Rapid synthesis of sulfide-based solid electrolyte

Abstract

Provided herein are methods for synthesizing a sulfide-based solid state electrolyte, including a sulfide-based solid state electrolyte having an argyrodite phase. The methods generally include mixing an electrolyte precursor in a blend of solvents, the blend of solvents including a catalytic solvent and a spectator solvent.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This Patent Cooperation Treaty (PCT) application is related to and claims priority from U.S. patent application No. 63 / 426,969, filed on November 21, 2022, entitled “Rapid Synthesis of a Sulfide-Based Solid Electrolyte,” the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0003] Various embodiments described herein relate to the field of primary and secondary electrochemical cells, solid-state electrolytes and electrolyte materials, and corresponding methods of making and using the same. Background Art

[0004] The production of solid-state electrolytes is a time-consuming process. Solid-state electrolytes containing an argyrodite phase have recently been identified as being of good quality for commercial use. As demand for such electrolytes increases, the need for efficient production of solid-state electrolytes, including those containing an argyrodite phase, has also increased. Summary of the Invention

[0005] Provided herein is a method for producing a sulfide-based solid electrolyte. The method generally comprises mixing an alkali metal sulfide or alkaline earth metal sulfide, a secondary sulfide, and optionally an alkali halide or pseudo-halide to produce a sulfide-based solid electrolyte, wherein the mixing occurs in a blend of solvents comprising a catalytic solvent and a bystander solvent; and crystallizing the sulfide-based solid electrolyte. In some embodiments, the method further comprises heating the sulfide-based solid electrolyte. In some aspects, the sulfide-based solid electrolyte is heated to a temperature of about 350°C to about 550°C. In some embodiments, the method further comprises grinding the mixture. In still other embodiments, the method further comprises drying the sulfide-based solid electrolyte under vacuum or at atmospheric pressure.

[0006] In some embodiments, the sulfide-based solid electrolyte comprises Li3PS4 (LPS). In some instances, the Li3PS4 is crystalline. In other instances, the Li3PS4 is amorphous. In some embodiments, the sulfide-based solid electrolyte comprises at least 60% crystalline phase. In some aspects, the crystalline phase is metastable. In some embodiments, the sulfide-based solid electrolyte comprises an argyrodite phase. In some embodiments, the phase purity of the sulfide-based solid electrolyte is at least 90% (wt%).

[0007] In some embodiments, the sulfide-based solid electrolyte comprises fewer impurities than a sulfide-based solid electrolyte prepared with a non-coordinating, non-reactive solvent. In some aspects, the ionic conductivity of the sulfide-based solid electrolyte is at least 25% greater than the ionic conductivity of the sulfide-based solid electrolyte prepared with a non-coordinating, non-reactive solvent.

[0008] In some embodiments, the method further comprises mixing the alkali halide. In some aspects, the alkali halide comprises LiX, wherein X is one or more of F, Cl, Br, and I. In some examples, the sulfide-based solid electrolyte comprises less than 1% LiCl.

[0009] In some embodiments, the method further comprises producing a phosphorothioate intermediate. In some aspects, the phosphorothioate intermediate comprises P2S6 4- and / or PS( 4-x )O x , wherein x is between 0 and 4. In some further aspects, the phosphorothioate intermediate comprises PS4 3- In still further aspects, the phosphorothioate intermediate comprises P2S7 4- . The term "intermediate" is used to emphasize the fact that in certain syntheses, this particular phase is not desired, especially in the final product, but can be observed to form during heat treatment of a mixture of solid electrolyte materials or precursors. In general, the composition and structure of the intermediate phase can provide information about the effectiveness of the method used to combine the precursor materials to form the desired product. For example, if the desired phase contains 4 elements, but the intermediate phase is observed to contain only 3 elements, then the subsequent addition of the fourth element to form the final product may be difficult and require one or more of further mixing, additional heat treatment time, or increased heat treatment temperature. However, if the desired phase contains 4 elements and the intermediate phase is observed to contain the same 4 elements, the intermediate phase indicates that the method for combining the precursor materials is effective and that the subsequent heat treatment time and / or temperature required to produce the desired product can be reduced and a product with a higher purity can be produced.

[0010] In some embodiments, the alkali metal sulfide comprises A2S, wherein A is one or more of Li and Na. In some examples, the sulfide-based solid electrolyte comprises less than 1% Li2S.

[0011] In some embodiments, the secondary sulfide comprises one or more of P2S5, SiS2, Sb2S3, GeS2, and SnS2.

[0012] In some embodiments, the catalytic solvent comprises no more than 0.1 wt % to 6 wt % of the blend of solvents. In some aspects, the catalytic solvent comprises no more than 0.3 wt % to 4.5 wt % of the blend of solvents. In some further aspects, the catalytic solvent comprises no more than 0.5 wt % to 1.5 wt % of the blend of solvents. In still further aspects, the catalytic solvent comprises no more than 0.6 wt % to 0.9 wt % of the blend of solvents.

[0013] In some embodiments, the catalytic solvent comprises one or more nitrile solvents. In some aspects, the one or more nitrile solvents can be selected from the group consisting of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and combinations thereof.

[0014] In some embodiments, the spectator solvent comprises 94.0 wt% to 99.9 wt% of the blend of solvents. In some aspects, the spectator solvent comprises 98.5 wt% to 99.9 wt% of the blend of solvents.

[0015] In some embodiments, the spectator solvent comprises a hydrocarbon-based solvent. In some aspects, the spectator solvent comprises an alkane, a blend of alkanes, xylene, toluene, benzene, decalin, 1,2,3,4-tetrahydronaphthalene, or a combination thereof.

[0016] It will be appreciated that there can be a variety of ways to consider the amount of catalytic solvent and bystander solvent. In many of the examples presented herein, the amount of solvent is discussed from the perspective of the weight % (wt%) of the catalytic solvent relative to the combined mass of the catalytic solvent and the bystander solvent. These amounts can also be described by volume %, mole % or wt% relative to the precursor material used. In particular, it may be desirable to consider the amount of catalytic solvent in terms of a mass ratio or molar ratio to one or more precursor materials. Using the Li3PS4 (LPS) system prepared by a combination of Li2S and P2S5 as an example, the ratio of catalytic solvent to Li2S precursor, the ratio of catalytic solvent to P2S5 precursor or the ratio of catalytic solvent to Li2S+P2S5 precursor can be considered. This ratio can be defined by mass, mole or volume.

[0017] When further considering the amounts of the catalytic solvent, the bystander solvent, and the precursor material, the amount of solvent relative to the amount of the precursor material can be considered. In this case, a "solids %" can be defined, which can be conveniently described as the weight ratio of the precursor material relative to the combined weight of the precursor material and the solvent. It will be appreciated that adjusting the solids % may require adjusting the ratio of the catalytic solvent to the bystander solvent so that the appropriate and desired ratio of each solvent to the precursor material can be maintained.

[0018] In an exemplary embodiment, the sulfide-based solid electrolyte comprises an argyrodite phase, the alkali metal sulfide comprises Li2S, the secondary sulfide comprises P2S5, and the alkali halide, when present, comprises LiX, and wherein X=F, Cl, Br, or I.

[0019] Further provided herein is a method for producing a sulfide-based solid electrolyte having an argyrodite phase. The method generally comprises mixing Li2S, P2S5, and LiX in a blend of solvents to produce a sulfide-based solid electrolyte having an argyrodite phase, the blend of solvents comprising a catalytic solvent and a spectator solvent, wherein X=F, Cl, Br, or I; and crystallizing the sulfide-based solid electrolyte, wherein in the presence of the catalytic solvent, the production of the sulfide-based solid electrolyte is at least twice as fast. In a preferred embodiment, the production of the sulfide-based solid electrolyte is 4 to 25 times faster in the presence of the catalytic solvent.

[0020] The present invention further provides a method for producing a sulfide-based solid electrolyte having an argyrodite phase. The method generally comprises mixing a sulfide solid electrolyte precursor in a blend of solvents to produce a sulfide-based solid electrolyte having an argyrodite phase, the sulfide solid electrolyte precursor comprising Li2S, P2S5 and LiX, the blend of solvents comprising a catalytic solvent and a spectator solvent, wherein X=F, Cl, Br or I; and crystallizing the sulfide-based solid electrolyte, wherein in the presence of the catalytic solvent, the mixing time of the sulfide-based solid electrolyte precursor is at least twice as fast. In a preferred embodiment, in the presence of the catalytic solvent, the mixing time of the sulfide-based solid electrolyte precursor is 4 to 25 times faster.

[0021] Further provided herein is a method for producing a sulfide-based solid electrolyte having an argyrodite phase. The method generally comprises mixing Li2S, P2S5, and LiX in a blend of solvents to produce a sulfide-based solid electrolyte having an argyrodite phase, the blend of solvents comprising a catalytic solvent and a spectator solvent, wherein X=F, Cl, Br, or I; and crystallizing the sulfide-based solid electrolyte, wherein the production of the sulfide-based solid electrolyte occurs in less than 20 hours. In some aspects, the production of the sulfide-based solid electrolyte occurs in less than 15 hours. In other aspects, the production of the sulfide-based solid electrolyte occurs in less than 10 hours. In still other aspects, the production of the sulfide-based solid electrolyte occurs in less than 8 hours. In still other aspects, the production of the sulfide-based solid electrolyte occurs in less than 6 hours. In still other aspects, the production of the sulfide-based solid electrolyte occurs in less than 5 hours.

[0022] In some embodiments, the sulfide-based solid electrolyte comprises an argyrodite phase. In some further embodiments, the sulfide-based solid electrolyte comprises at least 85% of a crystalline phase. In some aspects, the crystalline phase is metastable.

[0023] In some embodiments, the sulfide-based solid electrolyte has a purity of at least 90% (wt%). In some further embodiments, the sulfide-based solid electrolyte contains less than 1% LiCl. In further embodiments, the sulfide-based solid electrolyte contains less than 1% Li2S.

[0024] Further provided herein is a method for producing a sulfide-based solid electrolyte having an argyrodite phase. The method generally comprises mixing a sulfide-based solid electrolyte precursor comprising Li2S, P2S5, and LiX in a blend of solvents, the blend of solvents comprising a catalytic solvent and a spectator solvent, wherein X=F, Cl, Br, or I, to produce the sulfide-based solid electrolyte; and crystallizing the sulfide-based solid electrolyte, wherein the sulfide-based solid electrolyte precursor requires half (50%) or less of the mixing time required using only the spectator solvent in the presence of the catalytic solvent.

[0025] Further provided herein are methods for producing a sulfide-based solid electrolyte having an argyrodite phase. The methods generally comprise mixing Li2S, P2S5, and LiX in a blend of solvents comprising a catalytic solvent and a spectator solvent to produce a sulfide-based solid electrolyte having an argyrodite phase, wherein X=F, Cl, Br, or I; and crystallizing the sulfide-based solid electrolyte.

[0026] Further provided herein are compositions comprising Li3PS4 and a thiophosphate comprising one or more of PS4 and P2S7 and P2S6, and an argyrodite phase, wherein the composition comprises 0.01 wt% to 0.90 wt% of a nitrile selected from the group consisting of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and combinations thereof.

[0027] Further provided herein is a method for producing a sulfide-based solid electrolyte having an argyrodite phase. The method generally comprises mixing Li2S, P2S5, and LiX in a solvent blend to produce the sulfide-based solid electrolyte having an argyrodite phase, the solvent blend comprising a catalytic solvent and a spectator solvent, wherein X=F, Cl, Br, or I, and the ratio of the catalytic solvent to the spectator solvent is from 1:15 to 1:1000 by weight; and crystallizing the sulfide-based solid electrolyte.

[0028] Further provided herein is a method for producing a sulfide-based solid electrolyte having an argyrodite phase. The method generally comprises mixing Li2S, P2S5, and LiX to produce a sulfide-based solid electrolyte having an argyrodite phase, wherein the mixing occurs in a blend of solvents comprising a catalytic solvent and a spectator solvent, and X=F, Cl, Br, or I; and crystallizing the sulfide-based solid electrolyte by incorporating less than 0.5 wt% of the catalytic solvent into the sulfide-based solid electrolyte.

[0029] Further provided herein is a composition comprising a sulfide-based solid electrolyte having an argyrodite phase, the composition comprising less than 0.1 wt% of a nitrile selected from the group consisting of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and combinations thereof. In some embodiments, less than 0.05 wt% of the nitrile is incorporated into the sulfide-based solid electrolyte. In some further embodiments, less than 0.01 wt% of the nitrile is incorporated into the sulfide-based solid electrolyte. In still further embodiments, less than 0.001 wt% of the nitrile is incorporated into the sulfide-based solid electrolyte. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] This patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0031] The present disclosure can be understood by reference to the following detailed description in conjunction with the accompanying drawings which are briefly described below.It should be noted that for purposes of clarity of illustration, some elements in the drawings may not be drawn to scale.

[0032] Figure 1 X-ray diffraction (XRD) spectra of solid electrolyte materials synthesized using various methods of the present disclosure are shown.

[0033] Figure 2 XRD spectra of solid electrolyte materials synthesized using various methods of the present disclosure are shown. The solid electrolyte materials of batches 2 and 4 may include 2θ (2Theta) values ​​of 15.6±0.5, 18.1±0.5, 25.7±0.5, 30.2±0.5, 31.6±0.5, and 34.8±0.5, which may correspond to argyrodite phase values. Figure 1 The solid-state electrolyte material in may comprise at least three, at least four, or at least five 2θ (2Theta) values ​​selected from the group consisting of 15.6±0.5, 18.1±0.5, 25.7±0.5, 30.2±0.5, 31.6±0.5, and 34.8±0.5, and may correspond to argyrodite phase values.

[0034] Figure 3 XRD spectra of solid electrolyte materials synthesized using various methods of the present disclosure are shown.

[0035] Figure 4 XRD spectra of solid electrolyte materials synthesized using various methods of the present disclosure are shown.

[0036] Figure 5 Shown are XRD spectra of solid electrolyte materials synthesized using non-coordinating and non-reactive solvents.

[0037] Figure 6 The ionic conductivity of solid electrolyte materials synthesized using non-coordinating and non-reactive solvents is shown.

[0038] Figure 7 Shown are XRD spectra of solid electrolyte materials synthesized using a coordinating and reactive solvent including an ester.

[0039] Figure 8 The ionic conductivity of solid electrolyte materials synthesized using coordinating and reactive solvents including esters is shown.

[0040] Figure 9Shown are XRD spectra of solid electrolyte materials synthesized using coordinating and reactive solvents including nitrile.

[0041] Figure 10 The ionic conductivity of solid electrolyte materials synthesized using a coordinating and reactive solvent containing nitrile is shown.

[0042] Figure 11 Shown is an overlay of the ionic conductivities of solid electrolyte materials synthesized using a non-coordinating and non-reactive solvent, a coordinating and reactive solvent comprising an ester, and a coordinating and reactive solvent comprising a nitrile and heated for 3 hours.

[0043] Figure 12 Shown is an overlay of the ionic conductivities of solid electrolyte materials synthesized using a non-coordinating and non-reactive solvent, a coordinating and reactive solvent comprising an ester, and a coordinating and reactive solvent comprising a nitrile and heated for 12 hours.

[0044] Figure 13 Particle size distributions of solid electrolyte materials synthesized using a coordinating and reactive solvent comprising an ester and a coordinating and reactive solvent comprising a nitrile are shown after milling for 3 hours.

[0045] Figure 14 Shown are XRD spectra of solid-state electrolyte materials synthesized using a coordinating and reactive solvent including nitrile and heated during milling.

[0046] Figure 15 Photographs of materials synthesized using the methods of the present disclosure are shown.

[0047] Figure 16 Shown is a graph of the molar ratio of aliphatic compound (IBN) to aromatic solvent (BZN) versus conductivity for some examples of the present disclosure. DETAILED DESCRIPTION

[0048] In the following description, specific details are provided to provide a thorough understanding of the various embodiments of the present disclosure. After reading and understanding the specification, claims, and drawings herein, those skilled in the art will understand that some embodiments may be practiced without being bound by some of the specific details set forth herein. In addition, to avoid obscuring the present disclosure, some well-known methods, processes, devices, and systems used in the various embodiments described herein are not disclosed in detail.

[0049] Provided herein is a method for producing a sulfide-based solid electrolyte. Also provided herein is a method for producing a sulfide-based solid electrolyte having an argyrodite phase. The method comprises mixing (1) an alkali metal sulfide and / or an alkaline earth metal sulfide, (2) a secondary sulfide, and (3) a halide or pseudohalide to produce a sulfide-based solid electrolyte or an intimate mixture of sulfide-based solid electrolyte precursor materials, and then applying energy input to complete a reaction between the precursor materials and / or crystallize the sulfide-based solid electrolyte. Also provided herein is a method for producing a sulfide-based solid electrolyte, the method comprising: mixing an alkali metal sulfide or an alkaline earth metal sulfide, a secondary sulfide, and optionally an alkali halide or pseudohalide to produce a sulfide-based solid electrolyte, wherein the mixing occurs in a blend of solvents, the blend of solvents comprising a catalytic solvent and a bystander solvent; and crystallizing the sulfide-based solid electrolyte. The resulting sulfide-based solid electrolyte may be in the argyrodite phase.

[0050] As used herein, the term "catalytic" may be used to describe a material, such as a solvent, that coordinates or bonds to the surface of a precursor material or combination of precursor materials in a manner that alters the size, morphology, and / or surface area of ​​the solid. For example, a nitrile solvent may be added to a reactive solvent in various amounts to improve the properties of the resulting electrolyte.

[0051] The mixing step can be completed using a blend of solvents including a catalytic solvent and a bystander solvent. Generally, the purpose of the catalytic solvent can include coordinating with the reactants, decomposing the reactants and / or changing the form of the reactants so that the subsequent reaction between the reactants is carried out faster and more thoroughly with less energy input. In addition, the effect of the catalytic solvent can include mediating the combination of reactants or the reaction between the reactants, promoting the combination of reactants or the reaction between the reactants, or accelerating the combination of reactants or the reaction between the reactants. An example of this effect can be P2S5 combined with Li2S to form Li3PS4. In addition, the catalytic solvent can coordinate or bond with the surface of the precursor material or the combination of precursor materials in a manner that changes the size, form and / or surface area of ​​the solid. The catalytic solvent can also be described as a coordinating solvent and / or a reactive solvent. According to the description herein, the use of the term "catalysis" can be different from other fields because some embodiments herein relate to the direct participation of the catalytic solvent in a chemical reaction that may cause the catalytic solvent to undergo a chemical change.

[0052] Understandably, P2S5 and P4S 10 may be referred to interchangeably, and all ratios based on this material should be adjusted according to appropriate calculations.

[0053] The purpose of a spectator solvent can include suspending, dispersing, distributing, and / or interacting with the reactants in a manner that improves the outcome of the synthesis (e.g., yield) without directly promoting, participating in, or causing a reaction between the reactants. A spectator solvent can also be described as an inert solvent, a non-reactive solvent, a non-coordinating solvent, a processing aid, and / or a fluidizing solvent.

[0054] The methods described herein can produce sulfide-based solid electrolytes (e.g., having an argyrodite phase) more efficiently than prior art processes. Improved production efficiency can be achieved by reducing the mixing or grinding energy input of the precursor materials, reducing the temperature required to remove any solvent, reducing the time required to remove any solvent, reducing the reaction or crystallization temperature and / or reducing the reaction or crystallization time. In addition, the sulfide-based solid electrolyte can include Li3PS4, Li7P3S 11 、Li4P2S6、Li7PS6、Li 7-x PS 6-x H x and / or Li 15+x P4S 16+x H 3-x (where H = halogen or pseudohalogen). Li3PS4, Li7P3S 11 、Li4P2S6、Li7PS6、Li 7-x PS 6-x H x and / or Li 15+x P4S 16+x H 3-x (where H = halogen or pseudohalogen) can be crystalline, amorphous, or a composite of crystalline domains or nanocrystalline domains with amorphous domains. Materials considered amorphous typically exhibit no peaks in x-ray diffraction measurements before heat treatment.

[0055] The alkali metal sulfide and / or alkaline earth metal sulfide may comprise any alkali metal sulfide or alkaline earth metal sulfide known in the art. For example, the alkali metal sulfide and / or alkaline earth metal sulfide may comprise Li2S, Na2S, K2S, MgS, CaS, BaS, and combinations thereof. In a preferred embodiment, the alkali metal sulfide and / or alkali metal sulfide comprises Li2S and / or Na2S.

[0056] The secondary sulfide can comprise any sulfide known in the art. For example, the secondary sulfide can comprise P2S5, As2S5, As2S3, Sb2S5, Sb2S3, Al2S3, SiS2, GeS2, SnS2 or PbS2, or a combination thereof. The secondary sulfide can also or alternatively comprise a transition metal sulfide, such as CoS2, Co3S4, CrS, Cr2S3, Cr3S4, CuS, CuS2, Cu2S, FeS, FeS2, Fe3S4, MnS, MnS2, MoS2, NiS, NiS2, Ni3S2, ScS, Sc2S3, SnS2, TiS, TiS2, Ti2S3, VS, VS2, V2S3, VS4, Y2S3, ZnS, ZrS2, WS2, or other transition metal sulfides known in the art, and combinations thereof.

[0057] The halide may include an alkali halide, a secondary halide, a semi-metal halide, a pseudo halide, and combinations thereof. For example, the halide may include LiF, LiCl, LiBr, LiI, BCl3, BBr3, BI3, AlF3, AlBr3, AlI3, AlCl3, SiF4, SiCl4, SiCl3, Si2Cl6, SiBr4, SiBrCl3, SiBr2Cl2, SiI4, PF3, PF5, PCl3, PCl5, POCl3, PBr3, POBr3, PI3, P2Cl4, P2I4, ​​SF2, SF4, SF6, S2F 10 , SCl2, S2Cl2, S2Br2, GeF4, GeCl4, GeBr4, GeI4, GeF2, GeCl2, GeBr2, GeI2, AsF3, AsCl3, AsBr3, AsI3, AsF5, SeF4, SeF6, SeCl2, SeCl4, Se2Br2, SeBr4, SnF4, SnC l4, SnBr4, SnI4, SnF2, SnCl2, SnBr2, SnI2, SbF3, SbCl3, SbBr3, SbI3, SbF5, SbC l5, PbF4, PbCl4, PbF2, PbCl2, PbBr2, PbI2, BiF3, BiCl3, BiBr3, BiI3, TeF4, Te2F 10 , TeF6, TeCl2, TeCl4, TeBr2, TeBr4, TeI4, NaI, NaF, NaCl, NaBr and combinations thereof. In addition, the halide may include pseudo-halides LiBH4, LiBF4, LiNH2, LiNO3, LiSCN, LiOCN and combinations thereof. In a specific embodiment, the halide may include one or more alkali metal halides having the formula LiX, wherein Li is an alkali metal and X=F, Cl, Br or I.

[0058] The catalytic solvent may comprise one or more of a ketone, an ether, an ester, an aldehyde, an amine, a nitro and / or a nitrile solvent. In particular, the catalytic solvent may comprise one or more nitrogen-containing nitrile solvents and / or aromatic solvents. Without wishing to be bound by theory, the catalytic solvent may allow the reaction to be diverted to produce a thermodynamically stable high-temperature phase, such as argyrodite and Li4PS4I. Compared to sulfide-based solid electrolytes prepared in the presence of only non-coordinated, non-reactive solvents, sulfide-based solid electrolytes prepared with one or more nitrile solvents may contain fewer impurities and may have higher ionic conductivity.

[0059] Surprisingly, it was found that the ionic conductivity of the solid electrolyte based on sulfide can be increased even when mixed and alloyed before introducing one or more nitrile solvents. In certain embodiments, the one or more nitrile solvents can include an alkyl solvent substituted by one or more nitrile groups. The alkyl solvent substituted by one or more nitrile groups can be acyclic. The alkyl solvent substituted by one or more nitrile groups can be linear or branched. The chain length of the alkyl solvent substituted by one or more nitrile groups can be 1 to 30 carbons, such as 1 to 20 carbons, 1 to 15 carbons, 1 to 10 carbons, 1 to 8 carbons or 1 to 6 carbons. In certain embodiments, the chain length of the alkyl solvent substituted by one or more nitrile groups can be 2 or more carbons, 3 or more carbons, 4 or more carbons, 5 or more carbons, 6 or more carbons, 7 or more carbons, 8 or more carbons etc. In certain embodiments, the alkyl solvent substituted by one or more nitrile groups can include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, decanenitrile, pivalonitrile, valeronitrile or a combination thereof.

[0060] In certain embodiments, one or more nitrile solvents can comprise the aryl solvents substituted by one or more nitrile groups.The aryl solvents substituted by one or more nitrile groups can comprise three or more carbon, four or more carbon, five or more carbon, six or more carbon, seven or more carbon, eight or more carbon, nine or more carbon, ten or more carbon etc.In certain embodiments, the aryl solvents substituted by one or more nitrile groups can comprise 3 to 12 carbon, as 3 to 10 carbon, 3 to 8 carbon, 4 to 6 carbon or 5 to 7 carbon.In certain embodiments, the aryl solvents substituted by one or more nitrile groups can comprise benzonitrile.

[0061] In certain embodiments, one or more nitrile solvents can comprise acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, decane nitrile, pivalonitrile, valeronitrile or other nitrile solvents known in the art and combinations thereof. In a specific embodiment, one or more nitrile solvents can be selected from the group consisting of: acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and combinations thereof.

[0062] In some embodiments, the alkyl solvent substituted with one or more nitrile groups and the aryl solvent substituted with one or more nitrile groups can be present in a volume ratio of about 5: 1 to about 10: 1. For example, the alkyl solvent substituted with one or more nitrile groups and the aryl solvent substituted with one or more nitrile groups can be present in a volume ratio of about 5: 1 to about 6: 1, about 5: 1 to about 7: 1, about 5: 1 to about 8: 1, about 5: 1 to about 9: 1, about 5: 1 to about 10: 1, about 6: 1 to about 10: 1, about 7: 1 to about 10: 1, about 8: 1 to about 10: 1, or about 9: 1 to about 10: 1.

[0063] In some embodiments, the alkyl solvent substituted with one or more nitrile groups and the aryl solvent substituted with one or more nitrile groups may be present in a mass ratio of about 4: 1 to about 8: 1. For example, the alkyl solvent substituted with one or more nitrile groups and the aryl solvent substituted with one or more nitrile groups may be present in a mass ratio of about 4: 1 to about 5: 1, about 4: 1 to about 6: 1, about 4: 1 to about 7: 1, about 4: 1 to about 8: 1, about 5: 1 to about 8: 1, about 6: 1 to about 8: 1, or about 7: 1 to about 8: 1.

[0064] In some embodiments, the alkyl solvent substituted with one or more nitrile groups and the aryl solvent substituted with one or more nitrile groups can be present in a molar ratio of about 2: 1 to about 22: 1. For example, the alkyl solvent substituted with one or more nitrile groups and the aryl solvent substituted with one or more nitrile groups can be present in a molar ratio of about 2: 1 to about 4: 1, about 4: 1 to about 8: 1, about 8: 1 to about 12: 1, about 7: 1 to about 15: 1, about 6: 1 to about 18: 1, about 6: 1 to about 22: 1, about 7: 1 to about 12: 1, about 8: 1 to about 12: 1, about 9: 1 to about 12: 1, about 10: 1 to about 12: 1, or about 11: 1 to about 12: 1.

[0065] In some embodiments, the aryl solvent substituted with one or more nitrile groups and the secondary sulfide can be present in a molar ratio of about 0.5: 1 to about 1.5: 1. For example, the aryl solvent substituted with one or more nitrile groups and the secondary sulfide can be present in a molar ratio of 0.5: 1 to about 0.75: 1, about 0.5: 1 to about 1: 1, about 0.5: 1 to about 1.25: 1, about 0.5: 1 to about 1.5: 1, about 0.75: 1 to about 1.5: 1, about 1: 1 to about 1.5: 1, or about 1.25: 1 to about 1.5: 1.

[0066] In some embodiments, the aryl solvent substituted with one or more nitrile groups and the secondary sulfide can be present in a molar ratio of about 0.1: 1 to about 3: 1. For example, the aryl solvent substituted with one or more nitrile groups and the secondary sulfide can be present in a molar ratio of about 0.1: 1 to about 0.25: 1, about 0.25: 1 to about 1: 1, about 0.7: 1 to about 2.5: 1, about 0.5: 1 to about 3: 1, about 0.75: 1 to about 1.5: 1, about 1: 1 to about 1.5: 1, or about 1.25: 1 to about 1.5: 1.

[0067] Specifically, the sulfide-based solid-state electrolyte prepared according to the methods described herein (e.g., with a nitrile solvent) can have a purity of at least about 90 weight percent (wt%), a purity of at least about 91 wt%, a purity of at least about 92 wt%, a purity of at least about 93 wt%, a purity of at least about 94 wt%, a purity of at least about 95 wt%, a purity of at least about 96 wt%, a purity of at least about 97 wt%, a purity of at least about 98 wt%, a purity of at least about 99 wt%, a purity of at least about 99.3 wt%, a purity of at least about 99.5 wt%, a purity of at least about 99.7%, or a purity of at least about 99.9%, as determined by x-ray diffraction (XRD). Sulfide-based solid electrolytes prepared according to the methods described herein (e.g., with a catalytic solvent) can have less than about 10 weight percent (wt%), less than about 9 wt%, less than about 8 wt%, less than about 7 wt%, less than about 6 wt%, less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, less than about 1 wt%, less than about 0.5 wt%, less than about 0.3 wt%, or less than about 0.1 wt% LiCl and / or LiS, as determined by XRD.

[0068] Without being bound by theory, the ionic conductivity of the sulfide-based solid electrolyte prepared according to the methods described herein (e.g., with a catalytic solvent) can be at least about 1.50E-03 S / cm to about 1.75E-03 S / cm, about 1.75E-03 S / cm to about 2.00E-03, about 2.00E-03 S / cm to 2.25E-03, about 2.25E-03 S / cm to about 2.50E-03, about 2.50E-03 S / cm to about 2.75E-03, about 2.75E-03 S / cm to about 3.00E-03 S / cm, about 3.00E-03 S / cm to about 3.25E-03 S / cm, about 3. S / cm to about 3.25E-03S / cm, about 3.50E-03S / cm to about 3.75E-03S / cm, about 3.75E-03S / cm to about 4.00E-03S / cm, about 4.00E-03S / cm to about 4.25E-03S / cm, about 4.25E-03S / cm to about 4.50E-03S / cm, about 4.50E-03S / cm to about 4.75E-03S / cm, about 4.75E-03S / cm to about 5.00E-03S / cm, about 5.00E-03S / cm to about 5.25E-03S / cm or about 5.25E-03S / cm or more. The sulfide-based solid-state electrolyte prepared according to the methods described herein (e.g., with a catalytic solvent) may have an ionic conductivity of at least about 1.00E-03S / cm to about 9.00E-03S / cm, 1.00E-03S / cm to about 7.00E-03S / cm, about 1.00E-03S / cm to about 6.00E-03S / cm, 1.50E-03S / cm to about 5.00E-03S / cm, about 1.50E-03S / cm to about 4.50E-03S / cm, about 1.50E-03S / cm to about 4.00E-03S / cm, about 1.50E-03S / cm to about 3.00E-03S / cm, or about 1.50E-03S / cm to about 2.50E-03S / cm.In alternative embodiments, the sulfide-based solid electrolyte prepared according to the methods described herein (e.g., with a catalytic solvent) may also have an ionic conductivity of at least about 1.00E-04S / cm to about 9.00E-03S / cm, 1.00E-04S / cm to about 7.00E-03S / cm, about 1.00E-04S / cm to about 6.00E-03S / cm, 1.50E-04S / cm to about 5.00E-03S / cm, about 1.50E-04S / cm to about 4.50E-03S / cm, about 1.50E-04S / cm to about 4.00E-03S / cm, about 1.50E-04S / cm to about 3.00E-03S / cm, or about 1.50E-04S / cm to about 2.50E-03S / cm. In yet another embodiment, the sulfide-based solid electrolyte prepared according to the methods described herein (e.g., with a catalytic solvent) may have an ionic conductivity of at least about 1.25 mS / cm to about 6.25 mS / cm, about 1.25 mS / cm to about 5.50 mS / cm, about 1.25 mS / cm to about 4.75 mS / cm, about 1.25 mS / cm to about 3.50 mS / cm, about 1.25 mS / cm to about 2.75 mS / cm, or about 1.25 mS / cm to about 3.50 mS / cm. mS / cm, about 1.25 mS / cm to about 1.75 mS / cm, about 2.00 mS / cm to about 2.75 mS / cm, 2.75 mS / cm to about 3.50 mS / cm, about 3.50 mS / cm to about 4.25 mS / cm, about 4.25 mS / cm to about 4.75 mS / cm, about 4.75 mS / cm to about 5.50 mS / cm, or about 5.50 mS / cm to about 6.25 mS / cm.

[0069] In some embodiments (see e.g. Figure 6), the solid electrolyte material synthesized using the method of the present disclosure may comprise an ionic conductivity of 1.77E-03S / cm to 2.65E-03S / cm, 2.65E-03S / cm to 2.48E-03S / cm, or 2.48E-03S / cm to 2.53E-03S / cm at 3 hours and 500 rpm, and may exhibit a range of conductivity values ​​after 3 hours of milling and heat treatment. The solid electrolyte material of the present disclosure may also comprise an ionic conductivity of 2.76E-03S / cm to 4.05E-03S / cm at 12 hours and 500 rpm, and may exhibit a range of conductivity values ​​after 12 hours of milling and heat treatment. In addition, the solid electrolyte material of the present disclosure may have an ionic conductivity of 3.98E-03S / cm to 4.05E-03S / cm, 4.05E-03S / cm to 3.20E-03S / cm, or 3.20E-03S / cm to 2.76E-03S / cm at 12 hours and 500 rpm. The heat treatment temperature may be 350°C to 400°C, 400°C to 450°C, or 450°C to 500°C (e.g., 350°C to 500°C or 350°C to 450°C).

[0070] In some embodiments (see e.g. Figure 8 ), Figure 8 The solid electrolyte material in the present disclosure may comprise an ionic conductivity of 2.65E-04S / cm to 6.00E-04S / cm, 6.00E-04S / cm to 3.26E-03S / cm, or 3.26E-03S / cm to 3.27E-03S / cm at 3 hours and 500 rpm. The solid electrolyte material of the present disclosure may also comprise an ionic conductivity of 2.65E-04S / cm to 3.27E-03S / cm at 500 rpm at 3 hours. The solid electrolyte material of the present disclosure may also comprise an ionic conductivity of 1.83E-03S / cm to 2.98E-03S / cm at 500 rpm at 12 hours. In addition, the solid electrolyte material of the present disclosure may have an ionic conductivity of 1.83E-03S / cm to 2.57E-03S / cm, 2.57E-03S / cm to 2.82E-03S / cm, or 2.82E-03S / cm to 2.98E-03S / cm at 12 hours and 500 rpm. The heat treatment temperature may be 350° C. to 400° C., 400° C. to 450° C., or 450° C. to 500° C. (e.g., or 350° C. to 500° C.).

[0071] In some embodiments (see e.g. Figure 10), the solid electrolyte material of the present disclosure may comprise an ionic conductivity of 4.91E-04S / cm to 9.81E-04S / cm, 9.81E-04S / cm to 4.40E-03S / cm, or 4.40E-03S / cm to 4.49E-03S / cm at 3 hours and 500 rpm. The solid electrolyte material of the present disclosure may also comprise an ionic conductivity of 4.91E-04S / cm to 4.49E-03S / cm at 500 rpm at 3 hours. The solid electrolyte material of the present disclosure may also comprise an ionic conductivity of 3.83E-03S / cm to 3.98E-03S / cm at 500 rpm at 12 hours. In addition, the solid electrolyte material of the present disclosure may have an ionic conductivity of 3.83E-03S / cm to 3.98E-03S / cm, 3.98E-03S / cm to 3.93E-03S / cm, or 3.93E-03S / cm to 3.92E-03S / cm at 12 hours and 500 rpm. The heat treatment temperature may be 350° C. to 400° C., 400° C. to 450° C., or 450° C. to 500° C. (e.g., or 350° C. to 500° C.).

[0072] In some embodiments (see e.g. Figure 11), the solid electrolyte material of the present disclosure may comprise an ionic conductivity of 1.77E-03S / cm to 2.65E-03S / cm, 2.65E-03S / cm to 2.48E-03S / cm, or 2.48E-03S / cm to 2.53E-03S / cm when the material is synthesized using a non-coordinating and non-reactive solvent. The solid electrolyte material of the present disclosure may also comprise an ionic conductivity of 1.77E-03S / cm to 2.65E-03S / cm when the material is synthesized using a non-coordinating and non-reactive solvent. The solid electrolyte material of the present disclosure may also include an ionic conductivity of 4.91E-04S / cm to 9.81E-04S / cm, 9.81E-04S / cm to 4.40E-03S / cm, or 4.40E-03S / cm to 4.49E-03S / cm when the material is synthesized using a coordination and reactive solvent comprising an ester. The solid electrolyte material of the present disclosure may also include an ionic conductivity of 4.91E-04S / cm to 4.49E-03S / cm when the material is synthesized using a coordination and reactive solvent comprising an ester. The solid electrolyte material of the present disclosure may also include an ionic conductivity of 2.65E-04S / cm to 3.26E-03S / cm or 3.26E-03S / cm to 3.27E-03S / cm when the material is synthesized using a coordination and reactive solvent comprising a nitrile. The solid electrolyte material of the present disclosure may also include an ionic conductivity of 2.65E-04S / cm to 3.27E-03S / cm when synthesizing the material using a coordinated and reactive solvent comprising nitrile. The heat treatment temperature may be 350°C to 400°C, 400°C to 450°C, or 450 to 500°C (e.g., or 350°C to 500°C).

[0073] In some embodiments (see e.g. Figure 12), the solid electrolyte material of the present disclosure may comprise an ionic conductivity of 3.98E-03S / cm to 4.05E-03S / cm, 4.05E-03S / cm to 3.20E-03S / cm, or 3.20E-03S / cm to 2.76E-03S / cm when the material is synthesized using a non-coordinating and non-reactive solvent. The solid electrolyte material of the present disclosure may also comprise an ionic conductivity of 2.76E-03S / cm to 4.05E-03S / cm when the material is synthesized using a non-coordinating and non-reactive solvent. The solid electrolyte material of the present disclosure may include an ionic conductivity of 1.83E-03S / cm to 2.57E-03S / cm, 2.57E-03S / cm to 2.82E-03S / cm, or 2.82E-03S / cm to 2.98E-03S / cm when the material is synthesized using a coordination and reactive solvent comprising an ester. The solid electrolyte material of the present disclosure may also include an ionic conductivity of 1.83E-04S / cm to 2.98E-03S / cm when the material is synthesized using a coordination and reactive solvent comprising an ester. The solid electrolyte material of the present disclosure may also include an ionic conductivity of 2.65E-04S / cm to 3.26E-03S / cm or 3.26E-03S / cm to 3.27E-03S / cm when the material is synthesized using a coordination and reactive solvent comprising a nitrile. The solid electrolyte material of the present disclosure may also include an ionic conductivity of 2.65E-04S / cm to 3.27E-03S / cm when synthesizing the material using a coordinated and reactive solvent comprising nitrile. The heat treatment temperature may be 350°C to 400°C, 400°C to 450°C, or 450 to 500°C (e.g., or 350°C to 500°C).

[0074] The specific surface area of ​​the solid electrolyte material based on the sulfide solid electrolyte prepared according to the method described herein is about 0.50 m 2 / g to about 9.00m 2 / g, about 1.50m 2 / g to about 7.00m 2 / g, about 1.50m 2 / g to about 5.50m 2 / g, about 1.75m 2 / g to about 6.00m 2 / g, about 2.50m 2 / g to about 5.00m 2 / g or about 2.50m 2 / g to about 4.5m 2 For example, the specific surface area of ​​the solid electrolyte material based on the sulfide solid electrolyte prepared according to the method described herein is about 1.50 m 2 / g to about 2.00m2 / g, about 2.00m 2 / g to about 2.50m 2 / g, about 2.50m 2 / g to about 3.00m 2 / g, about 3.00m 2 / g to about 3.50m 2 / g, about 3.50m 2 / g to about 4.00m 2 / g, about 4.00m 2 / g to about 4.50m 2 / g, about 4.50m 2 / g to about 5.00m 2 / g, about 5.00m 2 / g to about 5.50m 2 / g or about 5.50m 2 / g to about 6.00m 2 / g.

[0075] In some embodiments, the solid electrolyte material of the present disclosure may have a specific surface area of ​​1-5 m2 before heat treatment when synthesized using a non-coordinating and non-reactive solvent. 2 / g, and the specific surface area after heat treatment can be about 20-40% lower. The solid electrolyte material disclosed herein can have a specific surface area of ​​10-75m2 before heat treatment when the material is synthesized using a coordinated and reactive solvent. 2 / g, and can have a specific surface area that is about 70-95% lower after heat treatment.

[0076] The catalytic solvent can be present in the blend of solvents in an amount from about 0.1 wt% to about 6.0 wt%, from about 0.1 wt% to about 5.0 wt%, from about 0.1 wt% to about 4.5 wt%, from about 0.1 wt% to about 4.0 wt%, from about 0.1 wt% to about 3.0 wt%, from about 0.1 wt% to about 2.0 wt%, from about 0.1 wt% to about 1.5 wt%, from about 0.2 wt% to about 1.4 wt%, from about 0.3 wt% to about 1.3 wt%, from about 0.4 wt% to about 1.2 wt%, from about 0.5 wt% to about 1.1 wt%, from about 0.6 wt% to about 1.0 wt%, or from about 0.7 wt% to about 0.9 wt%. For example, the catalytic solvent may be present in an amount of about 0.1 wt % to about 0.2 wt %, about 0.1 wt % to about 0.3 wt %, about 0.1 wt % to about 0.4 wt %, about 0.1 wt % to about 0.5 wt %, about 0.1 wt % to about 0.6 wt %, about 0.1 wt % to about 0.7 wt %, about 0.1 wt % to about 0.8 wt %, about 0.1 wt % to about 0.9 wt %, about 0.1 wt % to about 1.0 wt %, about 0.1 wt % to about 1.1 wt %, about 0.1 wt % to about 1.2 wt %, about 0.1 wt % to about 1.3 wt %, about 0.1 wt % to about 1.4 wt %, about 0.1 wt % to about 1.5 wt %, about 0.2 wt % to about 1.5 wt %, about % to about 1.5 wt%, about 0.4 wt% to about 1.5 wt%, about 0.5 wt% to about 1.5 wt%, about 0.6 wt% to about 1.5 wt%, about 0.7 wt% to about 1.5 wt%, about 0.8 wt% to about 1.5 wt%, about 0.9 wt% to about 1.5 wt%, about 1.0 wt% to about 1.5 wt%, about 1.1 wt% to about 1.5 wt%, about 1.2 wt% to about 1.5 wt%, about 1.3 wt% to about 1.5 wt%, about 1.4 wt% to about 1.5 wt%, about 0.3 wt% to about 1.2 wt%, about 0.5 wt% to about 1.0 wt%, or about 0.6 wt% to about 0.9 wt% is present in the blend of solvents.

[0077] The spectator solvent may comprise a hydrocarbon solvent. The hydrocarbon solvent may comprise an alkane, a blend of alkanes, xylene (including p-xylene, m-xylene and o-xylene), toluene, benzene, heptane, octane, decalin, 1,2,3,4-tetralin or a combination thereof. Useful spectator solvents may comprise alkanes, olefins, alkynes and combinations thereof, including but not limited to alkanes, olefins, alkynes and combinations thereof having a linear structure, a branched structure or a cyclic structure and a boiling point between 30°C and 250°C. The alkane may have 4 to 20 carbon atoms.

[0078] The spectator solvent can be present in the blend of solvents in an amount from about 94.0 wt% to about 99.9 wt%, from about 95.0 wt% to about 99.9 wt%, from about 96.0 wt% to about 99.9 wt%, from about 97.0 wt% to about 99.9 wt%, from about 98.0 wt% to about 99.9 wt%, or from about 98.5 wt% to about 99.9 wt%. For example, the bystander solvent can be present at about 98.5 wt % to about 98.6 wt %, about 98.5 wt % to about 98.7 wt %, about 98.5 wt % to about 98.8 wt %, about 98.5 wt % to about 98.9 wt %, about 98.5 wt % to about 99.0 wt %, about 98.5 wt % to about 99.1 wt %, about 98.5 wt % to about 99.2 wt %, about 98.5 wt % to about 99.3 wt %, about 98.5 wt % to about 99.4 wt %, about 98.5 wt % to about 99.5 wt %, about 98.5 wt % to about 99.6 wt %, about 98.5 wt % to about 99.7 wt %, about 98.5 wt % to about 99.8 wt %, about 98.5 wt % to about 99.9 wt %, about 98.6 wt % to about 99.9 wt %, % to 99.9 wt%, about 98.7 wt% to about 99.9 wt%, about 98.8 wt% to about 99.9 wt%, about 98.9 wt% to about 99.9 wt%, about 99.0 wt% to about 99.9 wt%, about 99.1 wt% to about 99.9 wt%, about 99.2 wt% to about 99.9 wt%, about 99.3 wt% to about 99.9 wt%, about 99.4 wt% to about 99.9 wt%, about 99.5 wt% to about 99.9 wt%, about 99.6 wt% to about 99.9 wt%, about 99.7 wt% to about 99.9 wt%, about 99.8 wt% to about 99.9 wt%, about 98.8 wt% to about 99.7 wt%, about 99.0 wt% to about 99.5 wt%, or about 99.1 wt% to about 99.4 wt% is present in the blend of solvents.

[0079] The ratio of the catalytic solvent to the bystander solvent in the blend of solvents can be from about 1:10 to about 1:1000 by weight, from about 1:11 to about 1:1000 by weight, from about 1:12 to about 1:1000 by weight, from about 1:13 to about 1:1000 by weight, from about 1:14 to about 1:1000 by weight, from about 1:15 to about 1:1000 by weight, or from about 1:16 to about 1:1000 by weight. For example, the ratio of the catalytic solvent to the bystander solvent in the blend of solvents can be from about 1:10 to about 1:100, from about 1:15 to about 1:100, from about 1:50 to about 1:100, from about 1:50 to about 1:250, from about 1:50 to about 1:500, from about 1:50 to about 1:750, from about 1:50 to about 1:1000, from about 1:100 to about 1:2 ...50 to about 1:250, from about 1:50 to about 1:1000, from about 1:50 to about 1:250, from about 1:50 to about 1:1000, from about 1:50 to about 1:250, from about 1:50 to about 1:250, from about 1:50 to about 1:500, from about 1:50 to about 1:500, from about 1:50 to about 1:750, from about 1:50 to about 1:1000, from about 1:100 to about 1:250, from about 1:50 to about 1:250, from about 1:50 to about 1:250 From about 1:100 to about 1:500, from about 1:100 to about 1:750, from about 1:100 to about 1:1000, from about 1:250 to about 1:500, from about 1:250 to about 1:500, from about 1:250 to about 1:750, from about 1:250 to about 1:1000, from about 1:500 to about 1:750, from about 1:500 to about 1:1000, or from about 1:750 to about 1:1000.

[0080] The sulfide-based solid electrolyte may contain less than about 0.5 wt % of a catalytic solvent; that is, less than about 0.5 wt % of a catalytic solvent is incorporated into the sulfide-based solid electrolyte. As further described herein, the sulfide-based solid electrolyte may be dried to remove the catalytic solvent from the sulfide-based solid electrolyte. The sulfide-based solid electrolyte may contain less than about 0.5 wt %, less than about 0.4 wt %, less than about 0.3 wt %, less than about 0.2 wt %, less than about 0.1 wt %, less than about 0.05 wt % or less than about 0.01 wt % of a catalytic solvent. For example, the sulfide-based solid electrolyte may contain about 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.09 wt%, 0.08 wt%, 0.07 wt%, 0.06 wt%, 0.05 wt%, 0.04 wt%, 0.03 wt%, 0.02 wt%, 0.01 wt%, or less than about 0.01 wt% of a catalytic solvent.

[0081] In some embodiments (see e.g. Figure 13 ), the particle size of the solid electrolyte material of the present disclosure when synthesized using a coordination and reactive solvent including an ester can be in the range of about 0.2 μm to about 600 μm, wherein D 10 0.46μm, D 50 is 1.4 μm, and D 90The particle size of the solid electrolyte material disclosed herein when synthesized using a coordination and reactive solvent comprising nitrile can be in the range of about 0.2 μm to about 700 μm, wherein D 10 is 0.58 μm (for example, D 10 is about 0.55 μm to about 0.65 μm), D 50 2.8 μm (for example, D 50 is about 1.0 μm to about 5.0 μm), and D 90 is 24.2 μm (for example, D 90 is about 15 μm to about 35 μm).

[0082] The method may further comprise generating a phosphorothioate intermediate formed as a result of the interaction between the precursor and the catalytic solvent. The phosphorothioate intermediate may comprise PS4 -3 、P2S7 -4 and / or P2S6 4- In general, it was observed that the intermediate phase formed before the target phase formed. The formation of the intermediate phase containing the same general chemistry as the target phase indicates that the process described herein produces synthesis conditions that promote the complete reaction of all precursors to produce a sulfide-based solid-state electrolyte with high purity while reducing the time and energy requirements of the synthesis process.

[0083] The method may further include heating the sulfide-based solid electrolyte. The heating may occur after the synthesis solvent is removed. The sulfide-based solid electrolyte may be heated to a temperature of about 350°C to about 550°C. For example, the sulfide-based solid electrolyte may be heated to a temperature of about 350°C to about 375°C, about 350°C to about 400°C, about 350°C to about 425°C, about 350°C to about 450°C, about 350°C to about 475°C, about 350°C to about 500°C, about 350°C to about 525°C, about 350°C to about 550°C, about 375°C to about 550°C, about 400°C to about 550°C, about 425°C to about 550°C, about 450°C to about 550°C, about 475°C to about 550°C, about 500°C to about 550°C, about 525°C to about 550°C, or about 400°C to about 500°C. In other examples, the sulfide-based solid electrolyte may be heated to a temperature of about 350°C, about 375°C, about 400°C, about 425°C, about 450°C, about 475°C, about 500°C, about 525°C, or about 550°C.

[0084] The method may include heating during synthesis and may include heating and / or drying to crystallize after synthesis. The method may further include heating the sulfide-based solid electrolyte multiple times. Heating the sulfide-based solid electrolyte material multiple times can produce greater ionic conductivity compared to heating the sulfide-based solid electrolyte material only once. During the first heat treatment and / or the subsequent heat treatment, the sulfide-based solid electrolyte can be heated to a temperature of about 350°C to about 550°C. For example, the sulfide-based solid-state electrolyte can be heated to a temperature of about 350°C to about 375°C, about 350°C to about 400°C, about 350°C to about 425°C, about 350°C to about 450°C, about 350°C to about 475°C, about 350°C to about 500°C, about 350°C to about 525°C, about 350°C to about 550°C, about 375°C to about 550°C, about 400°C to about 550°C, about 425°C to about 550°C, about 450°C to about 550°C, about 475°C to about 550°C, about 500°C to about 550°C, about 525°C to about 550°C, or about 400°C to about 500°C. As another example, the sulfide-based solid-state electrolyte may be heated to a temperature of about 350°C, about 375°C, about 400°C, about 425°C, about 450°C, about 475°C, about 500°C, about 525°C, or about 550°C.

[0085] Method can further comprise grinding mixture.Grinding can occur before the solid electrolyte crystallization based on sulfide.Grinding can use grinding equipment known in the art to complete.For example, grinding can use autogenous mill, ball mill, buhrstone mill (buhrstone mill), gravel mill, rod mill, semi-autogenous mill, tower mill, vertical shaft impact mill or other grinding equipment known in the art to complete.Preferably, grinding uses planetary ball mill to use zirconium oxide grinding media to complete.Shorter grinding time is preferred, because surprisingly found that shorter overall grinding time can produce solid electrolyte material with higher ionic conductivity.Shorter grinding time can also produce each particle to have larger surface area and / or precursor particles or the solid electrolyte material particles therein between the surface area contact increased solid electrolyte material.

[0086] The method may further comprise drying the sulfide-based solid electrolyte under vacuum or at atmospheric pressure. Drying may be performed in an inert atmosphere, such as nitrogen, helium, argon, etc. Drying may be performed to remove any residual catalytic solvent and / or bystander solvent from the sulfide-based solid electrolyte.

[0087] In the presence of a catalytic solvent, the method can make the production of a sulfide-based solid electrolyte at least twice as fast. The sulfide-based solid electrolyte produced can include an argyrodite phase. The increase in production speed can be compared to the production of a sulfide-based solid electrolyte without a catalytic solvent, or compared to the production of a sulfide-based solid electrolyte using too little catalytic solvent, or compared to the production of a sulfide-based solid electrolyte using too much catalytic solvent. The catalytic solvent can be as low as 0.01 volume % or as high as 50 volume %. When there is too little catalytic solvent, the efficiency of the synthesis is not improved, and the purity and conductivity of the final product are not improved compared to not using a catalytic solvent. Alternatively, when there is too much catalytic solvent, the slurry of the reactants can exhibit rheological properties, and the purity or conductivity of the product produced is not improved compared to the synthesis without a catalytic solvent, and the rheological properties can reduce the efficiency of the synthesis. The limit is defined as the preferred range of the catalytic solvent described herein. In the presence of a catalytic solvent, the production of a sulfide-based solid electrolyte can be as fast as 25 times or more. In preferred embodiments, the production of the sulfide-based solid electrolyte is 4 to 25 times faster in the presence of a catalytic solvent, or more preferably, 8 to 25 times faster, 12 to 25 times faster, 16 to 25 times faster, or 20 to 25 times faster in the presence of a catalytic solvent. For example, the production of the sulfide-based solid electrolyte can be 4 times faster, 5 times faster, 6 times faster, 7 times faster, 8 times faster, 9 times faster, 10 times faster, 11 times faster, 12 times faster, 13 times faster, 14 times faster, 15 times faster, 16 times faster, 17 times faster, 18 times faster, 19 times faster, 20 times faster, 21 times faster, 22 times faster, 23 times faster, 24 times faster, 25 times faster, or more than 25 times faster in the presence of a catalytic solvent.

[0088] In the presence of a catalytic solvent, the method can make the mixing time of the sulfide-based solid electrolyte precursor at least twice as fast. The sulfide-based solid electrolyte produced can contain an argyrodite phase. The increase in mixing speed can be compared to mixing of a sulfide-based solid electrolyte without a catalytic solvent, or compared to mixing of a sulfide-based solid electrolyte with too little catalytic solvent, or compared to mixing of a sulfide-based solid electrolyte with too much catalytic solvent. When there is too little catalytic solvent, the efficiency of the synthesis is not improved, and the purity and conductivity of the final product are not improved compared to not using a catalytic solvent. Alternatively, when there is too much catalytic solvent, the slurry of the reactants can exhibit rheological properties, and the purity or conductivity of the product produced is not improved compared to synthesis without a catalytic solvent, and the rheological properties can reduce the efficiency of the synthesis. The limits are defined as the preferred ranges of the catalytic solvents described herein. In the presence of a catalytic solvent, the mixing time of the sulfide-based solid electrolyte precursor is up to 25 times or more faster. In a preferred embodiment, the mixing time of the sulfide-based solid electrolyte precursor can be 4 to 25 times faster in the presence of a catalytic solvent, or more preferably, can be 8 to 25 times faster, 12 to 25 times faster, 16 to 25 times faster, or 20 to 25 times faster in the presence of a catalytic solvent. For example, the mixing time of the sulfide-based solid electrolyte precursor can be 4 times faster, 5 times faster, 6 times faster, 7 times faster, 8 times faster, 9 times faster, 10 times faster, 11 times faster, 12 times faster, 13 times faster, 14 times faster, 15 times faster, 16 times faster, 17 times faster, 18 times faster, 19 times faster, 20 times faster, 21 times faster, 22 times faster, 23 times faster, 24 times faster, 25 times faster, or more than 25 times faster in the presence of a catalytic solvent.

[0089] The method can make the solid electrolyte based on sulfide produce in less than or equal to 20 hours.The time period produced is measured from precursor mixing to crystallization of the solid electrolyte based on sulfide.For example, the method can make the solid electrolyte based on sulfide produce in 20 hours or less, 19 hours or less, 18 hours or less, 17 hours or less, 16 hours or less, 15 hours or less, 14 hours or less, 13 hours or less, 12 hours or less, 11 hours or less, 10 hours or less, 9 hours or less, 8 hours or less, 7 hours or less, 6 hours or less, 5 hours or less, 4 hours or less, 3 hours or less, 2 hours or less or 1 hour or less. For example, the method can produce a sulfide-based solid-state electrolyte in 30 minutes to 1 hour, 1 hour to 2 hours, 1 hour to 4 hours, 1 hour to 6 hours, 1 hour to 8 hours, 1 hour to 12 hours, 2 hours to 4 hours, 2 hours to 6 hours, 2 hours to 8 hours, 2 hours to 12 hours, 4 hours to 8 hours, 4 hours to 12 hours, 8 hours to 12 hours, 8 hours to 16 hours, 12 hours to 16 hours, 16 hours to 20 hours, or 20 hours to 24 hours.

[0090] The mixing time of the sulfide-based solid electrolyte precursor can be less than or equal to 20 hours. For example, the mixing time of the sulfide-based solid electrolyte precursor can be 20 hours or less, 19 hours or less, 18 hours or less, 17 hours or less, 16 hours or less, 15 hours or less, 14 hours or less, 13 hours or less, 12 hours or less, 11 hours or less, 10 hours or less, 9 hours or less, 8 hours or less, 7 hours or less, 6 hours or less, 5 hours or less, 4 hours or less, 3 hours or less, 2 hours or less, or 1 hour or less. As another example, the mixing time of the sulfide-based solid electrolyte precursor can be 30 minutes to 1 hour, 1 hour to 2 hours, 1 hour to 4 hours, 1 hour to 6 hours, 1 hour to 8 hours, 1 hour to 12 hours, 2 hours to 4 hours, 2 hours to 6 hours, 2 hours to 8 hours, 2 hours to 12 hours, 4 hours to 8 hours, 4 hours to 12 hours, 8 hours to 12 hours, 8 hours to 16 hours, 12 hours to 16 hours, 16 hours to 20 hours, or 20 hours to 24 hours.

[0091] The mixing time of the sulfide-based solid electrolyte precursor in the presence of a catalytic solvent can be half (50%) of the mixing time using only a spectator solvent or less. For example, the mixing time of the sulfide-based solid electrolyte precursor in the presence of a catalytic solvent can be about 50%, about 60%, about 70%, about 80%, about 90% or about 95% or less of the mixing time using only a spectator solvent. As another example, the mixing time of the sulfide-based solid electrolyte precursor in the presence of a catalytic solvent can be about 50% to about 60%, about 50% to about 70%, about 50% to about 80%, about 50% to about 90%, about 50% to about 95%, about 60% to about 95%, about 70% to about 95%, about 80% to about 95% or about 90% to about 95% or less of the mixing time using only a spectator solvent.

[0092] The solid electrolyte material synthesized using the method of the present disclosure has a characteristic structure that distinguishes it from other solid electrolyte materials. In some embodiments (see, for example, Figure 1 ), the solid electrolyte material may contain 2θ (2Theta) values ​​of 15.5°±0.5°, 18.0°±0.5°, 25.5°±0.5°, 30.1±0.5° and 30.5°±0.5° when using Cukα radiation, which may correspond to the argyrodite phase values, the LPSC intermediate phase (Li 15 P4S 16Cl3-like phase), Li2S and / or LiCl. Specifically, 2θ (2Theta) values ​​of 15.6°±0.5°, 18.1°±0.5°, 25.7°±0.5°, 30.2°±0.5°, and 31.6°±0.5° can correspond to argyrodite phase values. In some embodiments, the solid-state electrolyte material can include 2θ (2Theta) values ​​of 15.6°±0.5°, 17.6°±0.5°, 18.1°±0.5°, 19.6°±0.5°, 23.3°±0.5°, 25.7°±0.5°, 29.3°±0.5°, 30.2°±0.5°, 30.6°±0.5°, 31.9°±0.5°, and 34.8°±0.5°, and can correspond to argyrodite phase values ​​and / or LPSC intermediate phase values. The solid-state electrolyte material may comprise at least three, at least four, or at least five 2θ (2Theta) values ​​selected from the group consisting of 15.6°±0.5°, 18.1°±0.5°, 25.7°±0.5°, 30.2°±0.5°, and 30.6°±0.5°, and may correspond to argyrodite phase values. The solid-state electrolyte material synthesized using the method of the present disclosure may include at least three, at least four, or at least five 2θ (2Theta) values ​​selected from the group consisting of 15.6°±0.5°, 17.6°±0.5°, 18.1°±0.5°, 19.6°±0.5°, 23.3°±0.5°, 25.7°±0.5°, 29.3°±0.5°, 30.2°±0.5°, 30.6°±0.5°, 31.9°±0.5°, and 34.8°±0.5°, and may correspond to argyrodite phase values ​​and / or LPSC mesophase values.

[0093] In some embodiments (see, e.g., Figure 2 ), may include 2θ (2Theta) values ​​of 15.6°±0.5°, 18.1°±0.5°, 25.7°±0.5°, 30.2°±0.5°, 31.6°±0.5°, and 34.8°±0.5°, and may correspond to argyrodite phase values. Figure 1 The solid-state electrolyte material in can include at least three, at least four, or at least five 2θ (2Theta) values ​​selected from the group consisting of 15.6°±0.5°, 18.1°±0.5°, 25.7°±0.5°, 30.2°±0.5°, 31.6°±0.5°, and 34.8°±0.5°, and can correspond to argyrodite phase values.

[0094] Further provided herein is a composition comprising a sulfide-based solid electrolyte having an argyrodite phase, wherein the sulfide-based solid electrolyte comprises a catalytic solvent in an amount of less than 0.1 wt %. The catalytic solvent may be any catalytic solvent described herein. In a preferred embodiment, the catalytic solvent is a nitrile selected from the group consisting of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and combinations thereof. In some embodiments, the sulfide-based solid electrolyte may comprise Li3PS4.

[0095] The sulfide-based solid electrolyte may contain a catalytic solvent in an amount of less than 0.3 wt%, less than 0.2 wt%, less than 0.1 wt%, less than 0.09 wt%, less than 0.08 wt%, less than 0.07 wt%, less than 0.06 wt%, less than 0.05 wt%, less than 0.04 wt%, less than 0.03 wt%, less than 0.02 wt% or less than 0.01 wt%.

[0096] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those of ordinary skill in the art to which this disclosure pertains. Although any methods and materials similar to or equivalent to those described herein may be used in the practice or testing of the subject matter of this disclosure, preferred methods and materials are described. For purposes of this disclosure, the following terms are defined below.

[0097] Concentrations, amounts, and other numerical data may be expressed or presented herein in a range format. It should be understood that such range format is used for convenience and brevity only and should be interpreted flexibly to include not only the values ​​explicitly recited as range limits, 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, within this numerical range are included 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 subranges 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, and the like. This same principle applies to ranges that list only one value as a minimum or maximum. Furthermore, such an interpretation should apply regardless of the breadth of the range or characteristic being described.

[0098] The term "about" will be understood by those of ordinary skill in the art and will vary to some extent depending on the context in which it is used. As used herein, when referring to a measurable value such as an amount, a duration of time, etc., the term "about" is meant to encompass variations of ±10% (including ±5%, ±1%, and ±0.1%) relative to the specified value, as such variations are suitable for performing the disclosed methods.

[0099] In the present disclosure, "comprises," "comprising," "containing," and "having," etc. may have the meanings ascribed thereto by U.S. Patent Law and may mean "includes," "including," etc., and are generally interpreted as open-ended terms. The term "consisting of" or "consists of" is a closed term and includes only the compositions, structures, steps, etc. specifically listed in conjunction with such terms and compositions, structures, steps, etc. that comply with U.S. Patent Law. "Consisting essentially of" or "consists essentially of" have the meanings generally ascribed thereto by U.S. Patent Law. In particular, such terms are generally closed terms, except that additional items, materials, compositions, steps, or elements that do not materially affect the basic and novel characteristics or functions of the items with which they are used are permitted to be included. For example, if a trace element that is present in a composition but does not affect the properties or characteristics of the composition is present in the language "consisting essentially of," then the trace element would be permitted even if not explicitly enumerated in the list of items following such terminology. In this specification, when open-ended terms such as "comprising" or "including" are used, it should be understood that direct support should also be provided for "consisting essentially of" language and "consisting of" language, as if explicitly stated, and vice versa.

[0100] Examples

[0101] Examples are set forth below for the purpose of illustrating and describing certain specific embodiments of the present disclosure. However, the scope of the claims is not limited in any way by the examples set forth herein. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art, and such changes and modifications may be made without departing from the spirit of the present disclosure and the scope of the appended claims, including but not limited to changes and modifications involving the chemical structures, substituents, derivatives, formulations, or methods of the present disclosure. The definitions of the variables in the structures in the schemes herein are consistent with the definitions of the corresponding positions in the chemical formulae presented herein.

[0102] Example 1: Effect of heat treatment conditions on materials - Li6PS5Cl

[0103] The precursors, including 9.4532 g of Li2S, 10.3933 g of P2S5 (Sigma-Aldrich Co.), and 5.1535 g of LiCl (Sigma-Aldrich Co.), were added to a zirconia grinding jar with zirconia grinding media. 135 mL of heptane, 0.64 mL of isobutyronitrile, and 0.28 mL of benzonitrile were added to the same zirconia grinding jar. The mixture was ground in a Retsch PM 100 planetary mill at 500 RPM for 3 hours. The material was collected and dried under vacuum at 90°C.

[0104] The material was then divided into four batches. In batch 1, the material was heated to a temperature of 350°C for 30 minutes. In batch 2, the material was heated to a temperature of 350°C for 240 minutes. In batch 3, the material was heated to a temperature of 350°C for 240 minutes, followed by heating at 450°C for another 30 minutes. In batch 4, the material was heated to a temperature of 450°C for 30 minutes.

[0105] The starting material and each batch were analyzed using X-ray diffraction, Figure 1 The results are shown in . In batches 3 and 4, structural differences were detected by changes in the peaks at about 2θ = 15.5 and 19.6. In addition, the batches showed greater ionic conductivity (4.67mS / cm and 4.40mS / cm for batches 3 and 4, respectively), while the ionic conductivity of batch 1 was only about 0.49mS / cm. Batch 2 also showed structural differences compared to batch 1; specifically, the LPSC mesophase (Li 15 P4S 16 The Cl3-like phase (like phase) formed more LPSC mesophase than in Batch 1. As shown here, the formation of the LPSC mesophase is positively correlated with the conductivity of the final target electrolyte phase. The incorporation of a nitrile-type catalytic solvent promotes the formation of the LPSC mesophase. The development of this mesophase requires good mixing and intimate contact between all precursor materials before extensive heat treatment is applied, and the use of a nitrile-type catalytic solvent has been shown to promote this good contact and intimate mixing.

[0106] Example 2: Effect of adding reactive solvents during synthesis - Li 5.5 PS 4.5 Cl 1.5

[0107] The precursor was added to a zirconia grinding jar with zirconia grinding media, comprising 8.6081 g of Li2S, 10.4318 g of P2S5 (Sigma-Aldrich), and 5.9619 g of LiCl (Sigma-Aldrich). 135 mL of xylene was added to the same zirconia grinding jar. The mixture was ground at 500 RPM for 3 hours in a Latsch PM 100 planetary mill. The material was left in the grinding jar and dried at 90°C under vacuum. 135 mL of xylene was added to the same zirconia grinding jar containing the dried material, and the mixture was ground at 500 RPM for 3 hours in a Latsch PM 100 planetary mill. A portion of this material was then collected (Batch 1). The remaining material was cooked at a temperature of 450°C for 30 minutes. A portion of this material was then collected (Batch 2).

[0108] Additional materials were prepared for comparison. A precursor comprising 8.6081 g of Li2S, 10.4318 g of P2S5 (Sigma-Aldrich) and 5.9619 g of LiCl (Sigma-Aldrich) was added to a zirconia grinding jar with zirconia grinding media. 135 mL of xylene was added to the same zirconia grinding jar. The mixture was ground at 500 RPM for 3 hours in a Latsch PM100 planetary mill. The material was left in the grinding jar and dried at 90°C under vacuum. 135 ml of xylene, 0.64 ml of isobutyronitrile and 0.28 ml of benzonitrile were added to the same zirconia grinding jar containing the dried material, and the mixture was ground at 500 RPM for 3 hours in a Latsch PM 100 planetary mill. A portion of this material was then collected (Batch 3). The remaining material was cooked at a temperature of 450°C for 30 minutes. A portion of this material was then collected (Batch 4).

[0109] The batch was then analyzed using X-ray diffraction, Figure 2 The results are shown in . Figure 2 Batch 4 showed fewer impurities than Batch 2, as indicated by the smaller peak at approximately 2θ = 35°. Additionally, the conductivity of Batch 4 (5.8 mS / cm) was greater than that of Batch 2 (4.2 mS / cm).

[0110] This result indicates that the nitrile cosolvent enhances conductivity even if initial mixing and / or alloying is performed before the nitrile cosolvent is introduced. Therefore, the effect of the cosolvent is independent of, but rather separate from and complementary to, milling or mixing.

[0111] Example 3: Synthesis of halogen-free SSE material - Li3PS4

[0112] The precursors, including 9.5572 g of Li2S and 15.4428 g of P2S5 (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 60 mL of xylene was added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 3 hours. The material was collected and dried under vacuum at 90°C. A portion of the material was collected (Batch 1). The remaining material was cooked at a temperature of 240°C for 30 minutes. A portion of this material was then collected (Batch 2).

[0113] The precursors, including 9.5572 g of Li2S and 15.4428 g of P2S5 (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 135 ml of heptane, 0.64 mL of isobutyronitrile, and 0.28 mL of benzonitrile were added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 3 hours. The material was collected and dried under vacuum at 90° C. A portion of the material (Batch 3) was collected. The remaining material was cooked at a temperature of 240° C. for 30 minutes. A portion of this material (Batch 4) was then collected.

[0114] The batch was then analyzed using X-ray diffraction, Figure 3 The results are shown in . The differences between the materials thus ground (i.e. batches 1 and 3) are Figure 3 It can be clearly seen in the figure, which shows that there are differences in the glass phase of the material, as evidenced by the different centroids of the glassy peaks in the range of 14-24°2θ. The presence of a coordination solvent causes the system to shift to a thermodynamically stable product rather than other metastable products (i.e., batch 4 compared to batch 2). Specifically, when a coordination catalytic solvent is utilized, the sulfide-based solid electrolyte material includes both the β and γ phases of Li3PS4 (LPS), while the traditional synthesis method only produces the β phase. The γ phase of LPS is thermodynamically stable at room temperature, while the β phase is only metastable at room temperature.

[0115] Example 4: Preparation of glass-ceramic SSE–Li7P2S8Br using nitrile as reactive solvent 0.5 I 0.5

[0116] The precursors, including 7.3155 g of Li2S and 11.820 g of P2S5 (Sigma-Aldrich), 2.3070 g of LiBr (Sigma-Aldrich), and 3.5568 g of LiI (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 60 mL of xylene was added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 3 hours. The material was collected and dried under vacuum at 90°C. A portion of the material (Batch 1) was collected. The remaining material was cooked at a temperature of 205°C for 30 minutes. A portion of this material (Batch 2) was then collected.

[0117] The precursors, including 7.3155 g Li2S and 11.8206 g P2S5 (Sigma-Aldrich), 2.3070 g LiBr (Sigma-Aldrich), and 3.5568 g LiI (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 135 mL heptane, 0.64 mL isobutyronitrile, and 0.28 mL benzonitrile were added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 3 hours. The material was collected and dried under vacuum at 90°C. A portion of the material (Batch 3) was collected. The remaining material was cooked at a temperature of 205°C for 30 minutes. A portion of this material (Batch 4) was then collected.

[0118] The batch was then analyzed using X-ray diffraction, Figure 4 The results are shown in . The results show that the use of reactive solvents shifts the system to thermodynamically stable high-temperature phases such as argyrodite and Li4PS4I (batches 3 and 4), while the synthesis using non-reactive solvents produces glass-ceramic phases (batches 1 and 2).

[0119] Here, it has been demonstrated that it is impossible to synthesize " glass ceramic " electrolyte with this approach, and it is more likely to synthesize " crystallization " electrolyte." Glass ceramic " is a material containing both glass domains and crystalline domains, in which case crystalline domains are typically nanometer-sized (<100nm), and can be considered as being embedded in a glass (amorphous) matrix. Glass ceramic solid electrolytes are typically glassy mixtures by first producing the precursor provided, and then applying subsequent heat treatment to synthesize crystalline domain nucleation and / or growth. In the case of given specific chemical composition, this process will typically produce metastable crystalline phases: known given precursors combine to form different phases with lower free energy, but due to the kinetic restrictions of the crystallization carried out by glass, on the contrary first form a phase with higher free energy. In some respects, metastable phases can be considered as the kinetically stable high temperature phase of a given chemical system, and thermodynamically stable phases can be considered as the phase or the lowest free energy phase of a given chemical system under given pressure and temperature conditions.

[0120] Here, the chemical Li7P2S8Br 0.5 I 0.5 The synthesis of known glass-ceramic materials is targeted by approaches using non-coordinating, non-reactive solvents and approaches using solvent blends containing coordinating or reactive solvents. As seen in the previous example, the use of coordinating or reactive solvents shifts the system to a thermodynamically stable, high-temperature phase (argyrodite + Li4PS4I), while the synthesis using non-coordinating, non-reactive solvents produces the known glass-ceramic phase Li7P2S8Br 0.5 I 0.5 .

[0121] Example 5: Duration of Milling and Temperature of Heat Treatment: Synthesis Using a Non-Coordinating Non-Reactive Solvent

[0122] The precursors, including 9.4532 g of Li2S, 10.3922 g of P2S5 (Sigma-Aldrich), and 5.1535 g of LiCl (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 60 mL of xylene was added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 3 hours. The material was collected and dried under vacuum at 90°C.

[0123] The material was divided into four batches. Batch 1 was cooked at 350°C for 30 minutes. Batch 2 was cooked at 400°C for 30 minutes. Batch 3 was cooked at 450°C for 30 minutes. Batch 4 was cooked at 500°C for 30 minutes.

[0124] The precursors, including 9.4532 g of Li2S, 10.3922 g of P2S5 (Sigma-Aldrich), and 5.1535 g of LiCl (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 60 mL of xylene was added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 12 hours. The material was collected and dried under vacuum at 90°C.

[0125] The material was divided into four batches. Batch 5 was cooked at 350°C for 30 minutes. Batch 6 was cooked at 400°C for 30 minutes. Batch 7 was cooked at 450°C for 30 minutes. Batch 8 was cooked at 500°C for 30 minutes.

[0126] The batch was then analyzed using X-ray diffraction, Figure 5 The results are shown in Figure 2. The ionic conductivity of each batch was also tested. Figure 6 The results are shown in . The results show that longer milling times lead to higher phase purity at lower temperatures and higher ionic conductivity overall. In addition, heat treatment above 400°C increases the level of impurities and reduces conductivity.

[0127] Example 6: Duration of Milling and Temperature of Heat Treatment: Synthesis with Coordinating or Reactive Solvents Including Ester

[0128] The precursor, comprising 9.4532 g of Li2S, 10.3922 g of P2S5 (Sigma-Aldrich), and 5.1535 g of LiCl (Sigma-Aldrich), was added to a zirconia grinding jar with zirconia grinding media. 108 mL of xylene and 32 mL of ethyl propionate were added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 3 hours. The material was collected and dried under vacuum at 90°C.

[0129] Divide the mixture into four batches. Batch 1 was cooked at 350°C for 30 minutes. Batch 2 was cooked at 400°C for 30 minutes. Batch 3 was cooked at 450°C for 30 minutes. Batch 4 was cooked at 500°C for 30 minutes.

[0130] The precursors, including 9.4532 g of Li2S, 10.3922 g of P2S5 (Sigma-Aldrich), and 5.1535 g of LiCl (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 108 mL of xylene and 32 mL of ethyl propionate were added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 12 hours. The material was collected and dried under vacuum at 90°C.

[0131] The mixture was divided into four batches. Batch 5 was cooked at 350°C for 30 minutes. Batch 6 was cooked at 400°C for 30 minutes. Batch 7 was cooked at 450°C for 30 minutes. Batch 8 was cooked at 500°C for 30 minutes.

[0132] The batch was then analyzed using X-ray diffraction, Figure 7 The results are shown in Figure 2. The ionic conductivity of each batch was also tested. Figure 8 The results are shown in . The results show that longer milling times result in higher phase purity at lower temperatures. The highest overall conductivity is achieved with shorter milling times. Therefore, it can be concluded that the beneficial effect of the solvent may be partially offset by long milling times, as low conductivity is observed. Without wishing to be bound by theory, the solvent may increase the surface area of ​​the solid, and prolonged milling may reduce the surface area gain.

[0133] Example 7: Duration of milling and temperature of heat treatment: Synthesis of coordinating or reactive solvents including nitrites

[0134] The precursors, including 9.4532 g of Li2S, 10.3922 g of P2S5 (Sigma-Aldrich), and 5.1535 g of LiCl (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 135 mL of heptane, 0.64 mL of isobutyronitrile, and 0.28 mL of benzonitrile were added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 3 hours. The material was collected and dried under vacuum at 90°C.

[0135] The material was divided into four batches. Batch 1 was cooked at 350°C for 30 minutes. Batch 2 was cooked at 400°C for 30 minutes. Batch 3 was cooked at 450°C for 30 minutes. Batch 4 was cooked at 500°C for 30 minutes.

[0136] The precursors, including 9.4532 g of Li2S, 10.3922 g of P2S5 (Sigma-Aldrich), and 5.1535 g of LiCl (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 135 mL of heptane, 0.64 mL of isobutyronitrile, and 0.28 mL of benzonitrile were added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 12 hours. The material was collected and dried under vacuum at 90°C.

[0137] The material was divided into four batches. Batch 5 was cooked at 350°C for 30 minutes. Batch 6 was cooked at 400°C for 30 minutes. Batch 7 was cooked at 450°C for 30 minutes. Batch 8 was cooked at 500°C for 30 minutes.

[0138] The batch was then analyzed using X-ray diffraction, Figure 9 The results are shown in Figure 2. The ionic conductivity of each batch was also tested. Figure 10 The results are shown in . The results show that longer milling times resulted in higher phase purity at lower temperatures, and the highest overall conductivity was achieved with shorter milling times, consistent with previous results. In addition, overall purity and conductivity were improved when using solvents containing nitrile.

[0139] Example 8: Ionic Conductivity

[0140] Figure 11 and 12 Shown is an overlay of the ionic conductivities of the electrolyte materials prepared in Examples 5-7. Figure 11 shows the trend of conductivity with respect to heat treatment temperature at shorter milling time (3 h), while Figure 12 The same trend is shown for a longer milling time (12 hours). It is hypothesized that the coordination effect of the reactive cosolvent creates a high surface area upon solvent removal, which promotes easy and more complete reaction of the precursors. In addition, the nitrile system produces the LPSC (also known as LPS-Cl) intermediate, which further promotes halogen uptake and improves conductivity and purity. The nitrile catalyzed solvent promotes the reaction between the precursors and may produce the best results in terms of the purity of the final product.

[0141] At longer milling times, increased LiCl incorporation was observed at lower temperatures, likely due to better or finer mixing of the precursors. Low-conductivity mesophase formation was largely bypassed at longer milling times. Longer milling resulted in higher conductivity in the xylene-only solvent system and lower conductivity in the reactive co-solvent system.

[0142] Example 9: Particle Size

[0143] Figure 13 The particle size of the materials prepared in Examples 6 and 7 and milled at 500 rpm for 3 hours is shown. The increase in surface area attributable to the solvent blend likely plays an important role in the development of high purity and high conductivity. It was also observed that simply producing the highest surface area after milling and solvent removal was not the only important factor in determining the purity and conductivity of the final product, as the batch prepared using ethyl propionate had the highest specific surface area, but the batch prepared using isobutyronitrile / benzonitrile had the highest purity and conductivity.

[0144] Example 10: Temperature during grinding

[0145] The precursors, including 9.4532 g of Li2S, 10.3933 g of P2S5 (Sigma-Aldrich), and 5.1535 g of LiCl (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 135 mL of heptane, 0.64 mL of isobutyronitrile, and 0.28 mL of benzonitrile were added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 3 hours. The material was collected and dried under vacuum at 90°C.

[0146] The above materials were divided into two batches. Batch 1 was cooked at 350°C for 30 minutes. Batch 2 was cooked at 450°C for 30 minutes.

[0147] The second material was synthesized in the same manner as above, except that the milling conditions were changed. The milling process followed an interval schedule of 2 minutes of milling and 10 minutes of rest, which was repeated over the course of 18 hours. This interval schedule provided 180 minutes of milling and 900 minutes of rest.

[0148] The above materials were divided into two batches. Batch 3 was cooked at 350°C for 30 minutes. Batch 4 was cooked at 450°C for 30 minutes.

[0149] The batch was then analyzed using X-ray diffraction, Figure 16 The results are shown in FIG. It can be understood that the interval milling schedule for batches 3 and 4 produced a lower milling temperature than the non-interval milling schedule for batches 1 and 2. Therefore, milling was performed at different temperatures. Figure 16 As shown, higher milling temperature promotes the development of LPSC mesophase rather than LPS mesophase. This may mean that the elevated temperature helps the solvent system to perform beneficial effects that result in high purity and high conductivity.

[0150] Examples 11-27: Effect of Solvent Composition and Amount During Synthesis of Example 11

[0151] The precursors, including 8.6081 g of Li2S, 10.4318 g of P2S5 (Sigma-Aldrich), and 5.9619 g of LiCl (Sigma-Aldrich), were added to a zirconia grinding jar with zirconia grinding media. 135 mL of heptane and 0.64 mL of isobutyronitrile were added to the same zirconia grinding jar. The mixture was ground in a Latsch PM 100 planetary mill at 500 RPM for 3 hours. The material was left in the grinding jar and dried under vacuum at 90°C. The material was collected and cooked at 450°C for 30 minutes.

[0152] Example 12

[0153] The electrolyte of Example 12 was synthesized in the same manner as in Example 1, except that 0.64 mL of isobutyronitrile was replaced with 0.30 mL of benzonitrile.

[0154] Example 13

[0155] The electrolyte of Example 13 was synthesized in the same manner as in Example 1, except that 0.64 mL of isobutyronitrile was replaced with a blend of 0.64 mL of isobutyronitrile and 0.28 mL of benzonitrile.

[0156] Example 14

[0157] The electrolyte of Example 14 was synthesized in the same manner as in Example 1, except that 0.64 mL of isobutyronitrile was replaced with a blend of 0.32 mL of isobutyronitrile and 0.56 mL of benzonitrile.

[0158] Example 15

[0159] The electrolyte of Example 15 was synthesized in the same manner as in Example 1, except that 0.64 mL of isobutyronitrile was replaced with a blend of 1.09 mL of isobutyronitrile and 0.28 mL of benzonitrile.

[0160] Example 16

[0161] The electrolyte of Example 16 was synthesized in the same manner as in Example 1, except that 0.64 mL of isobutyronitrile was replaced with a blend of 1.46 mL of isobutyronitrile and 0.28 mL of benzonitrile.

[0162] Example 17

[0163] The electrolyte of Example 17 was synthesized in the same manner as in Example 1, except that 0.64 mL of isobutyronitrile was replaced with a blend of 1.83 mL of isobutyronitrile and 0.28 mL of benzonitrile.

[0164] Example 18

[0165] The electrolyte of Example 18 was synthesized in the same manner as in Example 1, except that 0.64 mL of isobutyronitrile was replaced with a blend of 2.72 mL of isobutyronitrile and 0.28 mL of benzonitrile.

[0166] Example 19

[0167] The electrolyte of Example 19 was synthesized in the same manner as in Example 1, except that 0.64 mL of isobutyronitrile was replaced with a blend of 3.72 mL of isobutyronitrile and 0.28 mL of benzonitrile.

[0168] Example 20

[0169] The electrolyte of Example 20 was synthesized in the same manner as in Example 1, except that 0.64 mL of isobutyronitrile was replaced with a blend of 2.14 mL of isobutyronitrile and 0.28 mL of benzonitrile.

[0170] Example 21

[0171] The electrolyte of Example 21 was synthesized in the same manner as in Example 1, except that 1.61 mL of propionitrile was used instead of 0.64 mL of isobutyronitrile.

[0172] Example 22

[0173] The electrolyte of Example 22 was synthesized in the same manner as Example 1, except that 0.64 mL of isobutyronitrile was replaced with a blend of 1.21 mL of propionitrile and 0.28 mL of benzonitrile.

[0174] Example 23

[0175] The electrolyte of Example 23 was synthesized in the same manner as Example 1, except that 0.64 mL of isobutyronitrile was replaced with a blend of 1.61 mL of propionitrile and 0.28 mL of benzonitrile.

[0176] Example 24

[0177] The electrolyte of Example 24 was synthesized in the same manner as Example 1, except that 0.64 of isobutyronitrile was replaced with a blend of 2.42 mL of propionitrile and 0.28 mL of benzonitrile.

[0178] Example 25

[0179] The electrolyte of Example 25 was synthesized in the same manner as in Example 12, except that 0.28 mL of benzonitrile was replaced with 0.56 mL of benzonitrile.

[0180] Example 26

[0181] The electrolyte of Example 26 was synthesized in the same manner as in Example 12, except that 0.28 mL of benzonitrile was replaced with 24.55 mL, and the amount of heptane used was reduced from 135 mL to 110.45 mL.

[0182] Example 27

[0183] The electrolyte of Example 27 was synthesized in the same manner as in Example 12, except that 0.28 mL of benzonitrile was replaced with 48.1 mL, and the amount of heptane used was reduced from 135 mL to 86.9 mL.

[0184] Table 1 summarizes the solid electrolytes prepared using IBN solvent and BZN solvent blend compositions of Examples 11-20 and the corresponding conductivities.

[0185] Table 2 summarizes the solid electrolytes prepared using PrN and BZN solvent blend compositions of Examples 21-24 and the corresponding conductivities.

[0186] Table 3 summarizes the solid electrolytes prepared using IBN solvent and BZN solvent blend compositions for Examples 11-20, the ratio of solvent to phosphorus starting material, and the corresponding conductivities.

[0187] Table 4 summarizes the solid electrolytes prepared using IBN solvent and BZN solvent blend compositions for Examples 21-24, the ratio of solvent to phosphorus starting material, and the corresponding conductivities.

[0188] Effect of Nitrile Solvents on Electrolyte Conductivity

[0189] The conductivity of the electrolytes of Examples 12 and 25-27 was measured, and the results are presented in Table 5.

[0190] In Examples 12 and 25-27, a blend of two solvents was used during the synthesis of the solid-state electrolyte, one of which was a spectator solvent and the other was a nitrile-based solvent. In Example 27, the nitrile solvent was used in an amount of approximately 39 wt % of the total solvent used, and the ionic conductivity of the electrolyte material prepared in this example was 5.56 mS / cm. In Example 26, the nitrile solvent was used in an amount of approximately 19.5 wt % of the total solvent used, and the ionic conductivity of the electrolyte material prepared in this example was 3.78 mS / cm. In Example 25, the nitrile solvent was used in an amount of approximately 0.44 wt % of the total solvent used, and the ionic conductivity of the electrolyte material prepared in this example was 5.14 mS / cm. In Example 12, the nitrile solvent was used in an amount of approximately 0.22 wt % of the total solvent used, and the ionic conductivity of the electrolyte material prepared in this example was 5.82 mS / cm.

[0191] As shown in the conductivity of the electrolytes of Examples 27 to 26, large amounts of nitrile solvents produce electrolyte materials with higher ionic conductivity, with an ionic conductivity of 5.56 mS / cm when using 39 wt% nitrile solvent, compared to 3.78 mS / cm when using 19.5 wt%. This result alone is the motivation for using large amounts of nitrile. However, when the amount of nitrile solvent was significantly reduced, an unexpected result occurred. When the amount of nitrile solvent was 0.44 wt% as in Example 25, the ionic conductivity jumped to 5.14 mS / cm. Even more surprising was that when the amount of nitrile solvent used was further reduced to only 0.22% as in Example 12, the ionic conductivity of the electrolyte material increased by more than 10%, reaching 5.82 mS / cm. This result was unexpected and has not been reported previously.

[0192] Effect of Nitrile Solvent Blends on Electrolyte Conductivity

[0193] In Example 21, an aliphatic nitrile solvent (propionitrile, PrN) was used in combination with a spectator solvent to produce a solid electrolyte material with an ionic conductivity of 4.37 mS / cm. In Example 26, an aromatic nitrile solvent (benzonitrile, BZN) was used in combination with a spectator solvent (heptane) to produce a solid electrolyte material with an ionic conductivity of 3.78 mS / cm. In Example 24, an aliphatic nitrile solvent (PrN) and an aromatic nitrile (BZN) solvent were used in combination with a spectator solvent to produce a solid electrolyte material with an ionic conductivity of 5.27 mS / cm. The use of a blend of nitrile solvents in which at least one nitrile solvent is aliphatic and at least one nitrile solvent is aromatic produced an electrolyte material with an ionic conductivity that was superior to the ionic conductivity of the same electrolyte material prepared using only one aliphatic nitrile solvent or only one aromatic nitrile solvent.

[0194] Table 1: Solid electrolytes prepared from IBN solvent and BZN solvent blends and corresponding conductivities of Examples 11-20. The volume, mass, and molar ratio of the solvents are provided.

[0195]

[0196] Table 2: Solid electrolytes prepared from PrN solvent and BZN solvent blends and corresponding conductivities of Examples 11-20. The volume, mass, and molar ratio of the solvents are provided.

[0197]

[0198] Table 3: Preparation of solid electrolytes of IBN solvent and BZN solvent blends, ratios of solvent to phosphorus starting material, and corresponding conductivities for Examples 11-20. The volume, mass, and molar ratio of the solvents are provided.

[0199]

[0200] Table 4: Preparation of solid electrolytes of PrN(alkyl) and BZN(aryl) solvent blends, ratios of solvent to phosphorus starting material, and corresponding conductivities for Examples 21-24. The volume, mass, and molar ratio of the solvents are provided.

[0201]

[0202] Table 5: Solid electrolytes prepared with different amounts of BZN solvent, the ratio of solvent to phosphorus starting material, and the corresponding conductivity of Examples 12, 25-27.

[0203] Conductivity (mS / cm) Heptane (mL) BZN(mol) BZN(g) BZN(mol) BZN / P4S10 Example 12 5.82 135 0.3 0.2826 0.0027 0 Example 25 5.14 135 0.6 0.5652 0.0054 0.02 Example 26 3.78 135 26.3 24.7746 0.2367 0.74 Example 27 5.56 135 52.6 49.5492 0.4734 1.48

[0204] Changing the molar ratio of aliphatic nitrile solvent to aromatic nitrile solvent

[0205] In Example 13, the ratio between the molar amounts of the aliphatic nitrile (IBN) solvent and the aromatic nitrile (BZN) solvent used to produce the solid electrolyte material was 2.6. The ionic conductivity of the produced solid electrolyte material was 6.39 mS / cm.

[0206] In Example 15, the ratio between the molar amounts of the aliphatic nitrile (IBN) solvent and the aromatic nitrile (BZN) solvent used to produce the solid electrolyte material was 4.34. The ionic conductivity of the produced solid electrolyte material was 6.61 mS / cm.

[0207] In Example 17, the ratio between the molar amounts of the aliphatic nitrile (IBN) solvent and the aromatic nitrile (BZN) solvent used to produce the solid electrolyte material was 7.44. The ionic conductivity of the produced solid electrolyte material was 6.95 mS / cm.

[0208] In Example 19, the ratio between the molar amounts of the aliphatic nitrile (IBN) solvent and the aromatic nitrile (BZN) solvent used to produce the solid electrolyte material was 14.61. The ionic conductivity of the produced solid electrolyte material was 6.86 mS / cm.

[0209] The data show that a ratio of (X) moles of aliphatic nitrile solvent used during synthesis to (Y) moles of aromatic nitrile solvent used during synthesis between 1 and 15 produces a solid electrolyte with high ionic conductivity. Figure 16 A graphical representation of this result is depicted in .

[0210] Change the molar ratio of aromatic nitrile solvent (benzonitrile) to P2S5 to between 0.05 and 0.5

[0211] In Example 11, the ratio between the molar amount of the aromatic nitrile solvent (benzonitrile) and the molar amount of P2S5 used to produce the solid electrolyte material was less than 0.05. The ionic conductivity of the produced solid electrolyte material was 4.25 mS / cm.

[0212] In Example 14, the ratio between the molar amount of the aromatic nitrile solvent (benzonitrile) and the molar amount of P2S5 used to produce the solid electrolyte material was about 0.04. The ionic conductivity of the solid electrolyte material produced by Example 14 was 5.78 mS / cm.

[0213] In Example 13, the ratio between the molar amount of the aromatic nitrile solvent (benzonitrile) and the molar amount of P2S5 used to produce the solid electrolyte material was about 0.02. The ionic conductivity of the produced solid electrolyte material was 6.39 mS / cm.

[0214] In Example 26, the ratio between the molar amount of the aromatic nitrile solvent (benzonitrile) and the molar amount of P2S5 used to produce the solid electrolyte material was greater than 1.00. The ionic conductivity of the produced solid electrolyte material was 3.78 mS / cm.

[0215] Examples 11, 13, 14 and 26 show that when the ratio of the molar amount of aromatic nitrile (benzonitrile) (A) to the molar amount of P2S5 (B) used during the synthesis is between 0.05 and 0.5, a solid electrolyte with high ionic conductivity is produced.

[0216] Examples

[0217] The present disclosure relates to a method for producing a sulfide-based solid-state electrolyte, the method comprising: mixing an alkali metal sulfide or alkaline earth metal sulfide, a secondary sulfide, and optionally an alkali halide or pseudo-halide to produce a sulfide-based solid-state electrolyte, wherein the mixing occurs in a blend of solvents, the blend of solvents comprising a catalytic solvent and a bystander solvent; and crystallizing the sulfide-based solid-state electrolyte.

[0218] In some embodiments, the method may further include mixing an alkali halide, wherein the alkali halide comprises LiX, wherein X can be one or more of F, Cl, Br, and I. In some embodiments, the alkali metal sulfide may comprise A2S, wherein A can be one or more of Li and Na. In some embodiments, the secondary sulfide may comprise one or more of P2S5, SiS2, Sb2S3, GeS2, SnS2. In some embodiments, the sulfide-based solid electrolyte may comprise an argyrodite phase. In some embodiments, the purity of the sulfide-based solid electrolyte may be at least 90% (wt%). In some embodiments, the sulfide-based solid electrolyte may comprise at least 85% of a crystalline phase. In some embodiments, the crystalline phase may be metastable. In some embodiments, the sulfide-based solid electrolyte may comprise less than 1% LiCl.

[0219] In some embodiments, the sulfide-based solid electrolyte may contain less than 1% Li2S.

[0220] In some embodiments, the sulfide-based solid-state electrolyte may comprise an argyrodite phase, the alkali metal sulfide comprises Li2S, the secondary sulfide comprises P2S5, and the alkali halide, when present, comprises LiX, and wherein X═F, Cl, Br, or I.

[0221] In some embodiments, the catalytic solvent may comprise 0.1 wt% to 6 wt% of the blend of solvents.

[0222] In some embodiments, the catalytic solvent may comprise 0.3 wt% to 4.5 wt% of the blend of solvents.

[0223] In some embodiments, the catalytic solvent may comprise 0.5 wt% to 3 wt% of the blend of solvents.

[0224] In some embodiments, the catalytic solvent may comprise 0.6 wt% to 0.9 wt% of the blend of solvents.

[0225] In some embodiments, the spectator solvent may comprise 94.0 wt% to 99.9 wt% of the blend of solvents.

[0226] In some embodiments, the spectator solvent may comprise 98.5 wt% to 99.9 wt% of the blend of solvents.

[0227] In some embodiments, the catalytic solvent may comprise one or more nitrile solvents.

[0228] In some embodiments, the one or more nitrile solvents can be selected from the group consisting of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and combinations thereof.

[0229] In some embodiments, the catalytic solvent comprises an aryl solvent substituted with one or more nitrile groups, an alkyl solvent substituted with one or more nitrile groups, or a combination thereof.

[0230] In some embodiments, the aryl solvent substituted with one or more nitrile groups and the secondary sulfide can be present in a molar ratio of about 0.5:1 to about 1.5:1.

[0231] In some embodiments, the combination of the aryl solvent substituted with one or more nitrile groups and the alkyl solvent substituted with one or more nitrile groups and the secondary sulfide can be present in a molar ratio of about 0.5:1 to about 1.5:1.

[0232] In some embodiments, the alkyl solvent substituted with one or more nitrile groups and the aryl solvent substituted with one or more nitrile groups may be present in a volume ratio of about 5:1 to about 10:1.

[0233] In some embodiments, the alkyl solvent substituted with one or more nitrile groups and the aryl solvent substituted with one or more nitrile groups may be present in a mass ratio of about 4:1 to about 8:1.

[0234] In some embodiments, the alkyl solvent substituted with one or more nitrile groups and the aryl solvent substituted with one or more nitrile groups may be present in a molar ratio of about 6:1 to about 12:1.

[0235] In some embodiments, the spectator solvent may comprise a hydrocarbon-based solvent.

[0236] In some embodiments, the spectator solvent can comprise an alkane or a blend of alkanes, xylene, toluene, benzene, decalin, 1,2,3,4-tetrahydronaphthalene, or a combination thereof.

[0237] In some embodiments, the method further comprises heating the sulfide-based solid-state electrolyte.

[0238] In some embodiments, the sulfide-based solid-state electrolyte may be heated to a temperature of about 350°C to about 550°C.

[0239] Some embodiments of the method further comprise grinding the mixture.

[0240] Some embodiments of the method further include drying the sulfide-based solid-state electrolyte under vacuum or at atmospheric pressure.

[0241] Some embodiments of the method can further comprise producing a phosphorothioate intermediate.

[0242] In some embodiments, the phosphorothioate intermediate may comprise P2S6 4- and / or PS( 4-x)O x , wherein x may be between 0 and 4. In some embodiments, the phosphorothioate intermediate may comprise PS4 3- In some embodiments, the phosphorothioate intermediate may comprise P2S7 4- .

[0243] In some embodiments, the sulfide-based solid electrolyte may include Li 3 PS 4 . In some embodiments, the Li 3 PS 4 may be crystalline. In some embodiments, the Li 3 PS 4 may be amorphous.

[0244] In some embodiments, the sulfide-based solid electrolyte may contain fewer impurities compared to sulfide-based solid electrolytes prepared with non-coordinating, non-reactive solvents.

[0245] In some embodiments, the ionic conductivity of the sulfide-based solid-state electrolyte may be at least 25% greater than the ionic conductivity of a sulfide-based solid-state electrolyte prepared with a non-coordinating, non-reactive solvent.

[0246] In some embodiments, the use of a catalytic solvent produces a sulfide-based solid-state electrolyte that can be at least about 90% crystalline.

[0247] The present disclosure further relates to a method for producing a sulfide-based solid-state electrolyte having an argyrodite phase, the method comprising mixing a sulfide-based solid-state electrolyte precursor in a blend of solvents to produce a sulfide-based solid-state electrolyte, the sulfide-based solid-state electrolyte precursor comprising Li2S, P2S5, and LiX, the blend of solvents comprising a catalytic solvent and a spectator solvent, wherein X=F, Cl, Br, or I; and crystallizing the sulfide-based solid-state electrolyte, wherein the sulfide-based solid-state electrolyte precursor in the presence of the catalytic solvent can require half (50%) or less of the mixing time required using only a spectator solvent.

[0248] In some embodiments, the production of sulfide-based solid-state electrolytes is 4 to 25 times faster in the presence of a catalytic solvent.

[0249] The present disclosure further relates to a method for producing a sulfide-based solid electrolyte, the method comprising mixing a sulfide-based solid electrolyte precursor in a blend of solvents to produce a sulfide-based solid, the sulfide-based solid electrolyte precursor comprising Li2S, P2S5 and LiX, the blend of solvents comprising a catalytic solvent and a spectator solvent, wherein X=F, Cl, Br, I; and crystallizing the sulfide-based solid electrolyte, wherein the mixing time of the sulfide-based solid electrolyte can be less than 20 hours.

[0250] In some embodiments, the mixing time of the sulfide-based solid electrolyte precursor may be less than 15 hours.

[0251] In some embodiments, the mixing time of the sulfide-based solid electrolyte precursor may be less than 10 hours.

[0252] In some embodiments, the mixing time of the sulfide-based solid electrolyte precursor may be less than 8 hours.

[0253] In some embodiments, the mixing time of the sulfide-based solid electrolyte precursor may be less than 6 hours.

[0254] In some embodiments, the mixing time of the sulfide-based solid electrolyte precursor may be less than 5 hours.

[0255] In some embodiments, the sulfide-based solid electrolyte may include an argyrodite phase. In some embodiments, the purity of the sulfide-based solid electrolyte may be at least 90% (wt%). In some embodiments, the sulfide-based solid electrolyte may include at least 60% of a crystalline phase. In some embodiments, the crystalline phase may be metastable. In some embodiments, the sulfide-based solid electrolyte may include less than 1% LiCl. In some embodiments, the sulfide-based solid electrolyte may include less than 1% Li2S.

[0256] The present disclosure further relates to a method for producing a sulfide-based solid-state electrolyte having an argyrodite phase, the method comprising mixing Li2S, P2S5, and LiX in a blend of solvents to produce the sulfide-based solid-state electrolyte having an argyrodite phase, the blend of solvents comprising a catalytic solvent and a spectator solvent, wherein X=F, Cl, Br, or I; and crystallizing the sulfide-based solid-state electrolyte, wherein less than 15% (wt%) of the sulfide-based solid-state electrolyte may be in an amorphous phase.

[0257] The present disclosure further relates to a composition comprising Li3PS4 and a thiophosphate and an argyrodite phase, wherein the thiophosphate comprises one or more of PS4 and P2S7 and P2S6, wherein the composition comprises 0.01 wt% to 0.90 wt% of a nitrile selected from the group consisting of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and combinations thereof.

[0258] In some embodiments, less than 15% (wt%) of the phosphorothioate may be in an amorphous phase.

[0259] The present disclosure further relates to a method for producing a sulfide-based solid-state electrolyte having an argyrodite phase, the method comprising mixing Li2S, P2S5, and LiX in a blend of solvents to produce the sulfide-based solid-state electrolyte having an argyrodite phase, the blend of solvents comprising a catalytic solvent and a spectator solvent, wherein X=F, Cl, Br, or I, and the ratio of the catalytic solvent to the spectator solvent may be from 1:15 to 1:1000 by weight; and crystallizing the sulfide-based solid-state electrolyte.

[0260] The present disclosure further relates to a method for producing a sulfide-based solid-state electrolyte having an argyrodite phase, the method comprising mixing Li2S, P2S5, and LiX to produce a sulfide-based solid-state electrolyte having an argyrodite phase, wherein the mixing occurs in a blend of solvents comprising a catalytic solvent and a spectator solvent, and X=F, Cl, Br, or I; and crystallizing the sulfide-based solid-state electrolyte with less than 0.5 wt% of the catalytic solvent incorporated into the sulfide-based solid-state electrolyte.

[0261] The present disclosure further relates to a composition comprising a sulfide-based solid electrolyte having an argyrodite phase, the composition comprising less than 0.1 wt% of nitrile selected from the group consisting of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and combinations thereof. In some embodiments, less than 0.05 wt% of nitrile may be incorporated into the sulfide-based solid electrolyte. In some embodiments, less than 0.01 wt% of nitrile may be incorporated into the sulfide-based solid electrolyte. In some embodiments, less than 0.001 wt% of nitrile may be incorporated into the sulfide-based solid electrolyte.

[0262] The features described above, as well as the features claimed below, may be combined in various ways without departing from the scope of this document. It should be noted, therefore, that the contents contained in the above description or shown in the accompanying drawings should be interpreted as illustrative rather than restrictive. The above embodiments should be regarded as examples of the present invention and not as limiting the scope of the invention. In addition to the foregoing embodiments of the invention, a review of the detailed description and the accompanying drawings will show that there are other embodiments of such inventions. Therefore, many combinations, permutations, variations and modifications of the foregoing embodiments of the invention that are not explicitly set forth herein will still fall within the scope of such inventions. The following claims are intended to cover the general and specific features described herein, as well as all statements of the scope of the methods and systems of the present invention that can be said to fall therein in language.

Claims

1. A method for producing a sulfide-based solid electrolyte, the method comprising: mixing alkali metal sulfides and / or alkaline earth metal sulfides, secondary sulfides, and optionally alkali halides or pseudohalides to produce a sulfide-based solid electrolyte, wherein the mixing occurs in a blend of solvents comprising a catalytic solvent and a spectator solvent; and crystallizing the sulfide-based solid electrolyte.

2. The method of claim 1, further comprising mixing the alkali halide, the alkali halide comprising LiX, wherein X is one or more of F, Cl, Br, and I.

3. The method of claim 1, wherein the alkali metal sulfide comprises AS, wherein A is one or more of Li and Na.

4. The method according to claim 1, wherein the secondary sulfide comprises one or more of P2S5, SiS2, Sb2S3, GeS2, and SnS2.

5. The method of claim 1, wherein the sulfide-based solid electrolyte comprises less than 1 wt% LiCl or less than 1 wt% Li2S.

6. The method of claim 1 , wherein the sulfide-based solid electrolyte comprises an argyrodite phase, the alkali metal sulfide comprises Li2S, the secondary sulfide comprises P2S5, and the alkali halide, when present, comprises LiX, and wherein X═F, Cl, Br, or I.

7. The method of claim 1, wherein the catalytic solvent comprises 0.1 wt% to 6 wt% of the blend of solvents.

8. The method of claim 1, wherein the spectator solvent comprises 94.0 wt% to 99.9 wt% of the blend of solvents.

9. The method of claim 1, wherein the catalytic solvent comprises one or more nitrile solvents.

10. The method of claim 9, wherein the one or more nitrile solvents are selected from the group consisting of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and combinations thereof.

11. The method of claim 1, wherein the catalytic solvent comprises an aryl solvent substituted with one or more nitrile groups, an alkyl solvent substituted with one or more nitrile groups, or a combination thereof.

12. The method of claim 11, wherein the aromatic solvent substituted with one or more nitrile groups and the secondary sulfide are present in a molar ratio of about 0.5:1 to about 1.5:

1.

13. The method of claim 11, wherein the combination of the aryl solvent substituted with one or more nitrile groups and the alkyl solvent substituted with one or more nitrile groups and the secondary sulfide are present in a molar ratio of about 0.5:1 to about 1.5:

1.

14. The method of claim 11, wherein the alkyl solvent substituted with one or more nitrile groups and the aryl solvent substituted with one or more nitrile groups are present in a molar ratio of about 6:1 to about 12:

1.

15. The method of claim 1, wherein the bystander solvent comprises a hydrocarbon-based solvent.

16. The method of claim 15, wherein the spectator solvent comprises an alkane or a blend of alkanes, xylene, toluene, benzene, decalin, 1,2,3,4-tetralin, or a combination thereof.

17. The method of claim 1, further comprising heating the sulfide-based solid electrolyte to a temperature of about 350°C to about 550°C.

18. The method of claim 1, further comprising grinding the mixture or drying the sulfide-based solid electrolyte under vacuum or at atmospheric pressure.

19. The method of claim 1, further comprising producing a phosphorothioate intermediate.

20. The method of claim 19, wherein the phosphorothioate intermediate comprises P2S6 4- and / or PS( 4-x )O x , where x is between 0 and 4.

21. The method of claim 1, wherein the sulfide-based solid electrolyte comprises Li3PS4.

22. The method of claim 21, wherein the sulfide-based solid electrolyte comprises fewer impurities compared to a sulfide-based solid electrolyte prepared with a non-coordinating, non-reactive solvent.

23. The method of claim 21, wherein the ionic conductivity of the sulfide-based solid electrolyte is at least 25% greater than the ionic conductivity of a sulfide-based solid electrolyte prepared with a non-coordinating, non-reactive solvent.

24. A method for producing a sulfide-based solid-state electrolyte having an argyrodite phase, the method comprising: mixing a sulfide-based solid electrolyte precursor comprising Li2S, P2S5, and LiX in a blend of solvents comprising a catalytic solvent and a spectator solvent to produce a sulfide-based solid electrolyte, wherein X = F, Cl, Br or I; and crystallizing the sulfide-based solid electrolyte, The sulfide-based solid electrolyte precursor requires half (50%) or less of the mixing time required when using only a spectator solvent in the presence of the catalytic solvent.

25. A composition comprising Li3PS4 and a thiophosphate and an argyrodite phase, wherein the thiophosphate comprises one or more of PS4 and P2S7 and P2S6, wherein the composition comprises 0.01 wt% to 0.90 wt% of a nitrile selected from the group consisting of acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and combinations thereof.

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