Patent Grant
12129171
Lithium compound-containing electrochemical cells and batteries including such cells are modern means for storing energy. They exceed certain conventional secondary batteries with respect to capacity and life-time and, in many times, use of toxic materials such as lead can be avoided. However, in contrast to conventional lead-based secondary batteries, various technical problems have not yet been solved.
Secondary batteries based on cathodes including lithiated metal oxides such as LiCoO2, LiMn2O4, and LiFePO4 are well established. However, some batteries of this type are limited in capacity. For that reason, numerous attempts have been made to improve the electrode materials. Particularly promising are so-called lithium sulfur batteries. In such batteries, lithium will be oxidized and converted to lithium sulfides such as Li2S8-a, a being a number in the range from zero to 7. During recharging, lithium and sulfur will be regenerated. Such secondary cells have the advantage of a high capacity.
Sulfide materials of different compositions and nature are known to be lithium-ion conductors (e.g., Li2Sx/P2S5 glasses, Li2Sx/P2S5-derived glass ceramics, Li7P3S11, thio-LISICON, oxysulfide glasses). However, such materials may suffer from issues such as low stability against liquid organic electrolyte solutions, insufficient stability against metallic lithium or high voltage cathode materials, extreme sensitivity to moisture and/or air, and/or an intrinsically low ionic conductivity.
Accordingly, improved lithium-ion ionically conductive compounds are needed.
Articles, compositions, and methods involving ionically conductive compounds are provided. In some embodiments, the ionically conductive compounds are useful for electrochemical cells.
The subject matter of the present invention involves, in some cases, interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of one or more systems and/or articles.
In one aspect, articles for use in an electrochemical cell are provided. In some embodiments, the article comprises a compound of formula (I):
LixMyQwPzSuXt (I)
wherein M is selected from the group consisting of Na, K, Fe, Mg, Ag, Cu, Zr, and Zn, Q is absent or selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Fe, Ga, Al, As, and combinations thereof, and wherein Q, when present, is different than M, X is absent or selected from the group consisting of halide and pseudohalide, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8.
In certain embodiments, Q is present and Q is a combination of two or more atoms selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Fe, Ga, and Al, and wherein the stoichiometric ratio of each atom in Q is such that the total amount of atoms present in Q is w and is 0-3.
In certain embodiments, the compound has an argyrodite-type crystal structure.
In certain embodiments, Q is present and at least a portion of Q, and P are tetrahedrally coordinated in the argyrodite-type crystal structure.
In certain embodiments, at least a portion of Li and at least a portion of M occupy a Rietveld Refinement lithium lattice site on the crystal structure.
In certain embodiments, at least a portion of Li and at least a portion of M occupy a Rietveld Refinement 48 h lattice site on the crystal structure.
In certain embodiments, the article comprises a layer comprising the compound of formula (I).
In certain embodiments, the article comprises the compound of formula (I) deposited on a layer.
In another aspect, compounds are provided. In some embodiments, the compound of formula (I) has an argyrodite-type crystal structure:
LixMyQwPzSuXt (I),
wherein M is selected from the group consisting of Na, K, Fe, Mg, Ag, Cu, Zr, and Zn, Q is absent or selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Fe, Ga, Al, and combinations thereof, and wherein Q, when present, is different than M, X is absent or selected from the group consisting of halide and pseudohalide, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8.
In certain embodiments, the argyrodite-type crystal structure is the space group F43m.
In yet another aspect, methods for forming a composition are provided. In some embodiments, the method comprises heating a mixture of precursors comprising atoms of the elements Li, S, P, M, optionally Q, and optionally X, to a temperature ranging from 500° C. to 1200° C. for a duration ranging from 3 hours to 24 hours, cooling the mixture, and forming a composition comprising a compound of formula (I) having an argyrodite-type crystal structure:
LixMyQwPzSuXt (I)
Wherein M is selected from the group consisting of Na, K, Fe, Mg, Ag, Cu, Zr, and Zn, Q is absent or selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Fe, Ga, Al, and combinations thereof, and wherein Q, when present, is different than M, X is absent or selected from the group consisting of halide and pseudohalide, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8.
In certain embodiments, the mixture of precursors comprises at least two of Li2S, MSa, PbSc, QSd, LiX, Q, and S, wherein a is 0-8, b is 0-2, c is 0-8, such that b+c is 1 or greater, and d is 0-3.
In some embodiments, an electrochemical cell is provided comprising an article or compound described herein.
In certain embodiments, the electrochemical cell further comprises a liquid electrolyte.
In certain embodiments, the electrochemical cell comprises an anode comprising lithium or silicon. In certain embodiments, the electrochemical cell comprises a cathode comprising sulfur. In certain embodiments, the electrochemical cell comprises a cathode comprising a lithium-intercalation species.
In certain embodiments, M is monovalent. In certain embodiments, M is bivalent. In certain embodiments, M is trivalent. In certain embodiments, M is tetravalent. In certain embodiments, M is pentavalent. In certain embodiments, M is Fe.
In certain embodiments, X is absent. In certain embodiments, X is present and is a halide selected from the group consisting of Cl, I, and Br.
In certain embodiments, the article comprises a plurality of particles comprising the compound of formula (I). In certain embodiments, the plurality of particles have an average largest cross-sectional dimension of greater than or equal to 10 nm and less than or equal to 100 microns.
In certain embodiments, a layer including the compound of formula (I) has an average ion conductivity of greater than or equal to 10−5 S/cm. In certain embodiments, the layer comprising the compound of formula (I) is in direct contact with an electrode. In certain embodiments, the layer comprising the compound of formula (I) is a separator. In certain embodiments, the layer comprising the compound of formula (I) is a protective layer. In certain embodiments, the layer comprising the compound of formula (I) is a solid electrolyte layer. In certain embodiments, the layer comprising the compound of formula (I) has a thickness of greater than or equal to 0.05 microns and less than or equal to 200 microns. In certain embodiments, the layer comprising the compound of formula (I) is deposited on a lithium-intercalation electrode. In certain embodiments, at least a portion of the layer comprising the compound of formula (I) is crystalline (or wherein the compound of formula (I) is crystalline). In certain embodiments, the layer comprising the compound of formula (I) is greater than or equal to 50 wt. % and less than or equal to 99 wt. % crystalline.
In certain embodiments, prior to heating, the mixture is mixed by ball milling.
In certain embodiments, heating the mixture occurs at a pressure of between 0.1 MPa and 0.3 MPa.
In certain embodiments, depositing the compound of formula (I) on the layer comprises aerosol deposition. In certain embodiments, depositing the compound of formula (I) on the layer comprises vacuum deposition.
In certain embodiments, the layer on which the particles are deposited is an electrode. In certain embodiments, the layer on which the particles are deposited is a lithium metal layer. In certain embodiments, the layer on which the particles are deposited is a protective layer or a separator.
Other advantages and novel features of the present invention will become apparent from the following detailed description of various non-limiting embodiments of the invention when considered in conjunction with the accompanying figures. In cases where the present specification and a document incorporated by reference include conflicting and/or inconsistent disclosure, the present specification shall control. If two or more documents incorporated by reference include conflicting and/or inconsistent disclosure with respect to each other, then the document having the later effective date shall control.
Non-limiting embodiments of the present invention will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the invention shown where illustration is not necessary to allow those of ordinary skill in the art to understand the invention. In the figures:
Articles, compositions, and methods involving ionically conductive compounds are provided. In some embodiments, the ionically conductive compounds are useful for electrochemical cells. The disclosed ionically conductive compounds may be incorporated into an electrochemical cell (e.g., a lithium-sulfur electrochemical cell, a lithium-ion electrochemical cell, an intercalated-cathode based electrochemical cell) as, for example, a protective layer for an electrode, a solid electrolyte layer, and/or any other appropriate component within the electrochemical cell. In certain embodiments, electrode structures and/or methods for making electrode structures including a layer comprising an ionically conductive compound described herein are provided.
The incorporation of ionically conductive compounds as described herein into electrochemical cells may, for example, increase the stability of an electrode (e.g., a lithium electrode) in the electrochemical cell, increase ionic conductivity, and/or may facilitate fabrication (e.g., formation of thin layers), as compared to certain existing ionically conductive compounds used in electrochemical cells. Advantageously, in some cases, increasing the stability of an electrode may also increase the ionic conductivity and/or increase the overall safety of the battery. In some embodiments, the incorporation of ionically conductive compounds as described herein into electrochemical cells may prevent or reduce the occurrence of chemical reactions between a component of an electrolyte (e.g., polysulfides) and an electroactive material of an anode (e.g., an anode comprising lithium, such as metallic lithium) as compared to electrochemical cells with certain existing ionically conductive compounds and/or compared to electrochemical cells without the ionically conductive compounds described herein.
Layers comprising the ionically conductive compound, as described in more detail herein, may, in some cases, selectively conduct lithium cations but not anions, and may function as a barrier (e.g., protective structure) for electrolytes (e.g., liquid electrolytes). For example, the use of the ionically conductive compounds in a protective layer (e.g., in an electrochemical cell including a liquid electrolyte) may offer several advantages over certain existing protective layers, including reduction in the consumption of lithium (e.g., lithium metal) during charge/discharge of the electrochemical cell. The protective layer may be used to substantially inhibit direct contact of an electrode (e.g., the anode, the cathode) with an electrolyte and/or a particular species present in the electrolyte. In some embodiments, the use of ionically conductive compounds described herein in solid electrolyte layers (e.g., in solid state electrochemical cells) may offer several advantages over certain existing solid electrolytes including increased ion conductivity and/or increased chemical stability.
The disclosed ionically conductive compounds may be incorporated into electrochemical cells including primary batteries or secondary batteries, which can be charged and discharged numerous times. In certain embodiments, the articles, compositions, and methods described herein can be used in association with batteries including a liquid electrolyte. However, in other embodiments, the articles, compositions, and methods described herein can be used in association with solid state batteries.
In some embodiments, the materials, systems, and methods described herein can be used in association with lithium batteries (e.g., lithium-sulfur batteries). It should be appreciated, however, that while much of the description herein relates to lithium-sulfur batteries, the ionically conductive compounds and layers comprising ionically conductive compounds described herein may be applied to other lithium-based batteries, including other alkali metal-based batteries.
The electrochemical cells described herein may be employed in various applications, for example, making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks.
In some embodiments, the stability and/or conductivity of the ionically conductive compound (and/or layers comprising the ionically conductive compound) may be increased by doping the compound with an anion (e.g., a halide, a pseudohalide). Without wishing to be bound by theory, in certain embodiments, the anion may at least partially substitute an element, such as sulfur, within the compound.
In certain embodiments, the stability and/or conductivity of the ionically conductive compound (and/or layers comprising the ionically conductive compound) may also be, or alternatively be, increased by the incorporation of one or more cations into the compound. Without wishing to be bound by theory, in certain embodiments, the cation may at least partially substitute an element such as a phosphorous group (e.g., by a cation such as silicon, tin, germanium, zinc, iron, zirconium, aluminum) within the compound.
The inventors have discovered within the context of the description herein, in some embodiments, that the stability and/or conductivity of the ionically conductive compound (and/or layers comprising the ionically conductive compound) may also be, or alternatively be, increased by a partial substitution of lithium ions in the compound by one or more other cations such as Na, K, Fe, Mg, Ag, Cu, Zr, Zn, and combinations thereof. For example, the cation may, in some cases, occupy at least one lattice site on a lattice structure of the compound which would otherwise occupied by lithium ion if the cation were not present. In an exemplary embodiment, lithium ions in the compound are at least partially substituted by iron. Without wishing to be bound by theory, the cation (e.g., Na, K, Fe, Mg, Ag, Cu, Zr, Zn) may at least partially substitute lithium ions due to a similarity in structure (e.g., ionic radius) to that of lithium ion. For example, the cation which at least partially substitutes lithium ions in the compound may, in some cases, have an ionic radius that is within 25% (e.g., within 20%, within 15%, within 10%, within 5%) of the ionic radius of lithium ion.
In some embodiments, the ionically conductive compounds described herein may be doped with an anion and/or comprise one or more cations (e.g., at least partially substituting phosphorous and/or at least partially substituting lithium ions), e.g., such that the stability and/or conductivity of the ionically conductive compound is increased (e.g., as compared to an ionically conductive compound otherwise lacking the substituted anion and/or one or more cations).
In some embodiments, the ionically conductive compound has a composition as in formula (I):
LixMyQwPzSuXt (I),
wherein M is selected from the group consisting of Na, K, Fe, Mg, Ag, Cu, Zr, and Zn, wherein Q is absent or selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Fe, Ga, Al, As, and combinations thereof, wherein X is absent or selected from the group consisting of halide and pseudohalide, and wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8. In some embodiments, Q, when present, is different than M.
In some embodiments, the ionically conductive compound has a composition as in formula (I) and x is 8-22, 8-16, 8-12, 10-12, 10-14, 12-16, 14-18, 16-20, or 18-22. In some embodiments x is 8 or greater, 8.5 or greater, 9 or greater, 9.5 or greater, 10 or greater, 10.5 or greater, 11 or greater, 11.5 or greater, 12 or greater, 12.5 or greater, 13 or greater, 13.5 or greater, 14 or greater, 14.5 or greater, 15 or greater, 15.5 or greater, 16 or greater, 16.5 or greater, 17 or greater, 17.5 or greater, 18 or greater, 18.5 or greater, 19 or greater, 19.5 or greater, 20 or greater, 20.5 or greater, 21 or greater, or 21.5 or greater. In certain embodiments, x is less than or equal to 22, less than or equal to 21.5, less than or equal to 21, less than or equal to 20.5, less than or equal to 20, less than or equal to 19.5, less than or equal to 19, less than or equal to 18.5, less than or equal to 18, less than or equal to 17.5, less than or equal to 17, less than or equal to 16.5, less than or equal to 16, less than or equal to 15.5, less than or equal to 15, less than or equal to 14.5, less than or equal to 14, less than or equal to 13.5, less than or equal to 13, less than or equal to 12.5, less than or equal to 12, less than or equal to 11.5, less than or equal to 11, less than or equal to 10.5, less than or equal to 10, less than or equal to 9.5, or less than or equal to 9. Combinations of the above referenced ranges are also possible (e.g., greater than or equal to 8 and less than or equal to 22, greater than or equal to 10 and less than or equal to 12). Other ranges are also possible. In some embodiments, x is 10. In certain embodiments, x is 11. In some cases, x is 12. In certain embodiments, x is 13. In some embodiments, x is 14. In some cases, x is 18. In certain embodiments, x is 22.
In certain embodiments, the ionically conductive compound has a composition as in formula (I) and y is 0.1-3, 0.1-1, 0.1-1.5, 0.1-2, 0.5-3, 0.8-3, 1-3, or 2-3. For example, in some embodiments, y is 1. In some embodiments, y is greater than or equal to 0.1, greater than or equal to 0.2, greater than or equal to 0.25, greater than or equal to 0.4, greater than or equal to 0.5, greater than or equal to 0.6, greater than or equal to 0.75, greater than or equal to 0.8, greater than or equal to 1, greater than or equal to 1.2, greater than or equal to 1.25, greater than or equal to 1.4, greater than or equal to 1.5, greater than or equal to 1.6, greater than or equal to 1.75, greater than or equal to 1.8, greater than or equal to 2.0, greater than or equal to 2.25, greater than or equal to 2.4, greater than or equal to 2.5, greater than or equal to 2.6, greater than or equal to 2.75, or greater than or equal to 2.8. In certain embodiments, y is less than or equal to 3.0, less than or equal to 2.8, less than or equal to 2.75, less than or equal to 2.6, less than or equal to 2.5, less than or equal to 2.4, less than or equal to 2.25, less than or equal to 2.2, less than or equal to 2.0, less than or equal to 1.8, less than or equal to 1.75, less than or equal to 1.6, less than or equal to 1.5, less than or equal to 1.4, less than or equal to 1.25, less than or equal to 1.2, less than or equal to 1.0, less than or equal to 0.8, less than or equal to 0.75, less than or equal to 0.6, less than or equal to 0.5, less than or equal to 0.4, less than or equal to 0.25, or less than or equal to 0.2. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.1 and less than or equal to 3.0, greater than or equal to 1 and less than or equal to 3, greater than or equal to 0.1 and less than or equal to 2.5, greater than or equal to 1.0 and less than or equal to 2.0). Other ranges are also possible. In an exemplary embodiment, y is 1. In another exemplary embodiment, y is 0.5. In some embodiments, y is 0.75.
In certain embodiments, the ionically conductive compound has a composition as in formula (I) and w is 0-3, 0.1-3, 0.1-1, 0.1-1.5, 0.1-2, 0.5-3, 0.8-3, 1-3, or 2-3. For example, in some embodiments, w is 1. In some embodiments, w is greater than or equal to 0, greater than or equal to 0.1, greater than or equal to 0.2, greater than or equal to 0.25, greater than or equal to 0.4, greater than or equal to 0.5, greater than or equal to 0.6, greater than or equal to 0.75, greater than or equal to 0.8, greater than or equal to 1, greater than or equal to 1.2, greater than or equal to 1.25, greater than or equal to 1.4, greater than or equal to 1.5, greater than or equal to 1.6, greater than or equal to 1.75, greater than or equal to 1.8, greater than or equal to 2.0, greater than or equal to 2.25, greater than or equal to 2.4, greater than or equal to 2.5, greater than or equal to 2.6, greater than or equal to 2.75, or greater than or equal to 2.8. In certain embodiments, w is less than or equal to 3.0, less than or equal to 2.8, less than or equal to 2.75, less than or equal to 2.6, less than or equal to 2.5, less than or equal to 2.4, less than or equal to 2.25, less than or equal to 2.2, less than or equal to 2.0, less than or equal to 1.8, less than or equal to 1.75, less than or equal to 1.6, less than or equal to 1.5, less than or equal to 1.4, less than or equal to 1.25, less than or equal to 1.2, less than or equal to 1.0, less than or equal to 0.8, less than or equal to 0.75, less than or equal to 0.6, less than or equal to 0.5, less than or equal to 0.4, less than or equal to 0.25, less than or equal to 0.2, or less than or equal to 0.1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 and less than or equal to 3, greater than or equal to 0.1 and less than or equal to 3.0, greater than or equal to 1 and less than or equal to 3, greater than or equal to 0.1 and less than or equal to 2.5, greater than or equal to 1.0 and less than or equal to 2.0). Other ranges are also possible. In an exemplary embodiment, w is 1. In another exemplary embodiment, w is 0.5. In some embodiments, w is 0.75. In some cases, w is 0.
In certain embodiments, the ionically conductive compound has a composition as in formula (I) and z is 0.1-3, 0.1-1, 0.1-1.5, 0.1-2, 0.5-3, 0.8-3, 1-3, or 2-3. For example, in some embodiments, z is 1. In some embodiments, z is greater than or equal to 0.1, greater than or equal to 0.2, greater than or equal to 0.25, greater than or equal to 0.4, greater than or equal to 0.5, greater than or equal to 0.6, greater than or equal to 0.75, greater than or equal to 0.8, greater than or equal to 1, greater than or equal to 1.2, greater than or equal to 1.25, greater than or equal to 1.4, greater than or equal to 1.5, greater than or equal to 1.6, greater than or equal to 1.75, greater than or equal to 1.8, greater than or equal to 2.0, greater than or equal to 2.25, greater than or equal to 2.4, greater than or equal to 2.5, greater than or equal to 2.6, greater than or equal to 2.75, or greater than or equal to 2.8. In certain embodiments, z is less than or equal to 3.0, less than or equal to 2.8, less than or equal to 2.75, less than or equal to 2.6, less than or equal to 2.5, less than or equal to 2.4, less than or equal to 2.25, less than or equal to 2.2, less than or equal to 2.0, less than or equal to 1.8, less than or equal to 1.75, less than or equal to 1.6, less than or equal to 1.5, less than or equal to 1.4, less than or equal to 1.25, less than or equal to 1.2, less than or equal to 1.0, less than or equal to 0.8, less than or equal to 0.75, less than or equal to 0.6, less than or equal to 0.5, less than or equal to 0.4, less than or equal to 0.25, or less than or equal to 0.2. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.1 and less than or equal to 3.0, greater than or equal to 1 and less than or equal to 3, greater than or equal to 0.1 and less than or equal to 2.5, greater than or equal to 1.0 and less than or equal to 2.0). Other ranges are also possible. In an exemplary embodiment, z is 1. In another exemplary embodiment, z is 2.
In certain embodiments, the ionically conductive compound has a composition as in formula (I) and u is 7-20, 7-10, 8-14, 10-16, 12-18, or 14-20. For example, in some embodiments, u is greater than or equal to 7, greater than or equal to 7.5, greater than or equal to 8, greater than or equal to 8.5, greater than or equal to 9, greater than or equal to 9.5, greater than or equal to 10, greater than or equal to 10.25, greater than or equal to 10.5, greater than or equal to 10.75, greater than or equal to 11, greater than or equal to 11.25, greater than or equal to 11.5, greater than or equal to 11.75, greater than or equal to 12, greater than or equal to 12.25, greater than or equal to 12.5, greater than or equal to 12.75, greater than or equal to 13, greater than or equal to 13.25, greater than or equal to 13.5, greater than or equal to 13.75, greater than or equal to 14, greater than or equal to 14.25, greater than or equal to 14.5, greater than or equal to 14.75, greater than or equal to 15, greater than or equal to 15.25, greater than or equal to 15.5, greater than or equal to 15.75, greater than or equal to 16, greater than or equal to 16.5, greater than or equal to 17, greater than or equal to 17.5, greater than or equal to 18, greater than or equal to 18.5, greater than or equal to 19, or greater than or equal to 19.5. In certain embodiments, u is less than or equal to 20, less than or equal to 19.5, less than or equal to 19, less than or equal to 18.5, less than or equal to 18, less than or equal to 17.5, less than or equal to 17, less than or equal to 16.5, less than or equal to 16, less than or equal to 15.75, less than or equal to 15.5, less than or equal to 15.25, less than or equal to 15, less than or equal to 14.75, less than or equal to 14.5, less than or equal to 14.25, less than or equal to 14, less than or equal to 13.75, less than or equal to 13.5, less than or equal to 13.25, less than or equal to 13, less than or equal to 12.75, less than or equal to 12.5, less than or equal to 12.25, less than or equal to 12, less than or equal to 11.75, less than or equal to 11.5, less than or equal to 11.25, less than or equal to 11, less than or equal to 10.75, less than or equal to 10.5, less than or equal to 10.25, less than or equal to 10, less than or equal to 9.5, less than or equal to 9, less than or equal to 8.5, less than or equal to 8, or less than or equal to 7.5. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 7 and less than or equal to 20, greater than or equal to 11 and less than or equal to 18). Other ranges are also possible.
In some embodiments, the ionically conductive compound has a composition as in formula (I) and t is 0-8, 0.1-8, 0.1-1, 0.8-2, 1-3, 1.5-3.5, 2-4, 2.5-5, 3-6, or 4-8. For example, in some embodiments, t is 1. In some cases, t may be 2. In certain embodiments, t is 3. In some embodiments, t is greater than or equal to 0, greater than or equal to 0.1, greater than or equal to 0.2, greater than or equal to 0.4, greater than or equal to 0.5, greater than or equal to 0.6, greater than or equal to 0.8, greater than or equal to 1, greater than or equal to 1.5, greater than or equal to 2, greater than or equal to 2.5, greater than or equal to 3, greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, or greater than or equal to 7. In certain embodiments, t is less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2.5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1, less than or equal to 0.8, less than or equal to 0.6, less than or equal to 0.5, less than or equal to 0.4, less than or equal to 0.2, or less than or equal to 0.1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 and less than or equal to 8, greater than or equal to 0.1 and less than or equal to 8, greater than or equal to 1 and less than or equal to 3). Other ranges are also possible.
In some embodiments, M is selected from the group consisting of monovalent cations, bivalent cations, trivalent cations, tetravalent cations, and pentavalent cations. In certain embodiments, Q is absent, or Q is present and selected from the group consisting of monovalent cations, bivalent cations, trivalent cations, tetravalent cations, and pentavalent cations. In some embodiments, Q is different than M.
Non-limiting examples of suitable monovalent cations (for M) include Na, K, Rb, Ag, and Cu. Non-limiting examples of suitable bivalent cations include Ca, Mg, Zn, Cu, and Fe. Non-limiting examples of suitable trivalent cations include Fe, Al, Ga, As, Cr, Mn, and B. Non-limiting examples of suitable tetravalent cations include Mn, Sn, Ge, Zr, and Si. Non-limiting examples of suitable pentavalent cations include Ta, Nb, As, V, and P. Other cations are also possible. In some cases, cations may have one or another type of valence (e.g., in some embodiments, Ga is trivalent, in other embodiments Ga is bivalent, in yet other embodiments, Ga is monovalent). Those of ordinary skill in the art would be capable of determining the one or more valences of a particular atom in the ionically conductive compounds described herein, based upon the teachings of this specification in common with general knowledge in the art.
In some embodiments, M is selected from the group consisting of Na, K, Fe, Mg, Ag, Cu, Zr, and Zn. In certain embodiments, Q is absent (e.g., w=0). In other embodiments, Q is present, is different than M, and is selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Fe, Ga, Al, As, and combinations thereof.
In embodiments in which Q is a combination of two or more atoms (e.g., two or more atoms selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Fe, Ga, Al, and As), the stoichiometric ratio of each atom in Q is such that the total amount of atoms present in Q is w and is 0.1-3. In certain embodiments, each atom is present in Q in substantially the same amount and the total amount of atoms present in Q is w and within the range 0.1-3. In other embodiments, each atom may be present in Q in different amounts and the total amount of atoms present in Q is w and within the range 0.1-3. For example, in such an embodiment, each atom in Q may be either silicon or germanium, each present in substantially the same amount, and w is 1 since Qw is Si0.5Ge0.5. In another exemplary embodiment, the ionically conductive compound has a composition as in formula (I) and each atom in Q may be either silicon or germanium, each atom present in different amounts such that QW is Siw-pGep, where p is between 0 and w (e.g., w is 1 and p is 0.25 or 0.75). Other ranges and combinations are also possible. Those skilled in the art would understand that the value and ranges of w, in some embodiments, may depend on the valences of Q as a combination of two or more atoms, and would be capable of selecting and/or determining w based upon the teachings of this specification. As noted above, in embodiments in which a compound of formula (I) includes more than one atom in Q, the total w may be in the range of 0.1-3.
In some embodiments, the ionically conductive compound (e.g., an ionically conductive compound having a structure as in formula (I)) has an argyrodite-type crystal structure. In some such embodiments, the compound of formula (I) has a cubic crystal structure. For example, in certain embodiments, the ionically conductive compound has an argyrodite-type crystal structure in the space group F43m. The crystal structure of the ionically conductive compound may be determined by using x-ray power diffraction (XPRD) crystallography at a wavelength of 1.541 nm using a synchrotron of particles comprising the compound and characterizing the XPRD patterns using a single-phase Rietveld refinement.
In certain embodiments, when Q is present, at least a portion of Q and at least a portion of P in the structure each occupy a tetrahedral coordinated site in the argyrodite-type crystal structure. In some embodiments, at least a portion of Q in the compound occupies a tetrahedral coordinated site in the argyrodite-type crystal structure that would otherwise be occupied by P in the absence of Q. In some embodiments, the tetrahedral coordinated site is on Wyckoff position 4b (e.g., PS4-tetrahedra and/or QS4-tetrahedra located at Wyckoff position 4b). In some cases, S2- ions may be on Wyckoff positions 4a and/or 4c.
In some embodiments, at least a portion of Li and at least a portion of M in the structure each occupy a Rietveld Refinement lithium lattice site on the crystal structure. In certain embodiments, at least a portion of M in the compound occupies a site that would otherwise be occupied by Li in the crystal structure, in the absence of M. For example, in some embodiments, at least a portion of Li and/or at least a portion of M occupy a Rietveld Refinement 48 h lattice site on the crystal structure.
In a particular set of embodiments, M is Fe. For example, in some embodiments, the ionically conductive compound has a composition as in formula (IIA):
LixFeyQwPzSuXt, (IIA),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, and wherein Q is absent or selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V, P, Ga, Al, As, and combinations thereof.
In certain embodiments, X is a halide. Non-limiting examples of suitable halides include Cl, I, F, and Br. In some embodiments, X is a pseudohalide. Non-limiting examples of suitable pseudohalides include cyanide, isocyanide, cyanate, isocyanate, and azide. Other pseudohalides are also possible.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is absent, M is a monovalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (II):
Li2x-y+2-tMy-zP2Sx+6-0.5z-tXt (II),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, and wherein M is a monovalent cation, such that 2x-y+2-t is 8-22, y-z is 0.1-3, and/or x+6-0.5z-t is 7-20. In some cases, the composition as in formula (II) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a monovalent cation, Q is a monovalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (III):
Li2x-y+2+4w-tMy-zQwP2-wSx+6-0.5z-tXt (III),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a monovalent cation, and wherein Q is a monovalent cation, such that 2x-y+2+4w-t is 8 22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-0.5z-t is 7-20. In some cases, the composition as in formula (III) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is a bivalent cation, M is a monovalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (IV):
Li2x-y+2+3w-tMy-zQwP2-wSx+6-0.5z-tXt (IV),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a monovalent cation, and wherein Q is a bivalent cation, such that 2x-y+2+3w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-0.5z-t is 7-20. In some cases, the composition as in formula (IV) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a monovalent cation, Q is a trivalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (V):
Li2x-y+2+2w-tMy-zQwP2-wSx+6-0.5z-tXt (V),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a monovalent cation, and wherein Q is a trivalent cation, such that 2x-y+2+2w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-0.5z-t is 7-20. In some cases, the composition as in formula (V) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is a tetravalent cation, M is a monovalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (VI):
Li2x-y+2+w-tMy-zQwP2-wSx+6-0.5z-tXt (VI),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a monovalent cation, and wherein Q is a tetravalent cation, such that 2x-y+2+w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-0.5z-t is 7-20. In some cases, the composition as in formula (VI) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a monovalent cation, Q is a pentavalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (VII):
Li2x-y+2-tMy-zQwP2-wSx+6-0.5z-tXt (VII),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a monovalent cation, and wherein Q is a pentavalent cation, such that 2x-y+2-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-0.5z-t is 7-20. In some cases, the composition as in formula (VII) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is absent, M is a bivalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1 3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (VIII):
Li2x-2y+2-tMy-zP2Sx+6-z-tXt (VIII),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, and wherein M is a bivalent cation, such that 2x-2y+2-t is 8-22, y-z is 0.1-3, and/or x+6-z-t is 7-20. In some cases, the composition as in formula (VIII) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a bivalent cation, Q is a monovalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (IX):
Li2x-2y+2+4w-tMy-zQwP2-wSx+6-z-tXt (IX),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a bivalent cation, and wherein Q is a monovalent cation, such that 2x-2y+2+4w-t is 8-22, y-z is 0.1 3, 2-w is 0.1-3, and/or x+6-z-t is 7-20. In some cases, the composition as in formula (IX) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is a bivalent cation, M is a bivalent cation, x is 8-22, y is 0.1-3, w is 0 3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (X):
Li2x-2y+2+3w-tMy-zQwP2-wSx+6-z-tXt (X),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a bivalent cation, and wherein Q is a bivalent cation, such that 2x-2y+2+3w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-z-t is 7-20. In some cases, the composition as in formula (X) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a bivalent cation, Q is a trivalent cation, x is 8-22, y is 0.1-3, w is 0 3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XI):
Li2x-2y+2+2w-tMy-zQwP2-wSx+6-z-tXt (XI),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a bivalent cation, and wherein Q is a trivalent cation, such that 2x-2y+2+2w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-z-t is 7-20. In some cases, the composition as in formula (XI) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is a tetravalent cation, M is a bivalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XII):
Li2x-2y+2+w-tMy-zQwP2-wSx+6-z-tXt (XII),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a bivalent cation, and wherein Q is a tetravalent cation, such that 2x-2y+2+w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-z-t is 7-20. In some cases, the composition as in formula (XII) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a bivalent cation, Q is a pentavalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XIII):
Li2x-2y+2-tMy-zQwP2-wSx+6-z-tXt (XIII),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a bivalent cation, and wherein Q is a pentavalent cation, such that 2x-2y+2-t is 8-22, y-z is 0.1-3, 2 w is 0.1-3, and/or x+6-z-t is 7-20. In some cases, the composition as in formula (XIII) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is absent, M is a trivalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XIV):
Li2x-3y+2-tMy-zP2Sx+6-1.5z-tXt (XIV),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, and wherein M is a trivalent cation, such that 2x-3y+2-t is 8-22, y-z is 0.1-3, and/or x+6-1.5z-t is 7-20. In some cases, the composition as in formula (XIV) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a trivalent cation, Q is a monovalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XV):
Li2x-3y+2+4w-tMy-zQwP2-wSx+6-1.5z-tXt (XV),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a trivalent cation, and wherein Q is a monovalent cation, such that 2x-3y+2+4w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-1.5z-t is 7-20. In some cases, the composition as in formula (XV) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is a bivalent cation, M is a trivalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XVI):
Li2x-3y+2+3w-tMy-zQwP2-wSx+6-1.5z-tXt (XVI),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a trivalent cation, and wherein Q is a bivalent cation, such that 2x-3y+2+3w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-1.5z-t is 7-20. In some cases, the composition as in formula (XVI) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a trivalent cation, Q is a trivalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XVII):
Li2x-3y+2+2w-tMy-zQwP2-wSx+6-1.5z-tXt (XVII),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a trivalent cation, and wherein Q is a trivalent cation, such that 2x-3y+2+2w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-1.5z-t is 7-20. In some cases, the composition as in formula (XVII) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is a tetravalent cation, M is a trivalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XVIII):
Li2x-3y+2+w-tMy-zQwP2-wSx+6-1.5z-tXt (XVIII),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a trivalent cation, and wherein Q is a tetravalent cation, such that 2x-3y+2+w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-1.5z-t is 7-20. In some cases, the composition as in formula (XVIII) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a trivalent cation, Q is a pentavalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XIX):
Li2x-3y+2-tMy-zQwP2-wSx+6-1.5z-tXt (XIX),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a trivalent cation, and wherein Q is a pentavalent cation, such that 2x-3y+2-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-1.5z-t is 7-20. In some cases, the composition as in formula (XIX) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is absent, M is a tetravalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XX):
Li2x-4y+2-tMy-zP2Sx+6-2z-tXt (XX),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, and wherein M is a tetravalent cation, such that 2x-4y+2-t is 8-22, y-z is 0.1-3, and/or x+6-2z-t is 7-20. In some cases, the composition as in formula (XX) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a tetravalent cation, Q is a monovalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XXI):
Li2x-4y+2+4w-tMy-zQwP2-wSx+6-2z-tXt (XXI),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a tetravalent cation, and wherein Q is a monovalent cation, such that 2x-4y+2+4w-t is 8 22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-2z-t is 7-20. In some cases, the composition as in formula (XXI) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is a bivalent cation, M is a tetravalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XXII):
Li2x-4y+2+3w-tMy-zQwP2-wSx+b-2z-tXt (XXII),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a tetravalent cation, and wherein Q is a bivalent cation, such that 2x-4y+2+3w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-2z-t is 7-20. In some cases, the composition as in formula (XXII) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a tetravalent cation, Q is a trivalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XXIII):
Li2x-4y+2+2w-tMy-zQwP2-wSx+6-2z-tXt (XXIII),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a tetravalent cation, and wherein Q is a trivalent cation, such that 2x-4y+2+2w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-2z-t is 7-20. In some cases, the composition as in formula (XXIII) may have an argyrodite-type crystal structure.
In some embodiments, the ionically conductive compound has a composition as in formula (I), Q is a tetravalent cation, M is a tetravalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XXIV):
Li2x-4y+2+w-tMy-zQwP2-wSx+6-2z-tXt (XXIV),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a tetravalent cation, and wherein Q is a tetravalent cation, such that 2x-4y+2+w-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-2z-t is 7-20. In some cases, the composition as in formula (XXIV) may have an argyrodite-type crystal structure.
In certain embodiments, the ionically conductive compound has a composition as in formula (I), M is a tetravalent cation, Q is a pentavalent cation, x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, and t is 0-8. In some such embodiments, the ionically conductive compound may have a composition as in formula (XXV):
Li2x-4y+2-tMy-zQwP2-wSx+6-2z-tXt (XXV),
wherein x is 8-22, y is 0.1-3, w is 0-3, z is 0.1-3, u is 7-20, t is 0-8, wherein X is absent or selected from the group consisting of halide and pseudohalide, wherein M is a tetravalent cation, and wherein Q is a pentavalent cation, such that 2x-4y+2-t is 8-22, y-z is 0.1-3, 2-w is 0.1-3, and/or x+6-2z-t is 7-20. In some cases, the composition as in formula (XXV) may have an argyrodite-type crystal structure.
In an exemplary embodiment, Q and X are absent and the ionically conductive compound has a composition as in Li22MP2S18, wherein M is a tetravalent cation. In another exemplary embodiment, Q and X are absent and the ionically conductive compound has a composition as in Li18MP2S16, wherein M is a tetravalent cation. In another exemplary embodiment, Q and X are absent and the ionically conductive compound has a composition as in Li14MP2S14, wherein M is a tetravalent cation. In another exemplary embodiment, Q and X are absent and the ionically conductive compound has a composition as in Li12MP2S12, wherein M is a tetravalent cation. In yet another exemplary embodiment, Q and X are absent and the ionically conductive compound has a composition as in Li10MP2S12, wherein M is a tetravalent cation. In yet another exemplary embodiment, the ionically conductive compound has a composition as in Li14M2P2S13.5, wherein M is a tetravalent cation.
In an exemplary embodiment, Q is absent and the ionically conductive compound has a composition as in Li13MP2S13Cl. In another exemplary embodiment, Q is absent and the ionically conductive compound has a composition as in Li12MP2S12Cl2. In yet another exemplary embodiment, Q is absent and the ionically conductive compound has a composition as in Li11MP2S11Cl3. In yet another exemplary embodiment, Q is absent and the ionically conductive compound has a composition as in Li11MP2S11Br3.
Non-limiting examples of compounds having a composition as in formula (I) include Li10FeP2S12, Li11FeP2S11Cl3, Li12.5Fe0.75P2S12, Li13.5Fe0.75P2S12.25, Li13Fe0.5P2S12, Li13Fe0.75P2S12.25, Li13FeP2S12.5, Li14.5Fe0.75P2S13, Li14Fe0.5P2S12.5. Li14Fe0.75P2S12.75.
Li14FeP2S13, Li15Fe0.5P2S13, Li22FeP2S18, Li18FeP2S16, Li14FeP2S14, Li12FeP2S12, Li10FeP2S12, Li14Fe2P2S13.5, Li13FeP2S13Cl, Li12FeP2Si2Cl2, and Li13FeP2S13Br.
In some embodiments, the ionically conductive compound (e.g., the ionically conductive compound of formula (I)) is in the form of a particle. A plurality of particles comprising the ionically conductive compound may be conductive to ions of an electroactive material (e.g., lithium), e.g., may be substantially conductive to lithium ions. In some cases, the plurality of particles may have an average ion conductivity (e.g., lithium ion conductivity) of greater than or equal to 10−5 S/cm. In certain embodiments, the average ion conductivity of the plurality of particles is greater than or equal to 10−5 S/cm, greater than or equal to 10−4 S/cm, greater than or equal to 10−3 S/cm, greater than or equal to 10−2 S/cm, or greater than or equal to 10−1 S/cm. In some embodiments, the average ion conductivity of the plurality of particles is less than or equal to 1 S/cm, less than or equal to 10−1 S/cm, less than or equal to 10−2 S/cm, less than or equal to 10−3 S/cm, or less than or equal to 10−4 S/cm. Combinations of the above-reference ranges are also possible (e.g., an ion conductivity greater than or equal to 10−5S/cm and less than or equal to 10−1 S/cm, greater than or equal to 10−4 S/cm and less than or equal to 10−2 S/cm). Other ion conductivities are also possible.
In some embodiments, the average ion conductivity of the plurality of particles can be determined before the particles are incorporated into a layer of an electrochemical cell (e.g., a protective layer, a solid electrolyte layer, an intercalated electrode layer). The average ionic conductivity can be measured by pressing the particles between two copper cylinders at a pressure of up to 4 tons/cm2. As used herein, “tons” refer to metric tons. In certain embodiments, the average ion conductivity (i.e., the inverse of the average resistivity) can be measured at 500 kg/cm2 increments using a conductivity bridge (i.e., an impedance measuring circuit) operating at 1 kHz. In some such embodiments, the pressure is increased until changes in average ion conductivity are no longer observed in the sample. Conductivity may be measured at room temperature (e.g., 25 degrees Celsius).
In some embodiments, the average largest cross-sectional dimension of a plurality of particles (e.g., within a layer of an electrochemical cell, or prior to being incorporated into a layer) comprising the ionically conductive compound may be, for example, less than or equal to 100 microns, less than or equal to 50 microns, less than or equal to 25 microns, less than or equal to 10 microns, less than or equal to 5 microns, less or equal to 2 microns, less than or equal to 1 micron, less than or equal to 500 nm, less than or equal to 100 nm, or less than or equal to 50 nm. In some embodiments, the average largest cross-sectional dimension of the plurality of particles may be greater than or equal to 10 nm, greater than or equal to 100 nm, greater than or equal to 500 nm, greater than or equal to 1 micron, greater than or equal to 2 microns, greater than or equal to 5 microns, greater than or equal to 10 microns, greater than or equal to 25 microns, or greater than or equal to 50 microns. Combinations of the above-referenced ranges are also possible (e.g., a largest cross-sectional dimension of less than 100 microns and greater than 10 microns, less than 25 microns and greater than 1 micron, less than 2 microns and greater than 100 nm, less than 500 nm and greater than 10 nm).
The average largest cross-sectional dimension of the plurality of particles may be determined, for example, by imaging the particles with a scanning electron microscope (SEM). An image may be acquired at a magnification between 10× to 100,000×, depending on the overall dimensions of the plurality of particles. Those skilled in the art would be capable of selecting an appropriate magnification for imaging the sample. The average largest cross-sectional dimension of the plurality of particles can be determined by taking the longest cross-sectional dimension of each particle and averaging the longest cross-sectional dimensions (e.g., averaging the longest cross-sectional dimensions for 10 particles).
In some embodiments, particles comprising an ionically conductive compound described herein may be formed by heating a mixture of precursors, as described in more detail herein. In certain embodiments, the precursors comprise a mixture of the elements Li, S, P, M, Q (if present), and X (if present), where M is selected from the group consisting of Na, K, Fe, Mg, Ag, Cu, Zr, and Zn, Q is absent or selected from the group consisting of Cr, B, Sn, Ge, Si, Zr, Ta, Nb, V. P, Fe, Ga, Al, As, and combinations thereof, and X is absent or selected from the group consisting of halide and pseudohalide.
In some embodiments, the elements Li, S, P, M, Q, if present, and X, if present, are present either in elemental form or in chemically bound form. For example, Li, S, P, M, Q, and/or X may be provided in chemically bound form, such as in the form of a chemical compound comprising Li, S, P, M, Q, and/or X with atoms of one or more of the elements S, P, M, Q, and/or X as described above (e.g., Li2S, P2S5, FeS, FeS2, SiS2, GeS2, Ga2S3, MgS, ZnS, wherein M, Q, X, P, and S may be provided in elemental form). In some embodiments, the precursors comprise a mixture of the elements Li, S, P, and M. In certain embodiments, the precursors comprise a mixture of the elements Li, S, P. and Fe. In some cases, the precursors may comprise a mixture of the elements Li, S, P, Fe and Q. In some embodiments, the precursors may comprise a mixture of the elements Li and X.
In some embodiments, the mixture of precursors comprises a mixture of at least two of Li2S, MSa, PbSc, QSd, LiX, and S, where a is 0-8, b is 0-2, c is 0-8, such that b+c is 1 or greater, and d is 0-3. For example, in some embodiments, a is 0-3, b is 2, c is 0-5, and d is 0-2. Non-limiting examples of suitable precursors include Li2S, P2S5, FeS, FeS2, SiS2, GeS2, Ga2S3, MgS, ZnS, SnS2, Si, Ge, Sn, Fe, S2, S4, S8, P2S5, P, LiCl, LiBr, LiI, and combinations thereof.
In some embodiments, a is greater than or equal to 0, greater than or equal to 1, greater than or equal to 2, greater than or equal to 3, greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, or greater than or equal to 7. In certain embodiments, a is less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, or less than or equal to 2. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 and less than or equal to 8, greater than or equal to 1 and less than or equal to 4, greater than or equal to 2 and less than or equal to 6, greater than or equal to 4 and less than or equal to 8). In some cases, a may be 0, (i.e. the precursor is elemental M).
In certain embodiments, b is greater than or equal to 0, or greater than or equal to 1. In some cases, b may be less than or equal to 2, or less than or equal to 1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 and less than or equal to 2). In some embodiments, b is 0 (i.e., the precursor is elemental sulfur). In certain embodiments, b is 1. In some cases, b may be 2.
In some embodiments, c is greater than or equal to 0, greater than or equal to 1, greater than or equal to 2, greater than or equal to 3, greater than or equal to 4, greater than or equal to 5, greater than or equal to 6, or greater than or equal to 7. In certain embodiments, c is less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, or less than or equal to 2. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 and less than or equal to 8, greater than or equal to 1 and less than or equal to 4, greater than or equal to 2 and less than or equal to 6, greater than or equal to 4 and less than or equal to 8). In certain embodiments, c is 0 (i.e., the precursor is elemental phosphorous). In some embodiments, cis 1.
In some embodiments, b and c are selected such that b+c is 1 or greater (e.g., 2 or greater, 3 or greater, 4 or greater, 5 or greater, 6 or greater, 7 or greater, 8 or greater, or 9 or greater). In some cases b+c is less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, or less than or equal to 2. Combinations of the above-referenced ranges are also possible.
In certain embodiments, d is greater than or equal to 0, or greater than or equal to 1. In some cases, d may be less than or equal to 2, or less than or equal to 1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 and less than or equal to 2). In some embodiments, d is 0 (i.e., the precursor is elemental Q). In certain embodiments, d is 1. In some cases, d may be 2.
In certain embodiments, a mixture of precursors described herein has a stoichiometric ratio of the elements Li, S, P, M, X (if present), and Q (if present) as in formula (I), as described above (e.g., LixMyQwPzSuXt). In some embodiments, Li, S, P, M, X (if present) and Q (if present) have a stoichiometric ratio such that the plurality of particles formed from the mixture comprises a compound of formula (I). For example, in some cases, the mixture of precursors are selected such that the ratio of the elements Li, S, P, M, X, and Q result in the formation of an ionically conductive compound described herein, such as Li10FeP2Si2, Li11FeP2S11C13, Li12.5Fe0.75P2S12, Li13.5Fe0.75P2S12.25, Li13Fe0.5P2S12, Li13Fe0.75P2S12.25, Li13FeP2S12.5, Li14.5Fe0.75P2S13, Li14Fe0.5P2S12.5, Li14Fe0.75P2S12.75, Li14FeP2S13, Li15Fe0.5P2S13, Li22FeP2S18, Li18FeP2S16, Li14FeP2S14, Li12FeP2S12, Li10FeP2S12, Li14Fe2PS13.5, Li13FeP2S13Cl, Li12FeP2S12Cl2, and Li13FeP2S13Br.
Other suitable ratios for forming a compound as in formula (I) are also possible. For example, in certain cases, excess S may be present in the mixture (e.g., sulfur in excess of that included in a formula of an ionically conductive compound described herein). The excess S may, for example, compensate for sulfur loss during mixing. For instance, in some embodiments, the mixture of precursors described herein has a stoichiometric ratio of two or more of the elements Li2S, LiX, MSa, PbSc, QSd, LiX, and S where a, b, c, and d are as described above.
In some embodiments, the mixture of precursors comprise or consist of: Li2S, MS2 (e.g., FeS2) and P2S5; or Li2S, MS (e.g., FeS), and P2S5; or Li2S, M (e.g., Fe), S8 and P2S5; or Li2S, M (e.g., Fe), S8 and P; or Li2S, MS2 (e.g., FeS2), LiX (e.g., LiCl, LiBr) and P2S5; or Li2S, MS (e.g., FeS), LiX (e.g., LiCl, LiBr, LiI) and P2S5. Other mixtures of precursors are also possible.
For example, in some embodiments, Li2S is present in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) in an amount of greater than or equal to 20 wt %, greater than or equal to 25 wt %, greater than or equal to 27 wt %, greater than or equal to 30 wt %, greater than or equal to 35 wt %, greater than or equal to 40 wt %, greater than or equal to 45 wt %, greater than or equal to 50 wt %, or greater than or equal to 55 wt % versus the total weight of the mixture of precursors. In certain embodiments, Li2S is present in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) in an amount of less than or equal to 60 wt %, less than or equal to 55 wt %, less than or equal to 50 wt %, less than or equal to 45 wt %, less than or equal to 40 wt %, less than or equal to 35 wt %, less than or equal to 30 wt %, less than or equal to 27 wt %, or less than or equal to 25 wt % versus the total weight of the mixture of precursors. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 20 wt % and less than or equal to 60 wt %, greater than or equal to 27 wt % and less than or equal to 60 wt %). Other ranges are also possible.
In certain embodiments, MS (e.g., FeS) may be present in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) in an amount of greater than or equal to 5 wt %, greater than or equal to 7 wt %, greater than or equal to 10 wt %, greater than or equal to 15 wt %, greater than or equal to 20 wt %, greater than or equal to 25 wt %, greater than or equal to 26 wt %, greater than or equal to 29 wt % versus the total weight of the mixture of precursors. In some embodiments, MS may be present in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) in an amount of less than or equal to 30 wt %, less than or equal to 29 wt %, less than or equal to 26 wt %, less than or equal to 25 wt %, less than or equal to 20 wt %, less than or equal to 15 wt %, less than or equal to 10 wt %, or less than or equal to 7 wt % versus the total weight of the mixture of precursors. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 5 wt % and less than or equal to 30 wt %, greater than or equal to 7 wt % and less than or equal to 26 wt %). Other ranges of also possible.
In some embodiments, P2S5 may be present in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) in an amount of greater than or equal to 10 wt %, greater than or equal to 12 wt %, greater than or equal to 14 wt %, greater than or equal to 16 wt %, greater than or equal to 18 wt %, greater than or equal to 20 wt %, greater than or equal to 25 wt %, greater than or equal to 30 wt %, greater than or equal to 35 wt %, greater than or equal to 40 wt %, or greater than or equal to 45 wt % versus the total weight of the mixture of precursors. In some embodiments, P2S5 may be present in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) in an amount of less than or equal to 50 wt %, less than or equal to 45 wt %, less than or equal to 40 wt %, less than or equal to 35 wt %, less than or equal to 30 wt %, less than or equal to 25 wt %, less than or equal to 20 wt %, less than or equal to 18 wt %, less than or equal to 16 wt %, less than or equal to 14 wt %, or less than or equal to 12 wt % versus the total weight of the mixture of precursors. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 10 wt % and less than or equal to 50 wt %, greater than or equal to 16 wt % and less than or equal to 40 wt %). Other ranges of also possible.
In certain embodiments, LiX (e.g., LiCl, LiBr, LiI) may be present in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) in an amount of greater than or equal to 0 wt %, greater than or equal to 5 wt %, greater than or equal to 10 wt %, greater than or equal to 15 wt %, or greater than or equal to 20 wt % versus the total weight of the mixture of precursors. In some embodiments, LiX may be present in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) in an amount of less than or equal to 25 wt %, less than or equal to 20 wt %, less than or equal to 15 wt %, less than or equal to 10 wt %, or less than or equal to 5 wt % versus the total weight of the mixture of precursors. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 wt % and less than or equal to 25 wt %, greater than or equal to 0 wt % and less than or equal to 20 wt %). Other ranges of also possible.
In some embodiments, sulfur (e.g., excess sulfur such as S and/or S8, not already present in the mixture of precursors with other components such as LiS, MS, or P2S5) may be present in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) in an amount of greater than or equal to 0 wt %, greater than or equal to 2 wt %, greater than or equal to 5 wt %, greater than or equal to 7 wt %, greater than or equal to 10 wt %, or greater than or equal to 12 wt % versus the total weight of the mixture of precursors. In certain embodiments, sulfur (e.g., excess sulfur) may be present in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) in an amount of less than or equal to 15 wt %, less than or equal to 12 wt %, less than or equal to 10 wt %, less than or equal to 7 wt %, less than or equal to 5 wt %, or less than or equal to 2 wt % versus the total weight of the mixture of precursors. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0 wt % and less than or equal to 15 wt %, greater than or equal to 0 wt % and less than or equal to 10 wt %). Other ranges of also possible.
In some cases, Li2S and MS (e.g., FeS) may be present in the mixture of precursors in a particular ratio. In some embodiments, the ratio of Li2S to MS in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) is less than or equal to 12:1, less than or equal to 10:1, less than or equal to 8:1, less than or equal to 6:1, less than or equal to 4:1, less than or equal to 2:1, less than or equal to 1:1, or less than or equal to 0.8:1. In certain embodiments, the ratio of Li2S to MS in the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) is greater than or equal to 0.6:1, greater than or equal to 0.8:1, greater than or equal to 1:1, greater than or equal to 2:1, greater than or 4:1, greater than or equal to 6:1, greater than or equal to 8:1, or greater than or equal to 10:1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.6:1 and less than or equal to 12:1). Other ranges are also possible. In an exemplary set of embodiments, the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) comprises greater than or equal to 20 wt % and less than or equal to 60 wt % Li2S, greater than or equal to 5 wt % and less than or equal to 30 wt % MS (e.g., FeS), greater than or equal to 10 wt % and less than or equal to 50 wt % P2S5, greater than or equal to 0 wt % and less than or equal to 25 wt % LiX (e.g., LiCl, LiBr, LiI), and greater than or equal to 0 wt % and less than or equal to 15 wt % excess sulfur (versus the total weight of the mixture of precursors). In another embodiment, the mixture of precursors (e.g., prior to heating the mixture, during heating of the mixture) comprises greater than or equal to 27 wt % and less than or equal to 60 wt % Li2S, greater than or equal to 7 wt % and less than or equal to 26 wt % MS (e.g., FeS), greater than or equal to 16 wt % and less than or equal to 40 wt % P2S5, greater than or equal to 0 wt % and less than or equal to 20 wt % LiX (e.g., LiCl, LiBr, LiI), and greater than or equal to 0 wt % and less than or equal to 10 wt % excess sulfur (versus the total weight of the mixture of precursors). In some embodiments, excess sulfur is not present in the mixture of precursors.
Those of ordinary skill in the art would understand, based upon the teachings of this specification, that the amount of each component (e.g., Li2S, MS, P2S5, LiX, S, and/or other components) may be selected to produce a particular stoichiometry such as those described above in the context of the compounds described herein.
The mixture of precursors (e.g., comprising a mixture of the elements Li, S, P, M, Q (if present), and X (if present)) may be heated to any suitable temperature for forming a compound described herein. In certain embodiments, the mixture of precursors is heated to a temperature of greater than or equal to 500° C., greater than or equal to 550° C., greater than or equal to 600° C., greater than or equal to 650° C., greater than or equal to 700° C., greater than or equal to 750° C., greater than or equal to 800° C., greater than or equal to 850° C., greater than or equal to 900° C., greater than or equal to 950° C., greater than or equal to 1000° C., greater than or equal to 1050° C., greater than or equal to 1100° C., or greater than or equal to 1150° C. In some embodiments, the mixture of precursors is heated to a temperature less than or equal to 1200° C., less than or equal to 1150° C., less than or equal to 1100° C., less than or equal to 1050° C., less than or equal to 1000° C., less than or equal to 950° C., less than or equal to 900° C., less than or equal to 850° C., less than or equal to 800° C., less than or equal to 750° C., less than or equal to 700° C., less than or equal to 650° C., less than or equal to 600° C., or less than or equal to 550° C. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 500° C. and less than or equal to 1200° C., greater than or equal to 400° C. and less than or equal to 900° C., greater than or equal to 500° C. and less than or equal to 800° C., greater than or equal to 500° C. and less than or equal to 700° C., greater than or equal to 600° C. and less than or equal to 800° C.). Other ranges are also possible.
The mixture of precursors may be heated for any suitable amount of time. In some cases, the mixture of precursors may be heated for greater than or equal to 3 hours, greater than or equal to 5 hours, greater than or equal to 8 hours, greater than or equal to 12 hours, greater than or equal to 16 hours, or greater than or equal to 20 hours. In certain embodiments, the mixture of precursors is heated for less than or equal to 24 hours, less than or equal to 48 hours, less than or equal to 36 hours, less than or equal to 24 hours, less than or equal to 20 hours, less than or equal to 16 hours, less than or equal to 12 hours, less than or equal to 8 hours, or less than or equal to 5 hours. Combinations of the above referenced ranges are also possible (e.g., greater than or equal to 3 hours and less than or equal to 24 hours, greater than or equal to 5 hours and less than or equal to 12 hours, greater than or equal to 8 hours and less than or equal to 20 hours, greater than or equal to 12 hours and less than or equal to 24 hours). Other ranges are also possible.
The mixture of precursors may be heated at any suitable pressure. In some embodiments, the mixture of precursors are heated at a relatively low pressure. For example, in certain embodiments, the mixture of precursors is heated at a pressure of between 0.1 MPa and 0.3 MPa, or at other suitable pressures.
In certain embodiments, after heating the mixture of precursors, the mixture is cooled. For example, the mixture of precursors may be heated to a temperature between 500° C. and 1200° C. (e.g., between 500° C. and 900° C.) for between 3 hours to 24 hours, and the mixture may be cooled to a temperature less than 500° C. such as room temperature. The mixture may then be ground into a plurality of particles of desired size. Those skilled in the art would be capable of selecting suitable methods for grinding a material into particles including, for example, ball milling or blender crushing. In some embodiments, the mixture of precursors may be ground in a ball mill prior to and/or during heating. In some cases, the grinding of the plurality of particles is conducted at relative low pressures. For example, the grinding of the plurality of particles may be conducted at pressures less than or equal to about 1 GPa, less than or equal to about 500 MPa, less than or equal to about 100 MPa, less than or equal to about 50 MPa, less than or equal to about 10 MPa, less than or equal to about 5 MPa, less than or equal to about 1 MPa, or less than or equal to about 0.5 MPa. In certain embodiments, the grinding of the plurality of particles may be conducted at pressures of at least about 0.1 MPa, at least about 0.5 MPa, at least about 1 MPa, at least about 5 MPa, at least about 10 MPa, at least about 50 MPa, at least about 100 MPa, or at least about 500 MPa. Combinations of the above-referenced ranges are also possible (e.g., at least about 0.1 MPa and less than or equal to about 1 GPa). Other ranges are also possible.
In some embodiments, a compound described herein (e.g., the compounds of any one of formulas (I)—(XXV)) is deposited as a layer. In certain embodiments, a plurality of particles comprising the compound of formula (I) are deposited as a layer (e.g., in an electrochemical cell). As will be understood by one of ordinary skill in the art, the compounds of any one of formulas (I)—(XXV) refers to a compound of formula (I), a compound of formula (IIA), a compound of formula (II), a compound of formula(III), a compound of formula (IV), a compound of formula (V), a compound of formula (VI), a compound of formula (VII), a compound of formula (VIII), a compound of formula (IX), a compound of formula (X), a compound of formula (XI), a compound of formula (XII), a compound of formula (XIII), a compound of formula (XIV), a compound of formula (XV), a compound of formula (XVI), a compound of formula (XVII), a compound of formula (XVIII), a compound of formula (XIX), a compound of formula (XX), a compound of formula (XXI), a compound of formula (XXII), a compound of formula (XXIII), a compound of formula (XXIV), or a compound of formula (XXV).
A layer comprising a compound described herein (e.g., the compounds of formulas (I)—(XXV)) may be deposited on a surface (e.g., on another layer) by any suitable method such as sputtering (e.g., magnetron sputtering), ion beam deposition, molecular beam epitaxy, electron beam evaporation, vacuum thermal evaporation, aerosol deposition, sol-gel, laser ablation, chemical vapor deposition (CVD), thermal evaporation, plasma enhanced chemical vacuum deposition (PECVD), laser enhanced chemical vapor deposition, jet vapor deposition, etc. In some embodiments, a layer comprising a compound described herein is made by cold pressing. The technique used may depend on the desired thickness of the layer, the material being deposited on, etc. The compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) may be deposited in powder form, in some cases. In some embodiments, the particles comprising the compound of formula (I) may be deposited on a surface and sintered.
In an exemplary embodiment, a compound described herein (e.g., the compounds of formulas (I)—(XXV)) may be deposited (e.g., on a layer) using aerosol deposition.
In some embodiments, the layer comprising the compound of formula (I) is deposited on an electrode/electroactive material (e.g., an anode, a cathode). In certain embodiments, the layer comprising the compound of formula (I) is deposited on a separator, a protective layer, an electrolyte layer, or another layer of an electrochemical cell.
In certain embodiments, a layer comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV))) as described herein, is substantially crystalline. In certain embodiments, the layer comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)), or a plurality of particles comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) as described herein, is between 1 wt. % and 100 wt. % crystalline. That is to say, in some embodiments, the crystalline fraction of the compound of formula (I) comprised by the layer (or particles) is in the range of 1% to 100% based on the total weight of the compound of formula (I) comprised by the layer (or particles). In certain embodiments, the layer comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)), or a plurality of particles comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) as described herein, is greater than or equal to 1 wt. %, greater than or equal to 2 wt. %, greater than or equal to 5 wt. %, greater than or equal to 10 wt. %, greater than or equal to 20 wt. %, greater than or equal to 25 wt. %, greater than or equal to 50 wt. %, greater than or equal to 75 wt. %, greater than or equal to 90 wt. %, greater than or equal to 95 wt. %, greater than or equal to 98 wt. %, greater than or equal to 99 wt. %, or greater than or equal to 99.9 wt. % crystalline. In certain embodiments, the layer comprising the compound of formula (I), or a plurality of particles comprising the compound of formula (I) as described herein, is less than or equal to 99.9 wt. %, less than or equal to 98 wt. %, less than or equal to 95 wt. %, less than or equal to 90 wt. %, less than or equal to 75 wt. %, less than or equal to 50 wt. %, less than or equal to 25 wt. %, less than or equal to 20 wt. %, less than or equal to 10 wt. %, less than or equal to 5 wt. %, or less than or equal to 2 wt. % crystalline.
In some embodiments, a layer comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)), or a plurality of particles comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) as described herein, is greater than or equal to 99.2 wt. %, greater than or equal to 99.5 wt. %, greater than or equal to 99.8 wt. %, or greater than or equal to 99.9 wt. % crystalline. In some cases, a layer comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)), or a plurality of particles comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) as described herein, may be 100% crystalline. Combinations of the above referenced ranges are also possible (e.g., greater than or equal to 1 wt. % and less than or equal to 100 wt. %, greater than or equal to 50 wt. % and less than or equal to 100 wt. %).
In some embodiments, the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) may be present in a layer (e.g., a separator, a protective layer) in an amount of at least about 1 wt %, at least about 2 wt %, at least about 5 wt %, at least about 10 wt %, at least about 20 wt %, about 30 wt %, at least about 40 wt %, at least about 50 wt %, at least about 60 wt %, at least about 70 wt %, at least about 80 wt %, at least about 85 wt %, at least about 90 wt %, at least about 95 wt %, or at least about 98 wt % versus the total layer weight. In certain embodiments, the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) is present in the layer in an amount of less than or equal to about 100 wt %, less than or equal to about 99 wt %, less than or equal to about 98 wt %, less than or equal to about 95 wt %, less than or equal to about 90 wt %, less than or equal to about 85 wt %, less than or equal to about 80 wt %, less than or equal to about 70 wt %, less than or equal to about 60 wt %, less than or equal to about 50 wt %, less than or equal to about 40 wt %, less than or equal to about 30 wt %, less than or equal to about 20 wt %, less than or equal to about 10 wt %, less than or equal to about 5 wt %, or less than or equal to about 2 wt % versus the total layer weight. Combinations of the above-referenced ranges are also possible (e.g., at least about 1 wt % and less than or equal to about 100 wt %). Other ranges are also possible.
In some cases, the layer may comprise the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) and one or more additional materials (e.g., polymers, metals, ceramics, ionically-conductive materials) as described in more detail below.
In some embodiments, one or more layers of an electrochemical cell may comprise the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)). In some cases, the compound in the one or more layers is in the form of a plurality of particles. In some embodiments, the layer comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) is in direct contact with an electrode (e.g., an electroactive material of the electrode).
In certain embodiments, the layer comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) may allow ions (e.g., electrochemically active ions, such as lithium ions) to pass through the layer but may substantially impede electrons from passing across the layer. By “substantially impedes”, in this context, it is meant that in this embodiment the layer allows lithium ion flux greater than or equal to ten times greater than electron passage. Advantageously, particles and layers described herein (e.g., comprising the compound of formula (I)) may be capable of conducting specific cations (e.g., lithium cations) while not conducting certain anions (e.g., polysulfide anions) and/or may be capable of acting as a barrier to an electrolyte and/or a component in the electrolyte (e.g., a polysulfide species) for the electrode.
In some embodiments, the layer (e.g., a separator, a protective layer, a solid electrolyte layer) comprising the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) is ionically conductive. In some embodiments, the average ionic conductivity of the layer comprising the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) is greater than or equal to 10−5 S/cm, greater than or equal to 10−4 S/cm, greater than or equal to 10−3 S/cm, greater than or equal to 10−2 S/cm, greater than or equal to 100.1 S/cm. In certain embodiments, the average ionic conductivity of the layer comprising the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) may be less than or equal to 1 S/cm, less than or equal to 10−1 S/cm, less than or equal to 10−2 S/cm, less than or equal to 10−3 S/cm, or less than or equal to 10−4 S/cm. Combinations of the above-referenced ranges are also possible (e.g., an average ionic conductivity of greater than or equal to 10−5 S/cm and less than or equal to 10−1 S/cm). Other ion conductivities are also possible.
In some embodiments, the average ion conductivity of the layer comprising the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) can be determined by pressing the layer between two copper cylinders at a pressure of up to 3 tons/cmz. In certain embodiments, the average ion conductivity (i.e., the inverse of the average resistivity) can be measured at 500 kg/cm2 increments using a conductivity bridge (i.e., an impedance measuring circuit) operating at 1 kHz. In some such embodiments, the pressure is increased until changes in average ion conductivity are no longer observed in the sample. Conductivity may be measured at room temperature (e.g., 25 degrees Celsius).
As described herein, it may be desirable to determine if a layer including a compound described herein has advantageous properties as compared to a layer formed of other materials for particular electrochemical systems. Simple screening tests can be employed to help select between candidate materials. One simple screening test includes positioning a layer (e.g., comprising the compound of formula (I)) in an electrochemical cell, e.g., as a protective layer in a cell. The electrochemical cell may then undergo multiple discharge/charge cycles, and the electrochemical cell may be observed for whether inhibitory or other destructive behavior occurs compared to that in a control system. If inhibitory or other destructive behavior is observed during cycling of the cell, as compared to the control system, it may be indicative of degradation or other failure of the layer in question, within the assembled electrochemical cell. It is also possible to evaluate the electrical conductivity and/or ion conductivity of the layer using methods described herein and known to one of ordinary skill in the art. The measured values may be compared to select between candidate materials and may be used for comparison with baseline material(s) in the control (e.g., materials not comprising the compounds described herein).
In some embodiments, it may be desirable to test the layer (e.g., a layer comprising the compound of formula (I)) for swelling in the presence of a particular electrolyte or solvent to be used in an electrochemical cell. A simple screening test may involve, for example, pieces of the layer that are weighed and then placed in a solvent or an electrolyte to be used in an electrochemical cell for any suitable amount of time (e.g., 24 hours). The percent difference in weight (or volume) of the layer before and after the addition of a solvent or an electrolyte may determine the amount of swelling of the layer in the presence of the electrolyte or the solvent.
Another simple screening test may involve determining the stability (i.e., integrity) of a layer (e.g., a layer comprising the compound of formula (I)) to polysulfides. Briefly, the layer may be exposed to a polysulfide solution/mixture for any suitable amount of time (e.g., 72 hours) and the percent weight loss of the layer after exposure to the polysulfide solution may be determined by calculating the difference in weight of the layer before and after the exposure. For example, in some embodiments, the percent weight loss of the layer after exposure to the polysulfide solution may be less than or equal to 15 wt. %, less than or equal to 10 wt. %, less than or equal to 5 wt. %, less than or equal to 2 wt. %, less than or equal to 1 wt. %, or less than or equal to 0.5 wt. %. In certain embodiments, the percent weight loss of the layer after exposure to the polysulfide solution may be greater than or equal to 0.1 wt. %, greater than or equal to 0.5 wt. %, greater than or equal to 1 wt. %, greater than or equal to 2 wt. %, greater than or equal to 5 wt. %, or greater than or equal to 10 wt. %. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 0.1 wt. % and less than or equal to 5 wt. %).
Yet another simple screening test may involve determining the stability (i.e. integrity) of a layer (e.g., a layer comprising the compound of formula (I)) to metallic lithium. Briefly, a layer or a pellet comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) may be placed between two lithium metal foils in an electrochemical cell and one can measure the change in impedance over any suitable amount of time (e.g., 72 hours). In general, the lower impedance may result in a greater stability of the layer to metallic lithium.
The above described screening tests may also be adapted and used to determine the properties of individual components of the layer (e.g., a plurality of particles comprising the compound of formula (I)).
Turning now to the figures, the various embodiments of the current disclosure are described in more detail below. It should be understood that while certain layers depicted in the figures are disposed directly on one another, other intermediate layers may also be present between the depicted layers in certain embodiments. Accordingly, as used herein, when a layer is referred to as being “disposed on”, “deposited on”, or “on” another layer, it can either be directly disposed on, deposited onto, or on the layer, or an intervening layer may also be present. In contrast, a layer that is “directly disposed on”, “in contact with”, “directly deposited on”, or “directly on” another layer indicates that no intervening layer is present.
In some embodiments, one or more ionically conductive compounds described herein may be incorporated into a separator (e.g., separator 30 in
In some embodiments, the electrochemical cell comprises an electrolyte. In some embodiments, the separator is located between the electrolyte and an electrode (e.g., an anode, a cathode). For example, as illustrated in
In some embodiments, the separator comprises a polymeric material (e.g., polymeric material that does or does not swell upon exposure to electrolyte). The separator may optionally include an ionically conductive compound (or plurality of particles comprising the compound) of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)). In certain embodiments, the ionically conductive compound is directly deposited on at least a portion of a surface of the separator. In certain embodiments, the ionically conductive compound is incorporated into the separator.
The separator can be configured to inhibit (e.g., prevent) physical contact between a first electrode and a second electrode, which could result in short circuiting of the electrochemical cell. The separator can be configured to be substantially electronically non-conductive, which can inhibit the degree to which the separator causes short circuiting of the electrochemical cell. In certain embodiments, all or portions of the separator can be formed of a material with a bulk electronic resistivity of greater than or equal to 104, greater than or equal to 105, greater than or equal to 1010, greater than or equal to 1015, or greater than or equal to 1020 Ohm-meters. In some embodiments, the bulk electronic resistivity may be less than or equal to 1050 Ohm-meters. Bulk electronic resistivity may be measured at room temperature (e.g., 25 degrees Celsius).
In some embodiments, the separator can be a solid. The separator may be porous to allow an electrolyte solvent to pass through it. In some cases, the separator does not substantially include a solvent (like in a gel), except for solvent that may pass through or reside in the pores of the separator. In other embodiments, a separator may be in the form of a gel.
In some embodiments, the porosity of the separator can be, for example, greater than or equal to 30 vol %, greater than or equal to 40 vol %, greater than or equal to 50%, greater than or equal to 60 vol %, greater than or equal to 70 vol %, greater than or equal to 80 vol %, or greater than or equal to 90 vol %. In certain embodiments, the porosity is less than or equal to 90 vol %, less than or equal to 80 vol %, less than or equal to 70 vol %, less than or equal to 60 vol %, less than or equal to 50 vol %, less than or equal to 40 vol %, or less than or equal to 30 vol %. Other porosities are also possible. Combinations of the above-noted ranges are also possible. Porosity as used herein refers to the fraction of a volume of voids in a layer divided by the total volume of the layer and is measured using mercury porosimetry.
A separator can be made of a variety of materials. In some embodiments, the separator comprises the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)). Additional or alternatively, the separator may comprise a suitable separator material such as a polymer material. Examples of suitable polymer materials include, but are not limited to, polyolefins (e.g., polyethylenes, poly(butene-1), poly(n-pentene-2), polypropylene, polytetrafluoroethylene), polyamines (e.g., poly(ethylene imine) and polypropylene imine (PPI)); polyamides (e.g., polyamide (Nylon), poly(ϵ-caprolactam) (Nylon 6), poly(hexamethylene adipamide) (Nylon 66)), polyimides (e.g., polyimide, polynitrile, and poly(pyromellitimide-1,4-diphenyl ether) (Kapton®) (NOMEX®) (KEVLAR®)); polyether ether ketone (PEEK); vinyl polymers (e.g., polyacrylamide, poly(2-vinyl pyridine), poly(N-vinylpyrrolidone), poly(methylcyanoacrylate), poly(ethylcyanoacrylate), poly(butylcyanoacrylate), poly(isobutylcyanoacrylate), poly(vinyl acetate), poly (vinyl alcohol), poly(vinyl chloride), poly(vinyl fluoride), poly(2-vinyl pyridine), vinyl polymer, polychlorotrifluoro ethylene, and poly(isohexylcynaoacrylate)); polyacetals; polyesters (e.g., polycarbonate, polybutylene terephthalate, polyhydroxybutyrate); polyethers (poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), poly(tetramethylene oxide) (PTMO)); vinylidene polymers (e.g., polyisobutylene, poly(methyl styrene), poly(methylmethacrylate) (PMMA), poly(vinylidene chloride), and poly(vinylidene fluoride)); polyaramides (e.g., poly(imino-1,3-phenylene iminoisophthaloyl) and poly(imino-1,4-phenylene iminoterephthaloyl)); polyheteroaromatic compounds (e.g., polybenzimidazole (PBI), polybenzobisoxazole (PBO) and polybenzobisthiazole (PBT)); polyheterocyclic compounds (e.g., polypyrrole); polyurethanes; phenolic polymers (e.g., phenol-formaldehyde); polyalkynes (e.g., polyacetylene); polydienes (e.g., 1,2-polybutadiene, cis or trans-1,4-polybutadiene); polysiloxanes (e.g., poly(dimethylsiloxane) (PDMS), poly(diethylsiloxane) (PDES), polydiphenylsiloxane (PDPS), and polymethylphenylsiloxane (PMPS)); and inorganic polymers (e.g., polyphosphazene, polyphosphonate, polysilanes, polysilazanes). In some embodiments, the polymer may be selected from poly(n-pentene-2), polypropylene, polytetrafluoroethylene, polyamides (e.g., polyamide (Nylon), poly(ϵ-caprolactam) (Nylon 6), poly(hexamethylene adipamide) (Nylon 66)), polyimides (e.g., polynitrile, and poly(pyromellitimide-1,4-diphenyl ether) (Kapton®) (NOMEX®) (KEVLAR®)), polyether ether ketone (PEEK), and combinations thereof.
The mechanical and electronic properties (e.g., conductivity, resistivity) of these polymers are known. Accordingly, those of ordinary skill in the art can choose suitable materials based on their mechanical and/or electronic properties (e.g., ionic and/or electronic conductivity/resistivity), and/or can modify such polymers to be ionically conducting (e.g., conductive towards single ions) based on knowledge in the art, in combination with the description herein. For example, the polymer materials listed above and herein may further comprise salts, for example, lithium salts (e.g., LiSCN, LiBr, LiI, LiClO4, LiAsF6, LiSO3CF3, LiSO3CH3, LiBF4, LiB(Ph)4, LiPF6, LiC(SO2CF3)3, and LiN(SO2CF3)2), and/or the ionically conductive compound of formula (I) to enhance ionic conductivity, if desired.
The separator may be porous. In some embodiments, the separator pore size may be, for example, less than 5 microns. In some embodiments, the pore size may be less than or equal to 5 microns, less than or equal to 3 microns, less than or equal to 2 microns, less than or equal to 1 micron, less than or equal to 500 nm, less than or equal to 300 nm, less than or equal to 100 nm, or less than or equal to 50 nm. In some embodiments, the pore size may be greater than or equal to 50 nm, greater than or equal to 100 nm, greater than or equal to 300 nm, greater than or equal to 500 nm, or greater than or equal to 1 micron. Other values are also possible. Combinations of the above-noted ranges are also possible (e.g., a pore size of less than 300 nm and greater than or equal to 100 nm). In certain embodiments, the separator may be substantially non-porous.
The separator may have any suitable thickness. In some embodiments, the separator may have a thickness of greater than or equal to 500 nm, greater than or equal to 1 micron, greater than or equal to 5 microns, greater than or equal to 10 microns, greater than or equal to 15 microns, greater than or equal to 20 microns, greater than or equal to 25 microns, greater than or equal to 30 microns, greater than or equal to 40 microns, greater than or equal to 50 microns, greater than or equal to 60 microns, greater than or equal to 70 microns, greater than or equal to 80 microns, greater than or equal to 90 microns, greater than or equal to 100 microns, greater than or equal to 120 microns, greater than or equal to 140 microns, greater than or equal to 160 microns, or greater than or equal to 180 microns. In some embodiments, the thickness of the separator is less than or equal to 200 microns, less than or equal to 180 microns, less than or equal to 160 microns, less than or equal to 140 microns, less than or equal to 120 microns, less than or equal to 100 microns, less than or equal to 90 microns, less than or equal to 80 microns, less than or equal to 70 microns, less than or equal to 60 microns, less than or equal to 50 microns, less than or equal to 40 microns, less than or equal to 30 microns, less than or equal to 20 microns, less than or equal to 10 microns, or less than or equal to 5 microns. Other values are also possible. Combinations of the above-noted ranges are also possible (e.g., greater than or equal to 500 nm and less than or equal to 200 microns, greater than or equal to 1 micron and less than or equal to 50 microns). Other ranges are also possible.
The average thickness of the separator or other layers described herein is determined by scanning electron microscopy (SEM). Briefly, the layer can be imaged along a cross-section (e.g., by cutting the layer) after formation and the image may be acquired by SEM. The average thickness may be determined by taking an average of the thickness of the sample at several different locations along the cross-section (e.g., at least 10 locations). Those skilled in the art would be capable of selecting an appropriate magnification for imaging the sample.
In certain embodiments, a protective layer may comprise the conically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) and/or a plurality of particles comprising the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)). In some embodiments, a protective layer that incorporates the ionically conductive compounds described herein is substantially impermeable to the electrolyte. The protective layer may be configured such that it is unswollen in the presence of the electrolyte. However, in other embodiments, at least a portion of the protective layer can be swollen in the presence of the electrolyte. The protective layer may, in some cases, be substantially non-porous. The protective layer may be positioned directly adjacent an electrode, or adjacent the electrode via an intervening layer (e.g., another protective layer). Referring now to
Although in some embodiments the protective layer is an ion-conductive layer comprising the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)), other materials may also be used in addition to, or alternatively to, the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) to form the protective layer. Additionally, where more than one protective layer may be present, each of the layers may independently formed of one or more materials described herein. In some embodiments, the protective layer comprises a ceramic and/or a glass (e.g., an ion conducting ceramic/glass conductive to lithium ions). Suitable glasses and/or ceramics include, but are not limited to, those that may be characterized as containing a “modifier” portion and a “network” portion, as known in the art. The modifier may include a metal oxide of the metal ion conductive in the glass or ceramic. The network portion may include a metal chalcogenide such as, for example, a metal oxide or sulfide. For lithium metal and other lithium-containing electrodes, an ion conductive layer may be lithiated or contain lithium to allow passage of lithium ions across it. Ion conductive layers may include layers comprising a material such as lithium nitrides, lithium silicates, lithium borates, lithium aluminates, lithium phosphates, lithium phosphorus oxynitrides, lithium silicosulfides, lithium germanosulfides, lithium oxides (e.g., Li2O, LiO, LiO2, LiRO2, where R is a rare earth metal), lithium lanthanum oxides, lithium lanthanum zirconium oxides, lithium titanium oxides, lithium borosulfides, lithium aluminosulfides, lithium phosphates, and lithium phosphosulfides, and combinations thereof. The selection of the material will be dependent on a number of factors including, but not limited to, the properties of electrolyte, anode, and cathode used in the cell.
In one set of embodiments, the protective layer is a non-electroactive metal layer. The non-electroactive metal layer may comprise a metal alloy layer, e.g., a lithiated metal layer especially in the case where a lithium anode is employed. The lithium content of the metal alloy layer may vary from 0.5% by weight to 20% by weight, depending, for example, on the specific choice of metal, the desired lithium ion conductivity, and the desired flexibility of the metal alloy layer. Suitable metals for use in the ion conductive material include, but are not limited to, Al, Zn, Mg, Ag, Pb, Cd, Bi, Ga, In, Ge, Sb, As, and Sn. Sometimes, a combination of metals, such as the ones listed above, may be used in an ion conductive material.
The protective layer may have any suitable thickness. In some embodiments, the protective layer described herein may have a thickness of greater than or equal to 1 nm, greater than or equal to 2 nm, greater than or equal to 5 nm, greater than or equal to 10 nm, greater than or equal to 20 nm, greater than or equal to 50 nm, greater than or equal to 100 nm, greater than or equal to 500 nm, greater than or equal to 1 micron, greater than or equal to 2 microns, or greater than or equal to 5 microns. In certain embodiments, the protective layer may have a thickness of less than or equal to 10 microns, less than or equal to 5 microns, less than or equal to 2 microns, less than or equal to 1 micron, less than or equal to 500 nm, less than or equal to 100 nm, less than or equal to 50 nm, less than or equal to 20 nm, less than or equal to 10 nm, less than or equal to 5 nm, or less than or equal to 2 nm. Other values are also possible. Combinations of the above-noted ranges are also possible (e.g., greater than or equal to 1 nm and less than or equal to 10 microns, greater than or equal to 500 nm and less than or equal to 2 microns). Other ranges are also possible.
In some embodiments, the protective layer is a polymer layer or a layer that comprises a polymeric material. In some embodiments, the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) is incorporated into the polymer layer. Suitable polymer layers for use in electrochemical cells may be, for example, highly conductive towards lithium and minimally conductive towards electrons. Such polymers may include, for example, ionically conductive polymers, sulfonated polymers, and hydrocarbon polymers. The selection of the polymer will be dependent upon a number of factors including the properties of electrolyte, anode, and cathode used in the cell. Suitable ionically conductive polymers include, e.g., ionically conductive polymers known to be useful in solid polymer electrolytes and gel polymer electrolytes for lithium electrochemical cells, such as, for example, polyethylene oxides. Suitable sulfonated polymers include, e.g., sulfonated siloxane polymers, sulfonated polystyrene-ethylene-butylene polymers, and sulfonated polystyrene polymers. Suitable hydrocarbon polymers include, e.g., ethylene-propylene polymers, polystyrene polymers, and the like.
Polymer layers can also include crosslinked polymer materials formed from the polymerization of monomers such as alkyl acrylates, glycol acrylates, polyglycol acrylates, polyglycol vinyl ethers, and polyglycol divinyl ethers. For example, one such crosslinked polymer material is polydivinyl poly(ethylene glycol). The crosslinked polymer materials may further comprise salts, for example, lithium salts, to enhance ionic conductivity. In one embodiment, the polymer layer comprises a crosslinked polymer.
Other classes polymers that may be suitable for use in a polymer layer include, but are not limited to, polyamines (e.g., poly(ethylene imine) and polypropylene imine (PPI)); polyamides (e.g., polyamide (Nylon), poly(ϵ-caprolactam) (Nylon 6), poly(hexamethylene adipamide) (Nylon 66)), polyimides (e.g., polyimide, polynitrile, and poly(pyromellitimide-1,4-diphenyl ether) (Kapton)); vinyl polymers (e.g., polyacrylamide, poly(2-vinyl pyridine), poly(N-vinylpyrrolidone), poly(methylcyanoacrylate), poly(ethylcyanoacrylate), poly(butylcyanoacrylate), poly(isobutylcyanoacrylate), poly(vinyl acetate), poly (vinyl alcohol), poly(vinyl chloride), poly(vinyl fluoride), poly(2-vinyl pyridine), vinyl polymer, polychlorotrifluoro ethylene, and poly(isohexylcynaoacrylate)); polyacetals; polyolefins (e.g., poly(butene-1), poly(n-pentene-2), polypropylene, polytetrafluoroethylene); polyesters (e.g., polycarbonate, polybutylene terephthalate, polyhydroxybutyrate); polyethers (poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), poly(tetramethylene oxide) (PTMO)); vinylidene polymers (e.g., polyisobutylene, poly(methyl styrene), poly(methylmethacrylate) (PMMA), poly(vinylidene chloride), and poly(vinylidene fluoride)); polyaramides (e.g., poly(imino-1,3-phenylene iminoisophthaloyl) and poly(imino-1,4-phenylene iminoterephthaloyl)); polyheteroaromatic compounds (e.g., polybenzimidazole (PBI), polybenzobisoxazole (PBO) and polybenzobisthiazole (PBT)); polyheterocyclic compounds (e.g., polypyrrole); polyurethanes; phenolic polymers (e.g., phenol-formaldehyde); polyalkynes (e.g., polyacetylene); polydienes (e.g., 1,2-polybutadiene, cis or trans-1,4-polybutadiene); polysiloxanes (e.g., poly(dimethylsiloxane) (PDMS), poly(diethylsiloxane) (PDES), polydiphenylsiloxane (PDPS), and polymethylphenylsiloxane (PMPS)); and inorganic polymers (e.g., polyphosphazene, polyphosphonate, polysilanes, polysilazanes). The mechanical and electronic properties (e.g., conductivity, resistivity) of these polymers are known. Accordingly, those of ordinary skill in the art can choose suitable polymers for use in lithium batteries, e.g., based on their mechanical and/or electronic properties (e.g., ionic and/or electronic conductivity), and/or can modify such polymers to be ionically conducting (e.g., conductive towards single ions) and/or electronically conducting based on knowledge in the art, in combination with the description herein. For example, the polymer materials listed above may further comprise salts, for example, lithium salts (e.g., LiSCN, LiBr, LiI, LiClO4, LiAsF6, LiSO3CF3, LiSO3CH3, LiBF4, LiB(Ph)4, LiPF6, LiC(SO2CF3)3, and LiN(SO2CF3)2), to enhance ionic conductivity.
The polymeric materials can be selected or formulated to have suitable physical/mechanical characteristics by, for example, tailoring the amounts of components of polymer blends, adjusting the degree of cross-linking (if any), etc.
In some embodiments, a composite layer comprises a polymer material and an ionically conductive compound described herein (e.g., an ionically conductive compound of formula (I)). Such a composite layer may be formed by any suitable method including, for example: co-spraying (e.g., via aerosol deposition) the polymer material and the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) onto a substrate; casting the composite layer from a slurry, solution, or suspension comprising the polymer material and the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)); pressing particles comprising the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) into a polymer layer comprising a polymer material; and/or filling pores of a layer comprising the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) with a polymer material. Other methods for forming composite layers are also possible and are generally known in the art. The composite layer may be used for any suitable component of an electrochemical cell described herein, such as a protective layer. These and other methods for forming such composite layers are described in more detail in U.S. Patent Publication No. US 2016/0344067, filed May 20, 2016 and entitled “Protective Layers for Electrodes,” which is incorporated herein by reference in its entirety.
As described herein, in certain embodiments, the electrochemical cell comprises an electrolyte (e.g., electrolyte 40 in
In some embodiments, an electrolyte is in the form of a layer having a particular thickness. An electrolyte layer may have a thickness of, for example, greater than or equal to 50 nm, greater than or equal to 100 nm, greater than or equal to 200 nm, greater than or equal to 500 nm, greater than or equal to 1 micron, greater than or equal to 5 microns, greater than or equal to 10 microns, greater than or equal to 15 microns, greater than or equal to 20 microns, greater than or equal to 25 microns, greater than or equal to 30 microns, greater than or equal to 40 microns, greater than or equal to 50 microns, greater than or equal to 70 microns, greater than or equal to 100 microns, greater than or equal to 200 microns, greater than or equal to 500 microns, or greater than or equal to 1 mm. In some embodiments, the thickness of the electrolyte layer is less than or equal to 1 mm, less than or equal to 500 microns, less than or equal to 200 microns, less than or equal to 100 microns, less than or equal to 70 microns, less than or equal to 50 microns, less than or equal to 40 microns, less than or equal to 30 microns, less than or equal to 20 microns, less than or equal to 10 microns, less than or equal to 50 microns, less than or equal to 40 microns, less than or equal to 30 microns, less than or equal to 25 microns, less than or equal to 20 microns, less than or equal to 15 microns, less than or equal to 10 microns, less than or equal to 5 microns, less than or equal to 1 micron, less than or equal to 500 nm, less than or equal to 200 nm, or less than or equal to 100 nm. Other values are also possible. Combinations of the above-noted ranges are also possible.
In some embodiments, the electrolyte includes a non-aqueous electrolyte. Suitable non-aqueous electrolytes may include organic electrolytes such as liquid electrolytes, gel polymer electrolytes, and solid polymer electrolytes. These electrolytes may optionally include one or more ionic electrolyte salts (e.g., to provide or enhance ionic conductivity) as described herein. Examples of useful non-aqueous liquid electrolyte solvents include, but are not limited to, non-aqueous organic solvents, such as, for example, N-methyl acetamide, acetonitrile, acetals, ketals, esters (e.g., esters of carbonic acid), carbonates (e.g., ethylene carbonate, dimethyl carbonate), sulfones, sulfites, sulfolanes, suflonimidies (e.g., bis(trifluoromethane)sulfonimide lithium salt), aliphatic ethers, acyclic ethers, cyclic ethers, glymes, polyethers, phosphate esters (e.g., hexafluorophosphate), siloxanes, dioxolanes, N-alkylpyrrolidones, nitrate containing compounds, substituted forms of the foregoing, and blends thereof. Examples of acyclic ethers that may be used include, but are not limited to, diethyl ether, dipropyl ether, dibutyl ether, dimethoxymethane, trimethoxymethane, 1,2-dimethoxyethane, diethoxyethane, 1,2-dimethoxypropane, and 1,3-dimethoxypropane. Examples of cyclic ethers that may be used include, but are not limited to, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and trioxane. Examples of polyethers that may be used include, but are not limited to, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), higher glymes, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol dimethyl ether, and butylene glycol ethers. Examples of sulfones that may be used include, but are not limited to, sulfolane, 3-methyl sulfolane, and 3-sulfolene. Fluorinated derivatives of the foregoing are also useful as liquid electrolyte solvents.
In some cases, mixtures of the solvents described herein may also be used. For example, in some embodiments, mixtures of solvents are selected from the group consisting of 1,3-dioxolane and dimethoxyethane, 1,3-dioxolane and diethyleneglycol dimethyl ether, 1,3-dioxolane and triethyleneglycol dimethyl ether, and 1,3-dioxolane and sulfolane. The weight ratio of the two solvents in the mixtures may range, in some cases, from 5 wt. %:95 wt. % to 95 wt. %:5 wt. %.
Non-limiting examples of suitable gel polymer electrolytes include polyethylene oxides, polypropylene oxides, polyacrylonitriles, polysiloxanes, polyimides, polyphosphazenes, polyethers, sulfonated polyimides, perfluorinated membranes (NAFION resins), polydivinyl polyethylene glycols, polyethylene glycol diacrylates, polyethylene glycol dimethacrylates, derivatives of the foregoing, copolymers of the foregoing, cross-linked and network structures of the foregoing, and blends of the foregoing.
In some embodiments, the non-aqueous electrolyte comprises at least one lithium salt. For example, in some cases, the at least one lithium salt is selected from the group consisting of LiNO3, LiPF6, LiBF4, LiClO4, LiAsF6, Li2SiF6, LiSbF6, LiAlCl4, lithium bis-oxalatoborate, LiCF3SO3, LiN(SO2F)2, LiC(CnF2n+1SO2)3, wherein n is an integer in the range of from 1 to 20, and (CnF2n+1SO2)mQLi with n being an integer in the range of from 1 to 20, m being 1 when Q is selected from oxygen or sulfur, m being 2 when X is selected from nitrogen or phosphorus, and m being 3 when Q is selected from carbon or silicon. In some embodiments, the non-aqueous (e.g., solid) electrolyte comprises an anti-perovskite material (e.g., Li3OBr, Li3OCl).
In some cases, the electrolyte is a solid electrolyte layer comprising the ionically conductive compound of formula (I). Referring to
Non-limiting examples of other materials that may be suitable for a solid polymer electrolyte include polyethers, polyethylene oxides, polypropylene oxides, polyimides, polyphosphazenes, polyacrylonitriles, polysiloxanes, derivatives of the foregoing, copolymers of the foregoing, cross-linked and network structures of the foregoing, and blends of the foregoing.
A solid electrolyte layer (e.g., a solid electrolyte layer comprising the ionically conductive compound of formula (I)) may have any suitable thickness. For example, in some embodiments, the solid electrolyte layer has a thickness of greater than or equal to 50 nm, greater than or equal to 100 nm, greater than or equal to 200 nm, greater than or equal to 500 nm, greater than or equal to 1 micron, greater than or equal to 5 microns, greater than or equal to 10 microns, greater than or equal to 15 microns, or greater than or equal to 20 microns. In some embodiments, the thickness of the solid electrolyte layer is less than or equal to 25 microns, less than or equal to 20 microns, less than or equal to 10 microns, less than or equal to 5 microns, less than or equal to 1 micron, less than or equal to 500 nm, less than or equal to 200 nm, or less than or equal to 100 nm. Other values are also possible. Combinations of the above-noted ranges are also possible (e.g., greater than or equal to 50 nm and less than or equal to 25 microns, greater than or equal to 5 microns and less than or equal to 25 microns). Other ranges are also possible.
In some embodiments, an electrode described herein may be a cathode (e.g., a cathode of an electrochemical cell). In some embodiments, an electrode such as a cathode comprises the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)). In some embodiments, a layer comprising the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) is deposited on a cathode, as described herein. In certain embodiments, the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) is incorporated into the cathode (e.g., by mixing with a cathode active electrode material prior to the formation of the cathode).
In some embodiments, the electroactive material in the cathode comprises the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)). That is, the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) may be the active electrode species of the cathode. In certain embodiments, the compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)) is a lithium intercalation compound (e.g., a compound that is capable of reversibly inserting lithium ions at lattice sites and/or interstitial sites). In some embodiments, the cathode may be an intercalation electrode comprising the ionically conductive compound of formula (I) (or one or more of the compounds for formulas (IIA)-(XXV)). In an exemplary embodiment, the cathode comprises a compound selected from the group consisting of Li10FeP2Si2, Li11FeP2S11Cl3, Li12.5Fe0.75P2S12, Li13.5Fe0.75P2S12.25, Li13Fe0.5P2S12, Li13Fe0.75P2S12.25, Li13FeP2S12.5, Li14.5Fe0.75P2S13, Li14Fe0.5P2S12.5, Li14Fe0.75P2S12.75, Li14FeP2S13, Li15Fe0.5P2S13, Li22FeP2S18, Li18FeP2S16, Li14FeP2S14, Li12FeP2S12, Li10FeP2S12, Li14Fe2PS13.5, Li13FeP2S13Cl, Li12FeP2S12Cl2, and Li13FeP2S13Br.
Incorporation of other ionically conductive compounds in addition to or alternatively to those described above are also possible.
Additional non-limiting examples of suitable materials that may intercalate ions of an electroactive material (e.g., alkaline metal ions), and which may be included in an electrode (e.g., cathode), include oxides, titanium sulfide, and iron sulfide. Specific examples include LixCoO2, LixNiO2, LixMnO2, LixMn2O4, LixFePO4, LixCoPO4, LixMnPO4, and LixNiPO4, where (0<x≤1), and LiNixMnyCoxO2 where (x+y+z=1).
In some embodiments, the electroactive material in the cathode comprising the compound of formula (I) is present in the cathode in an amount of at least about 30 wt %, at least about 40 wt %, at least about 50 wt %, at least about 60 wt %, at least about 70 wt %, at least about 80 wt %, at least about 85 wt %, at least about 90 wt %, at least about 95 wt %, or at least about 98 wt % versus the total cathode weight. In certain embodiments, the electroactive material in the cathode comprising the compound of formula (I) is present in the cathode in an amount of less than or equal to about 100 wt %, less than or equal to about 99 wt %, less than or equal to about 98 wt %, less than or equal to about 95 wt %, less than or equal to about 90 wt %, less than or equal to about 85 wt %, less than or equal to about 80 wt %, less than or equal to about 70 wt %, less than or equal to about 60 wt %, or less than or equal to about 50 wt % versus the total cathode weight. Combinations of the above-referenced ranges are also possible (e.g., at least about 40 wt % and less than or equal to about 95 wt %). Other ranges are also possible.
In some embodiments, active electrode materials for use as cathode active material in the cathode of the electrochemical cells described herein may include, but are not limited to, electroactive transition metal chalcogenides, electroactive conductive polymers, sulfur, carbon, and/or combinations thereof. As used herein, the term “chalcogenides” pertains to compounds that contain one or more of the elements of oxygen, sulfur, and selenium. Examples of suitable transition metal chalcogenides include, but are not limited to, the electroactive oxides, sulfides, and selenides of transition metals selected from the group consisting of Mn, V, Cr, Ti, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, and Ir. In one embodiment, the transition metal chalcogenide is selected from the group consisting of the electroactive oxides of nickel, manganese, cobalt, and vanadium, and the electroactive sulfides of iron. In certain embodiments, the cathode may include as an electroactive species elemental sulfur, sulfides, and/or polysulfides.
In one embodiment, a cathode includes one or more of the following materials: manganese dioxide, iodine, silver chromate, silver oxide and vanadium pentoxide, copper oxide, copper oxyphosphate, lead sulfide, copper sulfide, iron sulfide, lead bismuthate, bismuth trioxide, cobalt dioxide, copper chloride, manganese dioxide, and carbon. In another embodiment, the cathode active layer comprises an electroactive conductive polymer. Examples of suitable electroactive conductive polymers include, but are not limited to, electroactive and electronically conductive polymers selected from the group consisting of polypyrroles, polyanilines, polyphenylenes, polythiophenes, and polyacetylenes. Examples of conductive polymers include polypyrroles, polyanilines, and polyacetylenes.
In some embodiments, active electrode materials for use as cathode active materials in electrochemical cells described herein include electroactive sulfur-containing materials (e.g., lithium-sulfur electrochemical cells). “Electroactive sulfur-containing materials,” as used herein, relates to cathode active materials which comprise the element sulfur in any form, wherein the electrochemical activity involves the oxidation or reduction of sulfur atoms or moieties. The nature of the electroactive sulfur-containing materials useful in the practice of this invention may vary widely, as known in the art. For example, in one embodiment, the electroactive sulfur-containing material comprises elemental sulfur. In another embodiment, the electroactive sulfur-containing material comprises a mixture of elemental sulfur and a sulfur-containing polymer. Thus, suitable electroactive sulfur-containing materials may include, but are not limited to, elemental sulfur and organic materials comprising sulfur atoms and carbon atoms, which may or may not be polymeric. Suitable organic materials include those further comprising heteroatoms, conductive polymer segments, composites, and conductive polymers.
In certain embodiments, the sulfur-containing material (e.g., in an oxidized form) comprises a polysulfide moiety, Sm, selected from the group consisting of covalent Sm moieties, ionic Sm moieties, and ionic Sm2-moieties, wherein m is an integer equal to or greater than 3. In some embodiments, m of the polysulfide moiety Sm of the sulfur-containing polymer is an integer equal to or greater than 6 or an integer equal to or greater than 8. In some cases, the sulfur-containing material may be a sulfur-containing polymer. In some embodiments, the sulfur-containing polymer has a polymer backbone chain and the polysulfide moiety Sm is covalently bonded by one or both of its terminal sulfur atoms as a side group to the polymer backbone chain. In certain embodiments, the sulfur-containing polymer has a polymer backbone chain and the polysulfide moiety Sm is incorporated into the polymer backbone chain by covalent bonding of the terminal sulfur atoms of the polysulfide moiety.
In some embodiments, the electroactive sulfur-containing material comprises more than 50% by weight of sulfur. In certain embodiments, the electroactive sulfur-containing material comprises more than 75% by weight of sulfur (e.g., more than 90% by weight of sulfur).
As will be known by those skilled in the art, the nature of the electroactive sulfur-containing materials described herein may vary widely. In some embodiments, the electroactive sulfur-containing material comprises elemental sulfur. In certain embodiments, the electroactive sulfur-containing material comprises a mixture of elemental sulfur and a sulfur-containing polymer.
In certain embodiments, an electrochemical cell as described herein comprises one or more cathodes comprising sulfur as a cathode active material. In some such embodiments, the cathode includes elemental sulfur as a cathode active material. In some embodiments, the compound of formula (I) is chosen such that the compound of formula (I) is different from the anode active material and different from the cathode active material.
As described herein, an electrochemical cell or an article for use in an electrochemical cell may include an electrode (e.g., an anode) comprising an anode active material. In some embodiments, a layer comprising the compound of formula (I) is deposited on an anode. In certain embodiments, the compound of formula (I) is incorporated into the electrode (e.g., by mixing with an active electrode material prior to the formation of the anode).
In some embodiments, the compound of formula (I) is present in the anode (e.g., as a layer on the anode or incorporated into the anode) in an amount of at least about 40 wt %, at least about 50 wt %, at least about 60 wt %, at least about 70 wt %, at least about 80 wt %, or at least about 85 wt % versus the total anode weight. In certain embodiments, the compound of formula (I) is present in the anode in an amount of less than or equal to about 90 wt %, less than or equal to about 85 wt %, less than or equal to about 80 wt %, less than or equal to about 70 wt %, less than or equal to about 60 wt %, or less than or equal to about 50 wt % versus the total anode weight. Combinations of the above-referenced ranges are also possible (e.g., at least about 40 wt % and less than or equal to about 90 wt %). Other ranges are also possible. In some embodiments, the total anode weight may be measured as the anode active layer itself or the anode active material including any protective layer(s).
Suitable active electrode materials for use as anode active material in the electrochemical cells described herein include, but are not limited to, lithium metal such as lithium foil and lithium deposited onto a conductive substrate, lithium alloys (e.g., lithium-aluminum alloys and lithium-tin alloys), and graphite. Lithium can be contained as one film or as several films, optionally separated by a protective material such as a ceramic material or an ion conductive material described herein. Suitable ceramic materials include silica, alumina, or lithium containing glassy materials such as lithium phosphates, lithium aluminates, lithium silicates, lithium phosphorous oxynitrides, lithium tantalum oxide, lithium aluminosulfides, lithium titanium oxides, lithium silcosulfides, lithium germanosulfides, lithium aluminosulfides, lithium borosulfides, and lithium phosphosulfides, and combinations of two or more of the preceding. Suitable lithium alloys for use in the embodiments described herein can include alloys of lithium and aluminum, magnesium, silicium (silicon), indium, and/or tin. While these materials may be preferred in some embodiments, other cell chemistries are also contemplated. For instance, in some embodiments, certain electrodes (e.g., anodes) may include other alkali metals (e.g., group 1 atoms) in some instances. In some embodiments, the anode may comprise one or more binder materials (e.g., polymers, etc.).
In other embodiments, a silicon-containing or silicon-based anode may be used.
In some embodiments, the thickness of the anode may vary from, e.g., 2 to 200 microns. For instance, the anode may have a thickness of less than 200 microns, less than 100 microns, less than 50 microns, less than 25 microns, less than 10 microns, or less than 5 microns. In certain embodiments, the anode may have a thickness of greater than or equal to 2 microns, greater than or equal to 5 microns, greater than or equal to 10 microns, greater than or equal to 25 microns, greater than or equal to 50 microns, greater than or equal to 100 microns, or greater than or equal to 150 microns. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 2 microns and less than or equal to 200 microns, greater than or equal to 2 microns and less than or equal to 100 microns, greater than or equal to 5 microns and less than or equal to 50 microns, greater than or equal to 5 microns and less than or equal to 25 microns, greater than or equal to 10 microns and less than or equal to 25 microns). Other ranges are also possible. The choice of the thickness may depend on cell design parameters such as the excess amount of lithium desired, cycle life, and the thickness of the cathode electrode.
In some embodiments, an electrochemical cell described herein comprises at least one current collector. Materials for the current collector may be selected, in some cases, from metals (e.g., copper, nickel, aluminum, passivated metals, and other appropriate metals), metallized polymers, electrically conductive polymers, polymers comprising conductive particles dispersed therein, and other appropriate materials. In certain embodiments, the current collector is deposited onto the electrode layer using physical vapor deposition, chemical vapor deposition, electrochemical deposition, sputtering, doctor blading, flash evaporation, or any other appropriate deposition technique for the selected material. In some cases, the current collector may be formed separately and bonded to the electrode structure. It should be appreciated, however, that in some embodiments a current collector separate from the electroactive layer may not be present or needed.
In some embodiments, an electrochemical cell comprises a lithium or silicon based anode, a cathode (e.g., a cathode comprising electroactive sulfur-containing material, an intercalation cathode) and a solid electrolyte layer comprising the compound of formula (I). The electrochemical cell may include other components as described herein.
In certain embodiments, an electrochemical cell comprises a lithium or silicon based anode, a cathode (e.g., a cathode comprising electroactive sulfur-containing material, an intercalation cathode), a liquid electrolyte, and a protective layer comprising the compound of formula (I). The electrochemical cell may include other components as described herein.
In some embodiments, an electrochemical cell comprises a lithium or silicon based anode, a cathode (e.g., a cathode comprising electroactive sulfur-containing material, an intercalation cathode), a liquid electrolyte, and a separator comprising the compound of formula (I). The electrochemical cell may include other components as described herein.
In certain embodiments, an electrochemical cell comprises a lithium or silicon based anode, an intercalated cathode (e.g., a cathode comprising the compound of formula (I) as an intercalation species), and an electrolyte (e.g., a liquid electrolyte). The electrochemical cell may include other components as described herein.
The following examples are intended to illustrate certain embodiments of the present invention, but do not exemplify the full scope of the invention.
This example describes the conductivity and composition of various ionically conductive compounds having the formula as in Formula (I).
For the ion conductive materials formed in Examples 2 to 3, the following procedure was followed. The precursor materials Li2S (99.9% purity), P2S5 (99% purity), FeS (99.9% purity) and elemental sulfur (99.9% purity) were thoroughly mixed together in the respective stoichiometric ratios. Sulfur was added in such amounts to oxidize FeS to FeS2 (e.g., including a 10% surplus to make up for losses due to evaporation in the reaction vessel). In compositions that included a halide, LiCl (99% purity) or LiBr (99.9% purity) were added in the respective stoichiometric amounts, as well. Due in part to the rather small reaction batches (overall between 5-15 g), homogeneous, fine mixtures were produced by grinding the powders together carefully by mortar and pistil.
The resulting mixtures were heated to 750° C. under inert atmosphere (Ar) overnight (generally between 14-18 hours) in a vitreous carbon crucible enclosed in a sealed steel cylinder (Cu gaskets on conflat (CF) flanges). The oven was flushed with Ar (e.g., in order to avoid undesired side reactions even in the event of a leakage of the steel reaction vessel). The reactants were subsequently slowly cooled down to room temperature before opening the steel cylinder. Without wishing to be bound by theory, it was anticipated that unreacted sulfur would condensate from the gas phase first on the cylinder walls and not back into the product mixture (for this reason a surplus of sulfur can be safely used to start with). The reacted powder was then removed from the crucible in an Ar-filled glove box and ground down before submitting samples for analysis.
Analytical Methods
EDX measurements were performed to verify the composition of the samples and identify impurities and contaminations, e.g., from undesired side reactions such as oxidation in case of a leakage of the reaction vessel.
Powder conductivity measurements were carried out by densifying a specified amount of powder under increasing pressures in a die (measurement takes place between two aluminum foils, which were sandwiched between two copper plates). From the measurement curve and the experimental conductivity values under very high pressure values (up to 5t on a 1″ pellet, corresponding to ˜968.5 bar), the bulk conductivity of the material under consideration was extrapolated.
EIS (electronic impedance spectroscopy) measurements were performed under the same conditions and setup to distinguish between the electronic and ionic contributions to the overall powder conductivity.
XRD measurements were used to verify the success and reproducibility of the synthesis (final reaction products are crystalline). It was shown that the XRD patterns are reminiscent of lithium-based argyrodites. Generally, Li21SiP2S17.5 was used for comparison.
The XRD powder diffractogram of Li21SiP2S17.5 as a typical representative is shown in
A comparison of both the diffractogram of Li21SiP2S17.5 (
LixFeP2Sx/2+7 (x=10-22) (Example Compound Having a Structure as in Formula (I), where x is 10-22, y is 1, z is 2, u is 12-18, M is Fe, Q is Absent, and X is Absent).
A comparison of the diffractograms (
Doping with halogens may be one viable strategy to increase the conductivity of the synthesized argyrodites. Therefore, Li14FeP2S14 was chosen to start with, given that it was found to be the (halogen-free) Fe-based compound with the highest intrinsic conductivity and purest argyrodite-type spectral pattern (see Example 2). In order to investigate the influence of halogen-doping in a systematic manner, Li2S units were consecutively replaced by LiCl entities in the Li14FeP2S14 material to yield Li13FeP2S13Cl, Li12FeP2S12Cl2 and Li11FeP2S11Cl3. The respective XRD spectra are shown in
It is interesting at this point to compare the findings described for the XRD patterns to the powder conductivities for the same compounds, shown in
As expected from the XRD spectra, the highest conductivity value is obtained for Li13FeP2S13Cl, displaying the purest argyrodite-type spectrum. However, it should be noted that a further increase in LiCl entails only a slight decrease in conductivity (within the error of these measurements/synthesis procedures), despite the increasing amount of unreacted LiCl within the product mix. In order to show that the overall powder conductivity is purely ionic, EIS spectra have been recorded. The spectrum for Li11FeP2S11Cl3 is exemplarily shown in
In order to check the influence of different halogen atoms, LiBr was used instead of LiCl to synthesize Li13FeP2S13Br. The XRD powder diffractogram is shown in
Table 3 summarizes an exemplary mixture of precursors, synthesis temperature, conductivity, and gross formula for exemplary ionically conductive compounds synthesized as described herein.
Samples of Li13FeP2S13Cl, Li13FeP2S13Br, and Li14FeP2S14 were placed into an argon-filled glovebox for x-ray diffraction measurements. Small amounts of the samples were ground in an agate mortar, filled into capillaries made of borosilicate glass (Hilgenberg GmbH, outer diameter 0.3 mm and 0.01 mm wall thickness), and flame-sealed. Standard powder X-ray diffraction data were recorded in Debye-Scherrer geometry with Ge(111)-monochromated Cu-Kα1 radiation (1.540596 Å) at 298 K on a STOE Stadi P powder diffractometer equipped with a DECTRIS MYTHEN 1K strip detector in the range 5-90°2θ. The Topas Academic software was used for analyses of the diffraction patterns.
The measurements of the Li14FeP2S14 samples resulted in diffraction patterns that indicate a cubic metric with a lattice parameter a=9.86888(10) Å, typical for the argyrodite structure type. The structure of the argyrodite compound Li7(PS4)S2 includes PS43--tetrahedra on Wyckoff position 4b, S2- ions on 4a and 4c, and Li+ ions on 48h (ICSD 421130; further Li sites are another 48h and a 24 g site). As described in Examples 2-3, iron could be incorporated into the structure, e.g., substituting P by Fe and synthesizing argyrodite derivatives of compositions Lix-u MyP3-ySz-tXt (with M=Fe and X═Br, Cl). For quantitative Rietveld analyses the aforementioned structure model was used as a starting point.
In a first attempt of refinement, Fe was allowed to replace P while retaining full occupation of the site. This resulted in a composition Li14.6(5)(Fe0.15(2)P0.85(2)S4)S2 with a Fe-ratio of 15% (instead of 33%, expected by the nominal composition Li14FeP2S14) on the P site. The occupancy of the Li+ ions refined to twice the value that is expected and required for charge balancing (14 instead of 7). Moreover, the structure revealed P/Fe—S bond lengths of 2.038(5) Å that are characteristic for pure P—S bonds without the influence of Fe (typical bond lengths in solids are: P—S: 2.04 Å; Fe—S: 2.3-2.4 Å). These results are all strong indications for Fe ions (Fe(II) or Fe(III), to be determined by Mößbauer spectroscopy) being located on the Li sites. Refinements allowing Fe on the Li sites resulted in the structure models indicated in Tables 4-6 (including estimated standard deviation (esd)).
†high errors in Li/Fe occupancy numbers is due to low data to parameter ratio
Although the standard deviations for the occupancies are high the formulas resulting from the second refinement with Fe on the Li positions are closer to the nominal composition than the other structure model (with Fe on the P position). Consequently, the assumption that all the Fe that was added to the synthesis mixture is contained in the argyrodite phase is supported by the fact that no other Fe-containing phases were detected in the diffraction patterns (although amorphous phases and sublimation should be also considered). With the structure model with 15% of Fe on the P position, left-over FeS, FeS2 or other Fe-containing phases would have been expected. Furthermore, the structure model with Fe ions on the Li+ positions could also explain that there is no significant enlargement in the lattice parameter of the Fe-containing phases compared to Li7(PS4)S2. The ionic radius of e.g. Fe3+ with r=49 pm (Coordination Number (CN) of CN=4) is smaller than the one of Li+ with r=59 pm (CN=4). Expansion of the lattice parameter would be expected if Fe replaces P because of the longer Fe—S distance, while experimentally most likely a small contraction was observed as outlined above.
The results of the modelling of the diffraction patterns measured from the Br- and the Cl-sample are shown in Tables 7-9. In these compounds, it appears that most of the Fe ions are located on the Li positions. The P—S distances do again not indicate any expansion. The incorporation of Br in these samples seems to have worked success fully: Excess electron density was found on positions 4a and 4d and no residual LiBr was found in the pattern. The incorporation of Cl appears to have worked as well as suggested indirectly by the absence of LiCl in the pattern, as S2- and Cl− on the 4a and 4d positions cannot be distinguished by XRD (e.g., they have the same amount of electrons and therefore the same scattering power). In both samples side phases were detected to be Li4P2S6 and lithium iron sulfide. Li2S has not been found in any of those samples.
†high errors in Li/Fe occupancy numbers is due to low data to parameter ratio
While several embodiments of the present invention have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the functions and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the present invention. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the teachings of the present invention is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, the invention may be practiced otherwise than as specifically described and claimed. The present invention is directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the scope of the present invention.
All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.
The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”
The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and/or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e. “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law.
As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
It should also be understood that, unless clearly indicated to the contrary, in any methods claimed herein that include more than one step or act, the order of the steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are recited.
In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.
This application is a continuation of U.S. application Ser. No. 15/988,182, filed May 24, 2018, which claims priority to U.S. Provisional Application No. 62/510,430, filed May 24, 2017, each of which is incorporated herein by reference in its entirety. Articles, compositions, and methods including ionically conductive compounds are provided. In some embodiments, the ionically conductive compounds are useful for electrochemical cells.
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| Number | Date | Country | |
|---|---|---|---|
| 20220255188 A1 | Aug 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62510430 | May 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15988182 | May 2018 | US |
| Child | 17558782 | US |
