2

291512
7


Li2ZnGeO4
1.00E−07
0.4
Pc
7

34362
13


Li4SiO4
5.00E−10
0.55
P21/m
11

238603
17


Li4SiS4
5.00E−08
0.56
P21/m
11

59708
15


Li3.7P0.3Si0.7O4
3.84E−7 

P21/m
11

35168
19


Li7.22Si1.5P0.5O8
1.64E−7 
0.48
P21/m
11

238602
16


Li2P2S6
7.80E−11
0.48
C2/m
12

253894
21


Li3InCl6
2.04E−3 
0.35
C2/m
12

89617
20


Li17Sb13S28
1.05E−9 
0.4
C2/m
12

429902
24


LiPO3
1.00E−09

P2/c
13

51630
28


LiAlSi4O10
1.01E−10

P2/c
13

194284
1


LaLiO2

<1E−10

0.92
P21/c
14

239278
36


LiBO2
1.00E−08
0.71
P21/c
14

200891
34


LiSbO2

<1E−10

0.88
P21/c
14

262075
39


LiYO2
1.80E−08
0.72
P21/c
14

45511
33


Li3BO3
7.40E−11
0.63
P21/c
14

9105
30


Li2SO4
1.40E−14
1.1
P21/c
14

2512
29


LiGaBr4
7.00E−6 
0.54
P21/c
14

61337
25


LiAlCl4
1.00E−06
0.47
P21/c
14

35275
32


Li6Ge2O7
8.50E−07
0.43
P21/c
14

31050
31


Li4Zn(PO4)2

<1E−10

1.3
P21/c
14
α-Li4Zn(PO4)2
255464
38


Li2.5V2(PO4)3
1.9E−7

P21/c
14

240269
37


La(Li0.76Mg0.08)O2
7.27E−10
0.66
P21/c
14

239280
36


(La0.9Sr0.1)LiO2
6.29E−10
0.62
P21/c
14

239279
36


Li2Sr2Al(PO4)3

<1E−10

1.02
P21/c
14

431319
40


LiClC3H7NO
1.6E−4
0.881
P21/c
14

238683
35


Li2CrCl4

<1E−10

1.22
C2/c
15

202627
49


Li2ZrO3
6.10E−10
0.78
C2/c
15

94894
33


Li6Zr2O7
5.20E−10
0.68
C2/c
15

73835
41


Li3AlF6
5.00E−07
0.54
C2/c
15

85171
42


Li2SnS3
1.50E−05
0.59
C2/c
15

251656
43


LiVO3
2.048E−9 

C2/c
15

51443
48


LiTa2PO8
1.6E−3
0.32
C2/c
15

267438
44


LiBaP2O7
1.00E−10

C2/c
15

280927
45


LiGd(PO3)4

<1E−10

1.7
C2/c
15

416442
47


Li3Na5(TiS4)2
8.80E−06
0.4
C2/c
15

391258
46


Li3.7Zn0.7Ga0.3(PO4)2

<1E−10

0.91
P212121
19
β′-Li3.7Zn0.7Ga0.3(PO4)2
255466
38


Li3SbS4
1.5E−6
0.518
Pmn21
31

8407
51


Li3PS4
2.60E−07
0.49
Pmn21
31
γ-Li3PS4
180318
52


Li3SbS3
1.00E−07
0.4
Pna21
33

424834
55


LiGaO2
2.40E−14
0.86
Pna21
33

18152
53


LiB6O9F
5.40E−24
1.38
Pna21
33

420286
54


LiSi2N3
6.17E−08
0.64
Cmc21
36

34118
56


Li2(PO2N)

<1E−10

0.57
Cmc21
36

188493
57


LiGa2GeS6
3.80E−08
0.47
Fdd2
43

254406
58


La0.595Li0.215TiO3
8.53E−4 

Pmmm
47

92234
59


La0.62Li0.14TiO3
4.42E−4 

Pmmm
47

92231
59


La0.64Li0.08TiO3
3.35E−4 

Pmmm
47

92228
59


Li0.02Na0.48La0.5Nb2O6
3.99E−6 

Pmmm
47

180635
60


Li0.04Na0.46La0.5Nb2O6
5.91E−6 

Pmmm
47

180634
60


Li0.07Na0.43La0.5Nb2O6
1.23E−5 

Pmmm
47

180633
60


Li0.1Na0.4La0.5Nb2O6
1.21E−5 

Pmmm
47

180632
60


Li0.2Na0.3La0.5Nb2O6
1.18E−5 

Pmmm
47

180631
60


Li0.3Na0.2La0.5Nb2O6
1.11E−5 

Pmmm
47

180630
60


Li0.4Na0.1La0.5Nb2O6
9.92E−6 

Pmmm
47

180629
60


Li5AlO4
5.00E−10
0.99
Pmmn
59

16229
64


Li14Nd5(Si11N19O5)O2F2
 1.7E−10
0.69
Pmmn
59

262923
65


Li2SiN2
1.60E−07

Pbca
61

420126
66


Li5GaO4
5.00E−09
0.71
Pbca
61
α-Li5GaO4
9082
64


Li3PO4
 4.2E−18
1.24
Pnma
62
γ-Li3PO4
79427
70


Li3PO4

<1E−10

1.14
Pnma
62
γ-Li3PO4
20208
68


Li3PS4
1.60E−04
0.36
Pnma
62
β-Li3PS4
180319
52


Li4SnS4
7.0E−5
0.29
Pnma
62

290832
80


Li4SnSe4

2E−5

0.45
Pnma
62

193768
76


Li4GeS4
2.00E−07
0.53
Pnma
62

290831
79


Li4GeS4

2E−7

0.53
Pnma
62

92200
71


Li(BH4)

1E−8


Pnma
62

239763
77


Li2ZnI4
4.00E−08
0.58
Pnma
62

402062
81


Li4Zn(PO4)2

<1E−10

1.1
Pnma
62
β-Li4Zn(PO4)2
255465
38


Li2Mg2(MoO4)3

<1E−10

0.71
Pnma
62

170956
75


Li0.2Ca0.4TaO3
3.53E−9 
0.54
Pnma
62

151936
74


Li3.5Ge0.5V0.5O4
1.77E−5 

Pnma
62

66576
84


Li3.75Ge0.75 V0.25O4
5.66E−6 

Pnma
62

150918
73


Li14Zn(GeO4)4
1.00E−06
0.24
Pnma
62

100169
72


Li3.70Ge0.85W0.15O4
3.80E−5 

Pnma
62

150920
73


Li6.6SiPO8
1.48E−7 
0.49
Pnma
62

238601
16


Li2.88PO3.73N0.14
 1.4E−13
0.97
Pnma
62

79426
70


Li6.5O8P1.5Si0.5
4.49E−07
0.44
Pnma
62

238600
16


Nd0.54Li0.36TiO3
3.42E−8 
0.50
Pnma
62

81047
86


Pr0.51Li0.39TiO2.96
5.34E−7 
0.44
Pnma
62

81048
86


LiZnSO4F
2.80E−05
0.2455
Pnma
62

261343
78


Li3.5Zn0.5Ga0.5(PO4)2

<1E−10

1.02
Pnma
62
β-Li3.5Zn0.5Ga0.5(PO4)2
255468
38


Li0.2(Ca0.36Sr0.04)TaO3
9.2E−9

Pnma
62

151937
74


Li4GeO4
2.80E−10
0.73
Cmcm
63

18096
87


Li4H8Cl4O4

1E−8

0.777
Cmcm
63
LiCl*H2O
281198
88


Li2MgBr4
7.80E−10
0.77
Cmmm
65

73276
89


Li0.18La0.61TiO3
2.0E−4
0.432
Cmmm
65

99398
90


LiBiO2
3.80E−08
0.1
Ibam
72

46022
30


LiZnPS4
5.4E−8

I4
82

95785
69


(Li1.19Zn0.9)PS4
0.65E−5 
0.25
I4
82

264463
69


(Li1.69Zn0.66)PS4
1.30E−4 
0.181
I4
82

264462
69


(Li0.5Ce0.5)(MoO4)
1.3E−8
0.4
I41/a
88

186450
91


(Li0.5Ce0.25Sm0.25)(MoO4)
 1.8E−10
0.5
I41/a
88

186452
91


(Li0.5Ce0.25Pr0.25)(MoO4)

1E−9

0.5
I41/a
88

186451
91


Li2TeO4

<1E−10

1.129
P4122
91

1485
92


Li3BN2
1.60E−10
0.67
P42212
94
α-Li3BN2
655673
93


Li2B4O7
1.00E−10

I41cd
110

65930
94


LiY(BH4)4
1.26E−6 

P42c
112

239762
77


LiPN2
1.6E−7
0.40
I42d
122

66007
95


Li0.33La0.5TiO3

1E−3

0.15
P4/mmm
123

82671
96


La0.5Li0.5TiO3
9.25E−4 
0.39
P4/mmm
123

92236
59


La0.52Li0.45TiO3
5.01E−4 

P4/mmm
123

50434
97


La0.565Li0.305TiO3
9.57E−4 

P4/mmm
123

92235
59


La0.58Li0.27TIO3
5.99E−4 

P4/mmm
123

82672
97


Li4PS4I
1.2E−4
0.37
P4/nmmZ
129

432169
101


Li(LaTiO4)

<1E−10

0.83
P4/nmmZ
129

91843
99


Li(NdTiO4)

<1E−10

0.87
P4/nmmZ
129

91844
99


La0.62Li0.14(Mg0.5W0.5)O3
1.2E−5
0.37
P4/nmm
129

151902
100


La0.63Li0.11(Mg0.5W0.5)O3
6.8E−6
0.38
P4/nmm
129

151901
100


La0.65Li0.05(Mg0.5W0.5)O3
1.8E−7
0.46
P4/nmm
129

151900
100


Li6ZnO4
9.40E−09
0.61
P42/nmc
137

62137
64


Li10SnP2S12
3.98E−3 
0.305
P42/nmc
137

255750
108


Li10SnP2S12

7E−3

0.27
P42/nmc C
137

193755
107


Li10GePS12
1.21E−2 

P42/nmc
137

188887
104


Li10GeP2S12
1.20E−02
0.25
P42/nmc
137

255749
110


Li10GeP2S12
2.46E−2 
0.274
P42/nmc
137

241439
108


Li10.35Ge1.35P1.65S12
1.44E−2 
0.269
P42/nmc S
137

193947
104


Li10.35Si1.35P1.65S12
6.5E−3

P42/nmcS
137

252037
109


Li9.81Sn0.81P2.19S12
5.5E−3

P42/nmc
137

252040
109


Li10(Ge0.776Sn0.224)P2S12
1.41E−2 
0.276
P42/nmc
137

255748
108


Li10.2(Sn0.2Si0.8)1.2P1.8S12
7.82E−3 

P42/nmcS
137

5667
111


Li10.2(Sn0.2Si0.8)1.2P1.8S12
2.69E−3 

P42/nmcS
137

257948
111


Li10.5(Sn0.2Si0.8)1.5P1.5S12
8.79E−3 

P42/nmcS
137

5668
111


LiLaNb2O7
 <1E−8

I4/mmm
139

72566
114


Li4Sr3Nb6O20

<1E−10


I4/mmm
139

87824
115


Li4Sr3.056Nb6O20

<1E−10

0.74
I4/mmm
139

109168
115


Li4Sr3Nb5.77Fe0.23O19.77

<1E−10


I4/mmm
139

87823
115


Li3BN2
8.70E−08
0.55
I41/amd
141
β-Li3BN2
155126
93


LiScO2

<1E−10

1.047
I41/amd
141

257819
117


LiScO2
1.00E−12
0.87
I41/amd
141

36124
33


Li4SrN2
2.30E−13
0.9
I41/amd
141

87413
116


LiAlO2
1.10E−12
0.97
I41/amd
141
r-LiAlO2
99517
33


Li0.9Sc0.9Zr0.1O2

<1E−10

0.912
I41/amd
141

257820
117


Li7La3Zr2O12
1.63E−6 
0.54
I41/acdZ
142
“tetraganol-LLZO”
183684
119


Li7La3Zr2O12
9.9E−6
0.43
I41/acdZ
142

238687
121


Li7La3HfO12
9.85E−7 
0.53
I41/acdZ
142
“tetragonal-LLHO”
174202
118


LiAlGeO4

<1E−10

0.97
R3H
146

257741
123


LiGaSiO4
3.00E−16
0.9
R3H
146

65125
122


LiGa0.5Al0.5GeO4

<1E−10

1.06
R3H
146

257740
123


LiGaGeO4

<1E−10

1.12
R3
148

257739
123


LiNaSO4
8.80E−10

P31c
159

14364
125


Li4P2S6
2.38E−07
0.29
P31m
162

242170
127


Li2.667Mg0.667P2S6
4.00E−06
0.46
P31m
162

95607
126


Li3.333Mg0.333P2S6
8.20E−8 
0.517
P31m
162

95606
126


Li3ErCl6
3.3E−4
0.41
P3m1
164

50151
129


Li5NCl2
1.20E−06
0.5
R3m
166

84763
131


LiGe2(PO4)3
3.33E−7 

R3cH
167

263767
2


LiGe2(PO4)3
4.83E−9 
0.654
R3cH
167

69763
133


LiZr2(PO4)3
2.96E−10

R3cH
167

201935
2


LiTi2(PO4)3
7.61E−6 
0.38
R3cH
167

95979
132


Li(Ti0.4Sn1.6)(PO4)3
3.15E−6 

R3cH
167

183677
135


Li(Ti0.6Sn1.4)(PO4)3
9.42E−6 

R3cH
167

183676
135


Li(Ti1.4Sn0.6)(PO4)3
2.28E−5 
0.32
R3cH
167

183672
135


Li1.3Al0.3Ti1.7(PO4)3

7E−4


R3cH
167

257190
139


Li1.3(Al0.3Ti1.7)(PO4)3
8.02E−7 

R3cH
167

253240
138


Li1.2Al0.2Ge1.8(PO4)3
4.83E−5 
0.387
R3cH
167

263760
133


Li1.3(Al0.23Y0.07Ti1.7)(PO4)3
3.84E−8 

R3cH
167

253243
138


Li1.3(Al0.23Sc0.07Ti1.7)(PO4)3
1.94E−7 

R3cH
167

253242
138


Li1.3(Al0.23Ga0.07Ti1.7)(PO4)3
4.46E−6 

R3cH
167

253241
138


LiIO3
1.90E−07

P63
173

35473
147


Li9Mg3(PO4)4F3

<1E−10

0.835
P63
173

426103
148


LiEu9Si6O26

<1E−10


P63/m
176

291220
150


LiLa9Si6O26

<1E−10


P63/m
176

291218
150


Li0.284Sm4.512Si3O12.91

<1E−10


P63/m
176

83279
150


Pb6.12Ca1.9Li1.96(PO4)6

<1E−10

1.05
P63/m
176

59615
149


Li3(NH2)2I

1E−5

0.58
P63mc
186

167528
152


Ba3LiTa5ZrSi4O26

<1E−10

0.79
P62m
189

239277
153


Li3N
1.2E−3
0.25
P6/mmm
191

26540
154


Li3N
3.00E−04
0.26
P6/mmm
191

156894
155


Fe2Na2K(Li3Si12O30)

<1E−10

1.22
P6/mcc
192

235750
156


Li3P
7.03E−4 
0.18
P63/mmc
194

642223
157


Li5La3Nb2O12

8E−6

0.43
I213
199

54865
159


(K0.1Li0.9)(SbO3)
1.36E−8 

Pn3Z
201

200984
160


Li8SiP4
4.5E−5
0.404
Pa3
205

235186
161


Li8GeP4
1.8E−5
0.435
Pa3
205
α-Li8GeP4
235184
161


Li3AlN2
5.00E−08
0.45
Ia3
206

257464
162


Li2ZnGe3O8

<1E−10

2.14
P4332
212

86169
163


Li2MgTi3O8

<1E−10

0.71
P4332
212

86165
163


Li2CoTi3O8

<1E−10

1.33
P4332
212

86166
163


(Li0.55Mg0.45)(Li0.445Mg0.055)Ti1.504
1.53E−11
0.786
P4332
212

168145
164


(Li0.61Mg0.39)(Li0.46Mg0.005Ti0.035)Ti1.504
6.56E−10
0.685
P4332
212

168144
164


Li2VCl4
6.95E−6 

F43m
216

74959
166


Li5NI2
4.00E−6 

F43m
216

16800
165


Li6PO5Cl
5.54E−10
0.66
F43m
216

421479
173


LiCe(BH4)3Cl
1.03E−4 

I43m
217

185218
178


Li7PN4
1.60E−07
0.4
P43n
218

69017
95


Li4B7O12Cl
2.4E−5

F43c
219

1125
179


Li9NS3
8.30E−07
0.52
Pm3m
221

240749
185


Li3OBr
1.10E−06
0.74
Pm3m
221

67265
194, 195


Li2(OH)Br
1.20E−6 
0.75
Pm3m
221

200874
184


(La0.55Li0.45)(Ti0.9Al0.1)O3
1.51E−3 

Pm3m
221

254045
186


(La0.6Li0.4)(Ti0.8Al0.2)O3
5.68E−4 

Pm3m
221

254046
186


(La0.65Li0.35)(Ti0.7Al0.3)O3
1.61E−4 

Pm3m
221

254047
186


(La0.402Li0.368Sr0.230)(TiO3)
2.87E−5 
0.36
Pm3m
221

190827
183


(La0.46Li0.429Sr0.111)(TiO3)
1.97E−4 
0.33
Pm3m
221

190826
183


(La0.49Li0.461Sr0.049)(TiO3)
7.09E−4 
0.33
Pm3m
221

190825
183


(Li0.16Sr0.69)(Ga0.25Ta0.75)O3
3.69E−6 
0.359
Pm3m
221

291520
187


Li0.31La0.63((Ti0.9Co0.1)O3
2.60E−4 

Pm3m
221

151533
182


LiI

1E−7


Fm3m
225

414244
197


Li7.2N1.6Cl2.4
8.4E−7
0.49
Fm3m
225

49646
131


Li0.19La0.67(Ti0.9Co0.1)O3
1.08E−4 

Fm3m
225

151535
182


LiCdCl4
5.80E−07
0.44
Fd3m
227

74958
199


Li2MgCl4
6.24E−7 

Fd3m
227

74957
166


Li2MnCl4
4.79E−6 

Fd3m
227

69678
166


Li(Li0.34Ti1.66)O4
6.03E−8 
0.506
Fd3m
227

168137
164


Li1.9Mn0.9Ga0.1Cl4
2.37E−7 

Fd3m
227

50305
198


(Li0.74Mg0.26)(Li0.40Mg0.04Ti1.56)O4
1.51E−9 
0.639
Fd3m
227

168142
164


(Li0.826Mg0.174)(Li0.374Mg0.026Ti1.60)O4
4.24E−9 
0.615
Fd3m
227

168141
164


LiSrTa2O6F

<1E−10

0.604
Fd3m
227

236010
200









Section IV. Wσ Optimization

Ward's minimum variance method applied to the conductivity labels (Wσ) is used to assess the utility of each descriptor-simplification combination. The Wσ is calculated after agglomerative clustering, for each clustering set:







W
σ

=






k
=
1





n
C









i


C
k






[



log

(

σ
RT

)

i

-



log


(

σ
RT

)


_

k


]

2









    • where nc is the number of clusters in a set, Ck is cluster k, and where log(σRT)k denotes the mean for all labels in cluster k. Lower Wσ values indicate that the descriptor-simplification combination results in clustering where structures with similar conductivity are grouped together. Whereas a large Wσ indicates that the clusters have little correlation to the conductivity labels.





A frozen-state strategy is employed to prevent any label from dropping out of the Wσ calculation. The frozen-state strategy operates by calculating the partial variance (PV) for each label at each clustering depth:







PV

x
,

C
k



=


[



log

(

σ
RT

)

x

-



log


(

σ
RT

)


_

k


]

2







    • where PVx,Ck is the partial variance for label x, when label x is assigned to cluster k. The PV for each label is saved before summing all the partial variances to yield the Wσ. At each subsequent clustering depth, all new clusters are checked to determine whether any cluster contains a single label. If a label is the only label in a cluster, then that label's partial variance is frozen: its PVx,Ck becomes equal to the saved state from the previous cluster depth:








PVx,Cj=PVx,Ck

    • where Cj denotes the cluster with only one label and Ck denotes the cluster that label x previously resided in. Without the frozen state strategy, poor models will reach desirable DA values at sufficient depths of clustering. The artificial depression of the Wσ value occurs because clusters that contain a single label evaluate to 0 (the label mean and cluster mean are the same). Whereas the frozen state strategy effectively “remembers” how well (or poorly) the label was clustered before it drops out.


Hyperparametertuning was employed for some of the descriptors. At least one Wσ representation exists for each unique combination of structure simplification and descriptor. However, some of the descriptors can be altered by tuning associated hyperparameters, resulting in more Wσ representations. The descriptors with hyperparameter tuning are the global instability index, radial distribution function, smooth overlap of atomic positions (SOAP), and mXRD. A grid search was done over the hyperparameters, for each descriptor, with parameters shown in Table 3.












TABLE 3






Hyper-

Values attempted in


Descriptor
parameter
Description
grid search







Global
r_cut
The distance, in angstroms, to search
[1.0, 1.1, . . . , 5.9, 6.0]


instability

for neighbors when calculating bond



index

valences.



Radial
cutoff
The distance, in angstroms, over which
[1, 2, . . . , 29, 30]


distribution

the radial distribution function should



function

be calculated.




bin_size
The radial distance, in angstroms, for
[0.01, 0.02, . . . , 0.09,




each bin.
0.1, 0.2, . . . , 0.9, 1.0]


Smooth
rcut
The radial cutoff for the local region in
[1, 2, . . . , 29, 30]


overlap of

angstroms.



atomic
nmax
The number of radial basis functions
[2, 3, . . . , 8, 9]


positions

used.



(SOAP)
lmax
The maximum degree of spherical
[1, 2, . . . , 8, 9]




harmonics used.




average
The averaging mode.
[‘outer’, ‘inner’]


mXRD
pattern_length
The number of 2θ values that will be
[101, 201, . . . , 901,




calculated between 0° and 90°.
1001]









Ultimately, the SOAP-CAN descriptor-simplification outperforms all other descriptor-simplifications when the averaging hyperparameter is set to ‘outer’. Setting the ‘outer’ hyperparameter results in averaging over the power spectrum of different sites. Whereas the ‘inner’ setting averages over the sites first, before summing up the magnetic quantum numbers. The other three hyperparameters (rcut, nmax, and Imax) are less consequential, with most combinations tested outperforming all other non-SOAP descriptors. To illustrate the point, three different SOAP-CAN outcomes are depicted in FIG. 4, plotted against the best-performing outcomes from density-CAN, mXRD-A40, orbital field matrix, and structure heterogeneity-A40. The three SOAP-CAN outcomes are those with the lowest Wσ mean for the depth of clustering ranges: 2-100, 101-200, and 201-300. The respective hyperparameters for the three SOAP-CAN descriptors are [rcut=2, nmax=4, Imax=2], [rcut=4, nmax=2, Imax=2], and [rcut=3, nmax=5, Imax=3].


Section V. WEa Optimization

Each clustering outcome is also assessed by labeling with approximate activation energies for ion hopping. The activation energies are calculated using a bond valence site energy (BVSE) method developed by Adams and Rao331,332. The strategy approximates the Ea as the sum of an attractive Morse-type potential term and a repulsive Coulombic interaction term. The Morse-type potential term represents mobile ion interactions with lattice anions. While the Coulombic interaction term represents mobile ion interactions with lattice cations. Relative to DFT-based methods, the BVSE method is a computationally lean approach that can be used to readily assess thousands of structures. However, the BVSE method tends to overestimate activation energies because it (1) does not allow for structural relaxation as the mobile ion moves and (2) does not consider repulsive interactions between mobile ions331,332. The BVSE method has been implemented by He et al. and is available for use through their python API333. Using the BVSE method, we label 6845 structures with activation energies (6845 is the number of structures successfully solved given a computing time cutoff of 20-minutes for each structure). Ward's minimum variance method applied to the activation energy labels (WEa) is calculated in a similar manner to the Wσ:







W

E

a


=




k
=
I


n
c






i


C
k





[



(

E


a
Reject


B

V

S

E


)

i

-


(


E


a
Reject


B

V

S

E


¯

)

k


]

2









    • where nc is the number of clusters in a set, Ck is cluster k, and where (Ea,BVSE)k denotes the mean for all labels in cluster k. Each descriptor's WEa results are shown in FIG. 5 for the first 50 clustering sets. For simplicity, only the best-performing simplification-descriptor combination is shown for each descriptor.





For Ea labels, all descriptor-simplification pairings result in better semi-supervised ML performance than randomized clustering. The SOAP descriptor performs well relative to most, but five other descriptors outperform it: CAVD, orbital field matrix-CAN, density, mXRD-CAMN, and the packing efficiency descriptors. The favorable performance of CAVD is anticipated because the BVSE calculation directly uses the CAVD descriptor as a parameter. The favorable performance of the density and packing efficiency descriptors may be explained by their similarity to CAVD: the Voronoi decomposition to encode void space is dependent on the density and packing efficiency of the structure. Similarly, the orbital field matrix descriptor relies on calculation of Voronoi polyhedra to understand the coordination environment for each atom. A mXRD-CAMN descriptor-simplification performs well on the BVSE label set; however, the mXRD representation used by Toyota (mXRD—A40) drops from to 14th best on the Ea label set. The result may suggest that the mXRD—A40 pairing does not generalize well. When comparing the top 10 descriptors for each label set, 6 descriptors are common to both approaches: SOAP, density, mXRD, structure heterogeneity, orbital field matrix, and bond fraction.


Section VI. Second-Order SOAP Descriptor

Semi-supervised ML models may be further improved by merging descriptors and clustering on the union representation. Second order descriptor unions are examined by combining the best-performing descriptors with all other descriptors. The two input descriptor vectors (dA and dB) were combined with a mixing ratio (α) to yield the union representation (dAB):







d
AB

=


d
A



α


d
B







The ideal mixing ratio is unknown for each union and we find that incremental changes to the mixing ratio do not result in continuous changes to the Wσ. Thus, outcomes are manually screened for mixing ratios from 10−6 to 106 (see supplemental information—section VI). Most descriptor unions result in no improvement to the Wσ, across all mixing ratios. However, the Wσ for SOAP when mixing with the non-simplified sine Coulomb matrix descriptor (for α=2·10−6-4·10−6) is lowered by 2-3%, with the exact percentage depending on the depth of clustering.


Almost no descriptor combinations are successful in reducing the Wσ. Excluding combinations that include the SOAP-CAN descriptor, no combinations outperform the 1st order SOAP-CAN representation. For combinations that include SOAP-CAN, some mixing ratios with the sine Coulomb matrix and the Ewald energy descriptors resulted in modest improvements in the Wσ. The best improvement is found when mixing SOAP-CAN with the sine Coulomb descriptor for α=2·10−6, 3·10−6, and 4·10−6. All three combinations result in the same improved curve, plotted below in FIG. 6.


The agglomerative dendrogram in the main text shows that the 2nd-order SOAP-CAN descriptor facilitates aggregation of high-conductivity labels. In the simplified 9-cluster representation, most of the high-conductivity (σRT>10−5 S cm−1) labels are contained within the 2nd “mega cluster”. The 2nd mega cluster accounts for only 15% of the input structure. By clustering further, increasingly dense representations are found. For example, at the 241st clustering depth, the 21 high-conductivity labels have been sorted into five subclusters (FIG. 7). Taken together, the five subclusters account for 52.5% of the high conductivity labels while containing only 2.2% of the input structures. We note that the control (random clustering) exhibits a Ward Variance 214% greater than the 2nd-order SOAP-CAN model at the 241st clustering depth. The difference in Ward Variance illustrates that the 2nd-order SOAP-CAN model is much better at identifying high-conductivity structures, relative to random selection.


Section VII. Climbing Image—Nudged Elastic Band

Migration barriers for Li ion hopping are evaluated with the Climbing Image—Nudged Elastic Band (CI-NEB) method as implemented in the QuantumESPRESSO PWheb software package334-337. Density-functional theory (DFT) calculations are performed using the Perdew-Burke-Emzerfof (PBE) generalized gradient approximation functional and projector-augmented wave (PAW) sets338,339. Convergence testing for the kinetic-energy cutoff of the plane-wave basis and the k-point sampling is performed for each structure to ensure an accuracy of 1 meV per atom. The lattice parameters and atomic positions of the as-retrieved structure are optimized. Supercells are created for each structure that are a minimum of 10 Å in each lattice direction to minimize interactions between periodic images of the mobile ion. To study the migration barrier in the dilute limit, a single Li vacancy is created in the boundary endpoint structures of each studied pathway. A uniform background charge is used to balance excess charge. Each boundary configuration is relaxed until the force on each atom is less than 3×10−4 eV/Å. Images are created by linearly interpolating framework atomic positions between the initial and final boundary configurations. The initial pathway for the mobile ion is generated from the BVSE output minimum energy pathway to promote faster convergence of the NEB calculation. An NEB force convergence threshold of 0.05 eV/Å is used. The calculation is first converged using the default NEB algorithm and then restarted with the Cl scheme to allow for the maximum energy of the pathway to be determined.


Section VIII. a-Li2.95B0.95Si0.05S3 Impedance


Electrochemical impedance data for the amorphized Si-substituted Li3BS3 (a-Li2.95B0.95Si0.05S3) suggests the presence of two RC features. The VSP-300 potentiostat can supply a maximum sinusoidal frequency of 3 MHz, sufficient to resolve a partial semicircle in the Nyquist impedance plot (FIG. 17). Attempted fits to the partial semicircle reveal that it would not intersect the origin at higher frequencies, suggesting the presence of an additional RC feature. It is plausible that two RC features exist, describing the bulk and grain-boundary transport of Li+. A more conservative estimate of the conductivity (σtot) can be derived by extrapolating a linear of the Warburg tail to the x intercept. While the more conservative estimate is used in the main manuscript, we note here that the actual bulk conductivity is likely higher.


Section IX. Full List of Promising Structures

Excluding the labeled dataset, there are 50 compounds that are predicted to be stable and to exhibit a Li-hopping activation energy below 600 meV. Ten of the predicted compounds have already been experimentally examined and are hereafter excluded: Li2O, Li2S, LiCl, LiI, LiBr, Li6AsS5I, Li4Ti5O12, Li2InCl3, LiInI4, Li6NiCl8. Another nine are excluded because they are used in cathodes, anodes, or glassy electrolyte formulations: LiFeCl4, Li2CO3, Li2PtO3, Li2NiGe3O8, Li2CrO4, Li2SeO4, LiAlS, Li2Mn3NiO8, LiInSe2. The remaining 31 promising structures are discussed below and plotted by ascending activation energy in FIG. 18.


a. Stable Compounds


Each structure is examined in order of ascending activation energy in FIGS. 20A-20AE.


b. Quasi-Stable Compounds (Ehull Below 15 meV)


Excluding the labeled dataset, there are 34 compounds that are predicted to be within 15 meV of the convex hull (Ehull) and to exhibit a Li-hopping activation energy below 600 meV. Ten of the predicted compounds have already been experimentally examined and are hereafter excluded: Li3SbS4, Li6AsS5I, Li6PS5I, Li3ScCl6, Li2MnBr4, Li3N, LiTi2P3O12, Li10SiP2S12, Li2ZnCl4, Li3InO3. Another three are currently being excluded because they are used in cathodes: Li3NbS4, Li3CuS2, Li6VCl8. The remaining 21 promising structures are discussed below and plotted by ascending activation energy in FIG. 19.


See FIGS. 22A-22U.


c. Unknown-Stability Compounds (Sans Materials Project Entry)


There are 18 predictions that have no associated Material's Project entry. These structures lack stability data. Seven of the predicted compounds have already been experimentally examined and are hereafter excluded: Li2O, Li2S, Li7Y7Zr9S32, Li4SnSe4O13, Li2MnBr4, Li5AlS4, Li3Fe2P3O12. Another five are currently being excluded because they are used in cathodes: Li2Mn3NiO8, Li2Mn3CoO8, Li5Mn16O32, Li2Mn15AlO32, Li3V2P3O12. The remaining 6 promising structures are discussed below and plotted in order of ascending activation energy in FIG. 21.


See FIGS. 24A-24F.


Example 2: Experimental Validation of the Semi-Supervised Learning Model: Li3BS3

From the ten most promising candidates, Li3BS3 was selected for synthesis and characterization. Li3BS3 stands out because it has been explored experimentally and computationally before. Experimentally, Vinatier et al. previously determined that Li3BS3 has a total DC conductivity of 2.5·10−7 S cm−1 with an activation energy of 700 meV62. The DC measurement was not included in our label set because DC measurements cannot differentiate between ionic and electronic conductivity, so they were categorically discounted from the label set (see supplemental information I for more details on label selection). Although the conductivity and activation energy reported by Vinatier et al. are underwhelming, there are promising theoretical reports. Density functional theory molecular dynamics (DFT-MD) simulations from Sendek et al.63 suggest that Li3BS3 should have a room temperature conductivity between 3.1·10−6 and 9.7·10−3 S cm−1. Our NEB-calculated activation energy for Li3BS3 is 260 meV, corroborating a previous NEB result from Bianchini et al.64. Additionally, Li3BS3 is practically attractive because: (1) Li3BS3 contains no redox-active metals, (2) band edge calculations have suggested stability against metallic Li65, (3) DFT-MD calculations have suggested a kinetic barrier for decomposition against metallic Li63, and (4) the synthesis is reported66. It is simpler to avoid redox active metals in the SSE as they may be reduced and oxidized at electrode interfaces. However, we note that Li0.5La0.5TiO3 is a widely studied SSE that contains redox active Ti67,68 so the compounds we report here that contain Mn, V, and Cu should not be categorically discounted. It is important to note that while studying Li3BS3 as a candidate Li-ion conductor for model validation, Kimura et al. reported that a so-called “Li3BS3 glass” exhibits an ionic conductivity of 3.6·10−4 S/cm−1 at 25° C.69.


Li3BS3 is prepared using solid-state synthesis from Li2S, B, and S precursors. The diffraction and quantitative Rietveld refinement are shown in FIG. 26A, suggesting a phase pure material. Electrochemical impedance spectroscopy (EIS) is employed at various temperatures and the resultant conductivity is plotted according to the Arrhenius-like relationship (FIG. 26B):






σ
=



σ
0

T



e

-


E
a



k
B


T











    • where T is the temperature, kB is the Boltzmann's constant, σ0 is the conductivity prefactor and Ea is the activation energy for ionic conductivity. The room temperature ionic conductivity (σ25° C.) is 7.16(±0.21)·10−7 S cm−1 and the activation energy is 400±47 meV. The low conductivity and high activation energy may be due to lack of charge-carrying defects in the Li3BS3 lattice70,71. Although a sufficient carrier concentration is necessary for facile ionic conduction in most materials, the descriptors in the semi-supervised model do not explicitly encode for charge-carrying defects. In the label set, conductivity is likely influenced by the defect concentration but defects are typically not reported. Still, the semi-supervised model may infer a structure's capacity to support conductive defects via correlation with the descriptors.


      Li3BS3 Synthesis:

    • Li3BS3 is synthesized by reaction of Li2S (Alfa Aesar, 99.9%), S8 (Acros Organics, >99.5%), and elemental B (SkySpring Nanomaterials, Inc. 99.99%). The reactants are first mixed stoichiometrically (300 rpm for 1 h) using a planetary ball mill (MSE PMV1-0.4L) in 50 mL ZrO2 jars with ZrO2 balls. Two grams of reactants are always combined with 2 large balls (10 mm diameter), 34 medium balls (5 mm diameter), and 8 grams of small balls (3 mm diameter). Loading of ball mill jars occurs in an Ar-filled glovebox (Mbraun) and the jars are sealed before removal. After the 1 h of milling, the precursor mixture is pumped back into the glovebox and 330-340 mg of the powder is loaded into carbon coated vitreous silica ampoules (10 mm ID×12 mm OD). The ampoules are evacuated (<10 mtorr) prior to sealing. Pure Li3BS3 is obtained via a four-step heating protocol in a Lindberg/Blue furnace: (1) ramp to 500° C. at 5° C. min−1, (2) hold at 500° C. for 12 h, (3) ramp to 800° C. at 5° C. min−1, and (4) hold at 800° C. for 6 h. The hot melt is then quenched from 800° C. into room temperature water. Recovered ingots are typically covered in a C shell. The C shell is either sanded off or the ingot is ground into smaller pieces and the C is manually removed.





Example 3: Defect Engineering of Lithium Solid State Electrolyte Material

To test the hypothesis, we use two strategies to engineer vacancies: aliovalent substitution and amorphization via extended ball milling. Aliovalent substitution has been shown to improve conductivity in Li-argyrodites, -sulfides, and -garnets by introducing vacancies70,71. Similarly, amorphization can introduce defects and vacancies that enable Li+ hopping69,71-73.


Aliovalent substitution of Li3BS3 is achieved by substituting Si for B. The XRD patterns and quantitative Rietveld refinements of Li2.975B0.975Si0.025S3 and Li2.95B0.95Si0.05S3 are shown in FIG. 26A. The lattice parameters from the refinements are plotted vs. stoichiometry with the Li3BS3 end-member in FIG. 26E. The linear trend shows that the materials obey Vegard's law and confirms that Si incorporates into the lattice as a solid-solution. Substitution to 7.5% Si continues the Vegard trend but unidentified impurities are present. With 5% Si substitution, the ionic conductivity is improved to 1.82(±0.21)·10−5 S cm−1 and the activation energy is decreased to 333±47 meV (FIG. 26D). All error bars reported for electrochemical measurements represent the standard deviation of three replicate cells. Kimura et al. demonstrated that extended ball milling of Li3BS3 causes amorphization and improves ionic conductivity, likely due to introduction of defects62,69. Extended ball milling is attempted on the 5%-substituted Li3BS3 to assess whether both defect engineering strategies are compatible. Planetary ball milling of the 5%-substituted Li3BS3 for 100 h achieves amorphization (a-Li2.95B0.95Si0.05S3), as verified by the lack of distinct peaks in the XRD pattern shown in FIG. 26A.


We find that amorphization significantly improves Li-ion conductivity. EIS measurements of a-Li2.95B0.95Si0.05S3 are shown in FIG. 26E. A high-frequency semicircle is partially resolved which may represent grain boundary or bulk ionic transport. A Warburg tail is evident at lower frequencies, indicating that electronic charge transfer is blocked. Although multiple high-frequency semicircles may exist (see Example 1B: section VII), a conservative estimate of the ionic conductivity is determined by linear fit of the Warburg tail and extrapolation to the x-intercept. The σ25° C. of a-Li2.95B0.95Si0.05S3 is 1.07(±0.08)·10−3 S cm−1 with an activation energy of 345±2 meV (FIG. 26D). The electronic conductivity as measured by DC polarization is less than 4·10−10 S cm−1.


To determine if the local structure in the crystalline material is maintained after amorphization, we turn to 7Li and 11B NMR. If the local structure is not altered by amorphization, then it is likely that the ion diffusion pathways are similar. Comparing the ion diffusion pathways is important because the machine learning points to the structure of the crystalline Li3BS3 phase. The 7Li NMR spectra of Li3BS3, Li2.95B0.95Si0.5S3, and a-Li2.95B0.95Si0.05S3 are shown in FIG. 26D. All materials show a single resonance at the same chemical shift, suggesting the Li local environment remains unchanged. The resonance width narrows significantly in the amorphous material due to the higher mobility. The 11B NMR measurements are shown in FIG. 26G. The 11B NMR for Li3BS3 and Li2.95B0.95Si0.05S3 show a single, quadrupolar environment that can be assigned to the [BS3]3- moieties69,74. The signal from the a-Li2.95B0.95Si0.05S3 shows a similar signal to that of the crystalline phases but the shape changes, similarly to the previous measurement for amorphous Li3BS369. Li3BS3, Li2.95B0.95Si0.05S3, and a-Li2.95B0.95Si0.05S3 all exhibit a major peak at ˜60 ppm and a relatively minor peak ˜0 ppm. The major peak is assigned to trigonal planar [BS3]3- while the minor peak likely indicates a minor impurity with tetrahedrally coordinated B75-77. The change in shape of the 11B spectrum upon amorphization is likely due an averaging of the quadrupolar couplings due to the fast Li dynamics. Thus, Li3BS3 and a-Li2.95B0.95Si0.05S3 have similar local structures and we can attribute the faster Li dynamics to the introduction of charge-carrying defects.


Although investigation of interfacial stability is beyond the scope of the model, we note that the Si-substituted Li3BS3 is a promising candidate for future investigations into interfacial stability. Work by Park et al. demonstrated that the (010) facet for Li3BS3 has a conduction band minimum 0.5 eV above the Li/Li+ couple65. Since decomposition of Li3BS3 is likely to be mediated by electron injection from Li, their results suggest that thermodynamic stability can be engineered via orientation. From a kinetic perspective, high-temperature DFT-MD simulations show no mobility for B and S, suggesting large kinetic diffusion barriers63. Since decomposition of Li3BS3 would entail the diffusion of these species, the reaction may be sluggish or wholly precluded. Interfacial stability has been previously demonstrated for a glassy electrode in the Li—B—S—Si—O phase space78. The result may indicate that stability can be engineered into Si-substituted Li3BS3 by partial isovalent substitution of 0 for S. Finally, recently-synthesized Li—B—S—X (X=Cl, Br, I) quaternaries have exhibited promising conductivities79. With similar elemental composition, the Si-substituted Li3BS3 may be a good candidate for a multi-electrolyte architecture with the halide-containing quaternaries13.


In addition to our experimental model validation, another of the predicted materials, KLi6TaO6, was recently synthesized with aliovalent Sn-substitution by Suzuki et al80. With a reported ionic conductivity near 10−5 S cm−1, KLi6TaO6 is better than 70% of the SSEs in the semi-supervised labels. Further improvement may be possible via extended amorphization to introduce structural defects, as is observed for Li3BS3.


Substituted Li3BS3:


Aliovalent substitution is accomplished by adding elemental Si (Acros, 99+%) into the precursor mixture prior to the 1 h mix. Si-substitution stoichiometry assumed that each Si atom replaces one Li and B: Li3−xB1−xSixS3. Aside from the addition of Si, all steps are the same as for the synthesis of Li3BS3. Amorphization is accomplished via extended planetary ball milling in Ar of the 5% Si-substituted Li3BS3 (Li2.95B0.95Si0.05S3). Approximately 1 g of Li2.95B0.95Si0.05S3 is combined in a ZrO2 ball mill jar with 3 large balls (10 mm diameter), 51 medium balls (5 mm diameter), and 12 g of small balls (3 mm diameter). The powder is ground in a planetary ball mill (MSE PMV1-0.4L), under Ar atmosphere, for 100 h.


Material Characterization:

Li3BS3 materials are characterized using powder X-ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS). XRD patterns are attained on a Rigaku Smartlab by scanning from 10° to 70° 28 at 2 degrees per minute. The Smartlab employs a Cu-Kα source with a 20 kV accelerating voltage. For EIS measurements, 50-100 mg of powder is first hot-pressed (100° C., 5 min) into a ¼″ diameter pellet. The pellet faces are polished using diamond lapping powder (Allied High Tech Products Inc.) in sequentially finer grits: 60, 30, 6, 0.5, and 0.1 micron. Au contacts are sputtered (90 s at 40 mA) onto the polished surfaces using a 108 Auto Sputter Coater (Cressington). Pellets are then assembled into a Swagelok ¼″ cell with stainless steel current collectors. After applying pressure with a hand vise (˜100 MPa), EIS data is collected on a VSP-300 with a Biologic low-current channel. All EIS data is collected to an upper frequency of 3 MHz. The lower frequency is case dependent, with a frequency cutoff selected such that the Warburg polarization feature is visible. 7Li and 11B MAS MAS NMR spectra were acquired using a Bruker DSX-500 spectrometer with a 4 mm ZrO2 rotor. The operating frequencies for 7Li and 11B are 190.5 and 160.5 MHz, respectively. The 7Li and 11B spectra were referenced to a 1 M LiCl aq. solution and BF3-OEt2, respectively. A spinning speed of 12 kHz was used, and the spectra were gathered after applying a single 0.5 μs to 15° pulse for both 7Li and 11B.


Further Discussion for Examples 1-3

Identification of functional materials is critical for improving technologies. Here, we show the utility of using semi-supervised learning as a method for guiding next-generation materials discovery in emerging fields. The method's focus on identifying the relationships between descriptors, prior to labeling, enables understanding of compositional spaces where most inputs are unlabeled. We demonstrate how semi-supervised learning can be used to identify descriptors correlated with superionic conductivity in Li SSEs. By analyzing all Li-containing structures from the ICSD and MP database, we identify 212 materials that show promise as SSEs. All 212 structures exhibit a BVSE-predicted Ea below 0.6 eV.


The results illustrate why careful screening of descriptors is useful when identifying new materials. While chemical intuition can be useful for descriptor selection, chemical intuition is often biased to favor previously investigated compositional spaces. For material discovery in emerging fields, use of handpicked descriptors may miss complex phenomena that more generally describe the dataset. Descriptor screening reveals which material properties are correlated to a property of interest to help enhance chemical intuition. In the case of Li SSEs, spatial descriptors excel over compositional, bonding, and electronic descriptors: the Smooth Overlap of Atomic Positions (SOAP), modified X-ray diffraction (mXRD), and general density descriptors are within the top four models. For spatial descriptors, simplification of the input structure tends to improve clustering outcomes. Removing the mobile ions from the structure and simplifying the remaining atoms, i.e. the “CAN” simplification, is most effective. Thus, the placement of framework atoms, but not their precise identity, is most correlated with ionic conductivity. Specifying the mobile ion positions hurts the model performance, suggesting a low correlation of mobile ion positions with ionic conductivity.


Predictions from the semi-supervised method are promising starting points for experimental identification of new superionic conductors but defects must be considered. The proposed materials are diverse, with the top thirty including halides, sulfides, tellurides, nitrides, oxides, and oxyhalides (see Example 1B: section IX). As a structure that falls outside of the eight routinely studied SSE classes, we demonstrate experimental characterization of Li3BS3 to confirm the utility of the approach. However, pure Li3BS3 exhibits poor ionic conductivity. Defects must be introduced into the material to achieve a superionic conductivity above 10−3 S cm−1, a value that surpasses most reported SSEs. We note that the defects are introduced while maintaining the local structure of the crystalline material and thus the ionic conduction pathways are likely similar. The need to introduce defects highlights the paramount importance that defects play when measuring real materials. Many of the highest performing SSEs contain charge-carrying defects that are not explicitly encoded in their structure files. It is likely that some of the descriptors indirectly encode information about defects. By using experimental conductivity values as the evaluation metric, we may be prioritizing descriptors that encode information about a structures ability to support charge-carrying defects. Although Li3BS3 is a poor conductor, it is clearly able to support charge-carrying defects. The large conductivity difference between pristine Li3BS3 and a-Li2.95B0.95Si0.05S3 highlights the importance of these defects. To improve predictive models and enhance chemical intuition, descriptors that explicitly encode defects are needed.


Now developed, the semi-supervised learning approach can serve as a template for material discovery beyond Li SSEs. The code is thoroughly documented following pythonic coding standards and made freely available on Github. Although the present effort focuses on Li SSEs, the approach is applicable to any material discovery space where labels are sparse. Discovery of new Li cathodes could be accomplished by using Li diffusivity, cathode capacity, and metal redox couple voltages as labels. Discovery of divalent SSEs (e.g. Mg2+, Ca2+, Zn2+) could foreseeably be accomplished in a similar manner. The semi-supervised learning strategy may accelerate identification of fast ionic conductors for ion exchange membranes, solid oxide fuel cells, and various sensor applications.


Example 4: Optional Aspects with Respect to Substitution for B in Lithium Thioborate

In some aspects, the “first dopant” Q in FX1 (Li3−z[B+Q]1[S+G]3) optionally comprises one or more transition metal elements. On the other hand, in some aspects, the “first dopant” Q in FX1 is free of transitional metal elements due to the propensity of transition metal elements to participate in redox reactions occurring in a solid state battery. Selection of the first dopant element (the one or more dopant element corresponding to first dopant Q) is generally dependent on application-specific particular chemistry, redox reactions, voltages, and other conditions.


Example 5: Particularly Useful Aspects

In an aspect, a particularly useful material disclosed herein has a composition characterized by formula FX15A: Li3−xB1−xSxS3 (FX15A); wherein x is greater than 0 and less than or approximately equal to 0.05. For example, in an aspect, a furthermore particularly useful material disclosed herein has a composition characterized by formula FX15B: LiaBbSixSc (FX15B); wherein a is approximately 2.95, b is approximately 0.95, x is approximately 0.05, and c is approximately 3.0. For example, in an aspect, a yet furthermore particularly useful material disclosed herein has a composition characterized by formula FX15C: Li2.95B0.95Si0.05S3 (FX15C). It is found that the compositions of FX15A, FX15B, and FX15C may correspond to an optimum or near-optimum doped composition of lithium thioborate with respect to ionic conductivity, optionally with respect to other additional features, where the undoped composition and low-doped composition (e.g., x being less than 0.025) have lower ionic conductivity and higher dopant amounts (e.g., x being greater than or equal to 0.075) cause formation of unfavorable impurities and/or other unfavorable features (e.g., too much disruption of crystallographic structure with respect to that of Li3BS3). It is found that compositions of FX15A, FX15B, and FX15C have high ionic conductivity and low electronic conductivity, especially if the material is amorphized. For example, as also discussed in Examples 1A-3, whereas a room temperature (e.g., 25° C.) ionic conductivity of undoped Li3BS3 without substitution may be approximately 7.2·10−7 S/cm substitution/doping of the composition thereby making Li2.95B0.95Si0.05S3 (FX15C) may result in an increase of ionic conductivity (relative to that of the undoped Li3BS3) by a factor of approximately 25 such as to an ionic conductivity of approximately 1.82(±0.21)·10−5 S cm−1 at room temperature (e.g., 25° C.). Amorphization of the composition Li2.95B0.95Si0.05S3 (FX15C) may further increase the ionic conductivity (relative to that of the undoped Li3BS3) by a factor of at least 1375 such as to an ionic conductivity of approximately 1.07(±0.08)·10−3 S cm−1 at room temperature (e.g., 25° C.) or even about 3·10−3 S cm−1 according to some aspects. In contrast, the electronic conductivity of these doped compositions of FX15A, FX15B, and FX15C have low electronic conductivity, such as, for example, in aspects, less than or equal to about 4·10−10 S/cm as measured by DC polarization at room temperature (e.g., 25° C.).


Example 6: Superionic Conductor Li3BS3 Enabled by Aliovalent Cl and Si Substitution
Results and Discussion
Structural Characterization

Samples of substituted Li3BS3 are prepared from stoichiometric mixtures of Li2S, B, S, Si, and LiCl. Aliquots of a mixture are sealed under vacuum in a carbon-coated vitreous silica tube, before a two-step heating process at 500° C. then 800° C., followed by quenching in room-temperature water. The resultant pellet of material is separated from the surrounding dark grey shell, then ground into a powder.


Powder X-ray diffraction (PXRD) is used to verify the purity of the material. Diffraction patterns of Cl-substituted Li3BS3 shown in FIG. 27A reveal synthesis of crystalline Li3−xBS3−xClx up until a Cl content of x=0.2. For compositions with x=0.3 and x=0.4, a broadened and flattened diffraction pattern with crystalline LiCl impurity peaks is observed, indicative of the Li3BS3 phase becoming amorphous. This is consistent with the synthesized material changing from an opaque off-white color to a transparent red-pink.


Raman spectroscopy is used to confirm local structure within the material. As shown in FIG. 27B, spectra obtained from substituted Li3BS3 samples are compared with the Raman spectrum of Li3BS3 calculated using Density Functional Theory (DFT). A strong peak from symmetric [BS3] unit stretching is observed in both experimental and calculated spectra, with a notable lack of [BS4] impurity stretches shown to appear around 495 cm−1.1 The amorphous compositions x=0.3 and x=0.4 also show a broad low-wavenumber packet instead of 6 discrete stretches, as well as a redshifted and broadened [BS3] stretching peak. These spectral differences are consistent with the greater variance and net elongation of bond lengths typical in an amorphous material.


PXRD patterns of Li3BS3 co-substituted with Si and Cl, shown in FIG. 28, reveal phase-pure synthesis of Li2.9B0.95Si0.05S2.95Cl0.05 and Li2.85B0.95Si0.05S2.9Cl0.1. The presence of a slight background around 26° to 33° 2θ suggests the formation of some amorphous fraction of these samples. Compositions with less Li content yield a broad diffraction background indicative of an amorphous material. Similar to the Cl-substituted materials, these changes in diffraction patterns are consistent from the material appearing opaque and off-white to transparent and red-pink.


Electrochemical Impedance Spectroscopy

Electrochemical impedance spectroscopy (EIS) is used characterize the ionic conductivity of the prepared Li3−xBS3−xClx compounds at various temperatures. The measured conductivity follows an Arrhenius-like relationship:









σ
=



σ
0

T



e

-


E
a



κ
B


T









(
1
)









    • where σ is the conductivity, σ0 is the pre-exponential factor, T is the absolute temperature, Eσ is the activation energy, and a is the Boltzmann constant. FIG. 29A displays the plot of In σT versus 1000/T for the Li3−xBS3−xClx compounds. In this plot, the slope and y-intercept are proportional to the activation energy and pre-exponential factor, respectively, as described by equation (1). The room-temperature ionic conductivity increases significantly with increasing Cl content and Li vacancy concentration in Li3−xBS3−xClx, as shown in FIG. 29B. This trend does not align with the activation energy trend, suggesting that the observed increase in conductivity is more likely dominated by the increase in available charge-carrying defects, which are included in the pre-exponential factor in equation (1).





Substituting Si for B in Li3−yB1−ySiyS3 results in a significant increase in ionic conductivity due to the introduction of vacancy defects in the structure.2 To examine this defect engineering strategy, the ionic conductivity of co-substituted compounds Li3−yB1-ySiyS3−xClx was investigated. For the same designed Li concentration of x=0.1 in Li3−xBS3−xClx and x=y=0.05 in Li3x−yB1−ySiyS3−xClx, the co-substituted compound exhibited a significantly higher ionic conductivity of 1.5×10−4 S cm−1 compared to 7.4×10−6 S cm−1. This is the highest conductivity observed for a compound with the crystalline structure of Li3BS3. Additionally, the activation energy is reduced from 414 meV for Li2.9BS2.9Cl0.1 to 356 meV for Li2.9B0.95Si0.05S2.95Cl0.05, suggesting that the co-substitution may also provide a more favorable pathway for ion migration. The conductivity further increased for compositions resulting in an amorphous structure but remained unchanged for further reductions in Li concentration after the amorphous transition, as shown in FIG. 30.


Materials and Methods
Material Preparation: Synthesis

All materials and samples are prepared in an Ar-filled glovebox with O2 and H2O levels under 1 ppm. To prepare samples of substituted Li3BS3, a precursor mix is made with stoichiometric amounts of Li2S (Thermo Scientific, 99.9%), B (SkySpring Nanomaterials, 99.99%), S (Acros Organics, 99.5%), Si (Acros Organics, 99%), and LiCl (Sigma-Aldrich, 99%) measured to a total sum of 2 g. These powders are added to a 50 mL zirconia ball mill jar containing 2 large (10 mm diameter), 34 medium (5 mm diameter), and 8 g of small (3 mm diameter) zirconia spheres. The jar then is mixed in a planetary ball mill (MSE PMV1-0.4L) at 300 rotations per minute for two intervals (each containing 15 minutes of counter clockwise rotation followed by 15 minutes of clockwise rotation), with an intermediate 15-minute rest. For each synthesis, 333 mg of precursor mix is loaded into a carbon-coated vitreous silica tube inside the glovebox and sealed under vacuum with an oxymethane torch. The resulting ampule is heated to 500° C. at 5° C. min−1, dwelled for 12 hours, heated to 500° C. at 5° C. min−1, dwelled for 6 hours, then subsequently quenched into room-temperature water. The ampule is opened in the glovebox, yielding either an opaque off-white pellet (for predominantly crystalline samples) or a transparent red-pink pellet (for predominantly amorphous samples), covered with a dark grey shell. The pellets are crushed, and the internal sample is separated from the dark gray shell. The separated sample is then ground for 5 minutes using an alumina mortar and pestle.


Material Characterization: X-Ray Powder Diffraction

PXRD patterns of powder samples are obtained using a Rigaku Smartlab Diffractometer with a Cu Kα radiation source. Scans are conducted from 10° to 70° 26, with a 0.03° step size and 5° min−1 scan rate. Powder samples are loaded into Rigaku airfree sample holders in an Ar-filled glovebox to minimize air exposure. Rietveld refinement was performed using GSAS-II software.3


Material Characterization: Raman Spectroscopy

Raman spectroscopy is conducted using an XplorRA PLUS Raman Spectrometer (Horiba Instruments). Samples are prepared by placing approximately 2 mg of sample on a glass microscope slide in an Ar glovebox atmosphere. The sample is taped down with Kapton tape to preserve an airfree sample environment for spectroscopy measurements. A 532 nm wavelength laser is used at 10% power, with a 50 μm slit and a 2400 grooves mm−1 grating, to obtain a spectrum averaged over 100 1 s acquisitions. The Raman spectrum for Li3BS3 was calculated using the Quantum ESPRESSO software package.4,5 The local density approximation (LDA) exchange-correlation functional was used with norm-conserving pseudopotentials. Converged kinetic energy and charge density cutoffs of 120 Ry and 480 Ry, respectively, were employed, along with a Monkhorst-Pack grid of 3×3×3 k-points for Brillouin zone sampling. Atomic positions and lattice parameters were optimized using the Broyden-Fletcher-Goldfarb-Shanno (BFGS) algorithm, with energy and force convergence thresholds of 1×10−6 a.u. and 1×10−5 a.u., respectively. Phonon frequencies were calculated using density functional perturbation theory (DFPT). Raman tensors were then obtained using the matdyn.x and dynmat.x utilities provided by Quantum ESPRESSO. The phonon modes were computed at the Gamma point, and the resulting Raman active modes and their intensities were extracted and plotted to generate the Raman spectrum.


Material Characterization: Electrochemical Impedance Spectroscopy

EIS is conducted using a BioLogic VMP potentiostat. To assemble samples for measurement, approximately 60 mg of active material is loaded into a hot press (6 mm diameter) and pressed under 2 tons of pressure at 100° C. for 5 minutes. Each circular face of the pellet is sputtered using a gold target for 60 seconds under 40 mA sputtering current. The pellet is loaded into a Teflon Swagelok cell to connect to the VSP potentiostat, with the sputtered faces in contact with stainless steel plungers. The Swagelok is held under hand-tight pressure in a vice, with temperature being controlled by an oven during measurements. EIS measurements is performed with an applied sinus amplitude of 25 mV and an upper frequency limit of 3 MHz. The lower frequency limit is adjusted until a blocking feature is observed.


REFERENCES ASSOCIATED WITH EXAMPLE 6



  • (1) Menetrier, M.; Hojjaji, A.; Levasseur, A.; Couzi, M.; Rao, K. Structural hypotheses and Raman spectroscopy investigations of glasses belonging to the B˜ 2S˜ 3-Li˜ 2S—LiI system. Phys. Chem. Glasses 1992, 33, 222-227.

  • (2) Laskowski, F. A.; McHaffie, D. B.; See, K. A. Identification of potential solid-state Li-ion conductors with semi-supervised learning. Energy & Environmental Science 2023, 16, 1264-1276.

  • (3) Toby, B. H.; Von Dreele, R. B. GSAS-II: the genesis of a modem open-source all purpose crystallography software package. Journal of Applied Crystallography 2013, 46, 544-549.

  • (4) Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. Journal of Physics: Condensed Matter 2009, 21, 395502.

  • (5) Giannozzi, P. et al. Advanced capabilities for materials modelling with QUANTUM ESPRESSO. Journal of Physics: Condensed Matter 2017, 29, 465901.



Example 7

The Li-ion all-solid-state battery (ASSB) is a promising template for next-generation energy storage. To commercialize Li-ion ASSBs, a suitable solid-state electrolyte is required. A solid-state electrolyte must exhibit a wide electrochemical stability window and ionic conductivity near that of traditional liquid electrolytes. Three compounds with near-liquid-electrolyte conductivity (˜10−2 S cm−1) have been discovered: Li10GeP2S12 (LGPS), Li6PS5Br argyrodite, and a Li7P3S11 glass ceramic. All three discovered electrolytes exhibit electrochemical instability against the Li anode, limiting application in commercial products. Li3BS3 has been predicted to have a wide electrochemical stability window, sufficient for resisting electron injection from the Li anode.1 However, the ionic conductivity of pure Li3BS3 is prohibitively low (10−7-10−6 S cm−1).


Herein we present methods and compositions to significantly enhance the ionic conductivity of Li3BS3 through aliovalent substitution and subsequent amorphization. By substituting up to 5% (e.g., greater than 0 and less than 5%, greater than 0.5% and less than 5%, greater than 1% and less than 5%) of the B sites with Si or S sites with Cl, Li3−xB1−xSxS3 and Li3−yBS3−yCly achieve ionic conductivities of 10−5 S cm−1 at room temperature. When the Si-substituted product is amorphized, through continuous ball milling, the ionic conductivity is further enhanced to above 10−3 S cm−1 at room temperature.


Improvements Over Existing Methods, Devices, or Materials:

Pure Li3BS3 has been previously characterized. The pure structure exhibits an ionic conductivity in the range of 10−7-10−6 S cm−1. Recent work by Kimura et al. has shown that the ionic conductivity of pure Li3BS3 can be enhanced via extended ball milling to near 10−4 S cm−1.2 The present methods and compositions significantly improve on both results. Aliovalent substitution of the Li3BS3 structure is thought to introduce vacancies which can act as charge carrying defects. Aliovalent substitution for 5% of the B results in Li2.95B0.95Si0.05S3 which exhibits a room temperature ionic conductivity of 1.82·10−5 S cm−1. Substitution of Cl for S to obtain Li2.9B0.9S2.9Cl0.1 also increases the conductivity to 10−5 S cm−1. Extended amorphization of the Li2.95B0.95Si0.05S3 further improves the ionic conductivity to between 1·10−3-3·10−3 S cm−1. Thus, through aliovalent substitution and amorphization, the ionic conductivity of Li3BS3 is improved, for example, to near that of conventional liquid electrolytes.


The amorphous Li2.95B0.95Si0.05S3 (a-Li2.95B0.95Si0.05S3) offers many unique advantages over most solid-state electrolyte candidates. The synthesis occurs at a relatively low temperature (˜800° C.) and pelletization can occur at room temperature. Unlike most oxide candidates, the a-Li2.95B0.95Si0.05S3 exhibits superb inter-grain conductivity without the need for a high-temperature grain-boundary sintering step. The precursor materials are also relatively low cost. For example, in comparing to LGPS, the a-Li2.95B0.95Si0.05S3 swaps Ge (˜$2400/kg) and P (˜$5/kg) for B (˜200/kg) and Si ($1/kg). Finally, all four constituent elements have a low atomic mass, which is conducive to making ASSBs with high gravimetric capacity.


Alternative Embodiments, Variations, or Applications

The present methods and compositions may also be useful in a variety of embodiments beyond solid-state electrolytes. Li2.95B0.9Si0.05S3 may be employed as an artificial interphase on the Li anode surface. In such a capacity, the Li2.95B0.95Si0.05S3 would facilitate ionic conduction while preventing the Li anode from reducing an adjacent SSE.


The methods and compositions may also be employed as an additive for electrodes or even for glass electrolyte mixtures. In both cases, Li2.95B0.95Si0.05S3 could foreseeably serve either or both of the following roles: (1) improving electrochemical stability of the electrode/electrolyte and (2) improving ionic conductivity of the electrode/electrolyte.


As is shown in FIG. 31, the introduction of defects in Li3BS3 increases ionic conductivity by approximately four orders of magnitude. FIG. 31 shows Arrhenius plots, room-temperature ionic conductivity values and activation energies for a-Li2.95B0.95Si0.05S3, Li2.95B0.95Si0.05S3, and Li3BS3.


As is shown in FIGS. 32A, 32B and 33, co-substitution of Si and Cl leads to significant higher ionic conductivity than that for same designed Li vacancy concentration with only Cl substitution. FIG. 32A shows Arrhenius plots and room-temperature ionic conductivity values for Li2.9B0.95Si0.05S2.95Cl0.05, Li2.95B0.95Si0.05S3, Li2.95BS2.95Cl0.05, and Li3BS3. FIG. 32B shows Arrhenius plots and room-temperature ionic conductivity values for Li3BS3, Li2.95 B0.95Si0.05 S3, a-Li2.95B0.95Si0.05S3, Li2.95BS2.95Cl0.05 and Li2.9BS2.9Cl0.1. FIG. 33 shows room-temperature ionic conductivity values and activation energies for Li3BS3, Li2.95BS2.95Cl0.05, Li2.9BS2.9Cl0.1, Li2.8BS2.8Cl0.2, Li2.95B0.95Si0.05S3, and Li2.9B0.95Si0.05S2.95Cl0.05.


Shown in FIG. 34 is a comparison of the room-temperature ionic conductivity values for Li3BS3, Li2.95BS2.95Cl0.05, Li2.9BS2.9Cl0.1, Li2.8BS2.8Cl0.2, Li2.95B0.95Si0.05S3, Li2.9B0.95Si0.05S2.95Cl0.05, a-Li2.95B0.95Si0.05S3, Li2.85B0.85Si0.15S3, Li2.85B0.9Si0.1S2.95Cl0.05, and Li2.6BS2.6Cl0.4. As can be seen from FIG. 34, Li3BS3, Li2.95BS2.95Cl0.05, Li2.9BS2.9Cl0.1, Li2.8BS2.8Cl0.2, and Li2.95B0.95Si0.05S3 are crystalline while a-Li2.95B0.95Si0.05S3, Li2.85B0.85Si0.15S3, Li2.85B0.9Si0.1S2.95Cl0.05, and Li2.6BS2.6Cl0.4 are amorphous. Further, Li2.9B0.95Si0.05S2.95Cl0.05, a-Li2.95B0.95Si0.05S3, Li2.85B0.85Si0.15S3, Li2.85B0.9Si0.1S2.95Cl0.05, and Li2.6BS2.6Cl0.4 are superionic.



FIG. 35 provides XRD patterns for Li3BS3, Li2.95 BS2.95 Cl0.005 and Li2.9BS2.9Cl0.1. The patterns do not appear to show any impurities.


REFERENCES CORRESPONDING TO EXAMPLES 1A, 2 AND 3



  • 1. Bachman, J. C. et al. Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction. Chem. Rev. 116, 140-162 (2016).

  • 2. Kamaya, N. et al. A lithium superionic conductor. Nat. Mater. 10, 682-686 (2011).

  • 3. Adeli, P. et al. Boosting solid-state diffusivity and conductivity in lithium superionic argyrodites by halide substitution. Angew. Chem. 131, 8773-8778 (2019).

  • 4. Seino, Y., Ota, T., Takada, K., Hayashi, A. & Tatsumisago, M. A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries. Energy Environ. Sci. 7, 627-631 (2014).

  • 5. Zhu, Y., He, X. & Mo, Y. First principles study on electrochemical and chemical stability of solid electrolyte-electrode interfaces in all-solid-state Li-ion batteries. J. Mater. Chem. A 4, 3253-3266 (2016).

  • 6. Richards, W. D., Miara, L. J., Wang, Y., Kim, J. C. & Ceder, G. Interface stability in solid-state batteries. Chem. Mater. 28, 266-273 (2016).

  • 7. Kerman, K., Luntz, A., Viswanathan, V., Chiang, Y.-M. & Chen, Z. Review—practical challenges hindering the development of solid state Ii ion batteries. J. Electrochem. Soc. 164, A1731 (2017).

  • 8. Wenzel, S. et al. Direct observation of the interfacial instability of the fast ionic conductor Li10GeP2S12 at the lithium metal anode. Chem. Mater. 28, 2400-2407 (2016).

  • 9. Zhu, Y., He, X. & Mo, Y. Origin of outstanding stability in the lithium solid electrolyte materials: insights from thermodynamic analyses based on first-principles calculations. ACS Appl. Mater. Interfaces 7, 23685-23693 (2015).

  • 10. Wenzel, S., Sedlmaier, S. J., Dietrich, C., Zeier, W. G. & Janek, J. Interfacial reactivity and interphase growth of argyrodite solid electrolytes at lithium metal electrodes. Solid State Ion. 318, 102-112 (2018).

  • 11. Ding, Z., Li, J., Li, J. & An, C. Review-interfaces: key issue to be solved for all solid-state lithium battery technologies. J. Electrochem. Soc. 167, 070541 (2020).

  • 12. Wang, S. et al. Interfacial challenges for all-solid-state batteries based on sulfide solid electrolytes. J. Materomics 7, 209-218 (2021).

  • 13. Sendek, A. D., Cheon, G., Pasta, M. & Reed, E. J. Quantifying the Search for Solid Li-Ion Electrolyte Materials by Anion: A Data-Driven Perspective. J. Phys. Chem. C 124, 8067-8079 (2020).

  • 14. Ren, F. et al. Accelerated discovery of metallic glasses through iteration of machine learning and high-throughput experiments. Sci. Adv. 4, eaaq1566 (2018).

  • 15. Tran, K. & Ulissi, Z. W. Active learning across intermetallics to guide discovery of electrocatalysts for CO2 reduction and H2 evolution. Nat. Catal. 1, 696-703 (2018).

  • 16. Lu, S. et al. Accelerated discovery of stable lead-free hybrid organic-inorganic perovskites via machine learning. Nat. Commun. 9, 3405 (2018).

  • 17. Xue, D. et al. Accelerated search for materials with targeted properties by adaptive design. Nat. Commun. 7,11241 (2016).

  • 18. D. Sendek, A. et al. Holistic computational structure screening of more than 12000 candidates for solid lithium-ion conductor materials. Energy Environ. Sci. 10, 306-320 (2017).

  • 19. Butler, K. T., Davies, D. W., Cartwright, H., Isayev, O. & Walsh, A. Machine learning for molecular and materials science. Nature 559, 547-555 (2018).

  • 20. Liu, Y., Zhao, T., Ju, W. & Shi, S. Materials discovery and design using machine learning. J. Materiomics 3, 159-177 (2017).

  • 21. Ziletti, A., Kumar, D., Scheffler, M. & Ghiringhelli, L. M. Insightful classification of crystal structures using deep learning. Nat. Commun. 9, 2775 (2018).

  • 22. Isayev, O. et al. Universal fragment descriptors for predicting properties of inorganic crystals. Nat. Commun. 8, 15679 (2017).

  • 23. Schutt, K. T., Arbabzadah, F., Chmiela, S., Müller, K. R. & Tkatchenko, A. Quantum-chemical insights from deep tensor neural networks. Nat. Commun. 8,13890 (2017).

  • 24. Ward, L. et al. Matminer: An open source toolkit for materials data mining. Comput. Mater. Sci. 152, 60-69 (2018).

  • 25. Himanen, L. et al. DScribe: Library of descriptors for machine learning in materials science. Comput. Phys. Commun. 247, 106949 (2020).

  • 26. Juan, Y., Dai, Y., Yang, Y. & Zhang, J. Accelerating materials discovery using machine learning. J. Mater. Sci. Technol. 79, 178-190 (2021).

  • 27. Suzuki, K. et al. Fast material search of lithium ion conducting oxides using a recommender system. J. Mater. Chem. A 8, 11582-11588 (2020).

  • 28. Wang, Z. et al. Harnessing artificial intelligence to holistic design and identification for solid electrolytes. Nano Energy 89, 106337 (2021).

  • 29. Zhong, M. et al. Accelerated discovery of CO2 electrocatalysts using active machine learning. Nature 581, 178-183 (2020).

  • 30. Wang, Z., Zhang, H. & Li, J. Accelerated discovery of stable spinels in energy systems via machine learning. Nano Energy 81, 105665 (2021).

  • 31. Yuan, R. et al. Accelerated discovery of large electrostrains in BaTiO3-based piezoelectrics using active learning. Adv. Mater. 30, 1702884 (2018).

  • 32. Li, J. et al. Accelerated discovery of high-strength aluminum alloys by machine learning. Commun. Mater. 1, 1-10 (2020).

  • 33. Butler, K. T., Oviedo, F. & Canepa, P. Machine Learning in Materials Science. vol. 29 (American Chemical Society, 2022).

  • 34. Zhang, Y. et al. Unsupervised discovery of solid-state lithium ion conductors. Nat. Commun. 10, 1-7 (2019).

  • 35. Liu, Y., Zhou, Q. & Cui, G. Machine learning boosting the development of advanced lithium batteries. Small Methods 5, 2100442 (2021).

  • 36. Forestier, G. & Wemmert, C. Semi-supervised learning using multiple clusterings with limited labeled data. Inf. Sci. 361-362, 48-65 (2016).

  • 37. Thangadurai, V., Narayanan, S. & Pinzaru, D. Garnet-type solid-state fast Li ion conductors for Li batteries: critical review. Chem. Soc. Rev. 43, 4714-4727 (2014).

  • 38. Gorai, P., Famprikis, T., Singh, B., Stevanović, V. & Canepa, P. Devil is in the defects: electronic conductivity in solid electrolytes. Chem. Mater. 33, 7484-7498 (2021).

  • 39. van Engelen, J. E. & Hoos, H. H. A survey on semi-supervised learning. Mach. Learn. 109, 373-440 (2020).

  • 40. Schütt, K. T. et al. SchNet: A continuous-filter convolutional neural network for modeling quantum interactions. ArXiv170608566 Phys. Stat (2017).

  • 41. Artrith, N. & Urban, A. An implementation of artificial neural-network potentials for atomistic materials simulations: Performance for TiO2. Comput. Mater. Sci. 114, 135-150(2016).

  • 42. Adams, S. & Rao, R. P. In structure and bonding, Vol. 158, Bond Valences, edited by ID Brown and KR Poeppelmeier. (Berlin, Heidelberg: Springer, 2014).

  • 43. Hansen, K. et al. Machine learning predictions of molecular properties: accurate many-body potentials and nonlocality in chemical space. J. Phys. Chem. Lett. 6, 2326-2331 (2015).

  • 44. Butler, M. A. & Ginley, D. S. Prediction of flatband potentials at semiconductor-electrolyte interfaces from atomic electronegativities. J. Electrochem. Soc. 125, 228 (1978).

  • 45. He, B. et al. CAVD, towards better characterization of void space for ionic transport analysis. Sci. Data 7, 153 (2020).

  • 46. Ward, L. et al. Including crystal structure attributes in machine learning models of formation energies via Voronoi tessellations. Phys. Rev. B 96, 024104 (2017).

  • 47. Ong, S. P. et al. Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis. Comput. Mater. Sci. 68, 314-319 (2013).

  • 48. Deml, A. M., O'Hayre, R., Wolverton, C. & Stevanović, V. Predicting density functional theory total energies and enthalpies of formation of metal-nonmetal compounds by linear regression. Phys. Rev. B 93, 085142 (2016).

  • 49. Ewald, P. P. Die Berechnung optischer und elektrostatischer Gitterpotentiale. Ann. Phys. 369, 253-287 (1921).

  • 50. Choudhary, K. et al. The joint automated repository for various integrated simulations (JARVIS) for data-driven materials design. Npj Comput. Mater. 6, 1-13 (2020).

  • 51. Meredig, B. et al. Combinatorial screening for new materials in unconstrained composition space with machine learning. Phys. Rev. B 89, 094104 (2014).

  • 52. Pham, T. L. et al. Machine learning reveals orbital interaction in materials. Sci. Technol. Adv. Mater. 18, 756-765 (2017).

  • 53. Rupp, M., Tkatchenko, A., Müller, K.-R. & von Lilienfeld, O. A. Fast and accurate modeling of molecular atomization energies with machine learning. Phys. Rev. Lett. 108, 058301 (2012).

  • 54. Faber, F., Lindmaa, A., Lilienfeld, O. A. von & Armiento, R. Crystal structure representations for machine learning models of formation energies. Int. J. Quantum Chem. 115, 1094-1101 (2015).

  • 55. Krivovichev, S. V. Structural complexity of minerals: information storage and processing in the mineral world. Mineral. Mag. 77, 275-326 (2013).

  • 56. Ward, L., Agrawal, A., Choudhary, A. & Wolverton, C. A general-purpose machine learning framework for predicting properties of inorganic materials. Npj Comput. Mater. 2, 1-7 (2016).

  • 57. Ward, J. H. Hierarchical grouping to optimize an objective function. J. Am. Stat. Assoc. 58, 236-244 (1963).

  • 58. Fung, V., Zhang, J., Juarez, E. & Sumpter, B. G. Benchmarking graph neural networks for materials chemistry. Npj Comput. Mater. 7, 1-8 (2021).

  • 59. He, X., Zhu, Y. & Mo, Y. Origin of fast ion diffusion in super-ionic conductors. Nat. Commun. 8,15893 (2017).

  • 60. Sun, W. et al. The thermodynamic scale of inorganic crystalline metastability. Sci. Adv. 2, e1600225 (2016).

  • 61. Electronic Structure. https://docs.materialsproject.org/methodology/materials-methodology/electronic-structure.

  • 62. Vinatier, P., Ménétrier, M. & Levasseur, A. Structure and ionic conduction in lithium thioborate glasses and crystals. Phys. Chem. Glas. 44, 135-142 (2003).

  • 63. Sendek, A. D. et al. Combining superionic conduction and favorable decomposition products in the crystalline lithium-boron-sulfur system: a new mechanism for stabilizing solid Ii-ion electrolytes. ACS Appl. Mater. Interfaces 12, 37957-37966 (2020).

  • 64. Bianchini, F., Fjellvåg, H. & Vajeeston, P. A first-principle investigation of the Li diffusion mechanism in the super-ionic conductor lithium orthothioborate Li3BS3 structure. Mater. Lett. 219, 186-189 (2018).

  • 65. Park, H., Yu, S. & Siegel, D. J. Predicting charge transfer stability between sulfide solid electrolytes and Li metal anodes. ACS Energy Lett. 6, 150-157 (2021).

  • 66. Vinatier, P., Gravereau, P., Ménétrier, M., Trut, L. & Levasseur, A. Li3BS3. Acta Crystallogr. C 50, 1180-1183 (1994).

  • 67. Zhang, L. et al. Lithium lanthanum titanate perovskite as an anode for lithium ion batteries. Nat. Commun. 11, 3490 (2020).

  • 68. Belous, A. G., Novitskaya, G. N., Polyanetskaya, S. V. & Gomikov, Y. I. Investigation into complex oxides of La2/3−xLi3xTiO3 composition. Izv AkadNauk SSSR Neorg Mater 23, 470-472 (1987).

  • 69. Kimura, T. et al. Characteristics of a Li3BS3 thioborate glass electrolyte obtained via a mechanochemical process. ACS Appl. Energy Mater. 5, 1421-1426 (2022).

  • 70. Zhou, L., Minafra, N., Zeier, W. G. & Nazar, L. F. Innovative approaches to Li-argyrodite solid electrolytes for all-solid-state lithium batteries. Acc. Chem. Res. 54, 2717-2728(2021).

  • 71. Zhao, W., Yi, J., He, P. & Zhou, H. Solid-state electrolytes for lithium-ion batteries: fundamentals, challenges and perspectives. Electrochem. Energy Rev. 2, 574-605 (2019).

  • 72. Lacivita, V., Artrith, N. & Ceder, G. Structural and compositional factors that control the Li-ion conductivity in LIPON electrolytes. Chem. Mater. 30, 7077-7090 (2018).

  • 73. Knauth, P. Inorganic solid Li ion conductors: An overview. Solid State Ion. 180, 911-916 (2009).

  • 74. Larink, D., Eckert, H. & Martin, S. W. Structure and ionic conductivity in the mixed-network former chalcogenide glass system [Na2S]2/3[(B2S3)x(P2S5)1−x]1/3. J. Phys. Chem. C 116, 22698-22710 (2012).

  • 75. Hwang, S.-J. et al. Structural study of xNa2S+(1−x)B2S3 glasses and polycrystals by multiple-quantum MAS NMR of 11B and 23Na. J. Am. Chem. Soc. 120, 7337-7346 (1998).

  • 76. Kaup, K. et al. A lithium oxythioborosilicate solid electrolyte glass with superionic conductivity. Adv. Energy Mater. 10, 1902783 (2020).

  • 77. Curtis, B., Francis, C., Kmiec, S. & Martin, S. W. Investigation of the short range order structures in sodium thioborosilicate mixed glass former glasses. J. Non-Cryst. Solids 521, 119456 (2019).

  • 78. Seino, Y. et al. Synthesis and electrochemical properties of Li2S—B2S3—Li4SiO4. Solid State Ion. 177, 2601-2603 (2006).

  • 79. Kaup, K., Assoud, A., Liu, J. & Nazar, L. F. Fast Li-Ion Conductivity in Superadamantanoid Lithium Thioborate Halides. Angew. Chem. Int. Ed. 60, 6975-6980 (2021).

  • 80. Suzuki, N. et al. Theoretical and experimental studies of KLi6TaO6 as a Li-ion solid electrolyte. Inorg. Chem. 60, 10371-10379 (2021).

  • 81. Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901-9904 (2000).

  • 82. Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978-9985 (2000).

  • 83. Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).

  • 84. Giannozzi, P. et al. Advanced capabilities for materials modelling with Quantum ESPRESSO. J. Phys. Condens. Matter 29, 465901 (2017).

  • 85. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865-3868 (1996).

  • 86. Dal Corso, A. Pseudopotentials periodic table: From H to Pu. Comput. Mater. Sci. 95, 337-350 (2014).



CITATIONS ASSOCIATED WITH EXAMPLE 1B



  • 1. Ross, S., Welsch, A.-M. & Behrens, H. Lithium conductivity in glasses of the Li2O—Al2O—SiO2 system. Phys. Chem. Chem. Phys. 17, 465-474 (2015).

  • 2. Aono, H., Sugimoto, E., Sadaoka, Y., Imanaka, N. & Adachi, G. The electrical properties of ceramic electrolytes for LiMxTi2−x(PO4)3+yLi2O, M=Ge, Sn, Hf, and Zr systems. J. Electrochem. Soc. 140, 1827 (1993).

  • 3. Mühle, C., Dinnebier, R. E., van Wüllen, L., Schwering, G. & Jansen, M. New insights into the structural and dynamical features of lithium hexaoxometalates Li7MO6 (M=Nb, Ta, Sb, Bi). Inorg. Chem. 43, 874-881 (2004).

  • 4. Mizuno, F., Hayashi, A., Tadanaga, K. & Tatsumisago, M. New, highly ion-conductive crystals precipitated from Li2S—P2S5 glasses. Adv. Mater. 17, 918-921 (2005).

  • 5. Yamane, H. et al. Crystal structure of a superionic conductor, Li7P3S11. Solid State Ion. 178, 1163-1167 (2007).

  • 6. Xiao, P. F., Lai, M. O. & Lu, L. Transport and electrochemical properties of high potential tavorite LiVPO4F. Solid State Ion. 242, 10-19 (2013).

  • 7. Hasegawa, T. & Yamane, H. Synthesis and crystal structure analysis of Li2NaBP2O8 and LiNa2B5P2O14. J. Solid State Chem. 225, 65-71 (2015).

  • 8. Voronin, V. I., Sherstobitova, E. A., Blatov, V. A. & Shekhtman, G. Sh. Lithium-cation conductivity and crystal structure of lithium diphosphate. J. Solid State Chem. 211, 170-175 (2014).

  • 9. Salanne, M., Marrocchelli, D. & Watson, G. W. Cooperative mechanism for the diffusion of Li+ ions in LiMgSO4F. J. Phys. Chem. C 116, 18618-18625 (2012).

  • 10. Strauss, F. et al. Impact of structural polymorphism on ionic conductivity in lithium copper pyroborate Li6CuB4O10. Inorg. Chem. 57, 11646-11654 (2018).

  • 11. Losilla, E. R., Aranda, M. A. G., Martinez-Lara, M. & Bruque, S. Reversible triclinic-rhombohedral phase transition in LiHf2(PO4)3: crystal structures from neutron powder diffraction. Chem. Mater. 9, 1678-1685 (1997).

  • 12. Busche, M. R. et al. In situ monitoring of fast Ii-ion conductor Li7P3S1I crystallization inside a hot-press setup. Chem. Mater. 28, 6152-6165 (2016).

  • 13. Ohtsuka, H. & Yamaji, A. Preparation and electrical conductivity of LISICON thin films. Solid State Ion. 8, 43-48 (1983).

  • 14. Kanno, R. & Murayama, M. Lithium ionic conductor thio-LISICON: The Li2S—GeS2—P2S5 system. J. Electrochem. Soc. 148, A742 (2001).

  • 15. Ahn, B. T. & Huggins, R. A. Synthesis and lithium conductivities of Li2SiS3 and Li4SiS4. Mater. Res. Bull. 24, 889-897 (1989).

  • 16. Deng, Y. et al. Structural and mechanistic insights into fast lithium-ion conduction in Li4SiO4—Li3PO4 solid electrolytes. J. Am. Chem. Soc. 137, 9136-9145 (2015).

  • 17. Khorassani, A. & West, A. R. Li+ ion conductivity in the system Li4SiO4□Li3VO4. J. Solid State Chem. 53, 369-375 (1984).

  • 18. Murayama, M. et al. Synthesis of new lithium ionic conductor thio-lisicon-lithium silicon sulfides system. J. Solid State Chem. 168, 140-148 (2002).

  • 19. Adachi, G., Imanaka, N. & Aono, H. Fast Li+ conducting ceramic electrolytes. Adv. Mater. 8, 127-135 (1996).

  • 20. Li, X. et al. Water-mediated synthesis of a superionic halide solid electrolyte. Angew. Chem. Int. Ed. 58, 16427-16432 (2019).

  • 21. Dietrich, C. et al. Synthesis, structural characterization, and lithium ion conductivity of the lithium thiophosphate Li2P2S6. Inorg. Chem. 56, 6681-6687 (2017).

  • 22. Holzmann, T. et al. Li0.6[Li0.2Sn0.8S2]—a layered lithium superionic conductor. Energy Environ. Sci. 9, 2578-2585 (2016).

  • 23. Dolbecq, A. et al. Synthesis, X-ray and neutron diffraction characterization, and ionic conduction properties of a new oxothiomolybdate Li3[Mo8S8O8(OH)8{HWO5(H2O)}]·18H2O. Chem. —Eur. J. 8, 349-356 (2002).

  • 24. Huber, S. & Pfitzner, A. Li17Sb13S28: A new lithium ion conductor and addition to the phase diagram Li2S-Sb2S3. Chem Eur J 21, 13683-13688 (2015).

  • 25. Tomita, Y., Ohki, H., Yamada, K. & Okuda, T. Ionic conductivity and structure of halocomplex salts of group 13 elements. Solid State Ion. 136-137, 351-355 (2000).

  • 26. Asano, T. et al. Solid halide electrolytes with high lithium-ion conductivity for application in 4 v class bulk-type all-solid-state batteries. Adv. Mater. 30, 1803075 (2018).

  • 27. Holzmann, T. et al. Li0.6[Li0.2Sn0.8S2]—a layered lithium superionic conductor. Energy Environ. Sci. 9, 2578-2585 (2016).

  • 28. Hockicko, P., Kudelcik, J., Munoz, F. & Munoz-Senovilla, L. Structural and electrical properties of LiPO3 glasses. Adv. Electr. Electron. Eng. 13, 198-205-205 (2015).

  • 29. Rao, S. R., Lingam, C. B., Rajesh, D., Vijayalakshmi, R. P. & Sunandana, C. S. Structural, conductivity and dielectric properties of Li2SO4. Eur. Phys. J. Appl. Phys. 66, 30906 (2014).

  • 30. Subban, C. V. et al. Search for Li-electrochemical activity and Li-ion conductivity among lithium bismuth oxides. Solid State Ion. 283, 68-74 (2015).

  • 31. Burmakin, E. I., Shehtman, G. S. & Alikin, V. N. Ionic conductivity of Li6Ge2O7 and its solid solutions. Materials Science Forum vol. 76 107-110/MSF.76.107 (1991).

  • 32. Weppner, W. & Huggins, R. A. Ionic conductivity of solid and liquid LiAlCl4. J. Electrochem. Soc. 124, 35 (1977).

  • 33. Hellstrom, E. E. & Van Gool, W. Li ion conduction in Li2ZrO3, Li4ZrO4, and LiScO2. Solid State Ion. 2, 59-64 (1981).

  • 34. Heitjans, P., Tobschall, E. & Wilkening, M. Ion transport and diffusion in nanocrystalline and glassy ceramics. Eur. Phys. J. Spec. Top. 161, 97-108 (2008).

  • 35. Chinnam, P. R., Clymer, R. N., Jalil, A. A., Wunder, S. L. & Zdilla, M. J. Bulk-phase ion conduction in cocrystalline LiCl·N,N-dimethylformamide: a new paradigm for solid electrolytes based upon the pearson hard-soft acid-base concept. Chem. Mater. 27, 5479-5482 (2015).

  • 36. Iqbal, M. et al. Lithium ion conduction in doped LaLiO2 system. Solid State Ion. 285, 33-37 (2016).

  • 37. Yin, S.-C., Strobel, P. S., Grondey, H. & Nazar, L. F. Li2.5V2(PO4)3: A room-temperature analogue to the fast-ion conducting high-temperature y-phase of Li3V2(PO4)3. Chem. Mater. 16, 1456-1465 (2004).

  • 38. Saha, S. et al. Polymorphism in Li4Zn(PO4)2 and stabilization of its structural disorder to improve ionic conductivity. Chem. Mater. 30, 1379-1390 (2018).

  • 39. de Laune, B. P., Bayliss, R. D. & Greaves, C. LiSbO2: synthesis, structure, stability, and lithium-ion conductivity. Inorg. Chem. 50, 7880-7885 (2011).

  • 40. Kim, S.-C., Kwak, H.-J., Yoo, C.-Y., Yun, H. & Kim, S.-J. Synthesis, crystal structure, and ionic conductivity of a new layered metal phosphate, Li2Sr2Al(PO4)3. J. Solid State Chem. 243, 12-17 (2016).

  • 41. Pantyukhina, M. I., Shchelkanova, M. S., Stepanov, A. P. & Buzlukov, A. L. Investigation of ion transport in Li8ZrO6 and Li6Zr2O7 solid electrolytes. Bull. Russ. Acad. Sci. Phys. 74, 653-655 (2010).

  • 42. Miyazaki, R. & Maekawa, H. Li+-ion conduction of Li3AlF6 mechanically milled with LiCl. ECS Electrochem. Lett. 1, A87 (2012).

  • 43. Brant, J. A. et al. Fast lithium ion conduction in Li2SnS3: synthesis, physicochemical characterization, and electronic structure. Chem. Mater. 27, 189-196 (2015).

  • 44. Kim, J., Kim, J., Avdeev, M., Yun, H. & Kim, S.-J. LiTa2PO8: a fast lithium-ion conductor with new framework structure. J. Mater. Chem. A 6, 22478-22482 (2018).

  • 45. Krichen, M., Megdiche, M., Guidara, K. & Gargouri, M. AC conductivity and mechanism of conduction study of lithium barium pyrophosphate Li2BaP2O7 using impedance spectroscopy. Ionics 21, 935-948 (2015).

  • 46. Huang, F. Q., Yao, J., Liu, Z., Yang, J. & Ibers, J. A. Synthesis, structure, and ionic conductivity of Na5Li3Ti2S6. J. Solid State Chem. 181, 837-841 (2008).

  • 47. Ettis, H., Naili, H. & Mhiri, T. The crystal structure, thermal behaviour and ionic conductivity of a novel lithium gadolinium polyphosphate LiGd(PO3)4. J. Solid State Chem. 179, 3107-3113 (2006).

  • 48. Muller, Ch., Valmalette, J.-C., Soubeyroux, J.-L., Bouree, F. & Gavarri, J.-R. Structural disorder and ionic conductivity in LiVO3: a neutron powder diffraction study from 340 to 890 k. J. Solid State Chem. 156, 379-389 (2001).

  • 49. Kanno, R. et al. Synthesis, structure, ionic conductivity, and phase transformation of new double chloride spinel, Li2CrCl4. J. Solid State Chem. 75, 41-51 (1988).

  • 50. Schlem, R. et al. Lattice dynamical approach for finding the lithium superionic conductor Li3Erle. ACS Appl. Energy Mater. 3, 3684-3691 (2020).

  • 51. Kimura, T. et al. Preparation and characterization of lithium ion conductive Li3SbS4 glass and glass-ceramic electrolytes. Solid State Ion. 333, 45-49 (2019).

  • 52. Liu, Z. et al. Anomalous high ionic conductivity of nanoporous β-Li3PS4. J. Am. Chem. Soc. 135, 975-978 (2013).

  • 53. Almond, D. P., Hunter, C. C. & West, A. R. The extraction of ionic conductivities and hopping rates from a.c. conductivity data. J. Mater. Sci. 19, 3236-3248 (1984).

  • 54. Cakmak, G., Nuss, J. & Jansen, M. LiB6O9F, the first lithium fluorooxoborate—crystal structure and ionic conductivity. Z. Für Anorg. Allg. Chem. 635, 631-636 (2009).

  • 55. Olivier-Fourcade, J., Maurin, M. & Philippot, E. Modification de la nature de la conductivite electrique par creation de sites vacants dans les phases a caractere semi-conducteur du systeme Li2SSb2S3. Solid State Ion. 9-10, 135-137 (1983).

  • 56. Yamane, H., Kikkawa, S. & Koizumi, M. Preparation of lithium silicon nitrides and their lithium ion conductivity. Solid State Ion. 25, 183-191 (1987).

  • 57. Senevirathne, K., Day, C. S., Gross, M. D., Lachgar, A. & Holzwarth, N. A. W. A new crystalline LiPON electrolyte: Synthesis, properties, and electronic structure. Solid State Ion. 233, 95-101 (2013).

  • 58. Seo, I. & Kim, Y. Synthesis and characterization of lithium germanogallium sulfide, Li2GeGa2S6. Solid State Ion. 261, 106-110 (2014).

  • 59. Ibarra, J. et al. Influence of composition on the structure and conductivity of the fast ionic conductors La2/3−xLi3xTiO3 (0.03≤x≤0.167). Solid State Ion. 134, 219-228 (2000).

  • 60. Belous, A. G., Gavrilenko, O. N., V'yunov, O. I., Kobilyanskaya, S. D. & Trachevskii, V. V. Effect of isovalent substitution on the structure and ionic conductivity of Li0.5−yNayLa0.5□Nb2O6. Inorg. Mater. 47, 308-312 (2011).

  • 61. Bohnke, O. et al. Lithium ion conductivity in new perovskite oxides [AgyLi1-y]3xLa2/3−xTiO3 (x=0.09 and 0≤y≤1). Chem. Mater. 13, 1593-1599 (2001).

  • 62. Itoh, M., Inaguma, Y., Jung, W.-H., Chen, L. & Nakamura, T. High lithium ion conductivity in the perovskite-type compounds Ln12Li12TiO3(Ln=La,Pr,Nd,Sm). Solid State Ion. 70-71, 203-207 (1994).

  • 63. Geng, H., Lan, J., Mei, A., Lin, Y. & Nan, C. W. Effect of sintering temperature on microstructure and transport properties of Li3xLa2/3−xTiO3 with different lithium contents. Electrochimica Acta 56, 3406-3414 (2011).

  • 64. Raistrick, I. D., Ho, C. & Huggins, R. A. Lithium ion conduction in Li5A104, Li5GaO4 and Li6ZnO4. Mater. Res. Bull. 11, 953-957 (1976).

  • 65. Saskia Lupart, Gregor, G., Maier, J. & Schnick, W. Li14Ln5[Si11N19O5]O2F2 with Ln=Ce, Nd—representatives of a family of potential lithium ion conductors. J. Am. Chem. Soc. 134, 10132-10137 (2012).

  • 66. Narimatsu, E., Yamamoto, Y., Takeda, T., Nishimura, T. & Hirosaki, N. High lithium conductivity in Li1-2 xCaxSi2N3. J. Mater. Res. 26, 1133-1142 (2011).

  • 67. Dissanayake, M. a. K. L. & West, A. R. Structure and conductivity of an Li4SiO4—Li2SO4 solid solution phase. J. Mater. Chem. 1, 1023-1025 (1991).

  • 68. Ivanov-Shitz, A. K., Kireev, V. V., Mel'nikov, O. K. & Demianets, L. N. Growth and ionic conductivity of γ-Li3PO4. Crystallogr. Rep. 46, 864-867 (2001).

  • 69. Kaup, K. et al. Correlation of structure and fast ion conductivity in the solid solution series Li1+2xZn1−xPS4. Chem. Mater. 30, 592-596 (2018).

  • 70. Wang, B., Chakoumakos, B. C., Sales, B. C., Kwak, B. S. & Bates, J. B. Synthesis, crystal structure, and ionic conductivity of a polycrystalline lithium phosphorus oxynitride with the γ-Li3PO4 structure. J. Solid State Chem. 115, 313-323 (1995).

  • 71. Kanno, R., Hata, T., Kawamoto, Y. & Irie, M. Synthesis of a new lithium ionic conductor, thio-LISICON-lithium germanium sulfide system. Solid State Ion. 130, 97-104(2000).

  • 72. Abrahams, I., Bruce, P. G., West, A. R. & David, W. I. F. Structure determination of LISICON solid solutions by powder neutron diffraction. J. Solid State Chem. 75, 390-396 (1988).

  • 73. Burmakin, E. I., Voronin, V. I. & Shekhtman, G. Sh. Crystalline structure and electroconductivity of solid electrolytes Li3.75Ge0.75V0.25O4 and Li3.70Ge0.85W0.15O4. Russ. J. Electrochem. 39, 1124-1129 (2003).

  • 74. Pham, Q. N., Crosnier-Lopez, M.-P., Le Berre, F., Fauth, F. & Fourquet, J.-L. Crystal structure of new Li+ ion conducting perovskites: Li2xCa0.5−xTaO3 and Li0.2[Ca1−ySry]0.4TaO3. Solid State Sci. 6, 923-929 (2004).

  • 75. Sebastian, L., Piffard, Y., K. Shukla, A., Taulelle, F. & Gopalakrishnan, J. Synthesis, structure and lithium-ion conductivity of Li2−2xMgb 2+x(MoO4)3 and Li3M(MoO4)3 (M III=Cr, Fe). J. Mater. Chem. 13, 1797-1802 (2003).

  • 76. Kaib, T. et al. Lithium chalcogenidotetrelates: LiChT-synthesis and characterization of new Li+ ion conducting Li/Sn/Se compounds. Chem. Mater. 25, 2961-2969 (2013).

  • 77. Roedem, E. et al. Solid state synthesis, structural characterization and ionic conductivity of bimetallic alkali-metal yttrium borohydrides MY(BH4)4 (M=Li and Na). J. Mater. Chem. A 4, 8793-8802 (2016).

  • 78. Barpanda, P. et al. LiZnSO4F made in an ionic liquid: a ceramic electrolyte composite for solid-state lithium batteries. Angew. Chem. Int. Ed. 50, 2526-2531 (2011).

  • 79. Murayama, M., Sonoyama, N., Yamada, A. & Kanno, R. Material design of new lithium ionic conductor, thio-LISICON, in the Li2S—P2S5 system. Solid State Ion. 170, 173-180 (2004).

  • 80. Kaib, T. et al. New lithium chalcogenidotetrelates, LiChT: synthesis and characterization of the Li+-conducting tetralithium ortho-sulfidostannate Li4SnS4. Chem. Mater. 24, 2211-2219 (2012).

  • 81. Maekawa, H., Iwatani, T., Shen, H., Yamamura, T. & Kawamura, J. Enhanced lithium ion conduction and the size effect on interfacial phase in Li2ZnI4-mesoporous alumina composite electrolyte. Solid State Ion. 178, 1637-1641 (2008).

  • 82. Morales, M. & West, A. R. Phase diagram, crystal chemistry and lithium ion conductivity in the perovskite-type system Pr0.5+xLi0.5−3xTiO3. Solid State Ion. 91, 33-43 (1996).

  • 83. Park, K.-H. et al. High-voltage superionic halide solid electrolytes for all-solid-state Li-ion batteries. ACS Energy Lett. 5, 533-539 (2020).

  • 84. Kuwano, J. & West, A. R. New Li+ ion conductors in the system, Li4GeO4-Li3VO4. Mater. Res. Bull. 15, 1661-1667 (1980).

  • 85. Sahu, G. et al. Air-stable, high-conduction solid electrolytes of arsenic-substituted Li4SnS4. Energy Environ. Sci. 7, 1053-1058 (2014).

  • 86. Inaguma, Y. et al. Effect of substitution and pressure on lithium ion conductivity in perovskites Ln12Li12TiO3 (Ln=La, Pr, Nd AND Sm). J. Phys. Chem. Solids 58, 843-852 (1997).

  • 87. Hodge, I. M., Ingram, M. D. & West, A. R. Ionic conductivity of Li4SiO4, Li4GeO4, and their solid solutions. J. Am. Ceram. Soc. 59, 360-366 (1976).

  • 88. Schwering, G., Hönnerscheid, A., van Wüllen, L. & Jansen, M. High lithium ionic conductivity in the lithium halide hydrates Li3-n(OHn)Cl (0.83≤n≤2) and Li3-n(OHn)Br (1≤n≤2) at ambient temperatures. ChemPhysChem 4, 343-348 (2003).

  • 89. Kanno, R. et al. Ionic conductivity and phase transition of the bromide spinels, Li2−2xM1+xBr4 (M=Mg, Mn). J. Electrochem. Soc. 133, 1052 (1986).

  • 90. Kwon, W. J. et al. Enhanced Li+ conduction in perovskite Li3xLa2/3−x□1/3−2xTiO3 solid-electrolytes via microstructural engineering. J. Mater. Chem. A 5, 6257-6262 (2017).

  • 91. Saha, D., Madras, G., Bhattacharyya, A. J. & Guru Row, T. N. Synthesis, structure and ionic conductivity in scheelite type Li0.5Ce0.5−xLnxMoO4 (x=0 and 0.25, Ln=Pr, Sm). J. Chem. Sci. 123, 5-13 (2011).

  • 92. González, C., López, M. L., Gaitán, M., Veiga, M. L. & Pico, C. Relationship between crystal structure and electric properties for lithium-containing spinels. Mater. Res. Bull. 29, 903-910 (1994).

  • 93. Yamane, H., Kikkawa, S. & Koizumi, M. High- and low-temperature phases of lithium boron nitride, Li3BN2: Preparation, phase relation, crystal structure, and ionic conductivity. J. Solid State Chem. 71, 1-11 (1987).

  • 94. Kim, C.-S., Hwang, Y.-H., Kim, H. K. & Kim, J. N. Ionic conductivity of crystalline and glassy Li2B4O7. Phys. Chem. Glas. 44, 166-169 (2003).

  • 95. Schnick, W. & Luecke, J. Lithium ion conductivity of LiPN2 and Li7PN4. Solid State Ion. 38, 271-273 (1990).

  • 96. Inaguma, Y. et al. High ionic conductivity in lithium lanthanum titanate. Solid State Commun. 86, 689-693 (1993).

  • 97. Harada, Y., Ishigaki, T., Kawai, H. & Kuwano, J. Lithium ion conductivity of polycrystalline perovskite La0.67−xLi3xTiO3 with ordered and disordered arrangements of the A-site ions. Solid State Ion. 108, 407-413 (1998).

  • 98. Zhang, H., Liu, X., Qi, Y. & Liu, V. On the La2/3−xLi3xTiO3/Al2O3 composite solid-electrolyte for Li-ion conduction. J. Alloys Compd. 577, 57-63 (2013).

  • 99. Thangadurai, V. et al. X-ray powder diffraction study of LiLnTiO4 (Ln=La, Nd): a lithium-ion conductor. Materials Science Forum vols 321-324 965-970/MSF.321-324.965 (2000).

  • 100. Katsumata, T., Takahata, M., Mochizuki, N. & Inaguma, Y. The relationship between Li ion conductivity and crystal structure for ordered perovskite compounds, (La2/3−1/3pLip)(Mg1/2W1/2)O3 (p=0.05, 0.11 and 0.14). Solid State Ion. 171, 191-198 (2004).

  • 101. Sedlmaier, S. J. et al. Li4PS4I: A Li+ superionic conductor synthesized by a solvent-based soft chemistry approach. Chem. Mater. 29, 1830-1835 (2017).

  • 102. Kato, Y. et al. High-power all-solid-state batteries using sulfide superionic conductors. Nat. Energy 1, 1-7 (2016).

  • 103. Takada, K. et al. Lithium ion conductive oxysulfide, Li3PO4—Li3PS4. Solid State Ion. 176, 2355-2359 (2005).

  • 104. Kwon, O. et al. Synthesis, structure, and conduction mechanism of the lithium superionic conductor Li10+δGe1+δP2−δS12. J. Mater. Chem. A 3, 438-446 (2015).

  • 105. Hori, S. et al. Synthesis, structure, and ionic conductivity of solid solution, Li10+δM1+δP2−δS12 (M=Si, Sn). Faraday Discuss. 176, 83-94 (2015).

  • 106. Whiteley, J. M., Woo, J. H., Hu, E., Nam, K.-W. & Lee, S.-H. Empowering the lithium metal battery through a silicon-based superionic conductor. J. Electrochem. Soc. 161, A1812 (2014).

  • 107. Bron, P. et al. Li10SnP2S12: an affordable lithium superionic conductor. J. Am. Chem. Soc. 135, 15694-15697 (2013).

  • 108. Krauskopf, T., Culver, S. P. & Zeier, W. G. Bottleneck of diffusion and inductive effects in Li10Ge1−xSnxP2S12. Chem. Mater. 30, 1791-1798 (2018).

  • 109. Hori, S. et al. Structure-property relationships in lithium superionic conductors having a Li10GeP2S12-type structure. Acta Crystallogr. Sect. B Struct. Sci. Cryst. Eng. Mater. 71, 727-736 (2015).

  • 110. Kamaya, N. et al. A lithium superionic conductor. Nat. Mater. 10, 682-686 (2011).

  • 111. Sun, Y., Suzuki, K., Hori, S., Hirayama, M. & Kanno, R. Superionic Conductors: Li10+δ[SnySi1−y]1+δP2−δS12 with a Li10GeP2S12-type Structure in the Li3PS4—Li4SnS4—Li4SiS4 Quasi-ternary System. Chem. Mater. 29, 5858-5864 (2017).

  • 112. Sun, Y. et al. A facile strategy to improve the electrochemical stability of a lithium ion conducting Li10GeP2S12 solid electrolyte. Solid State Ion. 301, 59-63 (2017).

  • 113. Weber, D. A. et al. Structural insights and 3D diffusion pathways within the lithium superionic conductor Li10GeP2S12. Chem. Mater. 28, 5905-5915 (2016).

  • 114. Sato, M., Abo, J., Jin, T. & Ohta, M. Structure and ionic conductivity of MLaNb2O7 (M=K, Na, Li, H). J. Alloys Compd. 192, 81-83 (1993).

  • 115. Bhuvanesh, N. S. P., Crosnier-Lopez, M. P., Bohnke, O., Emery, J. & Fourquet, J. L. Synthesis, crystal structure, and ionic conductivity of novel Ruddlesden-Popper related phases, Li4Sr3Nb5.77Fe0.23O19.77 and Li4Sr3Nb6O20. Chem. Mater. 11, 634-641 (1999).

  • 116. Cordier, G., Gudat, A., Kniep, R. & Rabenau, A. LiCaN and Li4SrN2, derivatives of the fluorite and lithium nitride structures. Angew. Chem. Int. Ed. Engl. 28, 1702-1703 (1989).

  • 117. Zhao, G., Muhammad, I., Suzuki, K., Hirayama, M. & Kanno, R. Synthesis, crystal structure, and the ionic conductivity of new lithium ion conductors, M-doped LiScO2 (M=Zr, Nb, Ta). Mater. Trans. 57, 1370-1373 (2016).

  • 118. Awaka, J. et al. Neutron powder diffraction study of tetragonal Li7La3Hf2O12 with the garnet-related type structure. J. Solid State Chem. 183, 180-185 (2010).

  • 119. Awaka, J., Kijima, N., Hayakawa, H. & Akimoto, J. Synthesis and structure analysis of tetragonal Li7La3Zr2O12 with the garnet-related type structure. J. Solid State Chem. 182, 2046-2052 (2009).

  • 120. Il'ina, E. A. & Pershina, S. V. Composite electrolytes based on tetragonal Li7La3Zr2O12 for lithium batteries. in Solid Electrolytes for Advanced Applications: Garnets and Competitors (eds. Murugan, R. & Weppner, W.) 167-193 (Springer International Publishing, 2019). doi:10.1007/978-3-030-31581-8_8.

  • 121. Inada, R., Kusakabe, K., Tanaka, T., Kudo, S. & Sakurai, Y. Synthesis and properties of Al-free Li7−xLa3Zr2−xTaxO12 garnet related oxides. Solid State Ion. 262, 568-572 (2014).

  • 122. Quintana, P. & West, A. R. Conductivity of lithium gallium silicates. Solid State Ion. 23, 179-182 (1987).

  • 123. Mukai, K. & Nunotani, N. Crystal structure and Ii-ion conductivity of LiGa1−xAlxGeO4 phenacite compounds with 0≤x≤1. J. Electrochem. Soc. 163, A2371 (2016).

  • 124. Arbi, K., Hoelzel, M., Kuhn, A., Garcia-Alvarado, F. & Sanz, J. Structural factors that enhance lithium mobility in fast-ion Li1+xTi2−xAlx(PO4)3 (0≤x≤0.4) conductors investigated by neutron diffraction in the temperature range 100-500 K. Inorg. Chem. 52, 9290-9296 (2013).

  • 125. Mellander, B.-E., Granéli, B. & Roos, J. Ionic conductivity of single crystal LiNaSO4. Solid State Ion. 40-41, 162-164 (1990).

  • 126. Takada, K. et al. Lithium ion conduction in lithium magnesium thio-phosphate. Solid State Ion. 147, 23-27 (2002).

  • 127. Hood, Z. D. et al. Structural and electrolyte properties of Li4P2S6. Solid State Ion. 284, 61-70 (2016).

  • 128. Dietrich, C. et al. Local structural investigations, defect formation, and ionic conductivity of the lithium ionic conductor Li4P2S6. Chem. Mater. 28, 8764-8773 (2016).

  • 129. Muy, S. et al. High-throughput screening of solid-state Li-ion conductors using lattice-dynamics descriptors. iScience 16, 270-282 (2019).

  • 130. Leube, B. T. et al. Lithium transport in Li4.4M0.4M′0.6S4 (M=Al3+, Ga3+, and M′=Ge4+, Sn4+): Combined crystallographic, conductivity, solid state NMR, and computational studies. Chem. Mater. 30, 7183-7200 (2018).

  • 131. Hartwig, P., Weppner, W. & Wichelhaus, W. Fast ionic lithium conduction in solid lithium nitride chloride. Mater. Res. Bull. 14, 493-498 (1979).

  • 132. Kahlaoui, R. et al. Cation miscibility and lithium mobility in NASICON Li1+xTi2-xScx(PO4)3 (0≤x≤0.5) series: A combined NMR and impedance study. Inorg. Chem. 56, 1216-1224 (2017).

  • 133. Weiss, M., Weber, D. A., Senyshyn, A., Janek, J. & Zeier, W. G. Correlating transport and structural properties in Li1+xAlxGe2−x(PO4)3 (LAGP) prepared from aqueous solution. ACS Appl. Mater. Interfaces 10, 10935-10944 (2018).

  • 134. Aono, H., Sugimoto, E., Sadaoka, Y., Imanaka, N. & Adachi, G. Ionic conductivity of solid electrolytes based on lithium titanium phosphate. J. Electrochem. Soc. 137, 1023 (1990).

  • 135. Bounar, N., Benabbas, A., Bouremmad, F., Ropa, P. & Carru, J.-C. Structure, microstructure and ionic conductivity of the solid solution LiTi2−xSnx(PO4)3. Phys. B Condens. Matter 407, 403-407 (2012).

  • 136. Li, Y., Liu, M., Liu, K. & Wang, C.-A. High Li+ conduction in NASICON-type Li1+xYxZr2−x(PO4)3 at room temperature. J. Power Sources 240, 50-53 (2013).

  • 137. Petit, D., Colomban, Ph., Collin, G. & Boilot, J. P. Fast ion transport in LiZr2(PO4)3: Structure and conductivity. Mater. Res. Bull. 21, 365-371 (1986).

  • 138. Kothari, D. H. & Kanchan, D. K. Effect of doping of trivalent cations Ga3+, Sc3+, Y3+ in Li1.3Al0.3Ti1.7(PO4)3 (LATP) system on Li+ ion conductivity. Phys. B Condens. Matter 501, 90-94 (2016).

  • 139. Aono, H., Sugimoto, E., Sadaaka, Y., Imanaka, N. & Adachi, G. Y. Ionic conductivity of the lithium titanium phosphate (Li1+xMxTi2−x(PO4)3, M=Al, Sc, Y, and La) systems. J. Electrochem. Soc. 136, 590 (1989).

  • 140. Xu, H., Wang, S., Wilson, H., Zhao, F. & Manthiram, A. Y-doped NASICON-type LiZr2(PO4)3 solid electrolytes for lithium-metal batteries. Chem. Mater. 29, 7206-7212 (2017).

  • 141. Fu, J. Fast Li+ ion conducting glass-ceramics in the system Li2O—Al2O3—GeO2—P2O5. Solid State Ion. 104, 191-194 (1997).

  • 142. Best, A. S., Forsyth, M. & MacFarlane, D. R. Stoichiometric changes in lithium conducting materials based on Li1+xAlxTi2−x(PO4)3: impedance, X-ray and NMR studies. Solid State Ion. 136-137, 339-344 (2000).

  • 143. Arbi, K. et al. Lithium mobility in Li1.2Ti1.8R0.2(PO4)3 compounds (R=Al, Ga, Sc, In) as followed by NMR and impedance spectroscopy. Chem. Mater. 16, 255-262 (2004).

  • 144. Šalkus, T. et al. Ionic conductivity of Li1.3Al0.3−xScxTi1.7(PO4)3 (x=0, 0.1, 0.15, 0.2, 0.3) solid electrolytes prepared by Pechini process. Solid State Ion. 225, 615-619 (2012).

  • 145. Pérez-Estébanez, M., Isasi-Marin, J., Többens, D. M., Rivera-Calzada, A. & León, C. A systematic study of Nasicon-type Li1+xMxTi2−x(PO4)3 (M: Cr, Al, Fe) by neutron diffraction and impedance spectroscopy. Solid State Ion. 266, 1-8 (2014).

  • 146. Aono, H., Sugimoto, E., Sadaoka, Y., Imanaka, N. & Adachi, G. Electrical properties and sinterability for lithium germanium phosphate Li1+xMxGe2−x(PO4)3, M=Al, Cr, Ga, Fe, Sc, and In systems. Bull. Chem. Soc. Jpn. 65, 2200-2204 (1992).

  • 147. Mugnier, Y., Galez, C., Crettez, J. M., Bourson, P. & Bouillot, J. Dielectric characterization and ionic conductivity of α-LiIO3 crystals related to the growth conditions. Solid State Commun. 115, 619-623 (2000).

  • 148. Yahia, H. B., Shikano, M., Takeuchi, T., Kobayashi, H. & Itoh, M. Crystal structures of the new fluorophosphates Li9Mg3[PO4]4F3 and Li2Mg[PO4]F and ionic conductivities of selected compositions. J. Mater. Chem. A 2, 5858-5869 (2014).

  • 149. Naddari, T., Savariault, J.-M., Feki, H. E., Salles, P. & Salah, A. B. Conductivity and structural investigations in Lacunary Pb6Ca2Li2(PO4)6 Apatite. J. Solid State Chem. 166, 237-244 (2002).

  • 150. Sato, M., Kono, Y., Ueda, H., Uematsu, K. & Toda, K. Bulk and grain boundary ionic conduction in lithium rare earth-silicates “LiLnSiO4” (Ln=La, Nd, Sm, Eu, Gd, Dy). Solid State Ion. 83, 249-256 (1996).

  • 151. Johnson, R. T., Morosin, B., Knotek, M. L. & Biefeld, R. M. Ionic conductivity in LiAlSiO4. Phys. Lett. A 54, 403-404 (1975).

  • 152. Matsuo, M. et al. Synthesis and lithium fast-ion conductivity of a new complex hydride Li3(NH2)2I with double-layered structure. Chem. Mater. 22, 2702-2704 (2010).

  • 153. Aimi, A. et al. Synthesis, structure and ionic conductivities of novel Li-ion conductor A3LixTa6−xZrxSi4O26 (A=Sr and Ba). Solid State Ion. 285, 19-28 (2016).

  • 154. Alpen, U. v., Rabenau, A. & Talat, G. H. Ionic conductivity in Li3N single crystals. Appl. Phys. Lett. 30, 621-623 (1977).

  • 155. Lapp, T., Skaarup, S. & Hooper, A. Ionic conductivity of pure and doped Li3N. Solid State Ion. 11, 97-103 (1983).

  • 156. Röska, B., Akter, I., Hoelzel, M. & Park, S.-H. Na+/Li+-ionic conductivity in Fe2Na2K[Li3Si12O30]. J. Solid State Chem. 264, 98-107 (2018).

  • 157. Nazri, G. Preparation, structure and ionic conductivity of lithium phosphide. Solid State Ion. 34, 97-102 (1989).

  • 158. Thangadurai, V. & Weppner, W. Effect of sintering on the ionic conductivity of garnet-related structure Li5La3Nb2O12 and In- and K-doped Li5La3Nb2O12. J. Solid State Chem. 179, 974-984 (2006).

  • 159. Thangadurai, V. & Weppner, W. Li6ALa2Nb2O12 (A=Ca, Sr, Ba): A new class of fast lithium ion conductors with garnet-like structure. J. Am. Ceram. Soc. 88, 411-418 (2005).

  • 160. Watelet, H., Picard, J.-P., Besse, J.-P., Baud, G. & Chevalier, R. Structure et proprietes de conduction du compose K0.1Li0.9SbO3. Solid State Ion. 2, 191-194 (1981).

  • 161. Eickhoff, H. et al. Lithium phosphidogermanates α- and β-Li8GeP4—A novel compound class with mixed Li+ ionic and electronic conductivity. Chem. Mater. 30, 6440-6448 (2018).

  • 162. Yamane, H., Kikkawa, S. & Koizumi, M. Lithium aluminum nitride, Li3AlN2 as a lithium solid electrolyte. Solid State Ion. 15, 51-54 (1985).

  • 163. Kawai, H., Tabuchi, M., Nagata, M., Tukamoto, H. & West, A. R. Crystal chemistry and physical properties of complex lithium spinels Li2MM′3O8 (M=Mg, Co, Ni, Zn; M′=Ti, Ge). J. Mater. Chem. 8, 1273-1280 (1998).

  • 164. Shiiba, H., Nakayama, M. & Nogami, M. Ionic conductivity of lithium in spinel-type Li4/3Ti5/3O4—LiMg1/2Ti3/2O4 solid-solution system. Solid State Ion. 181, 994-1001 (2010).

  • 165. Obayashi, H., Gotoh, A. & Nagai, R. Composition dependence of lithium ionic conductivity in lithium nitride-lithium iodide system. Mater. Res. Bull. 16, 581-585 (1981).

  • 166. Cros, C., Hanebali, L., Latie', L., Villeneuve, G. & Gang, W. Structure, ionic motion and conductivity in some solid-solutions of the LiClMCl2 systems (M=Mg,V,Mn). Solid State Ion. 9-10, 139-147 (1983).

  • 167. Kraft, M. A. et al. Influence of lattice polarizability on the ionic conductivity in the lithium superionic argyrodites Li6PS5X (X=cl, br, i). J. Am. Chem. Soc. 139, 10909-10918 (2017).

  • 168. Minafra, N., P. Culver, S., Krauskopf, T., Senyshyn, A. & G. Zeier, W. Effect of Si substitution on the structural and transport properties of superionic Li-argyrodites. J. Mater. Chem. A 6, 645-651 (2018).

  • 169. Inoue, Y., Suzuki, K., Matsui, N., Hirayama, M. & Kanno, R. Synthesis and structure of novel lithium-ion conductor Li7Ge3PS12. J. Solid State Chem. 246, 334-340 (2017).

  • 170. Sakuda, A. et al. Mechanochemically prepared Li2S—P2S5—LiBH4 solid electrolytes with an argyrodite structure. ACS Omega 3, 5453-5458 (2018).

  • 171. Boulineau, S., Courty, M., Tarascon, J.-M. & Viallet, V. Mechanochemical synthesis of Li-argyrodite Li6PS5X (X=Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application. Solid State Ion. 221, 1-5 (2012).

  • 172. Bernges, T., Culver, S. P., Minafra, N., Koerver, R. & Zeier, W. G. Competing structural influences in the Li superionic conducting argyrodites Li6PS5−xSexBr (0≤x≤1) upon Se substitution. Inorg. Chem. 57, 13920-13928 (2018).

  • 173. Kong, S.-T. et al. Li6PO5Br and Li6PO5Cl: The first lithium-oxide-argyrodites. Z. Für Anorg. Allg. Chem. 636, 1920-1924 (2010).

  • 174. Rao, R. P. & Adams, S. Studies of lithium argyrodite solid electrolytes for all-solid-state batteries. Phys. Status Solidi A 208, 1804-1807 (2011).

  • 175. Kraft, M. A. et al. Inducing high ionic conductivity in the lithium superionic argyrodites Li6+xP1−xGexS5I for all-solid-state batteries. J. Am. Chem. Soc. 140, 16330-16339 (2018).

  • 176. Deiseroth, H.-J. et al. Li7PS6 and Li6PS5X (X: Cl, Br, I): possible three-dimensional diffusion pathways for lithium ions and temperature dependence of the ionic conductivity by impedance measurements. Z. Für Anorg. Allg. Chem. 637, 1287-1294 (2011).

  • 177. Song, Y. B. et al. Tailoring solution-processable Ii argyrodites Li6+xP1−xMxS5I (M=Ge, Sn) and their microstructural evolution revealed by cryo-tem for all-solid-state batteries. Nano Lett. 20, 4337-4345 (2020).

  • 178. Ley, M. B. et al. LiCe(BH4)3Cl, a new lithium-ion conductor and hydrogen storage material with isolated tetranuclear anionic clusters. Chem. Mater. 24, 1654-1663 (2012).

  • 179. Jeitschko, W., Bither, T. A. & Bierstedt, P. E. Crystal structure and ionic conductivity of Li boracites. Acta Crystallogr. B 33, 2767-2775 (1977).

  • 180. Wagner, R. et al. Fast Li-ion-conducting garnet-related Li7-3xFexLa3Zr2O12 with uncommon I43d structure. Chem. Mater. 28, 5943-5951 (2016).

  • 181. H. Braga, M., A. Ferreira, J., Stockhausen, V., E. Oliveira, J. & El-Azab, A. Novel Li3ClO based glasses with superionic properties for lithium batteries. J. Mater. Chem. A 2, 5470-5480 (2014).

  • 182. Stramare, S. & Weppner, W. Structure and conductivity of B-site substituted (Li,La)TiO3. Mater. Sci. Eng. B 113, 85-90 (2004).

  • 183. Sotomayor, M. E., Várez, A., Bucheli, W., Jimenez, R. & Sanz, J. Structural characterisation and Li conductivity of Li1/2−xSr2xLa1/2−xTiO3 (0<x<0.5) perovskites. Ceram. Int. 39, 9619-9626 (2013).

  • 184. Li, Y. et al. Fluorine-doped antiperovskite electrolyte for all-solid-state lithium-ion batteries. Angew. Chem. 128, 10119-10122 (2016).

  • 185. J. Miara, L. et al. Li-ion conductivity in Li9S3N. J. Mater. Chem. A 3, 20338-20344 (2015).

  • 186. Sotomayor, M. E., Levenfeld, B., Varez, A. & Sanz, J. Study of the La1/2+1/2xLi1/2−1/2xTi1−xAxO3 (0≤x≤1) solid solution. A new example of percolative system in fast ion conductors. J. Alloys Compd. 720, 460-465 (2017).

  • 187. Phraewphiphat, T. et al. Syntheses, structures, and ionic conductivities of perovskite-structured lithium-strontium-aluminum/gallium-tantalum-oxides. J. Solid State Chem. 225, 431-437 (2015).

  • 188. Chen, C. H. et al. Stable lithium-ion conducting perovskite lithium-strontium-tantalum-zirconium-oxide system. Solid State Ion. 167, 263-272 (2004).

  • 189. Huang, B. et al. Li-ion conduction and stability of perovskite Li3/8Sr7/16Hf1/4Ta3/4O3. ACS Appl. Mater. Interfaces 8, 14552-14557 (2016).

  • 190. Yu, R., Du, Q.-X., Zou, B.-K., Wen, Z.-Y. & Chen, C.-H. Synthesis and characterization of perovskite-type (Li,Sr)(Zr,Nb)O3 quaternary solid electrolyte for all-solid-state batteries. J. Power Sources 306, 623-629 (2016).

  • 191. Braga, M. H., Ferreira, J. A., Stockhausen, V., Oliveira, J. E. & El-Azab, A. Novel Li3ClO based glasses with superionic properties for lithium batteries. J. Mater. Chem. A 2, 5470-5480 (2014).

  • 192. Inaguma, Y. & Itoh, M. Influences of carrier concentration and site percolation on lithium ion conductivity in perovskite-type oxides. Solid State Ion. 86-88, 257-260 (1996).

  • 193. Morata-Orrantia, A., Garcia-Martin, S. & Alario-Franco, M. A. New La2/3−xSrxLixTiO3 solid solution: structure, microstructure, and Li+ conductivity. Chem. Mater. 15, 363-367 (2003).

  • 194. Zhao, Y. & Daemen, L. L. Superionic conductivity in lithium-rich anti-perovskites. J. Am. Chem. Soc. 134, 15042-15047 (2012).

  • 195. Li, S. et al. Reaction mechanism studies towards effective fabrication of lithium-rich anti-perovskites Li3OX (X=Cl, Br). Solid State Ion. 284, 14-19 (2016).

  • 196. Howard, M. A., Clemens, O., Slater, P. R. & Anderson, P. A. Hydrogen absorption and lithium ion conductivity in Li6NBr3. J. Alloys Compd. 645, S174-S177 (2015).

  • 197. Liang, C. C. Conduction characteristics of the lithium iodide-aluminum oxide solid electrolytes. J. Electrochem. Soc. 120, 1289 (1973).

  • 198. Lutz, H. D., Steiner, H.-J. & Wickel, Ch. Fast ionic conductivity and crystal structure of spinel-type Li2−xMn1−xMxCl4 (M=Ga, In). Solid State Ion. 95, 173-181 (1997).

  • 199. Kanno, R., Takeda, Y. & Yamamoto, 0. Ionic conductivity of solid lithium ion conductors with the spinel structure: Li2MCl4 (M=Mg, Mn, Fe, Cd). Mater. Res. Bull. 16, 999-1005(1981).

  • 200. Phraewphiphat, T., Iqbal, M., Suzuki, K., Hirayama, M. & Kanno, R. Synthesis and lithium-ion conductivity of LiSrB2O6F (B=Nb5+, Ta5+) with a pyrochlore structure. custom-charactercustom-character65, 26-33 (2018).

  • 201. Murugan, R., Thangadurai, V. & Weppner, W. Lithium ion conductivity of Li5+xBaxLa3−xTa2O12 (x=0-2) with garnet-related structure in dependence of the barium content. Ionics 13, 195-203 (2007).

  • 202. Raskovalov, A. A., Il'ina, E. A. & Antonov, B. D. Structure and transport properties of Li7La3Zr2−0.75xAlxO12 superionic solid electrolytes. J. Power Sources 238, 48-52 (2013).

  • 203. Murugan, R., Ramakumar, S. & Janani, N. High conductive yttrium doped Li7La3Zr2O12 cubic lithium garnet. Electrochem. Commun. 13, 1373-1375 (2011).

  • 204. Wolfenstine, J., Ratchford, J., Rangasamy, E., Sakamoto, J. & Allen, J. L. Synthesis and high Li-ion conductivity of Ga-stabilized cubic Li7La3Zr2O12. Mater. Chem. Phys. 134, 571-575 (2012).

  • 205. Li, Y., Tao Han, J., An Wang, C., Xie, H. & B. Goodenough, J. Optimizing Li+ conductivity in a garnet framework. J. Mater. Chem. 22, 15357-15361 (2012).

  • 206. Wang, Y. & Lai, W. High ionic conductivity lithium garnet oxides of Li7−xLa3Zr2−xTaxO12 compositions. Electrochem. Solid State Lett. 15, A68 (2012).

  • 207. Lu, Y., Meng, X., Alonso, J. A., Fernández-Díaz, M. T. & Sun, C. Effects of fluorine doping on structural and electrochemical properties of Li6.25Ga0.25La3Zr2O12 as electrolytes for solid-state lithium batteries. ACS Appl. Mater. Interfaces 11, 2042-2049 (2019).

  • 208. Wang, D. et al. Toward understanding the lithium transport mechanism in garnet-type solid electrolytes: Li+ ion exchanges and their mobility at octahedral/tetrahedral sites. Chem. Mater. 27, 6650-6659 (2015).

  • 209. Rettenwander, D. et al. Synthesis, crystal chemistry, and electrochemical properties of Li7-2xLa3Zr2−xMoxO12 (x=0.1-0.4): stabilization of the cubic garnet polymorph via substitution of Zr4+ by Mo6+. Inorg. Chem. 54, 10440-10449 (2015).

  • 210. Deviannapoorani, C., Dhivya, L., Ramakumar, S. & Murugan, R. Lithium ion transport properties of high conductive tellurium substituted Li7La3Zr2O12 cubic lithium garnets. J. Power Sources 240, 18-25 (2013).

  • 211. He, M., Cui, Z., Chen, C., Li, Y. & Guo, X. Formation of self-limited, stable and conductive interfaces between garnet electrolytes and lithium anodes for reversible lithium cycling in solid-state batteries. J. Mater. Chem. A 6, 11463-11470 (2018).

  • 212. Thangadurai, V., Kaack, H. & Weppner, W. J. F. Novel fast lithium ion conduction in garnet-type Li5La3M2O12 (M=Nb, Ta). J. Am. Ceram. Soc. 86, 437-440 (2003).

  • 213. Murugan, R., Weppner, W., Schmid-Beurmann, P. & Thangadurai, V. Structure and lithium ion conductivity of bismuth containing lithium garnets Li5La3Bi2O12 and Li6SrLa2Bi2O12. Mater. Sci. Eng. B 143, 14-20 (2007).

  • 214. Percival, J., Kendrick, E. & Slater, P. R. Synthesis and characterisation of the garnet-related Li ion conductor, Li5Nd3Sb2O12. Mater. Res. Bull. 43, 765-770 (2008).

  • 215. O'Callaghan, M. P., Powell, A. S., Titman, J. J., Chen, G. Z. & Cussen, E. J. Switching on fast lithium ion conductivity in garnets: the structure and transport properties of Li3+xNd3Te2−xSbxO12. Chem. Mater. 20, 2360-2369 (2008).

  • 216. Murugan, R., Weppner, W., Schmid-Beurmann, P. & Thangadurai, V. Structure and lithium ion conductivity of garnet-like Li5La3Sb2O12 and Li6SrLa2Sb2O12. Mater. Res. Bull. 43, 2579-2591 (2008).

  • 217. Percival, J., Apperley, D. & Slater, P. R. Synthesis and structural characterisation of the Li ion conducting garnet-related systems, Li6ALa2Nb2O12 (A=Ca, Sr). Solid State Ion. 179, 1693-1696 (2008).

  • 218. Awaka, J., Kijima, N., Takahashi, Y., Hayakawa, H. & Akimoto, J. Synthesis and crystallographic studies of garnet-related lithium-ion conductors Li6CaLa2Ta2O12 and Li6BaLa2Ta2O12. Solid State Ion. 180, 602-606 (2009).

  • 219. Allen, J. L., Wolfenstine, J., Rangasamy, E. & Sakamoto, J. Effect of substitution (Ta, Al, Ga) on the conductivity of Li7La3Zr2O12. J. Power Sources 206, 315-319(2012).

  • 220. Janani, N., Deviannapoorani, C., Dhivya, L. & Murugan, R. Influence of sintering additives on densification and Li+ conductivity of Al doped Li7La3Zr2O12 lithium garnet. RSC Adv. 4, 51228-51238 (2014).

  • 221. Buschmann, H. et al. Structure and dynamics of the fast lithium ion conductor “Li7La3Zr2O12”. Phys. Chem. Chem. Phys. 13, 19378-19392 (2011).

  • 222. Kokal, I., Ramanujachary, K. V., Notten, P. H. L. & Hintzen, H. T. Sol-gel synthesis and lithium ion conduction properties of garnet-type Li6BaLa2Ta2O12. Mater. Res. Bull. 47, 1932-1935 (2012).

  • 223. A. Howard, M. et al. Synthesis, conductivity and structural aspects of Nd3Zr2Li7-3xAlxO12. J. Mater. Chem. A 1, 14013-14022 (2013).

  • 224. Matsuda, Y. et al. Phase formation of a garnet-type lithium-ion conductor Li7-3xAlxLa3Zr2O12. Solid State Ion. 277, 23-29 (2015).

  • 225. Narayanan, S., Ramezanipour, F. & Thangadurai, V. Enhancing Li ion conductivity of garnet-type Li5La3Nb2O12 by Y- and Li-codoping: synthesis, structure, chemical stability, and transport properties. J. Phys. Chem. C 116, 20154-20162 (2012).

  • 226. Zeier, W. G., Zhou, S., Lopez-Bermudez, B., Page, K. & Melot, B. C. Dependence of the Li-ion conductivity and activation energies on the crystal structure and ionic radii in Li6MLa2Ta2O12. ACS Appl. Mater. Interfaces 6, 10900-10907 (2014).

  • 227. Thangadurai, V. & Weppner, W. Li6ALa2Ta2O12 (A=Sr, Ba): Novel garnet-like oxides for fast lithium ion conduction. Adv. Funct. Mater. 15, 107-112 (2005).

  • 228. Thompson, T. et al. A tale of two sites: on defining the carrier concentration in garnet-based ionic conductors for advanced Li batteries. Adv. Energy Mater. 5, 1500096 (2015).

  • 229. Shin, D. O. et al. Synergistic multi-doping effects on the Li7La3Zr2O12 solid electrolyte for fast lithium ion conduction. Sci. Rep. 5, 18053 (2015).

  • 230. Hamao, N., Kataoka, K. & Akimoto, J. Li-ion conductivity and crystal structure of garnet-type Li6.5La3M1.5Ta0.5O12 (M=Hf, Sn) oxides. J. Ceram. Soc. Jpn. 125, 272-275(2017).

  • 231. Abdel-Basset, D. M., Mulmi, S., El-Bana, M. S., Fouad, S. S. & Thangadurai, V. Structure, ionic conductivity, and dielectric properties of Li-rich garnet-type Li5+2xLa3Ta2−xSmxO12 (0≤x≤0.55) and their chemical stability. Inorg. Chem. 56, 8865-8877 (2017).

  • 232. Shimonishi, Y. et al. Synthesis of garnet-type Li7−xLa3Zr2O12−1/2x and its stability in aqueous solutions. Solid State Ion. 183, 48-53 (2011).

  • 233. Narayanan, S. & Thangadurai, V. Effect of Y substitution for Nb in Li5La3Nb2O12 on Li ion conductivity of garnet-type solid electrolytes. J. Power Sources 196, 8085-8090(2011).

  • 234. Rangasamy, E., Wolfenstine, J. & Sakamoto, J. The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li7La3Zr2O12. Solid State Ion. 206, 28-32 (2012).

  • 235. El Shinawi, H. & Janek, J. Stabilization of cubic lithium-stuffed garnets of the type “Li7La3Zr2O12” by addition of gallium. J. Power Sources 225, 13-19 (2013).

  • 236. Howard, M. A. et al. Effect of Ga incorporation on the structure and Li ion conductivity of La3Zr2Li7O12. Dalton Trans. 41, 12048-12053 (2012).

  • 237. Ramakumar, S., Satyanarayana, L., Manorama, S. V. & Murugan, R. Structure and Li+ dynamics of Sb-doped Li7La3Zr2O12 fast lithium ion conductors. Phys. Chem. Chem. Phys. 15, 11327-11338 (2013).

  • 238. Wang, D. et al. The synergistic effects of Al and Te on the structure and Li+-mobility of garnet-type solid electrolytes. J. Mater. Chem. A 2, 20271-20279 (2014).

  • 239. Tong, X., Thangadurai, V. & Wachsman, E. D. Highly conductive Li garnets by a multielement doping strategy. Inorg. Chem. 54, 3600-3607 (2015).

  • 240. O'Callaghan, M. P., Lynham, D. R., Cussen, E. J. & Chen, G. Z. Structure and ionic-transport properties of lithium-containing garnets Li3Ln3Te2O12 (Ln=Y, Pr, Nd, Sm—Lu). Chem. Mater. 18, 4681-4689 (2006).

  • 241. Chen, R.-J. et al. Effect of calcining and Al doping on structure and conductivity of Li7La3Zr2O12. Solid State Ion. 265, 7-12 (2014).

  • 242. Cussen, E. J., Yip, T. W. S., O'Neill, G. & O'Callaghan, M. P. A comparison of the transport properties of lithium-stuffed garnets and the conventional phases Li3Ln3Te2O12. J. Solid State Chem. 184, 470-475 (2011).

  • 243. Arbi, K., Bucheli, W., Jiménez, R. & Sanz, J. High lithium ion conducting solid electrolytes based on NASICON Li1+xAlxM2−x(PO4)3 materials (M=Ti, Ge and 0≤x≤0.5). J. Eur. Ceram. Soc. 35, 1477-1484 (2015).

  • 244. Rangasamy, E., Wolfenstine, J., Allen, J. & Sakamoto, J. The effect of 24c-site (A) cation substitution on the tetragonal-cubic phase transition in Li7−xLa3−xAxZr2O12 garnet-based ceramic electrolyte. J. Power Sources 230, 261-266 (2013).

  • 245. Xu, X., Wen, Z., Yang, X. & Chen, L. Dense nanostructured solid electrolyte with high Li-ion conductivity by spark plasma sintering technique. Mater. Res. Bull. 43, 2334-2341 (2008).

  • 246. Hayashi, A., Hama, S., Minami, T. & Tatsumisago, M. Formation of superionic crystals from mechanically milled Li2S—P2S5 glasses. Electrochem. Commun. 5, 111-114 (2003).

  • 247. Minami, K., Hayashi, A., Ujiie, S. & Tatsumisago, M. Electrical and electrochemical properties of glass-ceramic electrolytes in the systems Li2S—P2S5—P2S3 and Li2S—P2S5—P2O5. Solid State Ion. 192, 122-125 (2011).

  • 248. Fukushima, A., Hayashi, A., Yamamura, H. & Tatsumisago, M. Mechanochemical synthesis of high lithium ion conducting solid electrolytes in a Li2S—P2S5—Li3N system. Solid State Ion. 304, 85-89 (2017).

  • 249. Ohta, S., Kobayashi, T. & Asaoka, T. High lithium ionic conductivity in the garnet-type oxide Li7−xLa3(Zr2−x, Nbx)O12 (X=0-2). J. Power Sources 196, 3342-3345 (2011).

  • 250. Zaiß, T., Ortner, M., Murugan, R. & Weppner, W. Fast ionic conduction in cubic hafnium garnet Li7La3Hf2O12. Ionics 16, 855-858 (2010).

  • 251. Kuhn, A., Duppel, V. & V. Lotsch, B. Tetragonal Li10GeP2S12 and Li7GePS8—exploring the Li ion dynamics in LGPS Li electrolytes. Energy Environ. Sci. 6, 3548-3552 (2013).

  • 252. Kato, Y. et al. Synthesis, structure and lithium ionic conductivity of solid solutions of Li10(Ge1−xMx)P2S12 (M=Si, Sn). J. Power Sources 271, 60-64 (2014).

  • 253. Pradel, A., Pagnier, T. & Ribes, M. Effect of rapid quenching on electrical properties of lithium conductive glasses. Solid State Ion. 17, 147-154 (1985).

  • 254. Bemuy-Lopez, C. et al. Atmosphere controlled processing of Ga-substituted garnets for high Li-ion conductivity ceramics. Chem. Mater. 26, 3610-617 (2014).

  • 255. Ramakumar, S., Satyanarayana, L., V. Manorama, S. & Murugan, R. Structure and Li+ dynamics of Sb-doped Li7La3Zr2O12 fast lithium ion conductors. Phys. Chem. Chem. Phys. 15, 11327-11338 (2013).

  • 256. Gombotz, M., Rettenwander, D. & Wilkening, H. M. R. Lithium-ion transport in nanocrystalline spinel-type Li[InxLiy]Br4 as seen by conductivity spectroscopy and NMR. Front. Chem. 8, (2020).

  • 257. Tomita, Y., Matsushita, H., Kobayashi, K., Maeda, Y. & Yamada, K. Substitution effect of ionic conductivity in lithium ion conductor, Li3InBr6−xClx. Solid State Ion. 179, 867-870 (2008).

  • 258. Kanno, R., Takeda, Y., Takada, K. & Yamamoto, O. Ionic conductivity and phase transition of the spinel system Li2−2xM1+xCl4 (M=Mg, Mn, Cd). J. Electrochem. Soc. 131, 469 (1984).

  • 259. Yin, L., Yuan, H., Kong, L., Lu, Z. & Zhao, Y. Engineering Frenkel defects of anti-perovskite solid-state electrolytes and their applications in all-solid-state lithium-ion batteries. Chem. Commun. 56, 1251-1254 (2020).

  • 260. Hood, Z. D., Wang, H., Samuthira Pandian, A., Keum, J. K. & Liang, C. Li2OHCl crystalline electrolyte for stable metallic lithium anodes. J. Am. Chem. Soc. 138, 1768-1771 (2016).

  • 261. Bruce, P. G. & West, A. R. Ionic conductivity of LISICON solid solutions, Li2+2xZn1−xGeO4. J. Solid State Chem. 44, 354-365 (1982).

  • 262. Han, X. et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nat. Mater. 16, 572-579 (2017).

  • 263. Inoishi, A., Nishio, A., Yoshioka, Y., Kitajou, A. & Okada, S. A single-phase all-solid-state lithium battery based on Li1.5Cr0.5Ti1.5(PO4)3 for high rate capability and low temperature operation. Chem. Commun. 54, 3178-3181 (2018).

  • 264. Wu, Z. et al. Utmost limits of various solid electrolytes in all-solid-state lithium batteries: A critical review. Renew. Sustain. Energy Rev. 109, 367-385 (2019).

  • 265. Pradel, A. & Ribes, M. Electrical properties of lithium conductive silicon sulfide glasses prepared by twin roller quenching. Solid State Ion. 18-19, 351-355 (1986).

  • 266. Mercier, R., Malugani, J.-P., Fahys, B. & Robert, G. Superionic conduction in Li2S—P2S5—LiI—glasses. Solid State Ion. 5, 663-666 (1981).

  • 267. Kennedy, J. H. Ionically conductive glasses based on SiS2. Mater. Chem. Phys. 23, 29-50 (1989).

  • 268. Wada, H., Menetrier, M., Levasseur, A. & Hagenmuller, P. Preparation and ionic conductivity of new B2S3—Li2S—LiI glasses. Mater. Res. Bull. 18, 189-193 (1983).

  • 269. Sahami, S., Shea, S. W. & Kennedy, J. H. Preparation and conductivity measurements of SiS2—Li2S—LiBr lithium ion conductive glasses. J. Electrochem. Soc. 132, 985 (1985).

  • 270. Kennedy, J. H., Sahami, S., Shea, S. W. & Zhang, Z. Preparation and conductivity measurements of SiS2□Li2S glasses doped with LiBr and LiCl. Solid State Ion. 18-19, 368-371 (1986).

  • 271. Kennedy, J. H. & Yang, Y. A highly conductive Li+-glass system: (1−x) (0.4SiS2-0.6Li2S)-xLiI. J. Electrochem. Soc. 133, 2437 (1986).

  • 272. Kennedy, J. H. & Yang, Y. Glass-forming region and structure in SiS2□Li2SLiX (X=Br, I). J. Solid State Chem. 69, 252-257 (1987).

  • 273. Kennedy, J. H. & Zhang, Z. Improved stability for the SiS2—P2S5—Li2S—LiI glass system. Solid State Ion. 28-30, 726-728 (1988).

  • 274. Ribes, M., Barrau, B. & Souquet, J. L. Sulfide glasses: Glass forming region, structure and ionic conduction of glasses in Na2S—XS2 (X=Si; Ge), Na2S—P2S5 and Li2S—GeS2 systems. J. Non-Cryst. Solids 38-39, 271-276 (1980).

  • 275. Seino, Y., Ota, T., Takada, K., Hayashi, A. & Tatsumisago, M. A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries. Energy Environ. Sci. 7, 627-631 (2014).

  • 276. Mizuno, F., Hayashi, A., Tadanaga, K. & Tatsumisago, M. High lithium ion conducting glass-ceramics in the system Li2S—P2S5. Solid State Ion. 177, 2721-2725 (2006).

  • 277. Morimoto, H., Yamashita, H., Tatsumisago, M. & Minami, T. Mechanochemical synthesis of new amorphous materials of 60Li2S-40SiS2 with high lithium ion conductivity. J. Am. Ceram. Soc. 82, 1352-1354 (1999).

  • 278. Minami, T., Hayashi, A. & Tatsumisago, M. Preparation and characterization of lithium ion-conducting oxysulfide glasses. Solid State Ion. 136-137, 1015-1023 (2000).

  • 279. Hirai, K., Tatsumisago, M. & Minami, T. Thermal and electrical properties of rapidly quenched glasses in the systems Li2S—SiS2-LixMOy (LixMOy=Li4SiO4, Li2SO4). Solid State Ion. 78, 269-273 (1995).

  • 280. Abrahams, I. & Hadzifejzovic, E. Lithium ion conductivity and thermal behaviour of glasses and crystallised glasses in the system Li2O—Al2O3—TiO2—P2O5. Solid State Ion. 134, 249-257 (2000).

  • 281. Hayashi, A., Yamashita, H., Tatsumisago, M. & Minami, T. Characterization of Li2S—SiS2-LixMOy (M=Si, P, Ge) amorphous solid electrolytes prepared by melt-quenching and mechanical milling. Solid State Ion. 148, 381-389 (2002).

  • 282. Hayashi, A., Hama, S., Morimoto, H., Tatsumisago, M. & Minami, T. High lithium ion conductivity of glass-ceramics derived from mechanically milled glassy powders. Chem. Lett. 30, 872-873 (2001).

  • 283. Mizuno, F., Hayashi, A., Tadanaga, K. & Tatsumisago, M. New lithium-ion conducting crystal obtained by crystallization of the Li2S—P2S5 glasses. Electrochem. Solid State Lett. 8, A603 (2005).

  • 284. Hayashi, A., Komiya, R., Tatsumisago, M. & Minami, T. Characterization of Li2S—SiS2-Li3MO3 (M=B, Al, Ga and In) oxysulfide glasses and their application to solid state lithium secondary batteries. Solid State Ion. 152-153, 285-290 (2002).

  • 285. Hayashi, A., Ishikawa, Y., Hama, S., Minami, T. & Tatsumisago, M. Fast lithium-ion conducting glass-ceramics in the system Li2S—SiS2—P2S5. Electrochem. Solid State Lett. 6, A47 (2003).

  • 286. Iio, K., Hayashi, A., Morimoto, H., Tatsumisago, M. & Minami, T. Mechanochemical synthesis of high lithium ion conducting materials in the system Li3N-SiS2. Chem. Mater. 14, 2444-2449 (2002).

  • 287. Machida, N., Yamamoto, H. & Shigematsu, T. A new amorphous lithium-ion conductor in the system Li2S-P2S3. Chem. Lett. 33, 30-31 (2003).

  • 288. Sakamoto, R., Tatsumisago, M. & Minami, T. Preparation of fast lithium ion conducting glasses in the system Li2S—SiS2—Li3N. J. Phys. Chem. B 103, 4029-4031 (1999).

  • 289. Abdel-Baki, M., Salem, A. M., Abdel-Wahab, F. A. & El-Diasty, F. Bond character, optical properties and ionic conductivity of Li2O/B2O3/SiO2/Al2O3 glass: Effect of structural substitution of Li2O for LiCl. J. Non-Cryst. Solids 354, 4527-4533 (2008).

  • 290. Machida, N., Yoneda, Y. & Shigematsu, T. Mechano-chemical synthesis of lithium ion conducting materials in the system Li2O—Li2S—P2S5. J. Jpn. Soc. Powder Powder Metall. 51, 91-97 (2004).

  • 291. Hayashi, A. et al. Thermal and electrical properties of rapidly quenched Li2S—SiS2—Li2O—P2O5 oxysulfide glasses. Solid State Ion. 113-115, 733-738 (1998).

  • 292. Zhang, Y., Chen, K., Shen, Y., Lin, Y. & Nan, C.-W. Synergistic effect of processing and composition x on conductivity of xLi2S-(100−x)P2S5 electrolytes. Solid State Ion. 305, 1-6 (2017).

  • 293. custom-character, custom-character& custom-character. custom-charactercustom-characterLiI—Li2S-SiS2custom-charactercustom-charactercustom-charactercustom-character, custom-charactercustom-character 49, 799-806 (2002).

  • 294. Hayashi, A., Hirai, K., Tatsumisago, M., Takahashi, M. & Minami, T. Preparation of Li6Si2S7—Li6B4X9 (X=S, O) glasses by rapid quenching and their lithium ion conductivities. Solid State Ion. 86-88, 539-542 (1996).

  • 295. Yersak, T. A., Salvador, J. R., Pieczonka, N. P. W. & Cai, M. Dense, melt cast sulfide glass electrolyte separators for Li metal batteries. J. Electrochem. Soc. 166, A1535(2019).

  • 296. Dietrich, C. et al. Lithium ion conductivity in Li2S—P2S5 glasses—building units and local structure evolution during the crystallization of superionic conductors Li3PS4, Li7P3S11 and Li4P2S7. J. Mater. Chem. A 5, 18111-18119 (2017).

  • 297. Yamauchi, A., Sakuda, A., Hayashi, A. & Tatsumisago, M. Preparation and ionic conductivities of (100−x)(0.75Li2S·0.25P2S5)·xLiBH4 glass electrolytes. J. Power Sources 244, 707-710 (2013).

  • 298. Xu, R., Xia, X., Wang, X., Xia, Y. & Tu, J. Tailored Li2S—P2S5 glass-ceramic electrolyte by MoS2 doping, possessing high ionic conductivity for all-solid-state lithium-sulfur batteries. J. Mater. Chem. A 5, 2829-2834 (2017).

  • 299. Xu, R. et al. All-solid-state lithium-sulfur batteries based on a newly designed LiP2.9Mn0.1S10.7I0.3 superionic conductor. J. Mater. Chem. A 5, 6310-6317 (2017).

  • 300. Zhou, P., Wang, J., Cheng, F., Li, F. & Chen, J. A solid lithium superionic conductor Li11AlP2S12 with a thio-LISICON analogous structure. Chem. Commun. 52, 6091-6094 (2016).

  • 301. Hood, Z. D. et al. The “filler effect”: A study of solid oxide fillers with β-Li3PS4 for lithium conducting electrolytes. Solid State Ion. 283, 75-80 (2015).

  • 302. Rangasamy, E. et al. A high conductivity oxide-sulfide composite lithium superionic conductor. J. Mater. Chem. A 2, 4111-4116 (2014).

  • 303. Trevey, J. E., Jung, Y. S. & Lee, S.-H. Preparation of Li2S—GeSe2—P2S5 electrolytes by a single step ball milling for all-solid-state lithium secondary batteries. J. Power Sources 195, 4984-4989 (2010).

  • 304. Trevey, J. E., Gilsdorf, J. R., Miller, S. W. & Lee, S.-H. Li2S—Li2O—P2S5 solid electrolyte for all-solid-state lithium batteries. Solid State Ion. 214, 25-30 (2012).

  • 305. Hayashi, A., Muramatsu, H., Ohtomo, T., Hama, S. & Tatsumisago, M. Improvement of chemical stability of Li3PS4 glass electrolytes by adding MxOy (M=Fe, Zn, and Bi) nanoparticles. J. Mater. Chem. A 1, 6320-6326 (2013).

  • 306. Huang, B. et al. Li3PO4-doped Li7P3S11 glass-ceramic electrolytes with enhanced lithium ion conductivities and application in all-solid-state batteries. J. Power Sources 284, 206-211 (2015).

  • 307. Lu, P. et al. Study on (100−x)(70Li2S-30P2S5)-xLi2ZrO3 glass-ceramic electrolyte for all-solid-state lithium-ion batteries. J. Power Sources 356, 163-171 (2017).

  • 308. Bates, J. B. et al. Fabrication and characterization of amorphous lithium electrolyte thin films and rechargeable thin-film batteries. J. Power Sources 43, 103-110 (1993).

  • 309. Fleutot, B., Pecquenard, B., Martinez, H., Letellier, M. & Levasseur, A. Investigation of the local structure of LiPON thin films to better understand the role of nitrogen on their performance. Solid State Ion. 186, 29-36 (2011).

  • 310. Suzuki, N., Shirai, S., Takahashi, N., Inaba, T. & Shiga, T. A lithium phosphorous oxynitride (LiPON) film sputtered from unsintered Li3PO4 powder target. Solid State Ion. 191, 49-54 (2011).

  • 311. Ménétrier, M., Estournés, C., Levasseur, A. & Rao, K. J. Ionic conduction in B2S3—Li2S—LiI glasses. Solid State Ion. 53-56, 1208-1213 (1992).

  • 312. Takada, K., Aotani, N. & Kondo, S. Electrochemical behaviors of Li+ ion conductor, Li3PO4—Li2S-SiS2. J. Power Sources 43, 135-141 (1993).

  • 313. Minami, K., Hayashi, A. & Tatsumisago, M. Crystallization process for superionic Li7P3S11 glass-ceramic electrolytes. J. Am. Ceram. Soc. 94, 1779-1783 (2011).

  • 314. Schlaikjer, C. R. & Liang, C. C. Ionic conduction in calcium doped polycrystalline lithium iodide. J. Electrochem. Soc. 118, 1447 (1971).

  • 315. Poulsen, F. W., Andersen, N. H., Kindl, B. & Schoonman, J. Properties of LiI—Alumina composite electrolytes. Solid State Ion. 9-10, 119-122 (1983).

  • 316. Aono, H., Sugimoto, E., Sadaoka, Y., Imanaka, N. & Adachi, G. Electrical property and sinterability of LiTi2(PO4)3 mixed with lithium salt (Li3PO4 or Li3BO3). Solid State Ion. 47, 257-264 (1991).

  • 317. Aono, H., Sugimoto, E., Sadaoka, Y., Imanaka, N. & Adachi, G. Ionic conductivity of LiTi2(PO4)3 mixed with lithium salts. Chem. Lett. 19, 331-334 (1990).

  • 318. He, L. X. & Yoo, H. I. Effects of B-site ion (M) substitution on the ionic conductivity of (Li3xLa2/3−x)1+y/2(MyTi1−y)O3 (M=Al, Cr). Electrochimica Acta 48, 1357-1366 (2003).

  • 319. Inaguma, Y., Chen, L., Itoh, M. & Nakamura, T. Candidate compounds with perovskite structure for high lithium ionic conductivity. Solid State Ion. 70-71, 196-202 (1994).

  • 320. Chung, H.-T., Kim, J.-G. & Kim, H.-G. Dependence of the lithium ionic conductivity on the B-site ion substitution in (Li0.5La0.5)Ti1−xMxO3 (M=Sn, Zr, Mn, Ge). Solid State Ion. 107, 153-160 (1998).

  • 321. Thangadurai, V. & Weppner, W. Effect of B-site substitution of (Li,La)TiO3 perovskites by di-, tr-, tetra- and hexavalent metal ions on the lithium ion conductivity. Ionics 6, 70-77 (2000).

  • 322. Morata-Orrantia, A., Garcia-Martin, S., Morán, E. & Alario-Franco, M. Á. A New La2/3LixTi1−xAlxO3 solid solution: structure, microstructure, and Li+ conductivity. Chem. Mater. 14, 2871-2875 (2002).

  • 323. Kawai, H. & Kuwano, J. Lithium ion conductivity of A-site deficient perovskite solid solution La0.67−xLi3xTiO3. J. Electrochem. Soc. 141, L78 (1994).

  • 324. Zhang, Y., Chen, K., Shen, Y., Lin, Y. & Nan, C.-W. Enhanced lithium-ion conductivity in a LiZr2(PO4)3 solid electrolyte by Al doping. Ceram. Int. 43, S598-S602 (2017).

  • 325. Chowdari, B. V. R., Radhakrishnan, K., Thomas, K. A. & Subba Rao, G. V. Ionic conductivity studies on Li1−xM2−xM′xP3O12 (H=Hf, Zr; M′=Ti, Nb). Mater. Res. Bull. 24, 221-229 (1989).

  • 326. Ado, K., Saito, Y., Asai, T., Kageyama, H. & Nakamura, O. Li+-ion conductivity of Li1+xMxTi2−x(PO4)3 (M: Sc3+, Y3+). Solid State Ion. 53-56, 723-727 (1992).

  • 327. Xiong, L. et al. LiF assisted synthesis of LiTi2(PO4)3 solid electrolyte with enhanced ionic conductivity. Solid State Ion. 309, 22-26 (2017).

  • 328. Fu, J. Superionic conductivity of glass-ceramics in the system Li2O—Al2O3—TiO2—P2O5. Solid State Ion. 96, 195-200 (1997).

  • 329. Dhivya, L. & Murugan, R. Effect of simultaneous substitution of Y and Ta on the stabilization of cubic phase, microstructure, and Li+ conductivity of Li7La3Zr2O12 lithium garnet. ACS Appl. Mater. Interfaces 6, 17606-17615 (2014).

  • 330. Liu, Z., Huang, F., Yang, J., Wang, B. & Sun, J. New lithium ion conductor, thio-LISICON lithium zirconium sulfide system. Solid State Ion. 179, 1714-1716 (2008).

  • 331. Chen, H. & Adams, S. Bond softness sensitive bond-valence parameters for crystal structure plausibility tests. IUCrJ 4, 614-625 (2017).

  • 332. Adams, S. Practical considerations in determining bond valence parameters. in Bond Valences (eds. Brown, I. D. & Poeppelmeier, K. R.) 91-128 (Springer, 2014). doi:10.1007/430_2013_96.

  • 333. He, B. et al. A highly efficient and informative method to identify ion transport networks in fast ion conductors. Acta Mater. 203, 116490 (2021).

  • 334. Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901-9904 (2000).

  • 335. Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978-9985 (2000).

  • 336. Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).

  • 337. Giannozzi, P. et al. Advanced capabilities for materials modelling with Quantum ESPRESSO. J. Phys. Condens. Matter 29, 465901 (2017).

  • 338. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865-3868 (1996).

  • 339. Dal Corso, A. Pseudopotentials periodic table: From H to Pu. Comput. Mater. Sci. 95, 337-350 (2014).

  • 340. Xu, X. et al. Lithium reaction mechanism and high rate capability of VS4-graphene nanocomposite as an anode material for lithium batteries. J. Mater. Chem. A 2, 10847-10853 (2014).

  • 341. Britto, S. et al. Multiple redox modes in the reversible lithiation of high-capacity, Peierls-distorted vanadium sulfide. J. Am. Chem. Soc. 137, 8499-8508 (2015).

  • 342. Lian, R. et al. Nucleation and conversion transformations of the transition metal polysulfide VS4 in lithium-ion batteries. ACS Appl. Mater. Interfaces 11, 22307-22313 (2019).

  • 343. Geller, S. Refinement of the crystal structure of cryolithionite, {Na3}[Al2](Li3)F12. Am. Mineral. 56, 18-23 (1971).

  • 344. Xiao, R., Li, H. & Chen, L. Candidate structures for inorganic lithium solid-state electrolytes identified by high-throughput bond-valence calculations. J. Materiomics 1, 325-332 (2015).

  • 345. Liu, Z., Sun, Y., Singh, D. J. & Zhang, L. Switchable out-of-plane polarization in 2D LiAlTe2. Adv. Electron. Mater. 5, 1900089 (2019).

  • 346. Ma, C.-G. & Brik, M. G. First principles studies of the structural, electronic and optical properties of LiInSe2 and LiInTe2 chalcopyrite crystals. Solid State Commun. 203, 69-74 (2015).

  • 347. Augustine, A. M., Sudarsanan, V., Patra, L., Kavitha, M. & Ravindran, P. Li-rich Li6MnxFe(1−x)S4 as cathode material for Li-ion battery. AIP Conf. Proc. 2115, 030623 (2019).

  • 348. Isaenko, L. et al. LiGaTe2: A new highly nonlinear chalcopyrite optical crystal for the mid-IR. Cryst. Growth Des. 5, 1325-1329 (2005).

  • 349. Bianchini, F., Fjellvåg, H. & Vajeeston, P. A first-principle investigation of the Li diffusion mechanism in the super-ionic conductor lithium orthothioborate Li3BS3 structure. Mater. Lett. 219, 186-189 (2018).

  • 350. Suzuki, N. et al. Theoretical and experimental studies of KLi6TaO6 as a Li-ion solid electrolyte. Inorg. Chem. 60, 10371-10379 (2021).

  • 351. Kawasaki, Y. et al. Synthesis and electrochemical properties of Li3CuS2 as a positive electrode material for all-solid-state batteries. ACS Appl. Energy Mater. 4, 20-24 (2021).

  • 352. Huang, F. Q., Yang, Y., Flaschenriem, C. & Ibers, J. A. Syntheses and structures of LiAuS and Li3AuS2. Inorg. Chem. 40, 1397-1398 (2001).

  • 353. Kahle, L., Marcolongo, A. & Marzari, N. High-throughput computational screening for solid-state Li-ion conductors. Energy Environ. Sci. 13, 928-948 (2020).

  • 354. Muy, S. et al. High-throughput screening of solid-state Ii-ion conductors using lattice-dynamics descriptors. iScience 16, 270-282 (2019).

  • 355. Li, X. et al. Progress and perspectives on halide lithium conductors for all-solid-state lithium batteries. Energy Environ. Sci. 13, 1429-1461 (2020).

  • 356. Sendek, A. D. et al. Machine learning-assisted discovery of many new solid Li-ion conducting materials. ArXiv180802470 Cond-Mat Physicsphysics (2018).

  • 357. Kim, Y., Martin, S. W., Ok, K. M. & Halasyamani, P. S. Synthesis of the thioborate crystal ZnxBa2B2S5+x (x≈0.2) for second order nonlinear optical applications. Chem. Mater. 17, 2046-2051 (2005).

  • 358. Wang, Y. et al. Design principles for solid-state lithium superionic conductors. Nat. Mater. 14, 1026-1031 (2015).

  • 359. Li, P. & Liu, Z.-H. Hydrothermal synthesis, characterization, and thermodynamic properties of a new lithium borate, Li3B5O8(OH)2. J. Chem. Eng. Data 55, 2682-2686 (2010).

  • 360. Snydacker, D. H., Hegde, V. I. & Wolverton, C. Electrochemically stable coating materials for Li, Na, and Mg metal anodes in durable high energy batteries. J. Electrochem. Soc. 164, A3582 (2017).

  • 361. Sakuda, A. et al. Amorphous metal polysulfides: electrode materials with unique insertion/extraction reactions. J. Am. Chem. Soc. 139, 8796-8799 (2017).

  • 362. He, X. et al. Crystal structural framework of lithium super-ionic conductors. Adv. Energy Mater. 9, 1902078 (2019).

  • 363. D. Richards, W., Wang, Y., J. Miara, L., Chul Kim, J. & Ceder, G. Design of Li1+2xZn1−xPS4, a new lithium ion conductor. Energy Environ. Sci. 9, 3272-3278 (2016).

  • 364. Chen, E. M. & Poudeu, P. F. P. Thermal and electrochemical behavior of Cu4−xLixS2 (x=1, 2, 3) phases. J. Solid State Chem. 232, 8-13 (2015).

  • 365. Devlin, K. P. et al. Polymorphism and second harmonic generation in a novel diamond-like semiconductor: Li2MnSnS4. J. Solid State Chem. 231, 256-266 (2015).

  • 366. Steiner, H. J. & Lutz, H. D. Li2BeCl4 and Na2BeCl4: Two olivine-type chlorides. J. Solid State Chem. 100, 179-181 (1992).

  • 367. Rao, K. K., Yao, Y. & Grabow, L. C. Accelerated modeling of lithium diffusion in solid state electrolytes using artificial neural networks. Adv. Theory Simul. 3, 2000097 (2020).

  • 368. Körbel, S., L. Marques, M. A. & Botti, S. Stability and electronic properties of new inorganic perovskites from high-throughput ab initio calculations. J. Mater. Chem. C 4, 3157-3167 (2016).

  • 369. Prömper, S. W. & Frank, W. Lithium tetra-chlorido-aluminate, LiAlCl4: a new polymorph (oP12, Pmn21) with Li+ in tetra-hedral inter-stices. Acta Crystallogr. Sect. E Crystallogr. Commun. 73, 1426-1429 (2017).

  • 370. Abdel-Khalek, E. K., Mohamed, E. A., Salem, S. M., Ebrahim, F. M. & Kashif, I. Study of glass-nanocomposite and glass-ceramic containing ferroelectric phase. Mater. Chem. Phys. 133, 69-77 (2012).

  • 371. Rousse, G., Baptiste, B. & Lelong, G. Crystal structures of Li6B4O9 and Li3B11O18 and application of the dimensional reduction formalism to lithium borates. Inorg. Chem. 53, 6034-6041 (2014).

  • 372. Branford, W., Green, M. A. & Neumann, D. A. Structure and ferromagnetism in Mn4+ spinels: AM0.5Mn1.5O4 (A=Li, Cu; M=Ni, Mg). Chem. Mater. 14, 1649-1656 (2002).

  • 373. Li, G., Chu, Y. & Zhou, Z. From AgGaS2 to Li2ZnSiS4: realizing impressive high laser damage threshold together with large second-harmonic generation response. Chem. Mater. 30, 602-606 (2018).

  • 1. Park, H., Yu, S. & Siegel, D. J. Predicting Charge Transfer Stability between Sulfide Solid Electrolytes and U Metal Anodes. ACS Energy Lett. 6, 150-157 (2021).

  • 2. Kimura, T. et al. Characteristics of a U3BS3 Thioborate Glass Electrolyte Obtained via a Mechanochemical Process. ACS Appl. Energy Mater. 5, 1421-1426 (2022).



STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS

All references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference, to the extent each reference is at least partially not inconsistent with the disclosure in this application (for example, a reference that is partially inconsistent is incorporated by reference except for the partially inconsistent portion of the reference).


The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments, exemplary embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the present invention and it will be apparent to one skilled in the art that the present invention may be carried out using a large number of variations of the devices, device components, methods steps set forth in the present description. As will be obvious to one of skill in the art, methods and devices useful for the present methods can include a large number of optional composition and processing elements and steps.


As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural reference unless the context clearly dictates otherwise. Thus, for example, reference to “a cell” includes a plurality of such cells and equivalents thereof known to those skilled in the art. As well, the terms “a” (or “an”), “one or more” and “at least one” can be used interchangeably herein. It is also to be noted that the terms “comprising”, “including”, and “having” can be used interchangeably. The expression “of any of claims XX-YY” (wherein XX and YY refer to claim numbers) is intended to provide a multiple dependent claim in the alternative form, and in some embodiments is interchangeable with the expression “as in any one of claims XX-YY.”


When a group of substituents is disclosed herein, it is understood that all individual members of that group and all subgroups, including any isomers, enantiomers, and diastereomers of the group members, are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. When a compound is described herein such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomers and enantiomer of the compound described individual or in any combination. Additionally, unless otherwise specified, all isotopic variants of compounds disclosed herein are intended to be encompassed by the disclosure. For example, it will be understood that any one or more hydrogens in a molecule disclosed can be replaced with deuterium or tritium. Isotopic variants of a molecule are generally useful as standards in assays for the molecule and in chemical and biological research related to the molecule or its use. Methods for making such isotopic variants are known in the art. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently.


Certain molecules disclosed herein may contain one or more ionizable groups [groups from which a proton can be removed (e.g., —COOH) or added (e.g., amines) or which can be quaternized (e.g., amines)]. All possible ionic forms of such molecules and salts thereof are intended to be included individually in the disclosure herein. With regard to salts of the compounds herein, one of ordinary skill in the art can select from among a wide variety of available counterions those that are appropriate for preparation of salts of this invention for a given application. In specific applications, the selection of a given anion or cation for preparation of a salt may result in increased or decreased solubility of that salt.


Every device, cell, electrolyte, material, composition, and method described or exemplified herein can be used to practice the invention, unless otherwise stated.


Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition or concentration range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. It will be understood that any subranges or individual values in a range or subrange that are included in the description herein can be excluded from the claims herein.


All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art as of their publication or filing date and it is intended that this information can be employed herein, if needed, to exclude specific embodiments that are in the prior art.


As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, “consisting of” excludes any element, step, or ingredient not specified in the claim element. As used herein, “consisting essentially of” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In each instance herein any of the terms “comprising”, “consisting essentially of” and “consisting of” may be replaced with either of the other two terms. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.


One of ordinary skill in the art will appreciate that starting materials, biological materials, reagents, synthetic methods, purification methods, analytical methods, assay methods, and biological methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such materials and methods are intended to be included in this invention. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.

Claims
  • 1. A material comprising: a lithium thioborate composition characterized by formula FX4: Li3−yBS3−yGy  (FX4);wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;wherein y is a number greater than 0 and less than or equal to 0.40; andwherein G is one or more Group 17 (halogen) elements.
  • 2. A material comprising: a lithium thioborate composition characterized by formula FX2: Li3−x−yB1−xQxS3−yGy  (FX2);wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;wherein x is a number greater than 0 and less than or equal to 0.10;wherein y is a number greater than 0 and less than or equal to 0.40; andwherein G is one or more Group 17 (halogen) elements.
  • 3. The material of claim 1 having a greater ionic conductivity than that of an undoped stoichiometric Li3BS3 material by a factor of at least 10 at 25° C., wherein the undoped stoichiometric Li3BS3 is free of Q and G.
  • 4. The material of claim 1 being characterized by an ionic conductivity greater than 1·10−4 S/cm at 25° C.
  • 5. The material of claim 1 being characterized by an ionic conductivity greater than or equal to 1·10−3 S/cm at 25° C.
  • 6. The material of claim 2, wherein the composition is characterized by the ratio Q/(B+Q) being greater than 0.001 and less than 0.20.
  • 7. The material of claim 2, wherein the composition is characterized by the ratio Q/(B+Q) being greater than 0.020 and less than 0.075.
  • 8. The material of claim 2, wherein Q is Si and/or Ge.
  • 9. The material of claim 1, wherein the composition is characterized by the ratio G/(S+G) being greater than 0.001 and less than 0.20.
  • 10. The material of claim 1, wherein the composition is characterized by the ratio G/(S+G) being greater than 0.020 and less than 0.2.
  • 11. The material of claim 1, wherein G is Cl and/or Br.
  • 12. The material of claim 1, wherein y is selected from the range of 0.005 to 0.20.
  • 13. The material of claim 2, wherein x is selected from the range of 0.005 to 0.05.
  • 14. The material of claim 1 having a total crystallinity less than or equal to 20 wt. %.
  • 15. The material of claim 1 being characterized by an electronic conductivity less than 4·10−10 S/cm at 25° C.
  • 16. The material of claim 1 being characterized by an activation energy (Ea) for an ionic conductivity of less than 400 meV when its temperature-dependent ionic conductivity is fit to equation EQ1:
  • 17. The material of claim 1, wherein charge carriers of the material are monovalent.
  • 18. A device comprising: a material, the material comprising: a lithium thioborate composition characterized by formula FX4: Li3−yBS3−yGy  (FX4);wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;wherein y is a number greater than 0 and less than or equal to 0.40; andwherein G is one or more Group 17 (halogen) elements.
  • 19. A device comprising: a material, the material comprising: a lithium thioborate composition characterized by formula FX2: Li3−x−yB1−xQxS3−yGy  (FX2);wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;wherein x is a number greater than 0 and less than or equal to 0.10;wherein y is a number greater than 0 and less than or equal to 0.40; andwherein G is one or more Group 17 (halogen) elements.
  • 20. The device of claim 18 being an electrochemical cell.
  • 21. The device of claim 20, wherein the electrochemical cell comprises a solid state electrolyte having the material.
  • 22. The device of claim 18 being a rechargeable lithium battery.
  • 23. A solid state electrolyte comprising: a lithium thioborate composition characterized by formula FX4: Li3−yBS3−yGy  (FX4);wherein G is a dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;wherein y is a number greater than 0 and less than or equal to 0.40; andwherein G is one or more Group 17 (halogen) elements.
  • 24. A solid state electrolyte comprising: a lithium thioborate composition characterized by formula FX2: Li3−x−yB1−xQxS3−yGy  (FX2);wherein Q is a first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;wherein G is a second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;wherein x is a number greater than 0 and less than or equal to 0.10;wherein y is a number greater than 0 and less than or equal to 0.40; andwherein G is one or more Group 17 (halogen) elements.
  • 25. A method of making a material, the method comprising: combining a plurality of precursors comprising lithium, boron, sulfur, and a dopant; andheating the combined plurality of precursors to form the material having a lithium thioborate composition;wherein the lithium thioborate composition is characterized by formula FX4: Li3−yBS3−yGy  (FX4);wherein G is the dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;wherein z is a number greater than 0 and less than or equal to 0.40; andwherein G is one or more Group 17 (halogen) elements.
  • 26. A method of making a material, the method comprising: combining a plurality of precursors comprising lithium, boron, sulfur, a first dopant, and a second dopant; andheating the combined plurality of precursors to form the material having a lithium thioborate composition;wherein the lithium thioborate composition is characterized by formula FX2: Li3−x−yB1−xQxS3−yGy  (FX2);wherein Q is the first dopant being a substitute for B in the composition and being one or more elements each aliovalent with respect to B;wherein G is the second dopant being a substitute for S in the composition and being one or more elements each aliovalent with respect to S;wherein x is a number greater than 0 and less than or equal to 0.10;wherein y is a number greater than 0 and less than or equal to 0.40; andwherein G is one or more Group 17 (halogen) elements.
CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. Provisional Patent Application No. 63/470,512, filed Jun. 2, 2023, which is hereby incorporated by reference in its entirety. This application is also a continuation-in-part of U.S. patent application Ser. No. 18/205,179, filed Jun. 2, 2023, which application claims priority to U.S. Provisional Patent Application No. 63/348,603, filed Jun. 3, 2022, each of which are hereby incorporated by reference in their entirety.

Provisional Applications (2)
Number Date Country
63470512 Jun 2023 US
63348603 Jun 2022 US
Continuation in Parts (1)
Number Date Country
Parent 18205179 Jun 2023 US
Child 18680196 US