Synthesis of solid electrolyte using P4SX material

Abstract

In this specification, P4S x A method for forming a solid electrolyte material using a compound comprising P4S in the presence of one or more lithium compounds is described. x to form a solid electrolyte.

Description

Technical Field

[0001] This application claims priority to U.S. Patent Application No. 63 / 433,708, titled "Synthesis of Solid Electrolytes Using P4S X Materials," filed on December 19, 2022, the content of which is hereby incorporated by reference in its entirety.

[0002] This disclosure relates to a process for making solid electrolyte materials. Accordingly, this disclosure relates to the fields of chemistry, chemical engineering, and electrical engineering.

Background Art

[0003] Sulfide solid electrolytes, such as Li3PS4, etc., when exposed to air / moisture, undergo hydrolysis (exchange sulfur with oxygen) and transform into substances such as Li3PS 4-x O x etc. This reaction generates toxic hydrogen sulfide gas. When oxygen is incorporated, the lithium ion conduction ability of the solid electrolyte decreases, thereby reducing the ionic conductivity of the material. Exposure to air and moisture becomes relatively prominent on a relatively large manufacturing scale because it becomes relatively difficult and costly to dry large amounts of air, solvents, and precursor materials.

Summary of the Invention

Problems to be Solved by the Invention

[0004] There is a need for a process to produce solid electrolyte materials with low levels of oxygen contamination and high levels of sulfur.

Means for Solving the Problems

[0005] As used herein, a solid electrolyte material is provided that is produced by heating one or more lithium sources with a compound having the formula P4S x where 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) is such that X and W are each 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. In some embodiments, the solid electrolyte material is 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] Furthermore, provided herein is a process for synthesizing a solid electrolyte material, including heating one or more lithium sources with a compound having the formula P4S x to form the solid electrolyte material, where 10 < x ≦ 40. In some examples, the process further includes mixing a sulfur source with one or more lithium sources and a compound having the formula P4S x . In some embodiments, the compound having the formula P4S x is amorphous. In some embodiments, the sulfur source is P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10and includes a phosphorus-sulfur material selected from the group consisting of these and combinations thereof. In some embodiments, the one or more lithium sources include Li2S, Li2CO3, lithium halides, lithium pseudo-halides, 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 pseudo-halide 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 x is heated to a temperature of about 150°C to about 600°C.

[0007] Furthermore, provided herein is a solid battery including a positive electrode layer, a negative electrode layer, and a separator layer, wherein the separator layer includes a solid electrolyte material produced by heating one or more lithium sources with a compound having the formula P4S x where 10 < x ≦ 40. In some embodiments, the negative electrode layer includes a negative electrode active material and a solid electrolyte material produced by heating one or more lithium sources with a compound having the formula P4S x where 10 < x ≦ 40. In some embodiments, the positive electrode layer includes a positive electrode active material and a solid electrolyte material produced by heating one or more lithium sources with a compound having the formula P4S x where 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)where 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. In some embodiments, the solid electrolyte material is 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 with 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 explanation of the drawings]

[0008] [Figure 1] FIG. 1 shows a process flow diagram for the process of the present disclosure.

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

[0010] [Figure 3] FIG. 3 shows the X-ray diffraction patterns of the solid electrolyte materials synthesized in Example 1, Example 3, and Comparative Example 3. DETAILED DESCRIPTION OF THE INVENTION

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

[0012] Concentrations, amounts, and other numerical data may be expressed or presented in range format herein. Such range format is used merely for convenience and brevity and should be interpreted flexibly as including not only the numerical values ​​expressly recited as the limits of the range, but also all individual numerical values ​​or subranges subsumed within that range, as if each numerical value and subrange were expressly recited. For example, a numerical range of "about 2 to about 50" should be interpreted as including not only the numerical values ​​from 2 to 50 expressly recited, but also all individual numerical values ​​and subranges subsumed within that specified range. Thus, this numerical range includes 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, etc., as well as subranges, such as 1 to 3, 2 to 4, 5 to 10, 5 to 20, 5 to 25, 5 to 30, 5 to 35, 5 to 40, 5 to 50, 2 to 10, 2 to 20, 2 to 30, 2 to 40, 2 to 50, etc. This same principle also applies to ranges reciting only a single numerical value as the minimum or maximum value. Moreover, such interpretation should apply regardless of the breadth of the range or the recited characteristic.

[0013] As used herein, the term "about" is used to provide flexibility for the endpoints of numerical ranges by allowing for cases where a given value may be "slightly above" or "slightly below" the endpoint. For example, the endpoint may be within 10%, 8%, 5%, 3%, 2%, or 1% of the recited value. Furthermore, for convenience and brevity, a numerical range of "about 50 mg / mL to about 80 mg / mL" should be understood to provide support for the range "50 mg / mL to 80 mg / mL." Endpoints may be based on a range of variation recognized by appropriate regulatory agencies, e.g., FDA, USP, etc.

[0014] As used herein, the terms "comprise," "contain," and / or "have" mean to include (have) and are to be understood as open-ended terms.

[0015] As used herein, "pseudohalogens" and "pseudohalides" refer to compounds whose chemical properties resemble those of elemental halogens and halide ions. The terms "pseudohalogens" and "pseudohalides" may be used interchangeably with "superhalogens" or "superhalides," respectively.

[0016] In this specification, P4S x This paper describes a process for forming solid electrolyte materials using P4S as a precursor. x The high sulfur content of P4S results in the incorporation of sulfur atoms into the solid electrolyte material, thereby reducing the presence of oxygen species in the solid electrolyte material, which can be determined by analytical methods known in the art (e.g., Fourier transform infrared spectroscopy for detecting P-O and S-O bonds in the electrolyte material, phosphorus NMR for detecting P-O bonds in the electrolyte material, Raman spectroscopy for detecting S-O bonds in the electrolyte material, X-ray diffraction measurement for detecting decomposition products containing oxygen species, etc.) and / or by the identification of solid electrolyte powder material containing oxygen species and P4S with a reduced number of oxygen species. x This can be seen by the difference in color between the solid electrolyte powder material prepared using P4S. x by heating phosphorus and sulfur, or P4S 10-x It may be made by heating the material and elemental sulfur at a temperature of about 300°C, where 0 > x > 7. Pure P4S 10 The melting point of P4S is about 288°C, so the reaction temperature is about 300°C. x It is preferable to lower the reaction rate barrier to the formation of P4S, where x>10. x Since is produced at such high temperatures, P4S x does not decompose at the high temperatures required for the synthesis of the solid electrolyte materials described herein. Furthermore, the sulfur vapor pressure is x On P4S, the P4S is significantly lower than on sulfur alone. 10 and sulfur mixture to produce P4S xWhen generating, the temperature is preferably raised from the melting point of sulfur, through the stages of ring cleavage and decomposition of the sulfur ring, and finally to the melting point of the phosphorus sulfide. During this process, sulfur is added to the phosphorus sulfide by a combination reaction. This reaction can be simply described as P4S 10 +S=P4S 10+x The ring cleavage of elemental sulfur occurs at about 160 °C, at which point it becomes liquid, and the decomposition into relatively short chains of long-chain sulfur occurs at about 250 °C, which increases the reactivity of elemental sulfur, and thus, the reactivity of elemental sulfur with the P4S 10-x material may be improved, whereby the reaction temperature is reduced and the combination reaction proceeds relatively easily towards completion. Alternatively, the processing temperature can be made higher than either of the melting temperatures or decomposition temperatures described herein to promote mixing. The reaction mechanism is described in relatively detail in "Sulfur-Rich Phosphorus Sulfide Molecules for Use in Rechargeable Lithium Batteries" by Li, Xiaona et al., Angewandte Chemie, Vol. 56 Issue 11, PP. 2937~2941, 2017, the content of which is incorporated herein by reference in its entirety.

[0017] In the present disclosure, P4S x is used as a precursor material for forming a solid electrolyte material, where x is an integer greater than 10. In some embodiments, x is greater than 40, or 10 < x ≤ 40. In other embodiments, P4S x is used as a precursor material for forming a solid electrolyte material, where 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 being bound by theory, when 10 < x ≤ 14, P4S x is a crystalline phase material having preferred properties for forming a solid electrolyte material. When x is greater than about 14, P4S x is an amorphous phase material because of the relatively large amount of sulfur.

[0018] 1, the process 100 of the present disclosure may generally include heating precursors to form a solid electrolyte material. x may be referred to herein individually or collectively as "precursors" or "precursor materials." In one embodiment, the process may further include simultaneously mixing the precursors while heating.

[0019] The precursor can be heated to a temperature of about 150°C to about 600°C. The precursor can 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 25 It can be heated to a temperature of 0°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 may 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 understand that the temperature may be limited or adjusted based on factors such as the type of equipment used or atmospheric pressure.

[0020] The process 100 further comprises, in step 104, x The process may further include mixing one or more lithium sources with a precursor of formula P4S xThe mixing may include mixing with a compound having the formula (I) or (II). The mixing may 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 approximately evenly distributed throughout the composite material. The mixing may be performed by methods generally known in the art. Agitating the mixture during heat treatment reduces the scale of mixing, thus providing a relatively homogeneous article. The mixing may be performed by a variety of techniques that can be implemented by one skilled in the art, including stirrers, rotary kilns, high shear mixers, compounders, and stirred media mills. In some embodiments, stirrers, such as stirred media mills, twin-screw compounders, and other high shear devices, may be used to mix the materials to form a homogeneous composite.

[0021] Examples of lithium sources may include one or more of LiS, LiCO, lithium halides, lithium pseudohalides, LiO, LiPO, LiBO, LiBO, LiZrO, LiAlO, LiTiO, LiNbO, LiSiO, or mixtures thereof. Examples of lithium halides may include one or more of LiF, LiCl, LiBr, and LiI, while examples of lithium pseudohalides may include LiNO, LiOH, LiSO, LiN, LiNH, LiNH, LiBF, LiBH, 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 a reactive solvent or a non-reactive solvent. Reactive solvents can include ketone, ester, aldehyde, amine, nitro, and / or nitrile solvents. Non-reactive solvents can include alkanes, mixtures of alkanes, xylenes (e.g., para-, meta-, ortho-xylene, etc.), toluene, benzene, heptane, octane, decalin, 1,2,3,4-tetrahydronaphthalene, or combinations thereof.

[0023] In embodiments where the mixing comprises wet mixing, the solution containing the precursors is subsequently dried by methods known in the art (e.g., evaporation, etc.) before heating the precursors to form the final solid electrolyte material. Drying can be performed by evaporation, gravity filtration, vacuum filtration, centrifugation, drying, and other methods known in the art.

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

[0025] Process 100 may further include, in step 106, milling the precursor mixture to a desired particle size. Milling may include wet milling or dry milling. Dry milling may be performed without a solvent; thus, the milled mixture may be completely free of any solvent, or may be substantially free of any solvent. Wet milling may be performed in the presence of a solvent, such as a reactive or non-reactive solvent described herein. The precursor may be milled at a predetermined temperature for a predetermined period of time to achieve a desired particle size. Milling may be performed using an attritor mill, autogenous mill, ball mill, planetary ball mill, barstone mill, pebble mill, rod mill, semi-autogenous (SAG) mill, tower mill, vertical axis impact mill, or other milling equipment known in the art. Preferably, milling is performed in a planetary ball mill or attritor mill.

[0026] The mixing time and grinding time are not particularly limited as long as they allow for proper homogenization and reaction of the precursors to produce a solid electrolyte material. The mixing temperature is also not particularly limited as long as it allows for proper mixing and is not so high that the precursors become gaseous or a molten reactive flux is formed prematurely, as described later in this specification. The mixing and grinding can be carried out in an inert atmosphere, a moisture-free atmosphere, or an atmosphere at room temperature and pressure.

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

[0028] When removing the solvent by evaporation, the grinding mixture can be heated to a temperature of about 20°C to about 250°C. One skilled in the art will understand that the optimum temperature for evaporation will depend on the solvent used; for example, high molecular weight hydrocarbons will generally require higher temperatures to evaporate. The grinding 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] The amount of solvent removed can vary. In some embodiments, all or substantially all of the solvent can be removed from the milled mixture. In other embodiments, about 95%, about 90%, about 85%, about 80%, about 75%, or less than about 75% of the solvent can be removed. In still other embodiments, about 99% to about 75% of the solvent can be removed, such as about 99% to about 95%, about 99% to about 90%, about 99% to about 85%, about 99% to about 80%, about 99% to about 75%, about 95% to about 75%, about 90% to about 75%, about 85% to about 75%, or about 80% to about 75% of the solvent can be removed.

[0030] In some embodiments, the process 100 comprises combining a sulfur source with one or more lithium sources and P4S x The method may further include mixing with a sulfur source. Examples of sulfur sources may include, for example, elemental sulfur, sulfur vapor, polysulfides, or H2S gas. Non-limiting examples of polysulfides that may be used as sulfur sources include lithium polysulfide, sodium polysulfide, and potassium polysulfide. In some embodiments, the sulfur source is lithium polysulfide, e.g., Li2S xand the like, where x is an integer from 2 to 10. In embodiments where the sulfur source comprises sulfur vapor or HS gas, the sulfur vapor or HS gas can be blown through or over the composite while heat is applied and the reaction is occurring. 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 milling. Preferably, the elemental sulfur is added during the mixing step.

[0031] The precursor is P4S where x>10 x In addition to the above, the phosphorus and sulfur-containing compound may further be included. Examples of the phosphorus and sulfur-containing compound include P4S X (where x ranges from 3 to 10) and P2S5. In some embodiments, phosphorus sulfide (P4S x ) is P4S x where x is in the range of 3 to 10, and P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 , and P4S where x is not an integer x It can be a combination of:

[0032] If the precursor further contains a compound containing phosphorus and sulfur, then P4S where x>10 x can provide more than 0% of the phosphorus used in the synthesis of solid electrolyte materials. For example, P4S with x>10 x may provide more than 0%, more than 5%, more than 10%, more than 20%, more than 30%, more than 40%, more than 50%, more than 60%, more than 70%, more than 80%, more than 90%, or more than 95% of the phosphorus used in the synthesis of the solid electrolyte material.

[0033] When the precursor further comprises a phosphorus- and sulfur-containing compound, the phosphorus- and sulfur-containing compound may provide greater than 0% of the phosphorus used in the synthesis of the solid electrolyte material. For example, the phosphorus- and sulfur-containing compound may 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 a range of about 1 to about 4, e.g., 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 a range of about 1 to about 9, e.g., 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 a range of about 3 to about 12, e.g., 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, the sulfur is added in molar excess relative to the phosphorus and lithium.

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

[0036] 6Li2S+P4S (10+x) →4Li3PS (4+x) , where 0 <x≦30である。

[0037] 14Li2S+P4S (10+x) →4Li7PS (6+x) , where 0 <x≦30である。

[0038] 14Li2S+3P4S (10+x) →4Li7P3S (11+x) , where 0 <x≦30である。

[0039] The process described herein comprises reacting a compound of formula Li (7-y-z) PS (6-y-z) X (y) W (z) (wherein X and W are each independently selected from F, Cl, Br, and I, y and z are in the range of 0 to 2, and y + z is in the range of 0 to 2). Examples of solid electrolyte materials produced by the processes described herein 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 a crystalline glass ceramic.

[0040] The solid electrolyte produced by the process of the present disclosure contains Li 5.5 PS 4.5 Cl 1.5 The solid electrolyte may have an X-ray diffraction pattern with 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 processes described herein may further be carried out by reacting a compound of formula Li (7-y-z) PS (6-y-z-u) O u X (y) W (z)where X and W are each independently selected from F, Cl, Br, and I, y and z range from 0 to 2, u ranges from about 0 to about 6, and y + z ranges from 0 to 2. Examples of oxysulfide solid electrolyte materials produced by the processes described herein 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 O 0.4 Cl 1.5 , and Li 5.5 PS 3.5 OClBr 0.5 Examples include:

[0042] Exemplary Implementations

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

[0044] Embodiment 2: The process of embodiment 1, further comprising: <x≦40である、プロセス。

[0045] Embodiment 3: The process of embodiment 1, further comprising: <x≦14である、プロセス。

[0046] Embodiment 4: The process of any one of embodiments 1 to 3, further comprising P4S x is crystalline, a process.

[0047] Embodiment 5: The process of any one of embodiments 1 to 3, further comprising P4S x is amorphous, a process

[0048] Embodiment 6: A process for synthesizing a solid electrolyte material, comprising: reacting one or more lithium sources with a compound of formula P4S x forming a solid electrolyte material, wherein <x≦40である、プロセス。

[0049] Embodiment 7: The process of embodiment 6, further comprising providing the sulfur source in a solution of one or more lithium sources and a compound of formula P4S x with a compound having the formula:

[0050] Embodiment 8: The process of embodiment 7, wherein the one or more lithium sources comprise LiS, LiCO, lithium halides, lithium pseudohalides, LiO, LiPO, LiBO, LiBO, LiZrO, LiAlO, LiTiO, LiNbO, LiSiO, or mixtures thereof.

[0051] Embodiment 9: The process of embodiment 6, wherein the one or more lithium sources comprise LiS, LiCO, lithium halides, lithium pseudohalides, LiO, LiPO, LiBO, LiBO, LiZrO, LiAlO, LiTiO, LiNbO, LiSiO, or mixtures thereof.

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

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

[0054] Embodiment 12: The process of any of Embodiments 6-11, further comprising: reacting, with heating, one or more lithium sources and a compound of formula P4S x and simultaneously mixing compounds having the formula:

[0055] Embodiment 13: The process of any of embodiments 6-12, wherein the solid electrolyte is a crystalline glass-ceramic.

[0056] Embodiment 14: The process of any of embodiments 6-13, wherein the solid electrolyte comprises Formula (I): Li (7-y-z) PS (6-y-z) X (y) W (z) (I) where: X and W are independently selected from F, Cl, Br, and I; y and z each independently range from 0 to 2; y+z is in the range of 0 to 2.

[0057] Embodiment 15: The process of embodiment 14, wherein the solid electrolyte of formula (I) is selected from the group consisting of Li3PS4, Li4P2S6, Li7P3S 11 , Li5.5PS 4.5 Cl 1.5 , Li 5.5 PS 4.5 ClBr 0.5 , Li5PS4Cl2, and Li5PS4ClBr.

[0058] Embodiment 16: The process of any of Embodiments 6-15, wherein prior to heating, the one or more lithium sources are added to P4S x and mixing or grinding the mixture with the compound to form a homogeneous composite.

[0059] Embodiment 17: The process of embodiment 6, wherein the lithium source comprises Li2CO3.

[0060] Embodiment 18: The process of embodiment 6, wherein the lithium source comprises two lithium sources, comprising Li2CO3 and LiCl.

[0061] Embodiment 19: The process of any of embodiments 6-18, wherein the one or more lithium sources and P4S x to a temperature of about 150°C to about 600°C.

[0062] Embodiment 20: The process of any of embodiments 6-19, wherein heating further comprises heating a compound containing phosphorus and sulfur.

[0063] Embodiment 21: The process of embodiment 20, wherein the phosphorus and sulfur containing compound is P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 and combinations thereof.

[0064] Embodiment 22: The process of embodiment 16, wherein, prior to heating, the phosphorus- and sulfur-containing compound is reacted with one or more lithium sources and P4S x to form a homogeneous complex.

[0065] Embodiment 23: The process of embodiment 22, wherein the phosphorus and sulfur-containing compound is P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 and combinations thereof.

[0066] Embodiment 24: A solid electrolyte material produced by the process of any of embodiments 1-23, wherein the solid electrolyte material is of formula (I): Li (7-y-z) PS (6-y-z) X (y) W (z) (I) where: X and W are independently selected from F, Cl, Br, and I; y and z each independently range from 0 to 2; y+z is in the range of 0 to 2.

[0067] Embodiment 25: The solid electrolyte material of Embodiment 24, wherein the solid electrolyte material having the formula (I) is Li3PS4, Li4P2S6, Li7P3S 11 , Li 5.5 PS 4.5 Cl 1.5 , Li 5.5 PS 4.5 ClBr 0.5 , a solid electrolyte material selected from Li5PS4Cl2 and Li5PS4ClBr.

[0068] Embodiment 26: A process for synthesizing a solid electrolyte material: mixing one or more lithium sources with a compound having the formula P4S x to form a homogeneous composite, where 10 < x ≤ 40; and heating the homogeneous composite to form a solid electrolyte.

[0069] Embodiment 27: A process for synthesizing a solid electrolyte material: mixing one or more lithium sources with a compound having the formula P4S x to form a homogeneous composite, where 10 < x ≤ 40; grinding the mixture; and heating the homogeneous composite to form a solid electrolyte.

[0070] Embodiment 28: A process for synthesizing a solid electrolyte material: dissolving a precursor containing one or more lithium sources and a compound having the formula P4S x in a solvent, where 10 < x ≤ 40; removing the solvent; and heating the precursor to form a solid electrolyte.

[0071] Embodiment 29: A composition containing one or more precursors and a compound having the formula P4S x in a solvent, where 10 < x ≤ 40.

[0072] Embodiment 30: The composition of Embodiment 29, where 10 < x ≤ 14.

[0073] Embodiment 31: The composition of Embodiment 29, wherein P4S x is crystalline, the composition.

[0074] Embodiment 32: The composition of Embodiment 29, wherein P4S x is amorphous, the composition.

[0075] Embodiment 33: The composition of any one of Embodiments 29 to 32, wherein one or more precursors comprise one or more lithium sources, sulfur sources, or combinations thereof, the composition.

[0076] Embodiment 34: A solid electrolyte material produced by heating one or more lithium sources with a compound having the formula P4S x to form a solid electrolyte material, wherein 10 < x ≦ 40, the solid electrolyte material.

[0077] Embodiment 35: The solid electrolyte material of Embodiment 34, wherein the solid electrolyte material has the following formula: Li (7-y-z) PS (6-y-z) X (y) W (z) Here: X and W are each independently selected from F, Cl, Br, and I; y and z are each independently in the range of 0 to 2; y + z is in the range of 0 to 2.

[0078] Embodiment 36: The solid electrolyte of Embodiment 34 or 35, wherein the solid electrolyte material is Li3PS 4、 Li4P2S 6、 Li7P3S 11 、Li 5.5 PS 4.5 Cl 1.5、 Li 5.5 PS 4.5 ClBr 0.5、 Li5PS4Cl 2、 and selected from Li5PS4ClBr, the solid electrolyte.

[0079] Embodiment 37: The solid electrolyte material of any of Embodiments 34 to 36, wherein the solid electrolyte material is a compound represented by the following formula: Li (7-y-z) PS (6-y-z) X (y) W (z) wherein: 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, including Li3PS4, Li4P2S6, and Li7P3S 11 A solid electrolyte material comprising at least one solid electrolyte material selected from the following:

[0080] Embodiment 38: The solid electrolyte material of any one of embodiments 34 to 37, wherein 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°.

[0081] Embodiment 39: A process for synthesizing a solid electrolyte material, comprising: The one or more lithium sources are provided by a compound of the formula P4S x to form a solid electrolyte material, <x≦40である、プロセス。

[0082] Embodiment 40: The process of embodiment 39, further comprising providing the sulfur source in a solution of one or more lithium sources and a compound of formula P4S x with a compound having the formula:

[0083] Embodiment 41: The process of embodiment 39 or embodiment 40, wherein the compound of formula P4S x The compound having the process is amorphous.

[0084] Embodiment 42: The process of embodiment 40, wherein the sulfur source is selected from the group consisting of P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10A process comprising a phosphorus-sulfur material selected from the group consisting of and combinations thereof.

[0085] Embodiment 43: A process according to any of the processes of Examples 39 to 42, wherein one or more lithium sources include Li2S, Li2CO3, lithium halide, lithium pseudohalide, Li2O, Li3PO4, LiBO2, Li2B4O7, Li2ZrO3, LiAlO2, Li2TiO3, LiNbO3, Li2SiO3, or a mixture thereof.

[0086] Embodiment 44: A process according to the process of Embodiment 43, wherein the lithium halide is selected from the group consisting of LiF, LiCl, LiBr, LiI, and mixtures thereof.

[0087] Embodiment 45: A process according to any of the processes of Embodiment 43 or 44, wherein the lithium pseudohalide is LiNO 3、 LiOH, Li2SO 3、 Li3N, Li2NH, LiNH2, LiBF4, LiBH4, and mixtures thereof.

[0088] Embodiment 46: A process according to any of the processes of Embodiments 39 to 45, wherein one or more lithium sources and P4S x are heated to a temperature of about 150°C to about 600°C.

[0089] Embodiment 47: A solid-state battery comprising a positive electrode layer, a negative electrode layer, and a separator layer, wherein the separator layer contains a solid electrolyte material produced by heating one or more lithium sources with a compound having the formula P4S x to form a solid electrolyte material, where 10 < x ≤ 40.

[0090] Embodiment 48: A solid-state battery according to Embodiment 47, wherein the negative electrode layer comprises a negative electrode active material and one or more lithium sources with the formula P4S xA solid battery comprising a solid electrolyte material produced by heating a compound having the formula with a solid electrolyte material, where 10 < x ≦ 40.

[0091] Embodiment 49: The solid battery according to Embodiment 47, wherein the positive electrode layer comprises a positive electrode active material and one or more lithium sources, and a solid electrolyte material produced by heating a compound having the formula P4S x A solid battery comprising a solid electrolyte material produced by heating a compound having the formula with a solid electrolyte material, where 10 < x ≦ 40.

[0092] Embodiment 50: The solid battery according to any one of Embodiments 47 to 49, wherein the solid electrolyte material has the following formula: Li (7-y-z) PS (6-y-z) X (y) W (z) Where: X and W are each independently selected from F, Cl, Br, and I; y and z are each independently in the range of 0 to 2; y + z is in the range of 0 to 2.

[0093] Embodiment 51: The solid 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.

[0094] Embodiment 52: The solid battery according to any one of Embodiments 47 to 49, wherein the solid electrolyte material has the following formula: Li (7-y-z) PS (6-y-z) X (y) W (z)wherein: 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, including Li3PS4, Li4P2S6, and Li7P3S 11 A solid-state battery comprising at least one solid electrolyte material selected from the group consisting of:

[0095] Embodiment 53: The solid state battery of any one of embodiments 47 to 52, wherein the solid electrolyte material has an X-ray diffraction pattern with 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°. [Example]

[0096] Example 1: P4S x Materials used: Li 5.5 PS 4.5 Cl 1.5 Synthesis of solid electrolyte materials

[0097] First, P4S x Ingredients: 30g of P4S 10 and 2.25 g of elemental sulfur in a sealed vessel at 300 °C for 20 hours. The result of this process was a compound with the nominal composition P4S 11 and 10.7191 g of P4S. 11 The material was combined with 8.4406 g of LiS and 5.8403 g of LiCl and loaded into a 250 ml zirconia planetary mill jar containing 400 g of zirconia media. 92 g of heptane was added, the jar was sealed, and the mixture was milled at 500 rpm for 3 hours. The material obtained from this milling process was recovered by removing the heptane under vacuum at 90°C. Finally, the dried material was subjected to heat treatment at 450°C for 30 minutes. This recipe utilized a stoichiometric amount of phosphorus.

[0098] From the XRD pattern (Fig. 2), it is clear that Example 1 contains Li 5.5 PS 4.5 Cl 1.5 It can be observed that the electrolyte phase is a complex containing LiCl and unreacted LiCl. 5.5 PS 4.5 Cl 1.5 has peaks at 2θ=30.1° and 2θ=31.6°. LiCl has a peak at 34.9°.

[0099] Example 2: P4S x Materials used: Li 5.5 PS 4.5 Cl 1.5 Synthesis of solid electrolyte materials

[0100] First, P4S x Ingredients: 30g of P4S 10 and 2.25 g of elemental sulfur in a sealed vessel at 300 °C for 20 hours. The result of this process was a compound with the nominal composition P4S 11 and 10.4309 g of P4S. 11 The material was combined with 8.6073 g of Li2S and 5.9618 g of LiCl and loaded into a 250 ml zirconia planetary mill jar containing 400 g of zirconia media. 92 g of heptane was added, the jar was sealed, and the milling was carried out at 500 rpm (500 revolutions per minute) for 3 hours. The material obtained from this milling process was recovered by removing the heptane under vacuum at 90°C. Finally, the dried material was subjected to a heat treatment at 450°C for 30 minutes. This recipe is comparable to that used in a typical synthesis, such as Comparative Example 1 described below, for P4S. 10 The mass of the phosphorus-containing precursor corresponding to the mass of the phosphate group was used.

[0101] From the XRD pattern (Fig. 2), Example 2 shows that Li 5.5 PS 4.5 Cl 1.5 It can be observed that the electrolyte phase is a complex containing impurity 1 and unreacted LiCl. 5.5 PS 4.5 Cl 1.5has peaks at 2θ=30.1° and 2θ=31.6°. Impurity 1 has peaks at 29.25° and 33.9°. LiCl has a peak at 34.9°.

[0102] Comparative example 1: P4S 10 Materials used: Li 5.5 PS 4.5 Cl 1.5 Synthesis of solid electrolyte materials

[0103] 10.4311g of P4S 10 The starting materials, including 8.6078 g of Li2S, and 5.9626 g of LiCl, were combined and loaded into a 250 ml zirconia planetary mill jar containing 400 g of zirconia media. 92 g of heptane was added, the jar was sealed, and the milling was carried out at 500 rpm for 3 hours. The material obtained from this milling process was recovered by removing the heptane under vacuum at 90 °C. Finally, the dried material was subjected to heat treatment at 450 °C for 30 minutes. This recipe utilized a stoichiometric amount of phosphorus.

[0104] From the XRD pattern (Fig. 2), it is clear that Comparative Example 1 contains Li 5.5 PS 4.5 Cl 1.5 It can be observed that the electrolyte phase is a complex containing impurity 1 and unreacted LiCl. 5.5 PS 4.5 Cl 1.5 has peaks at 2θ=30.1° and 2θ=31.6°. Impurity 1 has peaks at 29.25° and 33.9°. LiCl has a peak at 34.9°.

[0105] Comparative Example 2: Excess P4S 10 Materials used: Li 5.5 PS 4.5 Cl 1.5 Synthesis of solid electrolyte materials

[0106] 10.9524g P4S 10The starting materials, including 8.6073 g of Li2S and 5.9618 g of LiCl, were combined and loaded into a 250 ml zirconia planetary mill jar containing 400 g of zirconia media. 92 g of heptane was added, the jar was sealed, and the mixture was milled at 500 rpm for 3 hours. The material obtained from this milling process was recovered by removing the heptane under vacuum at 90 °C. Finally, the dried material was subjected to heat treatment at 450 °C for 30 minutes. In this recipe, an excess of P4S was added. 10 as a way to incorporate excess sulfur.

[0107] From the XRD pattern (Fig. 2), it is clear that Comparative Example 2 contains Li 5.5 PS 4.5 Cl 1.5 It can be observed that the electrolyte phase is a complex containing impurity 1, impurity 2, and unreacted LiCl. 5.5 PS 4.5 Cl 1.5 has peaks at 2θ=30.1° and 2θ=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°.

[0108] Comparative Example 3: P4S subjected to pretreatment 10 Materials used: Li 5.5 PS 4.5 Cl 1.5 Synthesis of solid electrolyte materials

[0109] First, P4S 10 The material is treated in a closed vessel at 300°C for 20 hours, and 10.4309g of treated P4S is obtained. 10The material was combined with 8.6073 g of LiS and 5.9618 g of LiCl and loaded into a 250 ml zirconia planetary mill jar containing 400 g of zirconia media. 92 g of heptane was added, the jar was sealed, and the mixture was milled at 500 rpm for 3 hours. The material obtained from this milling process was recovered by removing the heptane under vacuum at 90°C. Finally, the dried material was subjected to heat treatment at 450°C for 30 minutes.

[0110] From the XRD pattern (FIG. 3), it can be seen that Comparative Example 3 contains Li 5.5 PS 4.5 Cl 1.5 It can be observed that the electrolyte phase is a complex containing impurity 1, impurity 2, and unreacted LiCl. 5.5 PS 4.5 Cl 1.5 has peaks at 2θ=30.1° and 2θ=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°.

[0111] X-ray diffraction patterns of the materials prepared in the above examples and comparative examples are shown in Figures 2 and 3. The X-ray diffraction patterns identify argyrodite phase (Arg) solid electrolyte material, LiCl, and two impurities.

[0112] Impurity #1 can be a material having the structural characteristics of P2S6 and / or P2S7. Considering that argyrodite-type materials contain only PS4 structural characteristics, the presence of P2S6 and / or P2S7 can be understood to be an indicator of sulfur deficiency. Thus, the present invention provides a process for correcting any sulfur deficiency, which results in a relatively high phase purity in the resulting electrolyte.

[0113] Impurity #2 can be Li4P2S6, a Li4P2S6 analog, or a material having the structural characteristics of P2S6 and / or P2S7. Considering that argyrodite-type materials contain only the structural characteristics of PS4, the presence of Li4P2S6 analog, P2S6 and / or P2S7 can be understood to be an indicator of sulfur deficiency. Thus, the present invention provides a process for correcting any sulfur deficiency, which results in relatively high phase purity in the resulting electrolyte.

[0114] The X-ray diffraction patterns of the materials synthesized in Examples 1-2 and Comparative Examples 1-2 are shown in Figure 2. The solid electrolyte material was identified as being in the argyrodite phase. Comparing Example 1 to Comparative Example 1, P4S 10 It can be seen that pre-treating the material with elemental sulfur before using it in the synthesis resulted in an electrolyte with relatively low levels of impurities. Furthermore, comparing Example 1 to Example 2, P4S x Correcting for variations in the phosphorus to sulfur ratio of the material may prove important in achieving improved purity.

[0115] Comparing Example 1 to Comparative Example 2, excess P4S 10 It can be seen that incorporating extra sulfur using does not result in an improvement in purity.

[0116] 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 are consistent with the P4S 10 Demonstrates the effect of pre-treating materials with elemental sulfur. 10 If the material is subjected to heat treatment without elemental sulfur, as in Comparative Example 3, P4S 10 The material is first pretreated with elemental sulfur and then P4S x There is no improvement in purity compared to producing materials.

[0117] Commercially available P4S 10 The material is P4S 10 , P4S 10-xand sulfur, where "x" can typically vary from 1 to 3. Without being bound by theory, P4S 10 In certain reactions or processes requiring P4S 10 Materials other than P4S 10-x In some cases, the availability of sulfur, such as elemental sulfur, may be poor, resulting in a sulfur deficiency in the reaction product or in the solid electrolyte prepared therefrom. Therefore, it is beneficial to ensure the full availability of sulfur by ensuring that the required amount of sulfur is present not in elemental form, but in a compound with other elements. Also, compounds such as P4S x or Li2S x It is also possible, and potentially beneficial, to provide an excess of sulfur by first producing, for example, a sulfur-containing catalyst such as methyl sulfide. The excess sulfur can serve to ensure that the necessary amount of sulfur is provided for the reaction while preventing the formation of undesirable oxygen-containing compounds that may form due to contamination of the reactant materials or accidental air entrainment during processing.

Claims

1. 1. A solid electrolyte material comprising one or more lithium sources, the lithium sources being represented by the formula P ４ S ｘ to form a solid electrolyte material, wherein 10<x≦40.

2. The solid electrolyte material has the following formula: Li （７－ｙ－ｚ） PS （６－ｙ－ｚ） 8 （ｙ） ﷷ （ｚ） where: X and W are independently selected from F, Cl, Br, and I; y and z each independently range from 0 to 2; and y+z ranges from 0 to 2; The solid electrolyte material according to claim 1 .

3. The solid electrolyte material is Li ３ P.S. ４ , Li ４ P ２ S ６ , Li ７ P ３ S １１ , Li ５．５ P.S. ４．５ Cl １．５ , Li ５．５ P.S. ４．５ ClBr ０ . ５ , Li ５ P.S. ４ Cl ２ , and Li ５ P.S. ４ 2. The solid electrolyte material of claim 1, wherein the cations are selected from ClBr.

4. The solid electrolyte material has the following formula: Li （７－ｙ－ｚ） P.S. （６－ｙ－ｚ） X （ｙ） W （ｚ） wherein: X and W are independently selected from F, Cl, Br, and I; y and z are each in the range of 0 to 2; and y+z is in the range of 0 to 2, and ３ P.S. ４ , Li ４ P ２ S ６ , and Li ７ P ３ S １１ The solid electrolyte material according to claim 1, comprising at least one solid electrolyte material selected from:

5. 2. The solid electrolyte material of claim 1, wherein the solid electrolyte material has an X-ray diffraction pattern with 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. 1. A process for synthesizing a solid electrolyte material, comprising: The lithium source or sources are each selected from the group consisting of: ４ S ｘ wherein 10<x≦40 to form a solid electrolyte material.

7. Further, a sulfur source is provided in the one or more lithium sources and a compound of formula P ４ S ｘ 7. The process of claim 6, comprising mixing with a compound having the formula:

8. The formula P ４ S ｘ 7. The process of claim 6, wherein the compound having the formula:

9. The sulfur source is P ４ S ３ , P ４ S ４ , P ４ S ５ , P ４ S ６ , P ４ S ７ , P ４ S ８ , P ４ S ９ , P ４ S １０ 7. The process of claim 6, wherein the phosphorus-sulfur material is selected from the group consisting of:

10. The one or more lithium sources are Li ２ S., Li. ２ CO ３ , lithium halides, lithium pseudohalides, Li ２ O, Li ３ P.O. ４ , LiBO ２ , Li ２ B ４ O ７ , Li ２ ZrO ３ , LiAlO ２ , Li ２ TiO ３ , LiNbO ３ , Li ２ SiO ３ or a mixture thereof.

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

12. The lithium pseudohalide is LiNO ３、 LiOH, Li ２ SO ３、 Li ３ N., Li. ２ NH, LiNH ２ , LiBF ４ , LiBH ４ 7. The process of claim 6, wherein the hydroxybenzoate is selected from the group consisting of:

13. The one or more lithium sources and P ４ S ｘ is heated to a temperature of about 150°C to about 600°C.

14. 1. A solid-state battery comprising a positive electrode layer, a negative electrode layer, and a separator layer, wherein the separator layer comprises one or more lithium sources, each of which is represented by a formula P ４ S ｘ wherein 10<x≦40.

15. The negative electrode layer comprises a negative electrode active material and one or more lithium sources, each of which is represented by the formula P ４ S ｘ and heating to form the solid electrolyte material, wherein 10<x≦40.

16. The positive electrode layer comprises a positive electrode active material and one or more lithium sources, the positive electrode active material and one or more lithium sources being represented by the formula P ４ S ｘ and heating to form the solid electrolyte material, wherein 10<x≦40.

17. The solid electrolyte material has the following formula: Li （７－ｙ－ｚ） PS （６－ｙ－ｚ） 8 （ｙ） ﷷ （ｚ） where: X and W are independently selected from F, Cl, Br, and I; y and z each independently range from 0 to 2; and y+z ranges from 0 to 2; The solid-state battery according to claim 14.

18. The solid electrolyte material is Li ３ P.S. ４ , Li ４ P ２ S ６ , Li ７ P ３ S １１ , Li ５．５ P.S. ４．５ Cl １．５ , Li ５．５ P.S. ４．５ ClBr ０．５ , Li ５ P.S. ４ Cl ２ , and Li ５ P.S. ４ 15. The solid-state battery of claim 14, wherein the Cr is selected from ClBr.

19. The solid electrolyte material has the following formula: Li （７－ｙ－ｚ） P.S. （６－ｙ－ｚ） X （ｙ） W （ｚ） wherein: 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 Li ３ P.S. ４ , Li ４ P ２ S ６ , and Li ７ P ３ S １１ 15. The solid-state battery according to claim 14, comprising at least one solid electrolyte material selected from:

20. 15. The solid-state battery of claim 14, wherein the solid electrolyte material has an X-ray diffraction pattern with 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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