Solid electrolyte synthesis using P4SX materials

Abstract

Methods of forming solid electrolyte materials using compounds comprising P4Sx are described herein. The methods generally include heating the P4Sx in the presence of one or more lithium compounds to produce a solid state electrolyte.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. patent application No. 63 / 433,708, filed on December 19, 2022, entitled “Solid State Electrolyte Synthesis Using P4Sx Materials,” the entire contents of which are incorporated herein by reference. Technical Field

[0002] The present disclosure relates to methods for preparing solid-state electrolyte materials. Accordingly, the present disclosure relates to the fields of chemistry, chemical engineering, and electrical engineering. Background Art

[0003] Sulfide solid electrolytes such as Li3PS4 hydrolyze (exchange sulfur for oxygen) when exposed to air / moisture and convert to Li3PS 4-x O x This reaction produces toxic hydrogen sulfide gas. The incorporation of oxygen weakens the solid electrolyte's ability to conduct lithium ions, thereby reducing the material's ionic conductivity. Exposure to air and moisture becomes more prevalent at larger manufacturing scales, as drying large amounts of air, solvents, and precursor materials becomes more challenging and costly.

[0004] What is needed is a method for producing solid electrolyte materials with low oxygen contamination and high sulfur content. Summary of the Invention

[0005] Provided herein are solid electrolyte materials that are prepared by combining one or more lithium sources with a solid electrolyte having the formula P4S x In some embodiments, the solid electrolyte material has the formula Li (7-y-z) PS (6-y-z) X (y) W (z) , wherein X and W are individually selected from F, Cl, Br and I; y and z are each individually in the range of 0 to 2; and wherein y+z is in the range of 0 to 2. In some embodiments, the solid electrolyte material is selected from Li3PS4, Li4P2S6, Li7P3S 11 、Li 5.5 PS 4.5 Cl 1.5 、Li 5.5 PS 4.5 ClBr 0.5, Li5PS4Cl2, and Li5PS4ClBr. In some embodiments, the solid electrolyte material has an X-ray diffraction pattern having peaks corresponding to 2θ of 17.5°±0.5°, 18.1°±0.5°, 19.9°±0.5°, 22.8°±0.5°, 25.95°±0.5°, 29.1°±0.5°, 29.9°±0.5°, and 31.1°±0.5°.

[0006] Further provided herein is a method for synthesizing a solid electrolyte material comprising reacting one or more lithium sources with a solid electrolyte material having the formula P4S x to form a solid electrolyte material, wherein 10 < x ≤ 40. In some embodiments, the method further comprises mixing a sulfur source with one or more lithium sources and a solid electrolyte material having the formula P4S x In some embodiments, the compound of formula P4S x In some embodiments, the sulfur source contains a phosphorus-sulfur material selected from the group consisting of: P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 and combinations thereof. In some embodiments, the one or more lithium sources comprise Li2S, Li2CO3, lithium halides, lithium pseudohalides, Li2O, Li3PO4, LiBO2, Li2B4O7, Li2ZrO3, LiAlO2, Li2TiO3, LiNbO3, Li2SiO3, or mixtures thereof. In some embodiments, the lithium halide is selected from the group consisting of: LiF, LiCl, LiBr, LiI, and mixtures thereof. In some embodiments, the lithium pseudohalide is selected from the group consisting of: LiNO3, LiOH, Li2SO3, Li3N, Li2NH, LiNH2, LiBF4, LiBH4, and mixtures thereof. In some embodiments, the one or more lithium sources and P4S are mixed. x Heating is performed to a temperature of about 150°C to about 600°C.

[0007] Further provided herein is a solid-state battery comprising a positive electrode layer, a negative electrode layer, and a separator layer, wherein the separator layer comprises a solid electrolyte material formed by combining one or more lithium sources with a solid electrolyte having the formula P4S x In some embodiments, the negative electrode layer contains a negative electrode active material and a solid electrolyte material, wherein the solid electrolyte material is prepared by heating a compound of the formula P4S xIn some embodiments, the positive electrode layer contains a positive electrode active material and a solid electrolyte material, wherein the solid electrolyte material is prepared by heating a compound of the formula P4S x The solid electrolyte material is prepared by heating a compound to form a solid electrolyte material, wherein 10 < x < 40. In some embodiments, the solid electrolyte material has the formula Li (7-y-z) PS (6-y-z) X (y) W (z) , wherein X and W are individually selected from F, Cl, Br and I; y and z are each individually in the range of 0 to 2; and wherein y+z is in the range of 0 to 2. In some embodiments, the solid electrolyte material is selected from Li3PS4, Li4P2S6, Li7P3S 11 、Li 5.5 PS 4.5 Cl 1.5 、Li 5.5 PS 4.5 ClBr 0.5 , Li5PS4Cl2, and Li5PS4ClBr. In some embodiments, the solid electrolyte material has an X-ray diffraction pattern having peaks corresponding to 2θ of 17.5°±0.5°, 18.1°±0.5°, 19.9°±0.5°, 22.8°±0.5°, 25.95°±0.5°, 29.1°±0.5°, 29.9°±0.5°, and 31.1°±0.5°. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 A process flow diagram showing the method of the present disclosure.

[0009] Figure 2 X-ray diffraction patterns of the solid electrolyte materials synthesized in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 are shown.

[0010] Figure 3 X-ray diffraction patterns of the solid electrolyte materials synthesized in Example 1, Example 3, and Comparative Example 3 are shown. DETAILED DESCRIPTION

[0011] Before disclosing and describing the present invention, it should be understood that the present invention is not limited to the specific processes, methods, compositions or materials disclosed herein, but extends to equivalents thereof that will be recognized by those skilled in the relevant art. It should also be understood that the terminology employed herein is used for the purpose of describing specific embodiments only and is not intended to be limiting.

[0012] Concentrations, amounts, and other numerical data may be expressed or presented herein in a range format. It should be understood that this type of range format is used for convenience and brevity and should be interpreted in a flexible manner to include not only the values ​​explicitly recited as the limits of the range, but also all individual values ​​or subranges encompassed within the range, as if each value and subrange were explicitly recited. As an illustration, a numerical range of "about 2 to about 50" should be interpreted to include not only the explicitly recited values ​​of 2 to 50, but also all individual values ​​and subranges within the indicated range. Thus, included within this numerical range are individual values ​​such as 2, 2.4, 3, 3.7, 4, 5.5, 10, 10.1, 14, 15, 15.98, 20, 20.13, 23, 25.06, 30, 35.1, 38.0, 40, 44, 44.6, 45, 48, and sub-ranges such as 1-3, 2-4, 5-10, 5-20, 5-25, 5-30, 5-35, 5-40, 5-50, 2-10, 2-20, 2-30, 2-40, 2-50, etc. This same principle applies to ranges that recite only one value, such as a minimum or maximum value. Furthermore, such an interpretation should apply regardless of the breadth of the range or the characteristics being described.

[0013] As used herein, the term "about" is used to provide flexibility to numerical range endpoints by specifying that a given value may be "slightly above" or "slightly below" the endpoint. For example, the endpoint can be within 10%, 8%, 5%, 3%, 2%, or 1% of the listed value. In addition, for convenience and brevity, a numerical range of "about 50 mg / mL to about 80 mg / mL" should also be understood to support a range of "50 mg / mL to 80 mg / mL." Endpoints can also be based on variability allowed by appropriate regulatory agencies (such as FDA, USP, etc.).

[0014] In this disclosure, the terms "including," "containing," and / or "having" are understood to mean inclusive and are open-ended terms.

[0015] As used herein, "pseudohalogen" and "pseudohalide" refer to compounds that are chemically similar to halogen elements and halide ions. The terms "pseudohalogen" and "pseudohalide" may be used interchangeably with "superhalogen" or "superhalide," respectively.

[0016] This article describes the use of P4S x Method for forming solid electrolyte materials as precursors. xThe high sulfur content of the solid electrolyte material is used to incorporate sulfur atoms into the solid electrolyte material, thereby reducing the presence of oxygen species in the solid electrolyte material. This can be achieved by analytical methods known in the art (e.g., Fourier-transform infrared spectroscopy for detecting PO and SO bonds in the electrolyte material, phosphorus NMR for detecting PO bonds in the electrolyte material, Raman spectroscopy for detecting SO bonds in the electrolyte material, X-ray diffraction measurement for detecting decomposition products including oxygen species, etc.) and / or by mixing the solid electrolyte powder material containing oxygen species with the solid electrolyte powder material using P4S x The color difference between the prepared solid electrolyte powder materials with reduced amounts of oxygen species is indicated. x It can be prepared by heating phosphorus and sulfur, or by heating P4S at a temperature of about 300°C. 10-x Materials and elemental sulfur, where 0 ≥ x ≥ 7. Since pure P4S 10 The melting temperature of P4S is about 288°C, so it is preferred to have a reaction temperature of about 300°C to reduce x The dynamic barrier formed, where x > 10. Because P4S x Made at these high temperatures, so P4S x It does not decompose at the high temperatures required to synthesize the solid electrolyte materials described herein. x The sulfur vapor pressure above is significantly lower than that above sulfur alone. 10 A mixture of sulfur and P4S x The temperature is preferably increased from the melting point of sulfur, through a sequence of sulfur ring opening and cracking, and finally reaches the melting point of phosphorus sulfide. During this process, sulfur is added to phosphorus sulfide through a combination of reactions. This reaction can be simply described as P4S 10 + S = P4S 10+x Since elemental sulfur ring opening occurs at about 160°C, when it becomes liquid, and the cleavage of long-chain sulfur into shorter chains occurs at about 250°C, which increases the reactivity of elemental sulfur, elemental sulfur materials are more likely to react with P4S. 10-xThe reactivity of the material can be enhanced, so that the reaction temperature is reduced and the combined reaction is easier to proceed to completion. Alternatively, the processing temperature can be increased to above either the melting or cracking temperature described herein to enhance mixing. The reaction mechanism is more fully described in Li, Xiaona et al., "Sulfur-Rich Phosphorus Sulfide Molecules for Use in Rechargeable Lithium Batteries", Angewandte Chemie, Vol. 56, No. 11, pp. 2937-2941, 2017, the entire contents of which are incorporated herein by reference.

[0017] In this disclosure, P4S x is used as a precursor material to form a solid electrolyte material, wherein x is an integer greater than 10. In some embodiments, x may be greater than 40, or 10 < x ≤ 40. In other embodiments, P4S x is used as a precursor material to form a solid electrolyte material, wherein 10 < x ≤ 35, 10 < x ≤ 30, 10 < x ≤ 25, 10 < x ≤ 20, 10 < x ≤ 15, 10 < x ≤ 14, 10 < x ≤ 13, 10 < x ≤ 12, or 10 < x ≤ 11. In a preferred embodiment, 10 < x ≤ 14. Without wishing to be bound by theory, when 10 < x ≤ 14, P4S x When x is greater than about 14, P4S is more preferable due to the large relative amount of sulfur. x It is an amorphous material.

[0018] See now Figure 1 The method 100 of the present disclosure may generally include heating the precursor to form a solid electrolyte material. The lithium source and P4S x may be referred to herein individually or collectively as a “precursor” or a “precursor material.” In one embodiment, the method may further comprise mixing the precursor while heating.

[0019] The precursor may be heated to a temperature of about 150° C. to about 600° C. The precursor may be heated to a temperature of about 150° C. to about 200° C., about 150° C. to about 250° C., about 150° C. to about 300° C., about 150° C. to about 350° C., about 150° C. to about 400° C., about 150° C. to about 450° C., about 150° C. to about 500° C., about 150° C. to about 550° C., about 150° C. to about 600° C., about 200° C. to about 600° C., about 250° C. to about 600° C., about 300° C. to about 600° C., about 350° C. to about 600° C., about 400° C. to about 600° C., about 450° C. to about 600° C., about 500° C. to about 600° C., about 550° C. to about 600° C., about 200° C. to about 400° C., about 200° C. to about 350° C., or about 250° C. to about 350° C. For example, the composite can be heated in step b) to a temperature of about 150° C., about 175° C., about 200° C., about 225° C., about 250° C., about 275° C., about 300° C., about 325° C., about 350° C., about 375° C., about 400° C., about 425° C., about 450° C., about 475° C., about 500° C., about 525° C., about 550° C., about 575° C., or about 600° C. One skilled in the art will appreciate that the temperature can be limited or adjusted based on factors such as the type of equipment used or the atmospheric pressure.

[0020] The method 100 may further include, at step 104, including the P4S x The method may further comprise mixing one or more lithium sources with a precursor having the formula P4S x The compounds are mixed. Mixing can form a homogeneous composite. As used herein, a "homogeneous composite" is understood to refer to a composite material in which all or substantially all of the components (i.e., precursors) of the composite material are roughly evenly distributed throughout the composite material. Mixing can be achieved by methods generally known in the art. Stirring the mixture during heat treatment reduces the scale of mixing, thereby providing a more homogeneous product. Mixing can be performed by a variety of techniques practiced by those skilled in the art. This includes agitators, rotary calciners, high shear mixers, compounders, and stirred media mills. In some embodiments, agitators including stirred media mills, twin-screw compounders, and other high shear equipment can be used to mix the materials to form a homogeneous composite.

[0021] Exemplary lithium sources may include one or more of Li2S, Li2CO3, lithium halides, lithium pseudohalides, Li2O, Li3PO4, LiBO2, Li2B4O7, Li2ZrO3, LiAlO2, Li2TiO3, LiNbO3, and Li2SiO4, or mixtures thereof. Exemplary lithium halides may include one or more of LiF, LiCl, LiBr, and LiI, while exemplary lithium pseudohalides may include LiNO3, LiOH, Li2SO3, Li3N, Li2NH, LiNH2, LiBF4, LiBH4, or mixtures thereof.

[0022] Mixing can include dry mixing or wet mixing. Dry mixing involves mixing the precursors without one or more solvents; thus, the resulting mixture can be solvent-free or substantially solvent-free. Wet mixing involves mixing the precursors with a solvent. The solvent can be reactive or non-reactive. Reactive solvents can include ketones, esters, aldehydes, amines, nitro and / or nitrile solvents. Non-reactive solvents can include alkanes, blends of alkanes, xylenes (including p-xylene, m-xylene, and o-xylene), toluene, benzene, heptane, octane, decalin, 1,2,3,4-tetralin, or combinations thereof.

[0023] In embodiments where mixing comprises wet mixing, the solution comprising the precursor is then dried by methods known in the art, such as evaporation, followed by heating the precursor to form the final solid electrolyte material. Drying can be achieved by evaporation, gravity filtration, vacuum filtration, centrifugation, desiccation, and other methods known in the art.

[0024] In some embodiments, mixing forms a homogeneous composite. Mixing the precursors to form a homogeneous composite ensures a uniform distribution of the precursors, which allows the materials to react in appropriate ratios. Mixing during the heating step can also help ensure a uniform reaction. In addition, mixing during the reaction can prevent gas accumulation. For example, materials such as Li2CO3 release CO2 and CO. In other embodiments, the gas may include SO2, SO2, H2S, CS2, and other gases.

[0025] Method 100 may further include, at step 106, grinding the mixture of precursors to a desired particle size. Grinding may include wet grinding or dry grinding. Dry grinding may be accomplished without the use of a solvent; thus, the ground mixture may be free of any solvent or substantially free of any solvent. Wet grinding may be accomplished in the presence of a solvent, such as a reactive solvent or a non-reactive solvent as described herein. The precursors may be ground at a predetermined temperature for a predetermined period of time to obtain the desired particle size. Grinding may be accomplished using an attritor mill, an autogenous mill, a ball mill, a planetary mill, a buhrstone mill, a pebble mill, a rod mill, a semi-autogenous mill, a tower mill, a vertical shaft impact mill, or other grinding apparatus known in the art. Preferably, grinding is accomplished in a planetary mill or an attritor mill.

[0026] The mixing and milling times are not particularly limited, so long as they allow for proper homogenization and reaction of the precursors to produce the solid electrolyte material. The mixing temperature is also not particularly limited, so long as it allows for proper mixing and is not so high as to cause the precursors to enter a gaseous state or prematurely form a molten reactive flux as further described herein. Mixing and milling can be achieved in an inert atmosphere, a moisture-free atmosphere, or an ambient atmosphere.

[0027] In embodiments where a solvent is used, method 100 may include removing the solvent at step 108. The solvent may be removed by various separation methods known in the art, such as evaporation and filtration. In certain embodiments, the solvent may be removed by evaporation, gravity filtration, vacuum filtration, centrifugation, drying, and other methods known in the art.

[0028] When the solvent is removed by evaporation, the ground mixture can be heated to a temperature of about 20°C to about 250°C. One skilled in the art will appreciate that the optimal temperature for evaporation will depend on the solvent used; for example, high molecular weight hydrocarbons will generally require higher temperatures for evaporation. The ground mixture can be heated to a temperature of about 20°C to about 50°C, about 20°C to about 100°C, about 20°C to about 150°C, about 20°C to about 200°C, about 20°C to about 250°C, about 50°C to about 250°C, about 100°C to about 250°C, about 150°C to about 250°C, or about 200°C to about 250°C.

[0029] In some embodiments, the amount of the solvent removed can vary. In certain embodiments, all or substantially all solvents can be removed from the mixture through grinding. In other embodiments, approximately 95%, approximately 90%, approximately 85%, approximately 80%, approximately 75% or less than approximately 75% solvent can be removed. In other embodiments, approximately 99% to approximately 75% solvent can be removed, such as approximately 99% to approximately 95%, approximately 99% to approximately 90%, approximately 99% to approximately 85%, approximately 99% to approximately 80%, approximately 99% to approximately 75%, approximately 95% to approximately 75%, approximately 90% to approximately 75%, approximately 85% to approximately 75% or approximately 80% to approximately 75% solvent can be removed.

[0030] In some embodiments, the method 100 may further include mixing a sulfur source with one or more lithium sources and P4S x Mix. Exemplary sulfur sources may include, for example, elemental sulfur, sulfur vapor, polysulfide, or H2S gas. Non-limiting examples of polysulfides that may be used as sulfur sources include lithium polysulfide, sodium polysulfide, and potassium polysulfide. In one embodiment, the sulfur source is lithium polysulfide, such as Li2S x , wherein x is an integer from 2 to 10. In embodiments where the sulfur source comprises sulfur vapor or H2S gas, the sulfur vapor or H2S gas can be bubbled through or over the composite as heat is applied and the reaction occurs. Alternatively, in embodiments where the sulfur source comprises elemental sulfur, the elemental sulfur can be added directly to the composite mixture during mixing and / or during milling. Preferably, the elemental sulfur is added during the mixing step.

[0031] Except P4S x In addition to the above, the precursor may further include a compound containing phosphorus and sulfur, wherein x> 10. Exemplary compounds containing phosphorus and sulfur may include, for example, P4S x (wherein x is in the range of 3 to 10) and P2S5. In one embodiment, phosphorus sulfide (P4S x ) including P4S x A mixture of wherein x is in the range of 3 to 10 and may be P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 and P4S x where x is a non-integer.

[0032] When the precursor further comprises a compound containing phosphorus and sulfur, wherein x>10 P4S x Can provide more than 0% phosphorus for solid electrolyte material synthesis. For example, P4S where x > 10 x Phosphorus for solid electrolyte material synthesis may be provided at greater than 0%, greater than 5%, greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95%.

[0033] When the precursor further includes a compound containing phosphorus and sulfur, the compound containing phosphorus and sulfur can provide greater than 0% of the phosphorus used in the synthesis of the solid electrolyte material. For example, the compound containing phosphorus and sulfur can provide greater than 0%, greater than 5%, greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of the phosphorus used in the synthesis of the solid electrolyte material.

[0034] The molar ratio of phosphorus to lithium to sulfur (P:Li:S) can be selected so that the reaction produces the desired solid electrolyte material. The molar amount of phosphorus in the molar ratio can be selected from about 1 to about 4, such as about 1 to about 2, about 1 to about 3, about 2 to about 3, about 2 to about 4, or about 3 to about 4. In some examples, the molar amount of phosphorus in the molar ratio can be 1, 1.5, 2, 2.5, 3, 3.5, or 4. The molar amount of lithium in the molar ratio can be selected from about 1 to about 9, such as about 1 to about 3, about 1 to about 5, about 1 to about 7, about 3 to about 5, about 3 to about 7, about 3 to about 9, about 5 to about 7, about 5 to about 9, or about 7 to about 9. In some examples, the molar amount of lithium in the molar ratio can be 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, or 9. The molar amount of sulfur in the molar ratio can be selected from about 3 to about 12, such as about 3 to about 6, about 3 to about 9, about 3 to about 12, about 6 to about 9, about 6 to about 12, or about 9 to about 12. In some examples, the molar amount of sulfur in the molar ratio can be 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, or 13. Thus, the molar ratio of phosphorus to lithium to sulfur can be 1-4: 1-9: 3-12. Preferably, sulfur is added in a molar excess compared to phosphorus and lithium.

[0035] As a non-limiting example, the molar ratios of phosphorus to lithium to sulfur used in the process can be according to the following reaction formula: Although the reactions are shown as stoichiometric equivalents, one skilled in the art will appreciate that one or more precursors can be provided in molar excess.

[0036] 6Li2S + P4S (10+x) → 4Li3PS (4+x) Where 0 < x ≤ 30.

[0037] 14Li2S + P4S (10+x) → 4Li7PS (6+x) Where 0 < x ≤ 30.

[0038] 14Li2S + 3P4S (10+x)→ 4Li7P3S (n+x) Where 0 < x ≤ 30.

[0039] The method described herein can be used to prepare Li (7-y-z) PS (6-y-z) X (y) W (z) Solid electrolyte materials (wherein X and W are each individually selected from F, Cl, Br and I, y and z are in the range of 0 to 2, and wherein y+z is in the range of 0 to 2). Exemplary solid electrolyte materials prepared by the methods described herein may include, for example, Li3PS4, Li4P2S6, Li 5.5 PS 4.5 Cl 1.5 、Li 5.5 PS 4.5 ClBr 0.5 , Li5PS4Cl2, Li5PS4ClBr and Li7P3S 11 The solid electrolyte material may be crystalline glass ceramics.

[0040] The solid electrolyte prepared by the method of the present disclosure may include Li 5.5 PS 4.5 Cl 1.5 The X-ray diffraction pattern of the solid electrolyte may have peaks corresponding to 2θ of 17.5°±0.5°, 18.1°±0.5°, 19.9°±0.5°, 22.8°±0.5°, 25.95°±0.5°, 29.1°±0.5°, 29.9°±0.5°, and 31.1°±0.5°.

[0041] The method described herein can be further used to prepare Li (7-y-z) PS (6-y-z-u) O u X (y) W (z) wherein X and W are each individually selected from F, Cl, Br, and I, y and z are in the range of 0 to 2, u is in the range of about 0 to about 6, and wherein y+z is in the range of 0 to 2. Exemplary oxysulfide solid electrolyte materials prepared by the methods described herein may include, for example, Li3PS 3.9 O 0.1 、Li3PS 3.5 O 0.5 、Li6PS 4.8 O 0.3 Cl、Li6PS 4.7 O 0.3 Br, Li 5.5 PS 4.1 O0.4 Cl 1.5 He Li 5.5 PS 3.5 OClBr 0.5 .

[0042] Examples

[0043] Example 1: A method for synthesizing a solid electrolyte material comprising: reacting one or more lithium sources with a solid electrolyte having the formula P4S x A compound of , wherein x is an integer greater than 10, is heated to form a solid electrolyte material.

[0044] Embodiment 2: The method according to embodiment 1, wherein 10 < x ≤ 40.

[0045] Embodiment 3: The method according to embodiment 1, wherein 10 < x≤ 14.

[0046] Embodiment 4: The method according to any one of embodiments 1 to 3, wherein the P4S x For crystallization.

[0047] Embodiment 5: The method according to any one of embodiments 1 to 3, wherein the P4S x It is amorphous.

[0048] Example 6: A method for synthesizing a solid electrolyte material comprising: reacting one or more lithium sources with a solid electrolyte having the formula P4S x wherein 10 < x ≤ 40.

[0049] Example 7: The method according to Example 6 further comprises mixing a sulfur source with the one or more lithium sources and the compound having the formula P4S x of compound mixture.

[0050] Example 8: A method according to Example 7, wherein the one or more lithium sources comprise Li2S, Li2CO3, lithium halide, lithium pseudohalide, Li2O, Li3PO4, LiBO2, Li2B4O7, Li2ZrO3, LiAlO2, Li2TiO3, LiNbO3, Li2SiO3 or a mixture thereof.

[0051] Example 9: A method according to Example 6, wherein the one or more lithium sources comprise Li2S, Li2CO3, lithium halide, lithium pseudohalide, Li2O, Li3PO4, LiBO2, Li2B4O7, Li2ZrO3, LiAlO2, Li2TiO3, LiNbO3, Li2SiO3 or a mixture thereof.

[0052] Embodiment 10: The method of embodiment 9, wherein the lithium halide is selected from the group consisting of LiF, LiCl, LiBr, LiI, and mixtures thereof.

[0053] Embodiment 11: The method of embodiment 9, wherein the lithium pseudohalide is selected from the group consisting of LiNO3, LiOH, Li2SO3, Li3N, Li2NH, LiNH2, LiBF4, LiBH4 and mixtures thereof.

[0054] Embodiment 12: The method according to any one of embodiments 6 to 11, further comprising mixing the one or more lithium sources and the lithium ion battery having the formula P4S while heating. x of compounds.

[0055] Embodiment 13: The method of any one of Embodiments 6 to 12, wherein the solid electrolyte is a crystalline glass ceramic.

[0056] Embodiment 14: The method according to any one of embodiments 6 to 13, wherein the solid electrolyte comprises formula (I):

[0057]

[0058] in:

[0059] X and W are individually selected from F, Cl, Br and I;

[0060] y and z are each independently in the range of 0 to 2; and

[0061] Where y+z is in the range of 0 to 2.

[0062] Embodiment 15: The method according to embodiment 14, wherein the solid electrolyte having formula (I) is selected from Li3PS4, Li4P2S6, Li7P3S 11 、Li 5.5 PS 4.5 Cl 1.5 、Li 5.5 PS 4.5 ClBr 0.5 , Li5PS4Cl2 and Li5PS4ClBr.

[0063] Embodiment 16: The method according to any one of embodiments 6 to 15, further comprising mixing the one or more lithium sources with the P4S prior to heating. x Mix or grind to form a homogeneous complex.

[0064] Embodiment 17: The method of embodiment 6, wherein the lithium source comprises Li2CO3.

[0065] Embodiment 18: The method of embodiment 6, wherein the lithium source comprises two lithium sources including Li2CO3 and LiCl.

[0066] Embodiment 19: The method according to any one of embodiments 6 to 18, wherein the one or more lithium sources and the P4S x Heating is performed to a temperature of about 150°C to about 600°C.

[0067] Embodiment 20: The method of any one of embodiments 6 to 19, wherein the heating further comprises heating a compound containing phosphorus and sulfur.

[0068] Embodiment 21: The method of embodiment 20, wherein the compound containing phosphorus and sulfur is selected from the group consisting of: P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 and combinations thereof.

[0069] Embodiment 22: The method of embodiment 16 further comprising mixing a compound containing phosphorus and sulfur with the one or more lithium sources and with the P4S prior to heating. x Mix or grind to form the homogenous complex.

[0070] Embodiment 23: The method of embodiment 22, wherein the compound containing phosphorus and sulfur is selected from the group consisting of: P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 and combinations thereof.

[0071] Embodiment 24: A solid electrolyte material prepared by the method according to any one of embodiments 1 to 23, wherein the solid electrolyte material has formula (I):

[0072]

[0073] in:

[0074] X and W are individually selected from F, Cl, Br and I;

[0075] y and z are each independently in the range of 0 to 2; and

[0076] y+z is in the range of 0 to 2.

[0077] Embodiment 25: The solid electrolyte material according to embodiment 24, wherein the solid electrolyte material having formula (I) is selected from Li3PS4, Li4P2S6, Li7P3S 11 、Li 5.5 PS4.5 Cl 1.5 、Li 5.5 PS 4.5 ClBr 0.5 , Li5PS4Cl2 and Li5PS4ClBr.

[0078] Example 26: A method for synthesizing a solid electrolyte material comprising: reacting one or more lithium sources with a solid electrolyte having the formula P4S x to form a homogeneous composite, wherein 10 < x ≤ 40; and heating the homogeneous composite to form the solid electrolyte.

[0079] Example 27: A method for synthesizing a solid electrolyte material comprising: reacting one or more lithium sources with a solid electrolyte having the formula P4S x to form a homogeneous composite, wherein 10 < x ≤ 40; and grinding the mixture; and heating the homogeneous composite to form the solid electrolyte.

[0080] Example 28: A method for synthesizing a solid electrolyte material, comprising: reacting a precursor comprising one or more lithium sources and a precursor having the formula P4S x dissolving a compound of α-HgCl2 in a solvent, wherein 10 < x ≤ 40; removing the solvent; and heating the precursor to form the solid electrolyte.

[0081] Example 29: A composition comprising one or more precursors and a precursor having the formula P4S in a solvent x where 10 < x ≤ 40.

[0082] Embodiment 30. The composition of embodiment 29, wherein 10 < x ≤ 14.

[0083] Embodiment 31: The composition of embodiment 29, wherein the P4S x For crystallization.

[0084] Embodiment 32: The composition of embodiment 29, wherein the P4S x It is amorphous.

[0085] Embodiment 33: The composition of any one of Embodiments 29 to 32, wherein the one or more precursors comprise one or more lithium sources, sulfur sources, or a combination thereof.

[0086] Example 34: A solid electrolyte material comprising one or more lithium sources and a material having the formula P4S x The solid electrolyte material is prepared by heating a compound of , wherein 10 < x ≤ 40.

[0087] Embodiment 35: The solid electrolyte material according to embodiment 34, wherein the solid electrolyte material has the following formula:

[0088]

[0089] in:

[0090] X and W are individually selected from F, Cl, Br and I;

[0091] y and z are each independently in the range of 0 to 2; and

[0092] y+z is in the range of 0 to 2.

[0093] Embodiment 36: The solid electrolyte according to embodiment 34 or 35, wherein the solid electrolyte material is selected from Li3PS4, Li4P2S6, Li7P3S 11 、Li 5.5 PS 4.5 Cl 1.5 、Li5 5PS 45 ClBr 05 , Li5PS4Cl2 and Li5PS4ClBr.

[0094] Embodiment 37: The solid electrolyte material according to any one of Embodiments 34 to 36, wherein the solid electrolyte material comprises a solid electrolyte material having the following formula: Li (7-y-z) PS (6-y-z) X (y) W (z) , wherein: X and W are individually selected from F, Cl, Br and I; y and z are each individually in the range of 0 to 2; and y+z is in the range of 0 to 2, and contains at least one selected from Li3PS4, Li4P2S6 and Li7P3S 11 solid electrolyte materials.

[0095] Embodiment 38: A solid electrolyte material according to any one of Embodiments 34 to 37, wherein the X-ray diffraction pattern of the solid electrolyte material has peaks corresponding to 2θ of 17.5° ± 0.5°, 18.1° ± 0.5°, 19.9° ± 0.5°, 22.8° ± 0.5°, 25.95° ± 0.5°, 29.1° ± 0.5°, 29.9° ± 0.5° and 31.1° ± 0.5°.

[0096] Example 39: A method for synthesizing a solid electrolyte material, comprising:

[0097] One or more lithium sources are mixed with a lithium-containing material having the formula P4S xThe compound is heated to form a solid electrolyte material, wherein 10 <x ≤ 40。

[0098] Example 40: The method of Example 39 further comprising mixing a sulfur source with the one or more lithium sources and the compound having the formula P4S x of compound mixture.

[0099] Embodiment 41: The method according to embodiment 39 or embodiment 40, wherein the compound has the formula P4S x The compound is amorphous.

[0100] Embodiment 42: The method of embodiment 40, wherein the sulfur source comprises a phosphorus-sulfur material selected from the group consisting of: P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 and combinations thereof.

[0101] Embodiment 43: The method of any one of Embodiments 39 to 42, wherein the one or more lithium sources comprise Li2S, Li2CO3, lithium halide, lithium pseudohalide, Li2O, Li3PO4, LiBO2, Li2B4O7, Li2ZrO3, LiAlO2, Li2TiO3, LiNbO3, Li2SiO3, or a mixture thereof.

[0102] Embodiment 44: The method of Embodiment 43, wherein the lithium halide is selected from the group consisting of LiF, LiCl, LiBr, LiI, and mixtures thereof.

[0103] Embodiment 45: The method of any of Embodiments 43 or 44, wherein the lithium pseudohalide is selected from the group consisting of LiNO3, LiOH, Li2SO3, Li3N, Li2NH, LiNH2, LiBF4, LiBH4, and mixtures thereof.

[0104] Embodiment 46: The method according to any one of embodiments 39 to 45, wherein the one or more lithium sources and the P4S x Heating is performed to a temperature of about 150°C to about 600°C.

[0105] Example 47: A solid-state battery comprising a positive electrode layer, a negative electrode layer, and a separator layer, wherein the separator layer comprises a solid electrolyte material, the solid electrolyte material being prepared by combining one or more lithium sources with a material having the formula P4S x The solid electrolyte material is prepared by heating a compound of , wherein 10 < x ≤ 40.

[0106] Embodiment 48: The solid-state battery of embodiment 47, wherein the negative electrode layer contains a negative electrode active material and a solid electrolyte material, wherein the solid electrolyte material is prepared by mixing one or more lithium sources with a material having the formula P4S x The solid electrolyte material is prepared by heating a compound of , wherein 10 < x ≤ 40.

[0107] Embodiment 49: A solid-state battery according to embodiment 47, wherein the positive electrode layer contains a positive electrode active material and a solid electrolyte material, wherein the solid electrolyte material is prepared by mixing one or more lithium sources with a material having the formula P4S x The solid electrolyte material is prepared by heating a compound of , wherein 10 < x ≤ 40.

[0108] Embodiment 50: The solid-state battery according to any one of embodiments 47 to 49, wherein the solid electrolyte material has the following formula:

[0109]

[0110] in:

[0111] X and W are individually selected from F, Cl, Br and I;

[0112] y and z are each independently in the range of 0 to 2; and

[0113] y+z is in the range of 0 to 2.

[0114] Embodiment 51: A solid-state battery according to any one of embodiments 47 to 49, wherein the solid electrolyte material is selected from Li3PS4, Li4P2S6, Li7P3S 11 、Li 5.5 PS 4.5 Cl 1.5 、Li 5.5 PS 4.5 ClBr 0.5 , Li5PS4Cl2 and Li5PS4ClBr.

[0115] Embodiment 52: The solid-state battery according to any one of embodiments 47 to 49, wherein the solid electrolyte material comprises a solid electrolyte material having the formula: Li (7-y-Z) PS (6-y-Z) X (y) W (z) , wherein: X and W are individually selected from F, Cl, Br and I; y and z are each individually in the range of 0 to 2; and wherein y+z is in the range of 0 to 2, and contains at least one selected from Li3PS4, Li4P2S6 and Li7P3S 11solid electrolyte materials.

[0116] Example 53: A solid-state battery according to any one of Examples 47 to 52, wherein the X-ray diffraction pattern of the solid electrolyte material has peaks corresponding to 2θ of 17.5° ± 0.5°, 18.1° ± 0.5°, 19.9° ± 0.5°, 22.8° ± 0.5°, 25.95° ± 0.5°, 29.1° ± 0.5°, 29.9° ± 0.5° and 31.1° ± 0.5°.

[0117] Examples

[0118] Example 1: Using P4S x Material synthesisLi 5.5 PS 4.5 Cl 1.5 Solid electrolyte materials

[0119] First, 30 g of P4S was treated in a sealed container at 300 °C. 10 and 2.25 g elemental sulfur for 20 h to produce P4S x The result of this process is a material with the nominal composition P4S 11 Then 10.7191 g of P4S 11 The material was combined with 8.4406 g of LiS and 5.8403 g of LiCl and placed in a 250 ml zirconium oxide planetary milling jar with 400 g of zirconium oxide media. 92 g of heptane was added, the jar was sealed, and milled at 500 rpm for 3 hours. The material resulting from this milling process was recovered by removing the heptane under vacuum at 90°C. Finally, the dried material was heat-treated at 450°C for 30 minutes. In this formulation, a stoichiometric amount of phosphorus was used.

[0120] From the XRD patterns ( Figure 2 ), it can be observed that Example 1 contains Li 5.5 PS 4.5 Cl 1.5 The electrolyte phase and the unreacted LiCl complex. 5.5 PS 4.5 Cl 1.5 There are peaks at 2θ = 30.1° and 31.6°. LiCl has a peak at 34.9°.

[0121] Example 2: Using P4S x Material synthesisLi 5.5 PS 4.5 Cl 1.5 Solid electrolyte materials

[0122] First, 30 g of P4S was treated in a sealed container at 300 °C. 10 and 2.25 g elemental sulfur for 20 h to produce P4S x The result of this process is a material with the nominal composition P4S 11 Then 10.4309 g of P4S 11 The material was combined with 8.6073 g of Li2S and 5.9618 g of LiCl and placed in a 250 ml zirconium oxide planetary milling jar with 400 g of zirconium oxide media. 92 g of heptane was added, the jar was sealed, and milled at 500 rpm for 3 h. The material resulting from this milling process was recovered by removing the heptane under vacuum at 90°C. Finally, the dried material was heat-treated at 450°C for 30 min. In this recipe, the mass of phosphorus-containing precursor used was equivalent to that of a typical synthesis, such as P4S in the synthesis of Comparative Example 1 described below. 10 quality.

[0123] From the XRD patterns ( Figure 2 ), it can be observed that Example 2 contains Li 5.5 PS 4.5 Cl 1.5 The electrolyte phase, impurity 1 and unreacted LiCl complex. 5.5 PS 4.5 Cl 1.5 There are peaks at 2θ = 30.1° and 31.6°. Impurity 1 has peaks at 29.25° and 33.9°. LiCl has a peak at 34.9°.

[0124] Comparative Example 1: Using P4S 10 Material synthesisLi 5.5 PS 4.5 Cl 1.5 Solid electrolyte materials

[0125] Will include 10.4311 g P4S 10 The starting materials of 1.5 g MgSO 40 ...

[0126] From the XRD patterns ( Figure 2 ), it can be observed that Comparative Example 1 contains Li 5.5 PS 4.5 Cl1.5 The electrolyte phase, impurity 1 and unreacted LiCl complex. 5.5 PS 4.5 Cl 1.5 There are peaks at 2θ = 30.1° and 31.6°. Impurity 1 has peaks at 29.25° and 33.9°. LiCl has a peak at 34.9°.

[0127] Comparative Example 2: Using Excessive P4S 10 Material synthesisLi 5.5 PS 4.5 Cl 1.5 Solid electrolyte materials

[0128] Will include 10.9524 g P4S 10 The starting materials of 1.5 g PO 4 S, 8.6073 g Li2S, and 5.9618 g LiCl were combined and charged into a 250 ml zirconia planetary milling jar with 400 g zirconia media. 92 g heptane was added, the jar was sealed, and milled at 500 rpm for 3 h. The material resulting from this milling process was recovered by removing the heptane under vacuum at 90°C. Finally, the dried material was heat treated at 450°C for 30 min. In this recipe, an excess of P4S was used. 10 as a method of incorporating excess sulfur.

[0129] From the XRD patterns ( Figure 2 ), it can be observed that Comparative Example 2 contains Li 5.5 PS 4.5 Cl 1.5 The electrolyte phase, impurity 1, impurity 2 and unreacted LiCl complex. 5.5 PS 4.5 Cl 1.5 There are peaks at 2θ = 30.1° and 31.6°. Impurity 1 has peaks at 29.25° and 33.9°. Impurity 2 has a peak at 32.7°. LiCl has a peak at 34.9°.

[0130] Comparative Example 3: Using pre-treated P4S 10 Material synthesisLi 5.5 PS 4.5 Cl 1.5 Solid electrolyte materials

[0131] First, P4S 10 The material was treated at 300 °C for 20 h in a sealed container. Then 10.4309 g of the treated P4S 10The material was combined with 8.6073 g of LiS and 5.9618 g of LiCl and placed in a 250 ml zirconium oxide planetary milling jar with 400 g of zirconium oxide media. 92 g of heptane was added, the jar was sealed, and milled at 500 rpm for 3 hours. The material resulting from this milling process was recovered by removing the heptane under vacuum at 90°C. Finally, the dried material was heat treated at 450°C for 30 minutes.

[0132] From the XRD patterns ( Figure 3 ), it can be observed that Comparative Example 3 contains Li 5.5 PS 4.5 Cl 1.5 The electrolyte phase, impurity 1, impurity 2 and unreacted LiCl complex. 5.5 PS 4.5 Cl 1.5 There are peaks at 2θ = 30.1° and 31.6°. Impurity 1 has peaks at 29.25° and 33.9°. Impurity 2 has a peak at 32.7°. LiCl has a peak at 34.9°.

[0133] The X-ray diffraction patterns of the materials produced in the above examples and comparative examples are shown in Figure 2 and Figure 3 Middle. X-ray diffraction patterns identify the argyrodite phase (Arg) solid electrolyte material, LiCl, and two impurities.

[0134] Impurity #1 may be a material containing P2S6 and / or P2S7 structural features. Given that argyrodite-type materials contain only PS4 structural features, it is understood that the presence of P2S6 and / or P2S7 is indicative of sulfur deficiency. Therefore, the present invention provides a method for correcting any sulfur deficiency, thereby improving the phase purity of the resulting electrolyte.

[0135] Impurity #2 can be Li4P2S6, a Li4P2S6-like material, or a material containing P2S6 and / or P2S7 structural features. Given that argyrodite-type materials contain only PS4 structural features, it can be understood that the presence of Li4P2S6-like materials, P2S6, and / or P2S7 is indicative of sulfur deficiency. Therefore, the present invention provides methods for correcting any sulfur deficiency, thereby improving the phase purity of the resulting electrolyte.

[0136] The X-ray diffraction patterns of the materials synthesized in Example 1-2 and Comparative Example 1-2 are shown in Figure 2 When comparing Example 1 with Comparative Example 1, it can be seen that when using P4S 10 P4S was pretreated with elemental sulfur before the material was synthesized. 10The material produces an electrolyte with a lower impurity content. In addition, comparing Example 1 with Example 2, it can be seen that the compensation of P4S x Changing the phosphorus to sulfur ratio of the material is important to achieve increased purity.

[0137] Comparing Example 1 with Comparative Example 2, it can be seen that by using an excess of P4S 10 Incorporating additional sulfur does not improve purity.

[0138] The X-ray diffraction patterns of the materials synthesized in Example 1 and Comparative Examples 1 and 3 are shown in Figure 3 These patterns show that P4S was pretreated with elemental sulfur. 10 If P4S is subjected to 10 The material was heat treated, such as in Comparative Example 3, then when compared to P4S pretreated with elemental sulfur 10 Materials to first generate P4S x When comparing materials, there is no improvement in purity.

[0139] Commercially available P4S 10 Materials can be understood to contain P4S 10 、P4S 10-x and sulfur, wherein "x" may generally vary within the range of 1 to 3. Without wishing to be bound by theory, P4S is required 10 Certain responses or treatments may not be successfully utilized with non-P4S 10 Materials such as P4S 10-x or elemental sulfur, which may result in sulfur deficiency in the reaction products or solid electrolytes prepared therefrom. Therefore, it is advantageous to ensure sufficient sulfur availability by ensuring that at least the required amount of sulfur is combined with other elements rather than being present in elemental form. By first generating a P4S x or Li2S x It is also possible and may be beneficial to provide excess sulfur using a compound of the formula (e.g., a sulfide or sulfide derivative) that is present in the reaction mixture. The excess sulfur can be used to ensure that the desired amount of sulfur is provided to the reaction while also preventing the formation of undesirable oxygenates that might otherwise form due to contamination of the reactant materials or accidental air intrusion during processing.

Claims

1. A solid electrolyte material comprising one or more lithium sources and a solid electrolyte having the formula P4S x The solid electrolyte material is prepared by heating a compound of , wherein 10 < x ≤ 40.

2. The solid electrolyte material according to claim 1, wherein the solid electrolyte material has the following formula: in: X and W are individually selected from F, Cl, Br and I; y and z are each independently in the range of 0 to 2; and Where y+z is in the range of 0 to 2.

3. The solid electrolyte according to claim 1, wherein the solid electrolyte material is selected from Li3PS4, Li4P2S6, Li7P3S 11 、Li 5.5 PS 4.5 Cl 1.5 、Li 5.5 PS 4.5 ClBr 0.5 , Li5PS4Cl2 and Li5PS4ClBr.

4. The solid electrolyte material according to claim 1, wherein the solid electrolyte material comprises a solid electrolyte material having the formula: Li (7-y-z) PS (6-y-Z) X (y) W (Z) ,in: X and W are independently selected from F, Cl, Br and I; y and z are each independently in the range of 0 to 2; and y+z is in the range of 0 to 2, and contains at least one selected from Li3PS4, Li4P2S6 and Li7P3S 11 solid electrolyte materials.

5. The solid electrolyte material according to claim 1, wherein the X-ray diffraction pattern of the solid electrolyte material has peaks corresponding to 2θ of 17.5°±0.5°, 18.1°±0.5°, 19.9°±0.5°, 22.8°±0.5°, 25.95°±0.5°, 29.1°±0.5°, 29.9°±0.5°, and 31.1°±0.5°.

6. A method for synthesizing a solid electrolyte material, comprising: One or more lithium sources are mixed with a lithium-containing material having the formula P4S x wherein 10 < x ≤ 40.

7. The method of claim 6, further comprising mixing a sulfur source with the one or more lithium sources and the compound having the formula P4S x of compound mixture.

8. The method according to claim 6, wherein the compound having the formula P4S x The compound is amorphous.

9. The method of claim 6, wherein the sulfur source comprises a phosphorus-sulfur material selected from the group consisting of: P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 and combinations thereof.

10. The method of claim 6, wherein the one or more lithium sources comprises Li2S, Li2CO3, lithium halide, lithium pseudohalide, Li2O, Li3PO4, LiBO2, Li2B4O7, Li2ZrO3, LiAlO2, Li2TiO3, LiNbO3, Li2SiO3, or mixtures thereof.

11. The method of claim 6, wherein the lithium halide is selected from the group consisting of LiF, LiCl, LiBr, LiI, and mixtures thereof.

12. The method of claim 6, wherein the lithium pseudohalide is selected from the group consisting of LiNO3, LiOH, Li2SO3, Li3N, Li2NH, LiNH2, LiBF4, LiBH4, and mixtures thereof.

13. The method of claim 6, wherein the one or more lithium sources and the P4S x Heating is performed to a temperature of about 150°C to about 600°C.

14. A solid-state battery comprising a positive electrode layer, a negative electrode layer and a separator layer, wherein the separator layer comprises a solid electrolyte material, the solid electrolyte material being prepared by combining one or more lithium sources with a lithium-ion battery having the formula P4S x The solid electrolyte material is prepared by heating a compound of , wherein 10 < x ≤ 40.

15. The solid-state battery according to claim 14, wherein the negative electrode layer contains a negative electrode active material and a solid electrolyte material, the solid electrolyte material being obtained by combining one or more lithium sources with a material having the formula P4S x The solid electrolyte material is prepared by heating a compound of , wherein 10 < x ≤ 40.

16. The solid-state battery according to claim 14, wherein the positive electrode layer contains a positive electrode active material and a solid electrolyte material, the solid electrolyte material being obtained by combining one or more lithium sources with a material having the formula P4S x The solid electrolyte material is prepared by heating a compound of , wherein 10 < x ≤ 40.

17. The solid-state battery according to claim 14, wherein the solid electrolyte material has the formula: in: X and W are individually selected from F, Cl, Br and I; y and z are each independently in the range of 0 to 2; and y+z is in the range of 0 to 2.

18. The solid-state battery according to claim 14, wherein the solid electrolyte material is selected from Li3PS4, Li4P2S6, Li7P3S 11 、Li 5.5 PS 4.5 Cl 1.5 、Li 5.5 PS 4.5 ClBr 0.5 , Li5PS4Cl2 and Li5PS4ClBr.

19. The solid-state battery according to claim 14, wherein the solid electrolyte material comprises a solid electrolyte material having the formula: Li (7-y-z) PS (6-y-z) X (y) W (z) ,in: X and W are independently selected from F, Cl, Br and I; y and z are each independently in the range of 0 to 2; and y+z is in the range of 0 to 2, and contains at least one selected from Li3PS4, Li4P2S6 and Li7P3S 11 solid electrolyte materials.

20. A solid-state battery according to claim 14, wherein the X-ray diffraction pattern of the solid electrolyte material has peaks corresponding to 2θ of 17.5° ± 0.5°, 18.1° ± 0.5°, 19.9° ± 0.5°, 22.8° ± 0.5°, 25.95° ± 0.5°, 29.1° ± 0.5°, 29.9° ± 0.5° and 31.1° ± 0.5°.

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