Catholytes for solid state rechargeable batteries, battery architectures suitable for use with these catholytes, and methods of making and using the same

Description

FIELD

The present disclosure sets forth high voltage-stable electrolytes, such as dinitrile solvents and mixtures of dinitrile solvents and nitrile solvents, and organic sulfur-including solvents which include lithium salts, electrochemical cells and devices which include these electrolytes, and methods of making and using the same.

BACKGROUND

Conventional lithium rechargeable batteries use a porous polyolefin separator which is soaked with liquid electrolytes. This separator electrically insulates the positive and negative electrodes of the battery but remains conductive towards Li⁺ ions. This conventional battery architecture relies on carbonate-based organic solvents, which suffer from flammability and leakage problems, to achieve commercially relevant ion-conductivity, cycle life, and shelf life metrics. Carbonates also have a limited (i.e., narrow) voltage stability window and are particularly unstable when stored at high voltages. Most importantly, carbonate solvents are not chemically compatible with all lithium metal negative electrodes.

Some researchers have attempted to use nitrile solvents in place of carbonate solvents. See, for example, Abu-Lebdeh, Y., et al., Journal of Power Sources 189 (2009) 576-579; Abu-Lebdeh, Y., et al., Journal of The Electrochemical Society, 156 (1) A60-A65 (2009); Long, S. et al., Solid State Ionics 161 (2003) 105-112; Geirhos, K. et al., The Journal of Chemical Physics, 143, 081101 (2015); Zachariah, M., et al. J. Phys. Chem. C 2015, 119, 27298-27306; and Alarco, P-J., et al., nature materials (3), July, 2004. However, these prior uses of nitrile solvents suffered from instability with low voltage anodes such as graphite or lithium metal which are used in high energy batteries. This was due in part because nitrile solvents are not able to form a passivating solid-electrolyte-interface (SEI) on low voltage anodes, such as lithium metal. To date, nitrile solvents have not, which makes nitrile solvents unusable in high energy (i.e., high voltage) batteries. As a result, these graphite and lithium metal anodes typically have, prior to the instant disclosure, required a carbonate co-solvent for the electrolyte.

Some researchers have electrospun or polymerized nitrile-based materials for battery applications, for example Zhou D., et al. (2015) In Situ Synthesis of a Hierarchical All-Solid-State Electrolyte Based on Nitrile Materials for High-Performance Lithium-Ion Batteries. Adv. Energy Mater., 5: 1500353. doi: 10.1002/aenm.201500353. However, the impedance observed in these electrospun or polymerized nitrile-based materials high, the low temperature power capability of the batteries which used these electrospun or polymerized nitrile-based materials is poor, and the electrospun or polymerized nitrile-based materials could not block the formation of lithium dendrites at commercially relevant current densities and commercially relevant throughput amounts of of lithium during electrochemical cycling.

Accordingly, there exists a need for improved electrolytes for rechargeable batteries. Set forth herein are such improved electrolytes as well as other solutions to problems in the relevant field.

SUMMARY

In one embodiment, set forth herein is an electrochemical cell which includes: a lithium metal negative electrode;

a solid separator; and

a positive electrode,

wherein the positive electrode includes an active material and a catholyte,

wherein the catholyte includes a catholyte solvent and a lithium salt, wherein the catholyte solvent comprises a nitrile solvent, a dinitrile solvent, an organic sulfur-including solvent, or a combination thereof.

In a second embodiment, set forth herein is a catholyte including a nitrile solvent and a lithium salt,

- wherein the nitrile solvent is selected from acetonitrile, butyronitrile, benzonitrile, glutaronitrile, hexanenitrile, fluoroacetonitrile, nitroacetonitrile, malononitrile, ethoxyacetonitrile, methoxyacetonitrile, pentanenitrile, propanenitrile, succinonitrile, adiponitrile, and iso-butyronitrile;
- wherein the lithium salt is selected from LiPF₆, LiBOB, LiTFSi, LiBF₄, LiClO₄, LiAsF₆, LiFSI, LiClO₄, LiI, and a combination thereof; and
- wherein the catholyte is chemically compatible with a solid separator set forth herein.

In a third embodiment, set forth herein is a catholyte comprising an organic sulfur-including solvent, optionally a co-solvent, and a lithium salt,

- wherein the organic sulfur-including solvent is selected from ethyl methyl sulfone, dimethyl sulfone, sulfolane, allyl methyl sulfone, butadiene sulfone, butyl sulfone, methyl methanesulfonate, dimethyl sulfite, wherein the co-solvent is a carbonate solvent;
- wherein the lithium salt is selected from LiPF₆, LiBOB, LiTFSi, LiBF₄, LiClO₄, LiAsF₆, LiFSI, LiClO₄, LiI, and a combination thereof.

In a fourth embodiment, set forth herein is a method of using an electrochemical cell set forth herein, comprising charging the electrochemical cell to a voltage greater than 4.3V.

In a fifth embodiment, set forth herein is a method of storing an electrochemical cell, including providing an electrochemical cell set forth herein, wherein the electrochemical cell has greater than 20% state-of-charge (SOC); and storing the battery for at least one day.

In a sixth embodiment, set forth herein is a method for making a catholyte set forth herein which includes a nitrile solvent and a lithium salt, wherein the method includes providing a nitrile solvent, providing a lithium salt, mixing the nitrile solvent and the lithium salt to form a mixture, and optionally heating the mixture.

In a seventh embodiment, set forth herein is a method for making a catholyte set forth herein which includes an organic sulfur-including solvent and a lithium salt, wherein the method includes providing an organic sulfur-including solvent, providing a lithium salt, mixing the organic sulfur-including solvent and the lithium salt to form a mixture, and optionally heating the mixture.

BRIEF DESCRIPTIONS OF THE DRAWINGS

FIG. 1 shows a schematic of an example of an electrochemical cell having a catholyte in the positive electrode space which includes a dinitrile solvent.

FIG. 2 shows a plot of the median charge ASR-DC (Ω-cm²) for two electrochemical cells, after storage at 4.6 V, and wherein one electrochemical cell includes a catholyte including succinonitrile (SCN) at 12 mol % LiBF₄and wherein the other electrochemical cell includes a catholyte including EC:EMC+1 M LiPF₆+2 wt % monofluoroethylene carbonate (FEC). In the figure, circles refer to succinonitrile+12 mol % LiBF₄, and triangles refer to EC:EMC+1 M LiPF₆+2 wt % FEC. Elyte in FIG. 2 refers to electrolyte. EC refers to ethyl carbonate solvent. EMC refers to ethyl methyl carbonate solvent.

FIG. 3 shows a plot of the median discharge ASR-DC (Ω-cm²) for two electrochemical cells, after storage at 4.6 V, and wherein one electrochemical cell includes a catholyte including succinonitrile (SCN) at 12 mol % LiBF₄and wherein the other electrochemical cell includes a catholyte including EC:EMC+1 M LiPF₆+2 wt % monofluoroethylene carbonate (FEC). In the figure, circles refer to succinonitrile+12 mol % LiBF₄, and triangles refer to EC:EMC+1 M LiPF₆+2 wt % FEC.

FIG. 4 shows a plot of active mass-specific discharge capacity (mAh/g) as a function of cycle index for devices made according to Example 2 with two different catholytes.

FIG. 5 shows a plot of the median charge and discharge ASR_dc(Ω-cm²) for two electrochemical cells, both stored at 4.6 V, and wherein one electrochemical cell includes a catholyte including succinonitrile at 12 mol % LiBF₄and wherein the other electrochemical cell includes a catholyte including EC:EMC+1 M LiPF₆+2 wt % FEC. In the figure, circles refer to succinonitrile+12 mol % LiBF₄, and triangles refer to EC:EMC at 3.7 w/w+1 M LiPF₆+2 wt % FEC.

FIG. 6 shows a plot of mass percent of Gel Polymer Soaked in Electrolyte for two electrochemical cells, wherein one electrochemical cell includes a catholyte including adiponitrile and 1M LiTFSi and wherein the other electrochemical cell includes a catholyte including EC:EMC+1 M LiPF₆+2 wt % FEC. In the figure, solid line is adiponitrile+1 M LiTFSi, and the doted line is EC:EMC+1 M LiPF₆+2 wt % FEC.

FIG. 7 shows a plot of charge ASR growth wherein the cell is prepared with sulfolane and ethylene carbonate (3:7 v/v)+2M LiPF₆vs ethyl-methyl carbonate, ethylene carbonate (3:7 v/v)+1M LiPF₆for 10 cycles, C/3 pulses, from 2.7-4.2 V at 45° C. The cathode is NMC, and the separator is solid-state separator material. Solid line is EC:EMC 3:7 v/v+1 MLiPF₆; dotted line is EC:Sulfolane 3:7 v/v+2 M LiPF₆.

FIG. 8 shows a plot of discharge and charge ASR versus cycle life for 500 cycles for a cell.

DETAILED DESCRIPTION
A. Definitions

As used herein, the term “about,” when qualifying a number, e.g., about 15% w/w, refers to the number qualified and optionally the numbers included in a range about that qualified number that includes ±10% of the number. For example, about 15% w/w includes 15% w/w as well as 13.5% w/w, 14% w/w, 14.5% w/w, 15.5% w/w, 16% w/w, or 16.5% w/w. For example, “about 75° C.,” includes 75° C. as well 68° C., 69° C., 70° C., 71° C., 72° C., 73° C., 74° C., 75° C., 76° C., 77° C., 78° C., 79° C., 80° C., 81° C., 82° C., or 83° C.

As used herein, the phrase “Li⁺ ion-conducting separator” refers to an electrolyte which conducts Li⁺ ions, is substantially insulating to electrons (e.g., the lithium ion conductivity is at least 10³times, and often 10⁶times, greater than the electron conductivity), and which acts as a physical barrier or spacer between the positive and negative electrodes in an electrochemical cell.

As used herein, the phrases “solid separator,” “solid electrolyte,” “solid-state separator,” and “solid-state electrolyte” refer to Li⁺ ion-conducting separators that are solids at room temperature and include at least 50 vol % ceramic material.

As used herein, “selected from the group consisting of” refers to a single member from the group, more than one member from the group, or a combination of members from the group. A member selected from the group consisting of A, B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C, as well as A, B, and C.

As used herein, the phrase “electrochemical cell” refers to, for example, a “battery cell” and includes a positive electrode, a negative electrode, and an electrolyte therebetween which conducts ions (e.g., Li⁺) but electrically insulates the positive and negative electrodes. In some embodiments, a battery may include multiple positive electrodes and/or multiple negative electrodes enclosed in one container.

As used herein the phrase “electrochemical stack” refers to one or more units which each include at least a negative electrode (e.g., Li, LiC₆), a positive electrode (e.g., Li-nickel-manganese-oxide or FeF₃, optionally combined with a solid-state electrolyte or a gel electrolyte), and a solid electrolyte (e.g., an oxide electrolyte set forth herein, a lithium-stuffed garnet film, or a lithium-stuffed garnet pellet) between and in contact with the positive and negative electrodes. In some examples, between the solid electrolyte and the positive electrode, there is an additional layer comprising a compliant (e.g., gel electrolyte). An electrochemical stack may include one of these aforementioned units. An electrochemical stack may include several of these aforementioned units arranged in electrical communication (e.g., serial or parallel electrical connection). In some examples, when the electrochemical stack includes several units, the units are layered or laminated together in a column. In some examples, when the electrochemical stack includes several units, the units are layered or laminated together in an array. In some examples, when the electrochemical stack includes several units, the stacks are arranged such that one negative electrode is shared with two or more positive electrodes. Alternatively, in some examples, when the electrochemical stack includes several units, the stacks are arranged such that one positive electrode is shared with two or more negative electrodes. Unless specified otherwise, an electrochemical stack includes one positive electrode, one solid electrolyte, and one negative electrode, and optionally includes a gel electrolyte layer between the positive electrode and the solid electrolyte. In some examples, the gel electrolyte layer is also included in the positive electrode. In some examples, the gel electrolyte includes any electrolyte set forth herein, including a nitrile, dinitrile, organic sulfur-including solvent, or combination thereof set forth herein.

As used herein, the term “electrolyte” refers to a material that allows ions, e.g., Li⁺, to migrate or conduct therethrough but which does not allow electrons to conduct therethrough. Electrolytes are useful for electrically isolating the cathode and anodes of a secondary battery while allowing ions, e.g., Li⁺, to transmit through the electrolyte. Solid electrolytes, in particular, rely on ion hopping through rigid structures. Solid electrolytes may be also referred to as fast ion conductors or super-ionic conductors. Solid electrolytes may be also used for electrically insulating the positive and negative electrodes of a cell while allowing for the conduction of ions, e.g., Li⁺, through the electrolyte. In this case, a solid electrolyte layer may be also referred to as a solid electrolyte separator or solid-state electrolyte separator.

As used herein, the phrases “gel electrolyte” unless specified otherwise, refers to a suitable Li⁺ ion conducting gel or liquid-based electrolyte, for example, those set forth in U.S. Pat. No. 5,296,318, entitled RECHARGEABLE LITHIUM INTERCALATION BATTERY WITH HYBRID POLYMERIC ELECTROLYTE. A gel electrolyte has a lithium ion conductivity of greater than 10⁻⁵S/cm at room temperature, a lithium transference number between 0.05-0.95, and a storage modulus greater than the loss modulus at some temperature. A gel electrolyte may comprise a polymer matrix, a solvent that gels the polymer, and a lithium containing salt that is at least partly dissociated into Li⁺ ions and anions. Alternately, a gel electrolyte may comprise a porous polymer matrix, a solvent that fills the pores, and a lithium containing salt that is at least partly dissociated into Li⁺ ions and anions where the pores have one length scale less than 10 μm.

As used herein, the term “laminating” refers to the process of sequentially depositing a layer of one precursor specie, e.g., a lithium precursor specie, onto a deposition substrate and then subsequently depositing an additional layer onto an already deposited layer using a second precursor specie, e.g., a transition metal precursor specie. This laminating process can be repeated to build up several layers of deposited vapor phases. As used herein, the term “laminating” also refers to the process whereby a layer comprising an electrode, e.g., positive electrode or cathode active material comprising layer, is contacted to a layer comprising another material, e.g., garnet electrolyte. The term “laminating” also refers to the process whereby at least two layers comprising a solid electrolyte material are contacted together. The laminating process may include a reaction or use of a binder which adheres of physically maintains the contact between the layers which are laminated. The process of laminating one layer to another layer results in one layer being laminated to the other layer.

As used herein, the phrase “directly contacts” refers to the juxtaposition of two materials such that the two materials contact each other sufficiently to conduct either an ion or electron current. As used herein, direct contact refers to two materials in contact with each other and which do not have any materials positioned between the two materials which are in direct contact.

As used herein, the terms “cathode” and “anode” refer to the electrodes of a battery. The cathode and anode are often referred to in the relevant field as the positive electrode and negative electrode, respectively. During a charge cycle in a Li-secondary battery, Li ions leave the cathode and move through an electrolyte, to the anode. During a charge cycle, electrons leave the cathode and move through an external circuit to the anode. During a discharge cycle in a Li-secondary battery, Li ions migrate towards the cathode through an electrolyte and from the anode. During a discharge cycle, electrons leave the anode and move through an external circuit to the cathode.

As used herein, the phrase “positive electrode” refers to the electrode in a secondary battery towards which positive ions, e.g., Li⁺, conduct, flow or move during discharge of the battery. As used herein, the phrase “negative electrode” refers to the electrode in a secondary battery from where positive ions, e.g., Li⁺, flow or move during discharge of the battery. In a battery comprised of a Li-metal electrode and a conversion chemistry, intercalation chemistry, or combination conversion/intercalation chemistry-including electrode (i.e., cathode active material; e.g., NiF_x, NCA, LiNi_xMn_yCo_zO₂[NMC] or LiNi_xAl_yCo_zO₂[NCA], wherein x+y+z=1), the electrode having the conversion chemistry, intercalation chemistry, or combination conversion/intercalation chemistry material is referred to as the positive electrode. In some common usages, cathode is used in place of positive electrode, and anode is used in place of negative electrode. When a Li-secondary battery is charged, Li ions move from the positive electrode (e.g., NiF_x, NMC, NCA) towards the negative electrode (e.g., Li-metal). When a Li-secondary battery is discharged, Li ions move towards the positive electrode and from the negative electrode.

As used herein, the term “catholyte” refers to a Li ion conductor that is intimately mixed with, or that surrounds and contacts, or that contacts the positive electrode active materials and provides an ionic pathway for Li⁺ to and from the active materials. Catholytes suitable with the embodiments described herein include, but are not limited to, catholytes having the acronyms name LPS, LXPS, LXPSO, where X is Si, Ge, Sn, As, Al, LATS, or also Li-stuffed garnets, or combinations thereof, and the like. Catholytes may also be liquid, gel, semi-liquid, semi-solid, polymer, and/or solid polymer ion conductors known in the art. In some examples, the catholyte includes a gel set forth herein. In some examples, the gel electrolyte includes any electrolyte set forth herein, including a nitrile, dinitrile, organic sulfur-including solvent, or combination thereof set forth herein.

In some examples, the electrolytes herein may include, or be layered with, or be laminated to, or contact a sulfide electrolyte. As used here, the phrase “sulfide electrolyte,” includes, but is not limited to, electrolytes referred to herein as LSS, LTS, LXPS, or LXPSO, where X is Si, Ge, Sn, As, Al, LATS. In these acronyms (LSS, LTS, LXPS, or LXPSO), S refers to the element S, Si, or combinations thereof, and T refers to the element Sn. “Sulfide electrolyte” may also include Li_aP_bS_cX_d, Li_aB_bS_cX_d, Li_aSn_bS_cX_dor Li_aSi_bS_cX_dwhere X═F, Cl, Br, I, and 10%≤a≤50%, 10%≤b≤44%, 24%≤c≤70%, 0≤d≤18% and may further include oxygen in small amounts. For example, oxygen may be present as a dopant or in an amount less than 10 percent by weight. For example, oxygen may be present as a dopant or in an amount less than 5 percent by weight.

As used herein, the phrase “sulfide based electrolytes” refers to electrolytes that include inorganic materials containing S which conduct ions (e.g., Li⁺) and which are suitable for electrically insulating the positive and negative electrodes of an electrochemical cell (e.g., secondary battery). Exemplary sulfide based electrolytes include, but are not limited to, those electrolytes set forth in International Patent Application PCT Patent Application No. PCT/US14/38283, SOLID STATE CATHOLYTE OR ELECTROLYTE FOR BATTERY USING Li_AMP_BS_C(M=SI, GE, AND/OR SN), filed May 15, 2014, and published as WO 2014/186634, on Nov. 20, 2014, which is incorporated by reference herein in its entirety; also, U.S. Pat. No. 8,697,292 to Kanno, et al, the contents of which are incorporated by reference in their entirety.

As used here, the phrase “sulfide electrolyte” includes, but are not limited to, LSS, LTS, LXPS, LXPSO, where X is Si, Ge, Sn, As, Al, LATS, also Li-stuffed garnets, or combinations thereof, and the like, S is S, Si, or combinations thereof, T is Sn.

As used herein, “SLOPS” includes, unless otherwise specified, a 60:40 molar ratio of Li₂S:SiS₂with 0.1-10 mol. % Li₃PO₄. In some examples, “SLOPS” includes Li₁₀Si₄S₁₃(50:50 Li₂S:SiS₂) with 0.1-10 mol. % Li₃PO₄. In some examples, “SLOPS” includes Li₂₆Si₇S₂₇(65:35 Li₂S:SiS₂) with 0.1-10 mol. % Li₃PO₄. In some examples, “SLOPS” includes Li₄SiS₄(67:33 Li₂S:SiS₂) with 0.1-5 mol. % Li₃PO₄. In some examples, “SLOPS” includes Li₁₄Si₃S₁₃(70:30 Li₂S:SiS₂) with 0.1-5 mol. % Li₃PO₄. In some examples, “SLOPS” is characterized by the formula (1−x)(60:40 Li₂S:SiS₂)*(x)(Li₃PO₄), wherein x is from 0.01 to 0.99. As used herein, “LBS-POX” refers to an electrolyte composition of Li₂S:B₂S₃:Li₃PO₄:LiX where X is a halogen (X═F, Cl, Br, I). The composition can include Li₃BS₃or Li₅B₇S₁₃doped with 0-30% lithium halide such as LiI and/or 0-10% Li₃PO₄.

As used here, “LBS” refers to an electrolyte material characterized by the formula Li_aB_bS_cand may include oxygen and/or a lithium halide (LiF, LiCl, LiBr, LiI) at 0-40 mol %.

As used here, “LPSO” refers to an electrolyte material characterized by the formula Li_xP_yS_zO_wwhere 0.33≤x≤0.67, 0.07≤y≤0.2, 0.4≤z≤0.55, 0≤w≤0.15. Also, LPSO refers to LPS, as defined above, that includes an oxygen content of from 0.01 to 10 atomic %. In some examples, the oxygen content is 1 atomic %. In other examples, the oxygen content is 2 atomic %. In some other examples, the oxygen content is 3 atomic %. In some examples, the oxygen content is 4 atomic %. In other examples, the oxygen content is 5 atomic %. In some other examples, the oxygen content is 6 atomic %. In some examples, the oxygen content is 7 atomic %. In other examples, the oxygen content is 8 atomic %. In some other examples, the oxygen content is 9 atomic %. In some examples, the oxygen content is 10 atomic %.

As used herein, the term “LBHI” or “LiBHI” refers to a lithium conducting electrolyte comprising Li, B, H, and I. More generally, it is understood to include aLiBH₄+bLiX where X═Cl, Br, and/or I and where a:b=7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or within the range a/b=2-4. LBHI may further include nitrogen in the form of aLiBH₄+bLiX+cLiNH₂where (a+c)/b=2-4 and c/a=0-10.

As used herein, the term “LPSI” refers to a lithium conducting electrolyte comprising Li, P, S, and I. More generally, it is understood to include aLi₂S+bP₂S_y+cLiX where X═Cl, Br, and/or I and where y=3-5 and where a/b=2.5-4.5 and where (a+b)/c=0.5-15.

As used herein, the term “LIRAP” refers to a lithium rich antiperovskite and is used synonymously with “LOC” or “Li₃OCl”. The composition of LIRAP is aLi₂O+bLiX+cLiOH+dAl₂O₃where X═Cl, Br, and/or I, a/b=0.7-9, c/a=0.01-1, d/a=0.001-0.1.

As used herein, “LSS” refers to lithium silicon sulfide which can be described as Li₂S—SiS₂, Li—SiS₂, Li—S—Si, and/or a catholyte consisting essentially of Li, S, and Si. LSS refers to an electrolyte material characterized by the formula Li_xSi_yS_zwhere 0.33≤x≤0.5, 0.1≤y≤0.2, 0.4≤z≤0.55, and it may include up to 10 atomic % oxygen. LSS also refers to an electrolyte material comprising Li, Si, and S. In some examples, LSS is a mixture of Li₂S and SiS₂. In some examples, the ratio of Li₂S:SiS₂is 90:10, 85:15, 80:20, 75:25, 70:30, 2:1, 65:35, 60:40, 55:45, or 50:50 molar ratio. LSS may be doped with compounds such as Li_xPO_y, Li_xBO_y, Li₄SiO₄, Li₃MO₄, Li₃MO₃, PS_x, and/or lithium halides such as, but not limited to, LiI, LiCl, LiF, or LiBr, wherein 0<x≤5 and 0≤y≤5.

As used herein, “LTS” refers to a lithium tin sulfide compound which can be described as Li₂S—SnS₂, Li₂S—SnS, Li—S—Sn, and/or a catholyte consisting essentially of Li, S, and Sn. The composition may be Li_xSn_yS_zwhere 0.25≤x≤0.65, 0.05≤y≤0.2, and 0.25≤z≤0.65. In some examples, LTS is a mixture of Li₂S and SnS₂in the ratio of 80:20, 75:25, 70:30, 2:1, or 1:1 molar ratio. LTS may include up to 10 atomic % oxygen. LTS may be doped with Bi, Sb, As, P, B, Al, Ge, Ga, and/or In. As used herein, “LATS” refers to LTS, as used above, and further comprising Arsenic (As).

As used herein, “LXPS” refers to a material characterized by the formula Li_aMP_bS_c, where M is Si, Ge, Sn, and/or Al, and where 2≤a≤8, 0.5≤b≤2.5, 4≤c≤12. “LSPS” refers to an electrolyte material characterized by the formula L_aSiP_bS_c, where 2≤a≤8, 0.5≤b≤2.5, 4≤c≤12. LSPS refers to an electrolyte material characterized by the formula L_aSiP_bS_c, wherein, where 2≤a≤8, 0.5≤b≤2.5, 4≤c≤12, d≤3. Exemplary LXPS materials are found, for example, in International Patent Application No. PCT/US14/38283, SOLID STATE CATHOLYTE OR ELECTROLYTE FOR BATTERY USING Li_AMP_BS_C(M=SI, GE, AND/OR SN), filed May 15, 2014, and published as WO 2014/186634, on Nov. 20, 2014, which is incorporated by reference herein in its entirety. Exemplary LXPS materials are found, for example, in U.S. patent application Ser. No. 14/618,979, filed Feb. 10, 2015, and published as Patent Application Publication No. 2015/0171465, on Jun. 18, 2015, which is incorporated by reference herein in its entirety. When M is Sn and Si—both are present—the LXPS material is referred to as LSTPS. As used herein, “LSTPSO” refers to LSTPS that is doped with, or has, O present. In some examples, “LSTPSO” is a LSTPS material with an oxygen content between 0.01 and 10 atomic %. “LSPS” refers to an electrolyte material having Li, Si, P, and S chemical constituents. As used herein “LSTPS” refers to an electrolyte material having Li, Si, P, Sn, and S chemical constituents. As used herein, “LSPSO” refers to LSPS that is doped with, or has, O present. In some examples, “LSPSO” is a LSPS material with an oxygen content between 0.01 and 10 atomic %. As used herein, “LATP,” refers to an electrolyte material having Li, As, Sn, and P chemical constituents. As used herein “LAGP” refers to an electrolyte material having Li, As, Ge, and P chemical constituents. As used herein, “LXPSO” refers to a catholyte material characterized by the formula Li_aMP_bS_cO_d, where M is Si, Ge, Sn, and/or Al, and where 2≤a≤8, 0.5≤b≤2.5, 4≤c≤12, d<3. LXPSO refers to LXPS, as defined above, and having oxygen doping at from 0.1 to about 10 atomic %. LPSO refers to LPS, as defined above, and having oxygen doping at from 0.1 to about 10 atomic %.

As used herein, “LPS” refers to an electrolyte having Li, P, and S chemical constituents. As used herein, “LPSO” refers to LPS that is doped with or has O present. In some examples, “LPSO” is a LPS material with an oxygen content between 0.01 and 10 atomic %. LPS refers to an electrolyte material that can be characterized by the formula Li_xP_yS_zwhere 0.33≤x≤0.67, 0.07≤y≤0.2 and 0.4≤z≤0.55. LPS also refers to an electrolyte characterized by a product formed from a mixture of Li₂S:P₂S₅wherein the molar ratio is 10:1, 9:1, 8:1, 7:1, 6:1 5:1, 4:1, 3:1, 7:3, 2:1, or 1:1. LPS also refers to an electrolyte characterized by a product formed from a mixture of Li₂S:P₂S₅wherein the reactant or precursor amount of Li₂S is 95 atomic % and P₂S₅is 5 atomic %. LPS also refers to an electrolyte characterized by a product formed from a mixture of Li₂S:P₂S₅wherein the reactant or precursor amount of Li₂S is 90 atomic % and P₂S₅is 10 atomic %. LPS also refers to an electrolyte characterized by a product formed from a mixture of Li₂S:P₂S₅wherein the reactant or precursor amount of Li₂S is 85 atomic % and P₂S₅is 15 atomic %. LPS also refers to an electrolyte characterized by a product formed from a mixture of Li₂S:P₂S₅wherein the reactant or precursor amount of Li₂S is 80 atomic % and P₂S₅is 20 atomic %. LPS also refers to an electrolyte characterized by a product formed from a mixture of Li₂S:P₂S₅wherein the reactant or precursor amount of Li₂S is 75 atomic % and P₂S₅is 25 atomic %. LPS also refers to an electrolyte characterized by a product formed from a mixture of Li₂S:P₂S₅wherein the reactant or precursor amount of Li₂S is 70 atomic % and P₂S₅is 30 atomic %. LPS also refers to an electrolyte characterized by a product formed from a mixture of Li₂S:P₂S₅wherein the reactant or precursor amount of Li₂S is 65 atomic % and P₂S₅is 35 atomic %. LPS also refers to an electrolyte characterized by a product formed from a mixture of Li₂S:P₂S₅wherein the reactant or precursor amount of Li₂S is 60 atomic % and P₂S₅is 40 atomic %.

As used herein, the term “rational number” refers to any number which can be expressed as the quotient or fraction (e.g., p/q) of two integers (e.g., p and q), with the denominator (e.g., q) not equal to zero. Example rational numbers include, but are not limited to, 1, 1.1, 1.52, 2, 2.5, 3, 3.12, and 7.

As used herein, the phrase “lithium stuffed garnet” refers to oxides that are characterized by a crystal structure related to a garnet crystal structure. U.S. Patent Application Publication No. U.S. 2015/0099190, which published Apr. 9, 2015 and was filed Oct. 7, 2014 as Ser. No. 14/509,029, is incorporated by reference herein in its entirety. This application describes Li-stuffed garnet solid-state electrolytes used in solid-state lithium rechargeable batteries. These Li-stuffed garnets generally having a composition according to Li_ALa_BM′_CM″_DZr_EO_F, Li_ALa_BM′_CM″_DTa_EO_F, or Li_ALa_BM′_CM″_DNb_EO_F, wherein 4<A<8.5, 1.5<B<4, 0≤C≤2, 0≤D≤2; 0≤E<2.5, 10<F<13, and M′ and M″ are each, independently in each instance selected from Ga, Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta, or Li_aLa_bZr_cAl_dMe″_eO_f, wherein 5<a<8.5; 2<b<4; 0<c≤2.5; 0≤d<2; 0≤e<2, and 10<f<13 and Me″ is a metal selected from Ga, Nb, Ta, V, W, Mo, and Sb and as otherwise described in U.S. Patent Application Publication No. U.S. 2015/0099190. As used herein, lithium-stuffed garnets, and garnets, generally, include, but are not limited to, Li_7.0La₃(Zr_t1+Nb_t2+Ta_t3)O₁₂+0.35Al₂O₃; wherein (t1+t2+t3=2) so that the La:(Zr/Nb/Ta) ratio is 3:2. Also, garnets used herein include, but are not limited to, Li_xLa₃Zr₂O_F+yAl₂O₃, wherein x ranges from 5.5 to 9; and y ranges from 0.05 to 1. In these examples, subscripts x, y, and F are selected so that the garnet is charge neutral. In some examples x is 7 and y is 1.0. In some examples, x is 5 and y is 1.0. In some examples, x is 6 and y is 1.0. In some examples, x is 8 and y is 1.0. In some examples, x is 9 and y is 1.0. In some examples x is 7 and y is 0.35. In some examples, x is 5 and y is 0.35. In some examples, x is 6 and y is 0.35. In some examples, x is 8 and y is 0.35. In some examples, x is 9 and y is 0.35. In some examples x is 7 and y is 0.7. In some examples, x is 5 and y is 0.7. In some examples, x is 6 and y is 0.7. In some examples, x is 8 and y is 0.7. In some examples, x is 9 and y is 0.7. In some examples x is 7 and y is 0.75. In some examples, x is 5 and y is 0.75. In some examples, x is 6 and y is 0.75. In some examples, x is 8 and y is 0.75. In some examples, x is 9 and y is 0.75. In some examples x is 7 and y is 0.8. In some examples, x is 5 and y is 0.8. In some examples, x is 6 and y is 0.8. In some examples, x is 8 and y is 0.8. In some examples, x is 9 and y is 0.8. In some examples x is 7 and y is 0.5. In some examples, x is 5 and y is 0.5. In some examples, x is 6 and y is 0.5. In some examples, x is 8 and y is 0.5. In some examples, x is 9 and y is 0.5. In some examples x is 7 and y is 0.4. In some examples, x is 5 and y is 0.4. In some examples, x is 6 and y is 0.4. In some examples, x is 8 and y is 0.4. In some examples, x is 9 and y is 0.4. In some examples x is 7 and y is 0.3. In some examples, x is 5 and y is 0.3. In some examples, x is 6 and y is 0.3. In some examples, x is 8 and y is 0.3. In some examples, x is 9 and y is 0.3. In some examples x is 7 and y is 0.22. In some examples, x is 5 and y is 0.22. In some examples, x is 6 and y is 0.22. In some examples, x is 8 and y is 0.22. In some examples, x is 9 and y is 0.22. Also, garnets as used herein include, but are not limited to, Li_xLa₃Zr₂O₁₂+yAl₂O₃. In one embodiment, the Li-stuffed garnet herein has a composition of Li₇Li₃Zr₂O₁₂. In another embodiment, the Li-stuffed garnet herein has a composition of Li₇Li₃Zr₂O₁₂.Al₂O₃. In yet another embodiment, the Li-stuffed garnet herein has a composition of Li₇Li₃Zr₂O₁₂0.22Al₂O₃. In yet another embodiment, the Li-stuffed garnet herein has a composition of Li₇Li₃Zr₂O₁₂.0.35Al₂O₃. In certain other embodiments, the Li-stuffed garnet herein has a composition of Li₇Li₃Zr₂O₁₂.0.5Al₂O₃. In another embodiment, the Li-stuffed garnet herein has a composition of Li₇Li₃Zr₂O₁₂.0.75Al₂O₃.

As used herein, garnet does not include YAG-garnets (i.e., yttrium aluminum garnets, or, e.g., Y₃Al₅O₁₂). As used herein, garnet does not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, hessonite, or cinnamon-stone, tsavorite, uvarovite and andradite and the solid solutions pyrope-almandine-spessarite and uvarovite-grossular-andradite. Garnets herein do not include nesosilicates having the general formula X₃Y₂(SiO₄)₃wherein X is Ca, Mg, Fe, and, or, Mn; and Y is Al, Fe, and, or, Cr.

As used herein, the phrase “inorganic solid-state electrolyte” is used interchangeably with the phrase “solid separator” refers to a material which does not include carbon and which conducts atomic ions (e.g., Li⁺) but does not conduct electrons. An inorganic solid-state electrolyte is a solid material suitable for electrically isolating the positive and negative electrodes of a lithium secondary battery while also providing a conduction pathway for lithium ions. Example inorganic solid-state electrolytes include oxide electrolytes and sulfide electrolytes, which are further defined below. Non-limiting example sulfide electrolytes are found, for example, in U.S. Pat. No. 9,172,114, which issued Oct. 27, 2015, and also in U.S. Provisional Patent Application No. 62/321,428, filed Apr. 12, 2016. Non-limiting example oxide electrolytes are found, for example, in US Patent Application Publication No. 2015-0200420 A1, which published Jul. 16, 2015. In some examples, the inorganic solid-state electrolyte also includes a polymer.

As used herein, examples of the materials in International Patent Application PCT Patent Application Nos. PCT/US2014/059575 and PCT/US2014/059578, GARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING AND USING GARNET MATERIALS, filed Oct. 7, 2014, which is incorporated by reference herein in its entirety, are suitable for use as the inorganic solid-state electrolytes described herein, also as the oxide based electrolytes, described herein, and also as the garnet electrolytes, described herein.

As used herein the phrase “casting a film” refers to the process of delivering or transferring a liquid or a slurry into a mold, or onto a substrate, such that the liquid or the slurry forms, or is formed into, a film. Casting may be done via doctor blade, Meyer rod, comma coater, gravure coater, microgravure, reverse comma coater, slot dye, slip and/or tape casting, and other methods known to those skilled in the art.

As used herein, the phrase “slot casting” refers to a deposition process whereby a substrate is coated, or deposited, with a solution, liquid, slurry, or the like by flowing the solution, liquid, slurry, or the like, through a slot or mold of fixed dimensions that is placed adjacent to, in contact with, or onto the substrate onto which the deposition or coating occurs. In some examples, slot casting includes a slot opening of about 1 μm to 100 μm in slot opening width.

As used herein, the phrase “dip casting” or “dip coating” refers to a deposition process whereby substrate is coated, or deposited, with a solution, liquid, slurry, or the like, by moving the substrate into and out of the solution, liquid, slurry, or the like, often in a vertical fashion.

As used herein the term “making” refers to the process or method of forming or causing to form the object that is made. For example, making an energy storage electrode includes the process, process steps, or method of causing the electrode of an energy storage device to be formed. The end result of the steps constituting the making of the energy storage electrode is the production of a material that is functional as an electrode.

As used herein, the phrase “providing” refers to the provision of, generation or, presentation of, or delivery of that which is provided.

As used herein, the phrase “garnet-type electrolyte” refers to an electrolyte that includes a garnet or lithium stuffed garnet material described herein as the ionic conductor.

As used herein, the phrase “antiperovskite” refers to an electrolyte characterized by the antiperovskite crystal structure. Exemplary antiperovskites are found, for example, in U.S. patent application Ser. No. 13/777,602, filed Feb. 26, 2013. Antiperovskites include but are not limited to Li₃OBr or Li₃OCl.

As used herein, the phrase “subscripts and molar coefficients in the empirical formulas are based on the quantities of raw materials initially batched to make the described examples” means the subscripts, (e.g., 7, 3, 2, 12 in Li₇La₃Zr₂O₁₂and the coefficient 0.35 in 0.35Al₂O₃) refer to the respective elemental ratios in the chemical precursors (e.g., LiOH, La₂O₃, ZrO₂, Al₂O₃) used to prepare a given material, (e.g., Li₇La₃Zr₂O₁₂.0.35Al₂O₃). As used here, the phrase “characterized by the formula” refers to a molar ratio of constituent atoms either as batched during the process for making that characterized material or as empirically determined.

As used herein, the term “solvent” refers to a liquid that is suitable for dissolving or solvating a component or material described herein. For example, a solvent includes a liquid, e.g., propylene carbonate, which is suitable for dissolving a component, e.g., the salt, used in the electrolyte.

As used herein, the phrase “removing a solvent” refers to the process whereby a solvent is extracted or separated from the components or materials set forth herein. Removing a solvent includes, but is not limited to, evaporating a solvent. Removing a solvent includes, but is not limited to, using a vacuum or a reduced pressure to drive off a solvent from a mixture, e.g., an unsintered thin film. In some examples, a thin film that includes a binder and a solvent is heated or also optionally placed in a vacuum or reduced atmosphere environment in order to evaporate the solvent to leave the binder, which was solvated, in the thin film after the solvent is removed.

As used herein, the phrase “nitrile” or “nitrile solvent” refers to a hydrocarbon substituted by a cyano group, or a solvent which includes a cyano (i.e., —C≡N) substituent bonded to the solvent. Nitrile solvents may include dinitrile solvents.

As used herein, the phrase “dinitrile” or “dinitrile solvent” refers to a linear hydrocarbon chain where both ends of the chain are terminated with a cyano (i.e., —C≡N) group. Example dinitrile solvents are characterized by Formula (I):

embedded image

wherein:

R¹, R², R³, and R⁴are, independently in each instance, selected from —CN, —NO₂, —CO₂, —SO₄, —H, —SO₃, —SO₂, —CH₂—SO₃, —CHF—SO₃, —CF₂—SO₃, —F, —Cl, —Br, and —I; and wherein subscript m is an integer from 1 to 1000.

Some exemplary nitrile and dinitrile solvents include, but are not limited to, acetonitrile, succinonitrile, glutaronitrile, malononitrile, hexanedinitrile (adiponitrile), sebaconitrile, suberonitrile, pimelonitrile, dodecanedinitrile, phthalonitrile, cis/trans-1,2-dicyanocyclohexane, and combinations thereof.

As used herein, the phrase “organic sulfur-including solvent” refers to a solvent selected from ethyl methyl sulfone, dimethyl sulfone, sulfolane, allyl methyl sulfone, butadiene sulfone, butyl sulfone, methyl methanesulfonate, and dimethyl sulfite.

As used herein, the phrase “impermeable to the catholyte” refers to a material that allows a low flux of catholyte to permeate, for example less than 1 g/cm²/year, through the material, e.g., a solid separator, which is impermeable to the catholyte or its constituent components.

As used herein, the phrase “bonding layer” refers to an ionically conductive layer between two other layers, e.g., between the cathode and the solid separator. Exemplary bonding layers include the gel electrolytes, and related separator bonding agents, set forth in U.S. Provisional Patent Application No. 62/336,474, filed May 13, 2016, the entire contents of which are herein incorporated by reference in its entirety for all purposes.

As used herein, the term “HOMO” or “Highest Occupied Molecular Orbital” refers to the energy of the electron occupying the highest occupied molecular orbital, as referenced to the vacuum energy. As used herein, the term “LUMO” refers to “Lowest Unoccupied Molecular Orbital.” HOMO and LUMO energy levels are calculated by DFT calculations referenced to the vacuum level. Unless otherwise specified, the DFT calculations use a B3LYP functional for exchange and correlation and a 6-311++g** basis set.

As used herein, the phrase “lithium transference” refers to the proportion of current carried by lithium ions relative to the total current. Lithium transference is a number between 0 and 1, inclusive and may be measured by the Bruce-Vincent method.

As used herein, the phrase “stability window” refers to the voltage range within which a material exhibits no reaction which materially or significantly degrades the material's function in an electrochemical cell. It may be measured in an electrochemical cell by measuring cell resistance and Coulombic efficiency during charge/discharge cycling. For voltages within the stability window (i.e. the working electrode vs reference electrode within the stability window), the increase of cell resistance is low. For example, this resistance increase may be less than 1% per 100 cycles.

As used herein, the term “LiBOB” refers to lithium bis(oxalato)borate.

As used herein, the term “LiBETI” refers to lithium bis(perfluoroethanesulfonyl)imide.

As used herein, the term “LIFSI” refers to lithium bis(fluorosulfonyl)imide.

As used herein, the term “LiTFSI” refer to lithium bis-trifluoromethanesulfonimide.

As used herein, voltage is set forth with respect to lithium (i.e., V vs. Li) metal unless stated otherwise.

As used herein, the term “LiBHI” refers to a combination of LiBH₄and LiX, wherein X is Br, Cl, I, or a combination thereof.

As used herein, the term “LiBNHI” refers to a combination of LiBH₄, LiNH₂, and LiX, wherein X is Br, Cl, I, or combinations thereof.

As used herein, the term “LiBHCl” refers to a combination of LiBH₄and LiCl.

As used herein, the term “LiBNHCl” refers to a combination of LiBH₄, LiNH₂, and LiCl.

As used herein, the term “LiBHBr” refers to a combination of LiBH₄and LiBr.

As used herein, the term “LiBNHBr” refers to a combination of LiBH₄, LiNH₂, and LiBr.

As used herein, viscosity is measured using a Brookfield viscometer DV2T.

As used herein, the term “monolith” refers to a shaped, fabricated article with a homogenous microstructure with no structural distinctions observed optically, which has a form factor top surface area between 10 cm²and 500 cm².

As used herein, the term “vapor pressure” refers to the equilibrium pressure of a gas above its liquid at the same temperature in a closed system. Measurement procedures often consist of purifying the test substance, isolating it in a container, evacuating any foreign gas, then measuring the equilibrium pressure of the gaseous phase of the substance in the container at different temperatures. Better accuracy is achieved when care is taken to ensure that the entire substance and its vapor are at the prescribed temperature. This is often done, as with the use of an isoteniscope, by submerging the containment area in a liquid bath.

As used herein, the term “lithium salt” refers to a lithium-containing compound that is a solid at room temperature that at least partially dissociates when immersed in a solvent such as EMC. Lithium salts may include but are not limited to LiPF₆, LiBOB, LiTFSi, LiFSI, LiAsF₆, LiClO₄, LiI, LiBETI, LiBF₄.As used herein, the term “carbonate solvent” refers to a class of solvents containing a carbonate group C(═O)(O—)₂. Carbonate solvents include but are not limited to ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, dimethyl ethylene carbonate, isobutylene carbonate, nitroethyl carbonate, Monofluoroethylene carbonate, fluoromethyl ethylene carbonate, 1,2-butylene carbonate, methyl propyl carbonate, isopropyl methyl carbonate, etc.

As used herein, the term “a high voltage-stable catholyte” refers to a catholyte which does not react at high voltage (4.2 V or higher versus Li metal) in a way that materially or significantly degrades the ionic conductivity of the catholyte when held at high voltage at room temperature for one week. Herein, a material or significant degradation in ionic conductivity is a reduction in ionic conductivity by an order of magnitude or more. For example, if the catholyte has an ionic conductivity of 10E-3 S/cm, and when charged to 4.2V or higher the catholyte has an ionic conductivity of 10E-4 S/cm, then the catholyte is not stable at 4.2V or higher since its ionic conductivity materially and significantly degraded at that voltage.” As used herein, the term “high voltage” means at least 4.2V versus lithium metal. High voltage may also refer to higher voltage, e.g., 4.3, 4.4, 4.5, 4.6, 4.7, 4.8. 4.9, 5.0 V or higher.

As used herein, the term “chemically compatible” means that two or more materials or chemicals are chemically compatible with each other if the materials can be physically exposed to each other and the materials do not react in a way which materially or significantly degrades the electrochemical performance. Herein, electrochemical performance refers to either ionic conductivity or area-specific resistance (ASR). A material or significant degradation in ionic conductivity is a degradation by an order of magnitude or more. A material or significant degradation in ASR is a degradation by a factor of 2 or more when held at room temperature for one week.

As used herein, ASR is measured by electrochemical cycling using Arbin or Biologic unless otherwise specified to the contrary.

As used herein, ionic conductivity is measured by electrical impedance spectroscopy methods known in the art.

B. General

Set forth herein are battery architectures for batteries which include a solid-state separator which physically isolates the cathode from the anode. These architectures allow, for the first time in a rechargeable lithium battery, the use of electrolytes in the cathode, i.e., catholytes, that have no stability requirement against lithium metal or graphite, e.g., high-voltage (greater than 4.3V) stable dinitrile electrolytes. These electrolytes have advantageous properties including safety, lifetime, cyclability, voltage stability, and rate performance. In some examples, set forth herein are devices that include a high voltage, nitrile, or dinitrile or organic sulfur-including cathode-electrolyte (i.e., catholyte) which is stable at high oxidation potentials within the cathode side of an electrochemical device having a solid-state separator. The new battery architectures presented for the first time herein are not possible in a conventional Li-ion battery. Conventional battery architectures use catholytes which penetrate the anode space and therefore must be stable and/or passivating at the anode voltage and also chemically compatible with the anode materials. It is only by using a solid-state separator that the nitrile and high voltage-stable catholytes herein can be used practically in electrochemical devices as catholytes or electrolytes within the cathode space. In some examples, set forth herein are nitrile catholytes which are stable at high voltages with respect to lithium but which are not stable at low voltages with respect to lithium. In some examples, set forth herein are organic sulfur-including catholytes which are stable at high voltages with respect to lithium but which are not stable at low voltages (e.g. less than 1.5V or less than 1V) with respect to lithium, meaning that they significantly degrade in impedance or conductivity at room temperature for one week.

As shown in FIG. 1, in one example, an electrochemical cell (100) includes a positive electrode 101 of 5-200 μm thickness. This electrode 101 includes active materials 102 surrounded by a cathode-electrolyte 103. Active materials 102 may be present in 20-80 vol %, and the catholyte may be present in 5-60 vol %. The electrode 101 is layered to a solid separator 104 (e.g., a lithium-stuffed garnet electrolyte monolith or thin film). The solid separator 104 is layered to a lithium-metal negative electrode 105. The solid separator 104 may be 100 nm-100 μm thick, and the lithium metal negative electrode 105 may be 1 μm-50 μm thick. The solid separator 104 is impermeable to the catholyte-electrolyte 103.

In certain examples, the positive electrode is from 30 μm to 300 μm thick. In some examples, the positive electrode is from 40 μm to 200 μm thick. In some of these examples, the positive electrode is about 30 μm thick. In some of these examples, the positive electrode is about 40 μm thick. In some of these examples, the positive electrode is about 50 μm thick. In some of these examples, the positive electrode is about 60 μm thick. In some of these examples, the positive electrode is about 70 μm thick. In some of these examples, the positive electrode is about 80 μm thick. In some of these examples, the positive electrode is about 90 μm thick. In some of these examples, the positive electrode is about 100 μm thick. In some of these examples, the positive electrode is about 110 μm thick. In some of these examples, the positive electrode is about 120 μm thick. In some of these examples, the positive electrode is about 130 μm thick. In some of these examples, the positive electrode is about 140 μm thick. In some of these examples, the positive electrode is about 150 μm thick. In some of these examples, the positive electrode is about 160 μm thick. In some of these examples, the positive electrode is about 170 μm thick. In some of these examples, the positive electrode is about 180 μm thick. In some of these examples, the positive electrode is about 190 μm thick. In some of these examples, the positive electrode is about 200 μm thick. In some of these examples, the positive electrode is about 210 μm thick. In some of these examples, the positive electrode is about 220 μm thick. In some of these examples, the positive electrode is about 230 μm thick. In some of these examples, the positive electrode is about 240 μm thick. In some of these examples, the positive electrode is about 250 μm thick. In some of these examples, the positive electrode is about 260 μm thick. In some of these examples, the positive electrode is about 270 μm thick. In some of these examples, the positive electrode is about 280 μm thick. In some of these examples, the positive electrode is about 290 μm thick. In some of these examples, the positive electrode is about 300 μm thick.

The active material (e.g., a nickel manganese cobalt oxide, i.e., NMC, a nickel cobalt aluminum oxide, i.e., NCA, a lithium cobalt oxide, i.e., LCO, a lithium-rich nickel manganese oxide, i.e., LNMO, FeF₃, CoF₂, CuF₂, CoF₃, and related or functionally equivalent active materials) may be present in a volume fraction of 20-95%. In some examples, the volume fraction is 50-75 v %. The cathode electrolyte, or catholyte, may be present in a volume fraction of 10-50%. In some examples, the catholyte is present in a volume fraction of 20-40 volume %. The solid separator may be 0.5-100 μm thick. In some examples, the solid separator is 1-30 μm thick. The negative electrode may be 3-80 μm thick. In some examples, the negative electrode is 20-50 μm thick in the charged state.

In any of the above examples, the carbon content in the positive electrode is less than 5% w/w. In any of the above examples, the binder content in the positive electrode is less than 5% w/w.

C. Catholytes and Solid Separator Electrolytes

In some examples, set forth herein is a high voltage-stable catholyte which includes a solvent and a lithium salt. In some examples, the solvent is a nitrile solvent. In some examples, the solvent is a dinitrile solvent. In yet other examples, the solvent is a combination of a nitrile and dinitrile solvent. In yet other example the solvent is a combination of a dinitrile and another dinitrile. In yet other example, the solvent is an organic sulfur-including solvent. In yet another example, the solvent is a combination of an organic sulfur-including solvent and another aprotic solvent.

In some examples, set forth herein is a catholyte which includes a nitrile or dinitrile solvent and a lithium salt.

In some of these examples, the solvent in the catholyte is selected from the group consisting of from acetonitrile, butyronitrile, benzonitrile, glutaronitrile, hexanenitrile, fluoroacetonitrile, nitroacetonitrile, ethoxyacetonitrile, methoxyacetonitrile, pentanenitrile, propanenitrile, succinonitrile, adiponitrile, iso-butyronitrile, malononitrile and combinations thereof. In certain examples, the catholyte solvent is fluoromethyl ethylene carbonate, ethyl nitroacetate, N-Methylpyrrolidone, γ-butyrolactone, ethyl methyl sulfone, dimethyl sulfone, sulfolane, allyl methyl sulfone, butadiene sulfone, butyl sulfone, methyl methanesulfonate, dimethyl sulfite, dimethyl sulfoxide, dimethylsulfate, 3-methyl-2-oxazolidinone, fluorinated cyclic carbonate, methylene methane disulfonate, methyl cyanoacetate. In certain examples, the solvent is acetonitrile. In certain examples, the solvent is butyronitrile. In certain examples, the solvent is glutaronitrile. In certain examples, the solvent is hexanenitrile. In certain examples, the solvent is fluoroacetonitrile. In certain examples, the solvent is nitroacetonitrile. In certain examples, the solvent is iso-butyronitrile. In certain examples, the solvent is ethoxyacetonitrile. In certain examples, the solvent is pentanenitrile. In certain examples, the solvent is propanenitrile. In certain examples, the solvent is succinonitrile. In certain examples, the solvent is adiponitrile. In certain examples, the solvent is malononitrile. In certain examples, the solvent is benzonitrile. In certain examples, the solvent is methoxyacetonitrile. In certain examples, the solvent is a combination of succinonitrile and adiponitrile. In certain examples, the solvent is a combination of succinonitrile and glutaronitrile.

In some examples, the electrochemical cell set forth herein includes a dinitrile solvent which includes a dinitrile represented by Formula (I):

embedded image

- wherein:
- R¹, R², R³, and R⁴are, independently in each instance, selected from —CN, —NO₂, —CO₂, —SO₄, —SO₃, —SO₂, —H, —CH₂—SO₃, —CHF—SO₃, —CF₂—SO₃, —F, —Cl, —Br, and —I; and
- subscript m is an integer from 1 to 1000.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —CN.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —NO₂.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —CO₂.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —SO₄. In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —SO₃. In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —SO₂.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —CH₂—SO₃.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —CHF—SO₃.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —CF₂—SO₃.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —F.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —Cl.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —Br.

In some of the examples herein, R¹, R², R³, and R⁴are, independently in each instance, —H or —I.

In some examples herein, the catholyte solvent includes a member selected from the group consisting of:

embedded image

and combinations thereof. In certain examples, the solvent is a combination of succinonitrile and adiponitrile. In certain examples, the solvent is a combination of succinonitrile and glutaronitrile.

In some examples herein, the catholyte solvent includes an organic sulfur-including solvent. In some examples herein, the organic sulfur-including solvent is selected from the group consisting of ethyl methyl sulfone, dimethyl sulfone, sulfolane, allyl methyl sulfone, butadiene sulfone, butyl sulfone, methyl methanesulfonate, and dimethyl sulfite.

In some of these examples, the lithium salt is selected from LiPF₆, LiBOB, LiTFSi, LiFSI, LiAsF₆, LiClO₄, LiI, LiBF₄, and a combination thereof. In certain examples, the lithium salt is LiPF₆, In certain examples, the lithium salt is LiBOB. In certain examples, the lithium salt is LiTFSi. In certain examples, the lithium salt is LiBF₄. In certain examples, the lithium salt is LiClO₄. In certain examples, the lithium salt is LiFSI. In certain examples, the lithium salt is LiAsF₆. In certain examples, the lithium salt is LiClO₄. In certain examples, the lithium salt is LiI. In certain examples, the lithium salt is LiBF₄.

In the examples herein, the catholyte is chemically stable when in contact with a solid separator.

In some of the examples herein, the electrochemical cell further includes a bonding layer which includes a solvent selected from ethylene carbonate (EC), diethylene carbonate, diethyl carbonate, dimethyl carbonate (DMC), ethyl-methyl carbonate (EMC), tetrahydrofuran (THF), γ-Butyrolactone (GBL), fluoroethylene carbonate (FEC), fluoromethyl ethylene carbonate (FMEC), trifluoroethyl methyl carbonate (F-EMC), fluorinated 3-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoropropane (i.e., 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane (F-EPE)), fluorinated cyclic carbonate (F-AEC), propylene carbonate (PC), dioxolane, acetonitrile (ACN), succinonitrile, adiponitrile, hexanedinitrile, pentanedinitrile, acetophenone, isophorone, benzonitrile, dimethyl sulfate, dimethyl sulfoxide (DMSO) ethyl-methyl carbonate, ethyl acetate, methyl butyrate, dimethyl ether (DME), diethyl ether, propylene carbonate, dioxolane, glutaronitrile, gamma butyrolactone, and combinations thereof. In some examples, the solvent is ethylene carbonate (EC). In some examples, the solvent is diethylene carbonate. In some examples, the solvent is dimethyl carbonate (DMC). In some examples, the solvent is ethyl-methyl carbonate (EMC). In some examples, the solvent is tetrahydrofuran (THF). In some examples, the solvent is γ-Butyrolactone (GBL). In some examples, the solvent is fluoroethylene carbonate (FEC). In some examples, the solvent is fluoromethyl ethylene carbonate (FMEC). In some examples, the solvent is trifluoroethyl methyl carbonate (F-EMC). In some examples, the solvent is fluorinated 3-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoropropane (i.e., 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane (F-EPE)). In some examples, the solvent is fluorinated cyclic carbonate (F-AEC). In some examples, the solvent is propylene carbonate (PC). In some examples, the solvent is dioxolane. In some examples, the solvent is acetonitrile (ACN). In some examples, the solvent is succinonitrile. In some examples, the solvent is adiponitrile/hexanedinitrile. In some examples, the solvent is acetophenone. In some examples, the solvent is isophorone. In some examples, the solvent is benzonitrile. In some examples, the solvent is dimethyl sulfate. In some examples, the solvent is dimethyl sulfoxide (DMSO). In some examples, the solvent is ethyl acetate. In some examples, the solvent is methyl butyrate. In some examples, the solvent is dimethyl ether (DME). In some examples, the solvent is diethyl ether. In some examples, the solvent is dioxolane. In some examples, the solvent is glutaronitrile. In some examples, the solvent is gamma butyrolactone. In some examples, the solvent is a combination of any solvents mentioned above. This bonding layer may be used to adhere or bond the cathode to the solid separator.

In some of the examples herein, the electrochemical cell further includes a bonding layer which includes a lithium salt in the bonding layer is selected from LiPF₆, LiBOB, LFTSi, or combinations thereof. In certain examples, the lithium salt in the bonding layer is LiPF₆at a concentration of 0.5 M to 2 M. In certain examples, wherein the lithium salt in the bonding layer is LiTFSI at a concentration of 0.5 M to 2 M.

In some of the examples herein, the catholyte solvent is a solvent having a permittivity of greater than 30. In certain of these examples, the catholyte solvent is a dinitrile-containing solvent.

In some of the examples herein, the catholyte solvent is a solvent having a viscosity of greater than 0.01 cP and less than 10 cP at 25° C.

In some of the examples herein, the catholyte solvent is a solvent having a flash point of greater than 50° C. and less than 400° C.

In some of the examples herein, the catholyte solvent is a solvent having a melting point higher than −50° C. and lower than 30° C.

In some of the examples herein, the catholyte solvent is a solvent having a boiling point of greater than 80° C.

In some of the examples herein, the catholyte solvent is a solvent having a HOMO level of more than 7.2 eV below the vacuum level as calculated by DFT (density fuctional theory) with a B3LYP (Becke, 3-parameter, Lee-Yang-Parr) exchange-correlation functional and 6-311++G** basis set. In some examples, the HOMO level is more than 7.8 eV below the vacuum level as calculated by DFT with a B3LYP exchange-correlation functional and 6-311++G** basis set. In some examples, the HOMO level is more than 8.2 eV below the vacuum level as calculated by DFT with a B3LYP exchange-correlation functional and 6-311++G** basis set. For example, for succinonitrile, the HOMO=−9.65 eV, and LUMO=−0.92 eV; for ethyl methyl sulfone HOMO=−8.08 eV, LUMO=−0.62 eV.

In some of the examples herein, the catholyte solvent is a solvent is polar and aprotic.

In some of the examples herein, the catholyte has a lithium transference number of greater than 0.2.

In some of the examples herein, the catholyte has a total ionic conductivity of greater than 1e-4 S/cm at 25° C.

In some of the examples herein, the catholyte solvent has a vapor pressure of lower than 2 Torr at 20° C. In some of the examples herein, the catholyte solvent has a vapor pressure of lower than 0.2 Torr at 20° C. In some of the examples herein, the catholyte solvent has a vapor pressure of lower than 2e-2 Torr at 20° C.

In some of the examples herein, the catholyte solvent has a boiling point of greater than 80° C.

In some of the examples herein, the catholyte solvent has a boiling point of greater than 250° C.

In some of the examples herein, the catholyte solvent has a viscosity of less than 10 centipoise (cP) at 25° C.

In some of the examples herein, the catholyte further comprises a carbonate solvent in addition to the nitrile or dinitrile solvent. In some examples, the catholyte further comprises a solvent selected from ethylene carbonate (EC), diethylene carbonate, diethyl carbonate, dimethyl carbonate (DMC), ethyl-methyl carbonate (EMC), tetrahydrofuran (THF), γ-Butyrolactone (GBL), fluoroethylene carbonate (FEC), fluoromethyl ethylene carbonate (FMEC), trifluoroethyl methyl carbonate (F-EMC), fluorinated 3-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoropropane/1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane (F-EPE), fluorinated cyclic carbonate (F-AEC), propylene carbonate (PC), dioxolane, acetonitrile (ACN), succinonitrile, malononitrile, hexanedinitrile (adiponitrile), pentanedinitrile (glutaronitrile), acetophenone, isophorone, benzonitrile, dimethyl sulfate, dimethyl sulfoxide (DMSO) ethyl-methyl carbonate, ethyl acetate, methyl butyrate, dimethyl ether (DME), diethyl ether, propylene carbonate, dioxolane, glutaronitrile, gamma butyrolactone, or combinations thereof. In some of the examples herein, the catholyte further comprises a carbonate solvent in addition to the organic sulfur-including solvent. In some examples, the catholyte comprises organic sulfur-including solvent and ethylene carbonate in a ratio of about 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, or 9:1.

In some of the examples herein, the catholyte solvent is stable up to 4.7V v. Lithium. In some of the examples herein, the catholyte solvent is stable up to 4.5V v. Lithium. In some of the examples herein, the catholyte solvent is stable up to 4.4V v. Lithium. In some examples herein, the catholyte solvent is stable up to 4.2V v. Lithium.

In some of the examples herein, the catholyte solvent is stable down to 1.5V.

In some of the examples herein, the catholyte solvent includes a nitrile represented by Formula (I):

embedded image

wherein:

- R¹, R², R³, and R⁴are, independently in each instance, selected from —CN, —NO₂, —CO₂, —SO₄, —SO₃, —SO₂, —CH₂—SO₃, —CHF—SO₃, —CF₂—SO₃, —H, —F, —Cl, —Br, and —I;
- and wherein subscript m is an integer from 1 to 1000.