Solid electrolyte material with increased water content

Abstract

Described in the present disclosure is a solid electrolyte material having a high water content. The electrolyte material may include Li, T, X, A, O, and optionally Y, where T is at least one element selected from the group consisting of P, As, Si, Ge, Al, and B; X and, if present, Y are halogens or pseudohalogens; and A is at least one element selected from the group consisting of S, Se, and N. The electrolyte material is generally produced by exposing an electrolyte precursor to a predetermined amount of water during production. A method for producing the solid electrolyte material, a method for producing the solid electrolyte material, and an electrochemical cell including the solid electrolyte material are also described in the present disclosure.

Description

[Technical Field]

[0001] Cross-reference of related applications This Patent Cooperation Treaty (PCT) application is related to and claims priority to U.S. Provisional Patent Application No. 63 / 291,835, “Solid-State Electrolyte Materials Having Increased Water Content,” filed on 20 December 2021, and its entire contents are incorporated herein by reference in full for any purpose.

[0002] This disclosure relates to solid electrolyte materials. Therefore, this disclosure relates to the fields of electronics, chemistry, and materials science. [Background technology]

[0003] The development of solid-state battery technology is progressing based on the known drawbacks of liquid electrolyte-based batteries, and simultaneously, in response to the explosive growth of battery-powered devices. Lithium-based solid electrolytes, including argyrodite-like materials such as Li6PS5Cl, are widely studied due to their high ionic conductivity. However, electrolytes such as argyrodite-like materials are also highly reactive with cathode materials. Generally, sulfur in the electrolyte, when placed near a nickel cathode, reacts with nickel to form nickel sulfide, degrading the cathode surface. This can lead to a decrease in the ion / electron separation of the cathode material and a reduction in its electrochemical performance.

[0004] Because water is an electrolyte precursor, its presence must be avoided during the synthesis of electrolyte materials. Therefore, in order to reduce the degradation of the electrolyte precursor and thereby maximize ionic conductivity, the production of electrolyte materials without water has been pursued.

[0005] A solid electrolyte material is needed that has high ionic conductivity and low reactivity with the cathode material. In particular, various embodiments of this disclosure have been devised in consideration of the above findings. [Overview of the Initiative]

[0006] The present invention describes a solid electrolyte material comprising Li, T, X, A, O, and optionally Y, where T is at least one element selected from the group consisting of P, As, Si, Ge, Al, and B; X and, when present, Y are a halogen or a pseudohalogen; A is at least one element selected from the group consisting of S, Se, and N; and the electrolyte material has FT-IR peaks at about 975 cm v , , , w , , z ,

[0007] ±25 cm -1 、690 cm -1 ±25 cm -1 、and 525 cm -1 ±25 cm -1 The solid electrolyte material having FT-IR peaks at -1 . In some embodiments, T is P. In some embodiments, X is Cl. In some embodiments, A is S. In some embodiments, the solid electrolyte material has the formula Li 7-w-z PS 6-w-z-v O v X w Y z represented by. In some aspects, 0 < v ≦ 1. In some embodiments, the solid electrolyte material may have an FT-IR spectrum as shown in FIG. 2. In some embodiments, the amount of oxygen present in the solid electrolyte material is based on exposure to 40 - 1000 ppm of water. In some embodiments, an electrochemical cell comprising the electrolyte material has a higher discharge capacity compared to an electrochemical cell comprising the same electrolyte material lacking an oxygen component synthesized with 0 ppm of H2O. In some embodiments, an electrochemical cell comprising the electrolyte material has a higher first cycle efficiency (FCE) compared to an electrochemical cell comprising the same electrolyte material lacking an oxygen component exposed to 0 ppm of H2O. In some embodiments, an electrochemical cell comprising the electrolyte material has a lower resistance increase compared to an electrochemical cell comprising the same electrolyte material lacking an oxygen component exposed to 0 ppm of H2O.

[0007] Further described herein is the following reaction: XLi2S(Appm H2O ) + YP2S 5(Bppm H2O) + ZLi X(Cppm H2O) + W solvent (Dppm H2O) → Li6P S5-E O E Cl + W solvent [Where E = (X * A) + (Y * B) + (Z * C) + (W * D), where A, B, C, and D are ppm of H2O per unit mass, and Z, Y, Z, and W are per unit mass.) Mix the reactants according to, to produce a solid electrolyte material of the formula Li6PS 5-E O E Cl, and control the ppm of water in each precursor and solvent to produce an electrolyte material having high ionic conductivity and low reactivity with a high nickel content cathode. A method for manufacturing a solid electrolyte material, which includes

[0008] Further described herein is an electrochemical cell including a positive electrode and an electrolyte material disposed between the positive electrode and the negative electrode, wherein the electrolyte material has a general structure Li 7-w-z PS 6-w-z-v O v X w Y z (where X and Y are each one or more of halogens or pseudohalogens, 0 ≦ w ≦ 2, 0 ≦ z ≦ 2, and 0 < v ≦ 1). In some embodiments, X and Y are each selected from the group consisting of F, Cl, Br, I, BF4, BH4, NO2, NO3, and mixtures thereof. In some embodiments, the electrolyte material has an FT-IR spectrum having absorption peaks at about 975 ± 25 cm -1 , 690 ± 25 cm -1 and 525 ± 25 cm -1 . In some embodiments, the electrochemical cell has a general formula Li 7-w-z PS 6-w-z X w Yz It has a higher discharge capacity compared to materials having the general formula Li. In some embodiments, the electrochemical cell is Li 7-w-z PS 6-w-z X w Y z It has a higher first-cycle efficiency compared to materials having the general formula Li. In some embodiments, the electrochemical cell has a first-cycle efficiency of at least about 88%. In some embodiments, the electrochemical cell has a general formula Li 7-w-z PS 6-w-z X w Y z It has a lower charging resistance compared to materials having [specific characteristics]. In some embodiments, the electrolyte material has at least 1 × 10 -4 mS / cm It may have the following ionic conductivity.

[0009] Further included herein are electrochemical cells comprising a positive electrode and an electrolyte material disposed between the positive electrode and a negative electrode, wherein the electrolyte material comprises Li, S, and P. In some embodiments, the electrolyte material further comprises at least one of halogens or pseudohalogens.

[0010] Further described herein are methods for producing an electrolyte material, comprising milling a mixture comprising: a plurality of electrolyte precursors, each comprising one or more lithium (Li)-containing materials; one or more phosphorus (P)-containing materials; a halide or pseudohalide; one or more solvents; and water. In some embodiments, the electrolyte precursor further comprises a sulfur (S)-containing material. In some embodiments, the electrolyte precursor further comprises one or more halide-containing materials or pseudohalide-containing materials. In some embodiments, the method further comprises heating the mixture after milling. In some embodiments, heating may result in crystallization of the mixture to form an electrolyte material. In some embodiments, the mixture may contain at least 100 ppm of water, about 250 ppm of water, about 500 ppm of water, about 1000 ppm of water, or about 100,000 ppm of water. In some embodiments, water is added to the solvent before milling. In some embodiments, at least one of the plurality of electrolyte precursors is an anhydrous. In some embodiments, the amount of water added is predetermined based on the amount of water contained in the electrolyte precursors and the amount of water contained in the solvent. In some embodiments, the solvent is a low-polarity aprotic solvent. In some aspects, the solvent may be selected from the group consisting of xylene, benzene, toluene, heptane and combinations thereof. In some additional embodiments, the solvent may include ethers, esters, nitriles, ketones, or alcohols.

[0011] Further described herein is an electrochemical cell comprising a positive electrode, an electrolyte material, and a negative electrode, wherein the electrolyte material is placed between the positive electrode and the negative electrode, and the electrolyte material is manufactured by a method comprising milling a mixture comprising: a plurality of electrolyte precursors, each electrolyte precursor comprising one or more lithium (Li)-containing materials; one or more phosphorus (P)-containing materials; a halide or pseudohalide; one or more solvents; and water. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 shows a flowchart of the process for manufacturing the solid electrolyte material of this disclosure.

[0013] [Figure 2] Figure 2 shows FT-IR plots of the electrolyte materials of this disclosure having water content of 0 ppm, 100 ppm, 250 ppm, 500 ppm, and 1000 ppm.

[0014] [Figure 3A] Figure 3A is a graph showing the performance characteristics of the electrolyte materials of this disclosure having water content of 0 ppm, 100 ppm, 250 ppm, 500 ppm, and 1000 ppm. [Figure 3B] Figure 3B is a graph showing the performance characteristics of the electrolyte materials of this disclosure having water content of 0 ppm, 100 ppm, 250 ppm, 500 ppm, and 1000 ppm. [Figure 3C] Figure 3C is a graph showing the performance characteristics of the electrolyte materials of this disclosure having water content of 0 ppm, 100 ppm, 250 ppm, 500 ppm, and 1000 ppm.

[0015] [Figure 4] Figure 4 shows a plot of X-ray diffraction measurements of a solid electrolyte material produced by the process of this disclosure.

[0016] [Figure 5] Figure 5 shows a plot of X-ray diffraction measurements of a solid electrolyte material manufactured by the process of this disclosure. [Modes for carrying out the invention]

[0017] Before the disclosure and description of the present invention, it should be understood that the present invention is not limited to the specific methods, compositions, or materials disclosed herein, but extends to equivalents thereof that would be recognized by those skilled in the art. It should also be understood that the terminology used herein is used solely for the purpose of describing specific embodiments and is not intended to limit them.

[0018] Concentration, quantity, and other numerical data may be expressed or presented in range form as specified herein. Such range forms are used solely for convenience and brevity and should be interpreted flexibly to include not only the numbers explicitly listed as limits to the range, but also all individual numbers or subranges contained within that range, as if each number and subrange were explicitly listed. For example, the numerical range “approximately 2 to approximately 50” should be interpreted to include not only the explicitly listed values ​​from 2 to 50, but also the individual values ​​and subranges within the indicated range. Therefore, this numerical range includes individual values ​​such as 2, 2.4, 3, 3.7, 4, 5.5, 10, 10.1, 14, 15, 15.98, 20, 20.13, 23, 25.06, 30, 35.1, 38.0, 40, 44, 44.6, 45, 48, 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, and 2-50. This same principle applies to ranges that list only one numerical value as the minimum or maximum value. Furthermore, such interpretations should apply regardless of the width of the range or feature described.

[0019] When used herein, the term “approximately” is used to give flexibility to the endpoints of a numerical range by defining that a given value can be “slightly above” or “slightly below” the endpoint. For example, the endpoints can be within 10%, 8%, 5%, 3%, 2%, or 1% of the enumerated value. Furthermore, for convenience and brevity, the numerical range “approximately 50 mg / mL to approximately 80 mg / mL” should be understood to also support the range “50 mg / mL to 80 mg / mL”. The endpoints may also be based on the variability permitted by the appropriate regulatory body, such as the FDA or USP.

[0020] In this disclosure, the terms “include,” “contain,” and / or “have” are understood to mean “include / contain,” and are open-ended terms.

[0021] As used herein, “pseudohalogen” and “pseudohalide” refer to compounds whose chemical properties are similar to those of halogen elements and halide ions. The terms “pseudohalogen” and “pseudohalide” may be used interchangeably with “superhalogen” or “superhalide,” respectively.

[0022] This specification describes solid electrolyte materials synthesized using a predetermined amount of water, which have superior performance characteristics compared to similar electrolyte materials synthesized with little or no exposure to water. In some preferred embodiments, the electrolyte materials described herein exhibit superior performance with respect to discharge capacity, efficiency, and charging resistance.

[0023] The solid electrolytic material of this disclosure may be a lithium argyrodite-like material, or a hydrate or solvate thereof. Lithium argyrodite-like materials are generally known and described in the art, and have a general structure Li + (12-n-y) T n+ A 2- (6-y) X - (y)It has. In some embodiments, the solid electrolyte material is Li3PS4, Li7PS6, Li7P3S 11 The formula may also include Li4PS4X and Li7P2S8X, where X is a halogen or pseudohalogen.

[0024] Generally, electrolyte materials such as lithium argyrodite-like materials are preferably synthesized in the absence of little to no water. Exposure to water during the manufacturing process introduces oxygen into the electrolyte material, which can substitute for atoms such as sulfur and / or phosphorus in the electrolyte material and / or form bridging oxygen bonds with sulfur (e.g., SOS) or phosphorus (e.g., POP). The resulting oxygenated electrolyte material has a significantly lower ionic conductivity than oxygen-free electrolyte material, sometimes by more than an order of magnitude (e.g., one-thousandth) lower. Therefore, electrolyte materials are generally manufactured in a dry, oxygen-free environment with highly controlled humidity and gas content.

[0025] Furthermore, the presence of oxygen reduces the reactivity of certain cathode materials, such as nickel and cobalt, which are highly reactive with sulfur. In electrochemical cells containing a sulfur-containing electrolyte and a nickel-containing cathode, nickel reacts with sulfur to form nickel sulfide. If the reaction continues, nickel sulfide and other by-products can ionically segregate the cathode material, potentially degrading the performance of the battery cell.

[0026] However, unexpectedly and surprisingly, it has been found that by synthesizing an electrolyte material using a predetermined amount of water, one or more aspects of the performance of an electrochemical cell comprising the electrolyte material can be improved. The water is present during the milling of the solid electrolyte precursor and is converted to lithium-oxygen species and H2S during electrolyte synthesis. Thus, the synthesized electrolyte material contains trace amounts of water or no water at all. That is, the inventors have found that initially the critical current density decreases significantly, but that increasing the oxygen content of the electrolyte material further results in an increase in ionic conductivity, approaching that of an oxygen-free electrolyte material. Furthermore, an electrochemical cell manufactured using the electrolyte material of the present disclosure has surprisingly been found to have a greater first cycle efficiency compared to an electrochemical cell manufactured using an oxygen-free electrolyte material. Without being bound by any particular theory, the performance improvement may be due to an improvement in the interfacial contact between the cathode material and the electrolyte material. In addition, the solid electrolyte material may form a more stable interface between itself and the cathode material, and as a result, the degradation of the cathode material may be reduced. If the electrolyte material itself contains a certain amount of oxygen, particularly near the surface where it can form an interface with an oxygen-containing cathode material, the driving force for the reaction is reduced, and thus the interfacial reaction is reduced.

[0027] Thus, the electrolyte material of the present disclosure strikes a surprising and unexpected balance between maintaining high ionic conductivity and reducing the activity of cathode materials such as nickel.

[0028] I. Electrolyte Material The solid electrolyte material of the present disclosure comprises lithium (Li), T, X, A, and oxygen (O). In some embodiments, the solid electrolyte material may also comprise Y. In some embodiments, the solid electrolyte material has the formula Li 7-w-z TA 6-w-z-v O v X w Y [[ID=..]] z (where 0 ≦ w ≦ 2, 0 ≦ z ≦ 2, and 0 < v ≦ 2).

[0029] In some embodiments, T can be selected from the group consisting of phosphorus (P), arsenic (As), silicon (Si), germanium (Ge), aluminum (Al), boron (B), and mixtures thereof. In an unrestricted example, T is phosphorus.

[0030] In some embodiments, X and, if present, Y can be halogens or pseudohalogens. In some embodiments, if X and / or Y are halogens, the halogens can be selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), or combinations thereof. In some embodiments, if X and / or Y are pseudohalogens, the pseudohalogens can be boron hydride (BH4). - ), fluoroboric acid (BF4 - ), azanide (NH2 - ), nitrogen trioxide (NO3 - ), cyanide (CN - ), hydroxide (OH - ), thiocyanate (SCN - ), hydrosulfide (SH - ) and other pseudohalogens known in the art, as well as combinations thereof. In a non-limiting example, X is chlorine.

[0031] In some embodiments, A may be at least one element selected from the group consisting of sulfur (S), selenium (Se), and nitrogen (N). In a non-limiting example, A is sulfur.

[0032] The solid electrolyte materials of this disclosure may have a unique FT-IR signal due to the presence of oxygen in the electrolyte material (see, for example, Figure 2). In some embodiments, the FT-IR spectrum of the electrolyte materials of this disclosure is approximately 975 cm⁻¹. -1 ±25cm -1 , about 690cm -1 ±25cm -1 and approximately 525cm -1 ±25cm -1It may have a peak. In some non-limiting examples, solid electrolyte materials may have FT-IR spectra as shown in Figure 2.

[0033] The solid electrolyte materials of this disclosure may have a unique X-ray diffraction pattern (XRD). For example, Li 5.5 PS 4.5 Solid electrolyte materials of the present disclosure containing Cl may have peaks at 2θ = 15.6°±0.5°, 18.0°±0.5°, 25.5°±0.5°, 29.9°±0.5°, and 31.5°±0.5°. As another example, solid electrolyte materials of the present disclosure containing LiCl may have a peak at 2θ = 34.8°±0.5°. As yet another example, solid electrolyte materials of the present disclosure containing Li2S may have a peak at 2θ = 27.2°±0.5°.

[0034] As described above, oxygen is incorporated into the electrolyte material by the presence of water during the synthesis process. In some embodiments, the amount of oxygen incorporated into the solid electrolyte material and the amount of water present during the synthesis process can be predetermined.

[0035] In some ways, the amount of oxygen present in a solid electrolyte material can be based on exposure to 40-5000 ppm of water during the synthesis process. Therefore, the amount of oxygen present in a solid electrolyte material can range from approximately 40 ppm to 100 ppm of water, approximately 100 ppm to approximately 200 ppm of water, approximately 200 ppm to approximately 300 ppm of water, approximately 300 ppm to approximately 400 ppm of water, approximately 400 ppm to approximately 500 ppm of water, approximately 500 ppm to approximately 600 ppm of water, and approximately 600 ppm to approximately 700 ppm of water. This can be obtained based on exposure to water at concentrations of approximately 700 ppm to 800 ppm, 800 ppm to 900 ppm, 900 ppm to 1000 ppm, 1000 ppm to 2000 ppm, 2000 ppm to 3000 ppm, 3000 ppm to 4000 ppm, or 4000 ppm to 5000 ppm. In some ways, the amount of oxygen present in a solid electrolyte material is approximately 40 ppm to 200 ppm, approximately 40 ppm to 300 ppm, approximately 40 ppm to 400 ppm, approximately 40 ppm to 500 ppm, approximately 40 ppm to 600 ppm, approximately 40 ppm to 700 ppm, approximately 40 ppm to 800 ppm, approximately 40 ppm to 900 ppm, approximately 40 ppm to 1000 ppm, approximately 40 ppm to 2000 ppm, approximately 40 ppm to 3000 ppm, approximately 40 ppm to 4000 ppm, and approximately 3 This can be based on exposure to water ranging from 000 ppm to approximately 5000 ppm, approximately 2000 ppm to approximately 5000 ppm, approximately 1000 ppm to approximately 5000 ppm, approximately 900 ppm to approximately 5000 ppm, approximately 800 ppm to approximately 5000 ppm, approximately 700 ppm to approximately 5000 ppm, approximately 600 ppm to approximately 5000 ppm, approximately 500 ppm to approximately 5000 ppm, approximately 400 ppm to approximately 5000 ppm, approximately 300 ppm to approximately 5000 ppm, approximately 200 ppm to approximately 5000 ppm, or approximately 100 ppm to approximately 5000 ppm.In yet another embodiment, the amount of oxygen present in the solid electrolyte material may be based on exposure to water of about 40 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 2000 ppm, 3000 ppm, 4000 ppm, or about 5000 ppm. In some embodiments, the amount of oxygen present in the solid electrolyte material may be based on exposure to water greater than about 5000 ppm. In some non-limiting examples, the amount of oxygen present in the solid electrolyte material may be based on exposure to water of about 100 ppm, about 250 ppm, about 500 ppm, or about 1000 ppm. In further embodiments, the amount of oxygen present in the solid electrolyte material may be based on exposure to at least about 40 ppm of water, at least about 100 ppm of water, at least about 200 ppm of water, at least about 300 ppm of water, at least about 400 ppm of water, at least about 500 ppm of water, at least about 600 ppm of water, at least about 700 ppm of water, at least about 800 ppm of water, at least about 900 ppm of water, at least about 1000 ppm of water, at least about 2000 ppm of water, at least about 3000 ppm of water, at least about 4000 ppm of water, or at least about 5000 ppm of water.

[0036] In some additional embodiments, the amount of oxygen present in the solid electrolyte material may be based on exposure to approximately 40 to approximately 100,000 ppm of water during the synthesis process. The amount of oxygen present in the solid electrolyte material may be based on exposure to approximately 40 ppm to approximately 100 ppm, approximately 100 ppm to approximately 500 ppm, approximately 500 ppm to approximately 1,000 ppm, approximately 1,000 ppm to approximately 5,000 ppm, approximately 5,000 ppm to approximately 10,000 ppm, approximately 10,000 ppm to approximately 25,000 ppm, approximately 25,000 ppm to approximately 50,000 ppm, approximately 50,000 ppm to approximately 75,000 ppm, or approximately 75,000 ppm to approximately 100,000 ppm. In addition, the amount of oxygen present in the solid electrolyte material is approximately 100 ppm to 500 ppm, approximately 100 ppm to 1,000 ppm, approximately 100 ppm to 5,000 ppm, approximately 100 ppm to 10,000 ppm, approximately 100 ppm to 25,000 ppm, approximately 100 ppm to 50,000 ppm, approximately 100 ppm to 75,000 ppm, and approximately 100 ppm to 100,000 ppm. This can be based on exposure levels of 0 ppm, approximately 500 ppm to approximately 100,000 ppm, approximately 1,000 ppm to approximately 100,000 ppm, approximately 5,000 ppm to approximately 100,000 ppm, approximately 10,000 ppm to approximately 100,000 ppm, approximately 25,000 ppm to approximately 100,000 ppm, approximately 50,000 ppm to approximately 100,000 ppm, or approximately 75,000 ppm to approximately 100,000 ppm. In some examples, the amount of oxygen present in the solid electrolyte material can be based on exposure levels of approximately 40 ppm, 100 ppm, 500 ppm, 1,000 ppm, 5,000 ppm, 10,000 ppm, 25,000 ppm, 50,000 ppm, 75,000 ppm, or 100,000 ppm.

[0037] In some embodiments, the solid electrolyte material of the present disclosure is of the general formula Li (7-w-z) PS (6-w-z) X w Y z(Where X and Y are each a halogen or a pseudohalogen, 0 ≦ w ≦ 2, 0 ≦ z ≦ 2, and w + z = 2), it may have improved performance compared to a solid electrolyte material. In some additional embodiments, the solid electrolyte material of the present disclosure may have improved performance compared to the same electrolyte material synthesized using 0 ppm of H2O and / or lacking an oxygen component. Criteria for measuring the improved performance include discharge capacity, first cycle efficiency, and lower charge resistance.

[0038] In some embodiments, the solid electrolyte material of the present disclosure generally has the general formula Li (7-w-z) PS (6-w-z) X w Y z (Where X and Y are each a halogen or a pseudohalogen, 0 ≦ w ≦ 2, 0 ≦ z ≦ 2, and w + z = 2), it has a lower ionic conductivity compared to a solid electrolyte material. In some additional embodiments, the solid electrolyte material of the present disclosure may have a lower ionic conductivity compared to the same electrolyte material synthesized using 0 ppm of H2O and lacking an oxygen component. However, the improvements in the other measurement criteria described above outweigh this loss of ionic conductivity in many applications. In some embodiments, the ionic conductivity of the solid electrolyte of the present disclosure can be at least about 1×10 -6 mS / cm . In some aspects, the ionic conductivity of the solid electrolyte of the present disclosure can be at least about 1×10 -5 mS / cm , at least about 1×10 -4 mS / cm , or at least about 1×10 -3 mS / cm .

[0039] II. Method for manufacturing a solid electrolyte material The solid electrolyte material described in Section I can be synthesized by mixing reactants according to the following reaction. αLi2A (appmの水) +βT2A 5(bppmの水) +γLiX (cppmの水) + δLiY (dppmの水) + ε solvent (eppmの水) → Li 7-w-z TA 6-w-z-v O v X w Y z + ε solvent where v = (α * a) + (β * b) + (γ * c) + (δ * d) + (ε * e), and a, b, c, d, and e are ppm of water per mole, α, β, γ, δ, and ε are moles.

[0040] The species of reactants A, T, X, and Y can be those described in Section I above. In some preferred embodiments, the reactive species may be anhydrides, i.e., the reactive species may each or collectively have a water content of 0 ppm. In other embodiments, the reactive species may each or collectively have a water content greater than 0 ppm. The water content of the reactants may be considered to determine how much water to add during the reaction to achieve the desired oxygen content of the electrolyte material. As used herein, the terms "reactant" and "reactive species" may be used interchangeably with the term "precursor" or "electrolyte precursor".

[0041] The solvent may be any low-polarity aprotic solvent. In some embodiments, the solvent may include one or more aromatic hydrocarbons (e.g., benzene, toluene, xylene), alkanes (e.g., pentane, hexane, heptane, octane, nonane, decane), cycloalkanes (e.g., cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane), chloroform, diethyl ether, and combinations thereof. In some embodiments, the solvent may have a low tendency to generate hydrogen sulfide gas when in contact with the electrolyte material precursor or the final electrolyte material. Preferably, the solvent may remain in a liquid state for at least part of the milling process or for the entire milling process (see Section III below). The solvent may have a water content of 0 ppm or more. In some embodiments, water may be added to the solvent to achieve a desired oxygen content in the electrolyte material. In some additional embodiments, the reaction may involve the use of one or more cosolvents selected from the above solvents.

[0042] The solvent may include ethers. Examples of ethers suitable for use in the methods described herein include tetrahydrofuran, diethyl ether, dibutyl ether, dipentyl ether, dimethoxyethane (DME), dioxane, anisole and combinations thereof, as well as other ethers known in the art.

[0043] The solvent may include esters. Examples of esters suitable for use in the methods described herein include ethyl acetate, ethyl butyrate, isobutyl acetate, butyl acetate, butyl butyrate, and butyl propanoate and combinations thereof, as well as other esters known in the art.

[0044] The solvent may include a nitrile. Examples of nitriles suitable for use in the methods described herein include acetonitrile, propionitrile, butyronitrile, isobutyronitrile and combinations thereof, as well as other nitriles known in the art.

[0045] The solvent may include an alcohol. Examples of alcohols suitable for use in the methods described herein include methanol, ethanol, propanol, butanol, isopropanol, isobutanol and combinations thereof, as well as other alcohols known in the art.

[0046] The solvent may include ketones. Examples of ketones suitable for use in the methods described herein include acetone, cyclohexanone, diacetone, methyl ethyl ketone, methyl isobutyl ketone and combinations thereof, as well as other ketones known in the art.

[0047] The ppm levels of each reactant and the solvent water can be controlled to produce an electrolyte material having high ionic conductivity and low reactivity to cathodes, such as those with a high nickel content.

[0048] In some embodiments, the total water content of the mixture (i.e., reactants and solvent) can be 40 to 5000 ppm of water. Therefore, the total water content of the mixture can be approximately 40 ppm to 100 ppm, approximately 100 ppm to 200 ppm, approximately 200 ppm to 300 ppm, approximately 300 ppm to 400 ppm, approximately 400 ppm to 500 ppm, approximately 500 ppm to 600 ppm, approximately 600 ppm to 700 ppm, approximately 700 ppm to 800 ppm, approximately 800 ppm to 900 ppm, approximately 900 ppm to 1000 ppm, approximately 1000 ppm to 2000 ppm, approximately 2000 ppm to 3000 ppm, approximately 3000 ppm to 4000 ppm, or approximately 4000 ppm to 5000 ppm. In some ways, the total water content of the mixture is approximately 40 ppm to 200 ppm, 40 ppm to 300 ppm, 40 ppm to 400 ppm, 40 ppm to 500 ppm, 40 ppm to 600 ppm, 40 ppm to 700 ppm, 40 ppm to 800 ppm, 40 ppm to 900 ppm, 40 ppm to 1000 ppm, 40 ppm to 2000 ppm, 40 ppm to 3000 ppm, 40 ppm to 4000 ppm, and 3000 ppm. It can be water at 100 ppm to approximately 5000 ppm, water at 2000 ppm to approximately 5000 ppm, water at 1000 ppm to approximately 5000 ppm, water at 900 ppm to approximately 5000 ppm, water at 800 ppm to approximately 5000 ppm, water at 700 ppm to approximately 5000 ppm, water at 600 ppm to approximately 5000 ppm, water at 500 ppm to approximately 5000 ppm, water at 400 ppm to approximately 5000 ppm, water at 300 ppm to approximately 5000 ppm, water at 200 ppm to approximately 5000 ppm, or water at 100 ppm to approximately 5000 ppm.In yet another embodiment, the total water content of the mixture may be about 40 ppm water, 100 ppm water, 200 ppm water, 300 ppm water, 400 ppm water, 500 ppm water, 600 ppm water, 700 ppm water, 800 ppm water, 900 ppm water, 1000 ppm water, 2000 ppm water, 3000 ppm water, 4000 ppm water, or about 5000 ppm water. In some embodiments, the total water content of the mixture may be more than about 5000 ppm water. In some non-limiting examples, the total water content of the mixture may be about 100 ppm water, about 250 ppm water, about 500 ppm water, or about 1000 ppm water. In further embodiments, the total water content of the mixture may be at least about 40 ppm of water, at least about 100 ppm of water, at least about 200 ppm of water, at least about 300 ppm of water, at least about 400 ppm of water, at least about 500 ppm of water, at least about 600 ppm of water, at least about 700 ppm of water, at least about 800 ppm of water, at least about 900 ppm of water, at least about 1000 ppm of water, at least about 2000 ppm of water, at least about 3000 ppm of water, at least about 4000 ppm of water, or at least about 5000 ppm of water.

[0049] In some additional ways, the total water content of the mixture can be about 40 to about 100,000 ppm of water. The total water content of the mixture can be about 40 ppm to about 100 ppm, about 100 ppm to about 500 ppm, about 500 ppm to about 1,000 ppm, about 1,000 ppm to about 5,000 ppm, about 5,000 ppm to about 10,000 ppm, about 10,000 ppm to about 25,000 ppm, about 25,000 ppm to about 50,000 ppm, about 50,000 ppm to about 75,000 ppm, or about 75,000 ppm to about 100,000 ppm. In addition, the total water content of the mixture is approximately 100 ppm to 500 ppm, 100 ppm to 1,000 ppm, 100 ppm to 5,000 ppm, 100 ppm to 10,000 ppm, 100 ppm to 25,000 ppm, 100 ppm to 50,000 ppm, 100 ppm to 75,000 ppm, and 100 ppm to 100,000 ppm. The levels can be approximately 500 ppm to 100,000 ppm, approximately 1,000 ppm to 100,000 ppm, approximately 5,000 ppm to 100,000 ppm, approximately 10,000 ppm to 100,000 ppm, approximately 25,000 ppm to 100,000 ppm, approximately 50,000 ppm to 100,000 ppm, or approximately 75,000 ppm to 100,000 ppm. In some examples, the total water content of the mixture can be approximately 40 ppm, 100 ppm, 500 ppm, 1,000 ppm, 5,000 ppm, 10,000 ppm, 25,000 ppm, 50,000 ppm, 75,000 ppm, or 100,000 ppm.

[0050] The reaction generally takes place in an inert atmosphere containing or consisting of argon (Ar) or nitrogen (N2) gas. In some embodiments, the inert atmosphere may have a water content of 0 ppm. This has the effect of controlling the amount of water added to the solid electrolyte material and preventing excess water from reacting with the solid electrolyte material. In other embodiments, the atmosphere may have a water content greater than 0 ppm.

[0051] The reaction can occur over a period of approximately 6 seconds to approximately 200 hours. In some embodiments, the reaction can occur over a period of 6 seconds, 15 seconds, 30 seconds, 1 minute, 5 minutes, 15 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 12 hours, 24 hours, 48 ​​hours, 100 hours, 200 hours, or more than 200 hours. Those skilled in the art will understand that the duration of the reaction may be influenced by several variables, such as energy input, temperature, particle size of reactants, and solvent type.

[0052] The final electrolyte material may contain impurities. In some embodiments, the impurities may include reactants that were not fully incorporated into the solid electrolyte material. In some examples, the impurities may include LiX (wherein X is a halogen or pseudohalogen), Li2S, or other reactants.

[0053] Normally, electrolyte materials synthesized in a dry state react with water and / or air in the environment, causing phosphorus and sulfur species in the electrolyte to combine with oxygen, releasing sulfur in the form of H2S. This reaction degrades the electrolyte material. Surprisingly, it has been found that by incorporating oxygen in the form of water into the synthesis of solid electrolyte materials and substituting some of the sulfur atoms with oxygen, the reaction between the electrolyte and water / air can be slowed down.

[0054] Furthermore, the presence of oxygen in the solid electrolyte material slows down the reaction between the electrolyte and the high-nickel-containing cathode. When the electrolyte comes into contact with the surface of a cathode containing a high concentration of nickel, the sulfur in the electrolyte reacts with the nickel to form nickel sulfide (NiS). This reaction degrades both the electrolyte and the cathode. Surprisingly, it was found that substituting sulfur atoms in the solid electrolyte material with oxygen reduces the reactivity of both the electrolyte material and the cathode, resulting in a slower degradation of both the electrolyte and the cathode.

[0055] In some embodiments, the degradation rate of the solid electrolyte and / or cathode can be determined by measuring the capacity of the electrochemical cell as it is charged and discharged over time. In some further embodiments, the degradation rate of the solid electrolyte and / or cathode can be determined by measuring the first cycle efficiency of the electrochemical cell.

[0056] III. Method for manufacturing electrolyte materials Figure 1 shows a flowchart of a process for producing the solid electrolyte compositions of the present disclosure. Process 100 begins with preparation step 110, where any preparatory operations such as precursor synthesis, purification, and apparatus preparation may be performed. After any initial preparation, process 100 proceeds to step 120, where lithium-containing materials, phosphorus-containing materials, sulfur-containing materials, selenium-containing materials, nitrogen-containing materials, and mixtures thereof, such as those described in Sections I and II, can be combined with one or more solvents and / or other liquids. Some materials may be classified into multiple categories. For example, lithium sulfide (Li2S) may be considered both a lithium-containing material and a sulfur-containing material. In some embodiments, each of the materials may be provided as a powder, granules, pellets, bricks, flakes, or other dry or solid form known in the art. In some examples, each of the materials may be provided in powder form. When the materials are provided in powder form, they may be provided as crystalline powders, amorphous powders, or both. One or more solvents may be one or more low-polarity aprotic solvents, such as those described in Section II.

[0057] In some embodiments, lithium-containing materials include lithium metal, lithium sulfide (Li2S), lithium chloride (LiCl), lithium nitride (Li3N), lithium borohydride (LiBH4), lithium fluoroborate (LiBF4), lithium amide (LiNH2), lithium nitrate (LiNO3), and mixtures thereof.

[0058] In some embodiments, the sulfur-containing material includes elemental sulfur, phosphorus pentasulfide (P2S5), and the material with the general chemical formula P4S5. x Examples include phosphorus sulfide (Li2S), lithium sulfide (Li2S), alkali metal sulfides, alkaline earth metal sulfides, boron sulfide (B2S3), aluminum sulfide (Al2S3), antimony trisulfide (Sb2S3), antimony pentasulfide (Sb2S5), germanium sulfide (Ge2S3), silicon trisulfide (Si2S3), copper sulfide (CuS), copper disulfide (CuS2), zinc sulfide (ZnS), iron sulfide (FeS2), tin sulfide (SnS), and mixtures thereof, all having the general chemical formula P4S. x Phosphorus sulfides having the following properties (where 3 ≤ x ≤ 10): P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 Or combinations thereof. Further examples of alkali metal sulfides include sodium sulfide (Na2S), potassium sulfide (K2S), rubidium sulfide (Rb2S), and cesium sulfide (Cs2S). Further examples of alkaline earth metal sulfides include beryllium sulfide (BeS), calcium sulfide (CaS), magnesium sulfide (MgS), strontium sulfide (SrS), and barium sulfide (BaS). In some embodiments, phosphorus-containing materials include elemental phosphorus, phosphorus sulfides such as phosphorus pentasulfide (P2S5), phosphorus oxides such as phosphorus pentoxide (P2S5), and phosphorus with the general chemical formula P4S x Examples include phosphorus sulfide, phosphorus chloride such as phosphorus trichloride (PCl3) and phosphorus pentachloride (PCl5), phosphorus oxychloride (POCl3), and mixtures thereof, all having the formula (wherein 3 ≤ x ≤ 10).

[0059] In some embodiments, selenium-containing materials include selenium sulfide (Se2S), selenium disulfide (SeS2), and mixtures thereof.

[0060] The ratio and amount of the reaction compounds are not particularly limited, as long as the water content of the reaction compounds and one or more solvents is predetermined to achieve the desired oxygen content of the solid electrolyte material. The amount of solvent added can be predetermined based on the water content of each reaction compound and the water content of the solvent. Therefore, the amount of solvent added can be adjusted to achieve the desired oxygen content in the final electrolyte material. Furthermore, water may be added to the solvent or to the mixture of reaction compounds and solvents to achieve the desired oxygen content of the electrolyte material. Additional materials such as cosolvents and polymers may be added during this step 120.

[0061] Next, in step 130, the compositions may be mixed and / or milled for a predetermined time and temperature to produce a solid electrolyte as described in sections I and II. Mixing can be achieved by methods known to those skilled in the art. In some non-limiting examples, mixing is achieved using a planetary ball mill or an attritor mill. The mixing time is not particularly limited, as long as adequate homogenization and reaction of the precursors for producing the solid electrolyte material is possible. The mixing temperature is not particularly limited, as long as adequate mixing is possible and the temperature is not so high that the precursors become gaseous.

[0062] In some embodiments, proper mixing can be achieved over a period of about 6 seconds to about 200 hours at temperatures ranging from about -20°C to about 200°C. Those skilled in the art will understand that the time required for proper mixing can be influenced by various factors such as energy input, temperature, precursor particle size, and solvent type. In some embodiments, proper mixing can be achieved over a period of about 6 seconds, 30 seconds, 1 minute, 5 minutes, 10 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 6 hours, 12 hours, 24 hours, 36 hours, 48 ​​hours, 100 hours, 200 hours, or more than 200 hours. In some examples, proper mixing can be achieved over a period of about 10 minutes to about 48 hours. In some additional aspects, a suitable mixture can be achieved at temperatures of approximately -20°C to approximately 0°C, approximately 0°C to approximately 25°C, approximately 25°C to approximately 50°C, approximately 50°C to approximately 75°C, approximately 75°C to approximately 100°C, approximately 100°C to approximately 125°C, approximately 125°C to approximately 150°C, approximately 150°C to approximately 175°C, or approximately 175°C to approximately 200°C.

[0063] By introducing water before step 130 and milling / mixing the composition with more than 0 ppm of water, the resulting electrolyte material contains oxygen uniformly distributed throughout the composition, in contrast to compositions that contain only a surface layer of oxygen.

[0064] Next, in step 140, the composition may be dried in an inert atmosphere such as argon or nitrogen, or under vacuum, for a predetermined time and at a predetermined temperature. Drying can be carried out by either a static drying operation or, preferably, a stirred drying operation. Following drying, a heat treatment may be performed in any step 150. The temperature of the heat treatment is not particularly limited, as long as it is above the temperature required to produce the crystalline phase of the solid electrolyte material of this disclosure, or above the temperature required to enhance the ionic conductivity or compatibility with lithium metal. The material obtained from the heat treatment step 150 may be a single phase, or may include other crystalline phases, glass phases, and small amounts of precursor phases.

[0065] Generally, the heat treatment time is not limited as long as it allows for the formation of the desired composition and phase. The time can be, for example, in the range of about 1 minute to about 24 hours. In some embodiments, the heat treatment can be carried out for about 1 minute, 10 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 6 hours, about 12 hours, about 18 hours, or about 24 hours. Furthermore, the heat treatment may be carried out in an inert gas atmosphere (e.g., argon or nitrogen), a reducing atmosphere (e.g., hydrogen), or under vacuum. The heat treatment step 150 may be completely omitted if the desired composition and phase are achieved during the initial mixing and drying steps.

[0066] IV. Electrochemical Cells The solid electrolyte materials described herein may be used in a solid electrochemical cell. The solid electrolyte material may be placed between the positive and negative electrodes in a solid electrolyte material layer. The solid electrolyte material layer may contain the solid electrolyte material of the Disclosure at a concentration of about 10% to about 100% by volume. In some embodiments, the concentration of the solid electrolyte material of the Disclosure in the solid electrolyte material layer may be about 10% to about 20% by volume, about 20% to about 30% by volume, about 30% to about 40% by volume, about 40% to about 50% by volume, about 50% to about 60% by volume, about 60% to about 70% by volume, about 70% to about 80% by volume, about 80% to about 90% by volume, or about 90% to about 100% by volume. In some additional embodiments, the concentration of the solid electrolyte material of this disclosure in the solid electrolyte material layer may be about 10% to about 30% by volume, about 10% to about 40% by volume, about 10% to about 50% by volume, about 10% to about 60% by volume, about 10% to about 70% by volume, about 10% to about 80% by volume, about 10% to about 90% by volume, about 20% to about 100% by volume, about 30% to about 10% by volume, about 40% to about 100% by volume, about 50% to about 100% by volume, about 60% to about 100% by volume, about 70% to about 100% by volume, or about 80% to about 100% by volume. In further embodiments, the concentration of the solid electrolyte material of the present disclosure in the solid electrolyte material layer may be about 10% by volume, 20% by volume, 30% by volume, 40% by volume, 50% by volume, 60% by volume, 70% by volume, 80% by volume, 90% by volume, or about 100% by volume.

[0067] In some embodiments, the solid electrolyte material layer may include a binder or other modifier. In some embodiments, the binder may include polyvinyl chloride, polyaniline, poly(methyl methacrylate), nitrile butadiene rubber, styrene butadiene rubber, polystyrene, polyvinylidene fluoride, self-healing polymers, polyethylene oxide, or other binders known in the art, and combinations thereof.

[0068] The solid electrolyte material layer may have a thickness of approximately 1 μm to approximately 1000 μm. In some embodiments, the solid electrolyte material layer may have thicknesses of approximately 1 μm to approximately 5 μm, approximately 5 μm to approximately 10 μm, approximately 10 μm to approximately 15 μm, approximately 15 μm to approximately 20 μm, approximately 20 μm to approximately 25 μm, approximately 25 μm to approximately 30 μm, approximately 30 μm to approximately 35 μm, approximately 35 μm to approximately 40 μm, approximately 40 μm to approximately 45 μm, approximately 45 μm to approximately 50 μm, and approximately 50 μm. It may have a thickness of approximately 100 μm, approximately 100 μm to approximately 200 μm, approximately 200 μm to approximately 300 μm, approximately 300 μm to approximately 400 μm, approximately 400 μm to approximately 500 μm, approximately 500 μm to approximately 600 μm, approximately 600 μm to approximately 700 μm, approximately 700 μm to approximately 800 μm, approximately 800 μm to approximately 900 μm, or approximately 900 μm to approximately 1000 μm. In some additional embodiments, the solid electrolyte material layer is approximately 1 μm to 10 μm, approximately 1 μm to 15 μm, approximately 1 μm to 20 μm, approximately 1 μm to 25 μm, approximately 1 μm to 30 μm, approximately 1 μm to 35 μm, approximately 1 μm to 40 μm, approximately 1 μm to 45 μm, approximately 1 μm to 50 μm, approximately 1 μm to 100 μm, approximately 1 μm to 200 μm, approximately 1 μm to 300 μm, approximately 1 μm to 400 μm, approximately 1 μm to 500 μm, approximately 1 μm to 600 μm, approximately 1 μm to 700 μm, approximately 1 μm to 800 μm, approximately 1 μm to 900 μm, approximately 5 μm to 1000 μm, approximately 10 μm It may have a thickness of approximately 1000 μm, 15 μm to 1000 μm, 20 μm to 1000 μm, 25 μm to 1000 μm, 30 μm to 1000 μm, 35 μm to 1000 μm, 40 μm to 1000 μm, 45 μm to 1000 μm, 50 μm to 1000 μm, 100 μm to 1000 μm, 200 μm to 1000 μm, 300 μm to 1000 μm, 400 μm to 1000 μm, 500 μm to 1000 μm, 600 μm to 1000 μm, 700 μm to 1000 μm, or 800 μm to 1000 μm. In yet another embodiment, the solid electrolyte material layer may have a thickness of 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or about 1000 μm.

[0069] An electrochemical cell may include a positive electrode. The positive electrode may be formed from a material including aluminum, nickel, titanium, stainless steel, and carbon. In some embodiments, the positive electrode may include a positive electrode current collector and a positive electrode composite. The positive electrode composite may include a positive electrode active material, a binder, and a conductive additive. In some embodiments, the positive electrode active material may include metal oxides, metal phosphates, metal sulfides, sulfur, lithium sulfide, oxygen, air, or other materials known in the art. The positive electrode active material may have a thickness of about 1 μm to about 1000 μm. The positive electrode active material may further contain the solid electrolyte material of this disclosure at a concentration of about 5 vol% to about 80 vol%. In some additional embodiments, the positive electrode binder may include polyvinyl chloride, polyaniline, poly(methyl methacrylate), nitrile butadiene rubber, styrene butadiene rubber, polystyrene, polyvinylidene fluoride, or other binders known in the art and combinations thereof. In further embodiments, the conductive additive may include carbon (e.g., carbon black, graphite, carbon nanotubes, carbon fibers, graphene, etc.), metal particles, filaments, or other structures, or other conductive additives known in the art and combinations thereof.

[0070] An electrochemical cell may include a negative electrode. The negative electrode may be formed from a material containing copper, nickel, stainless steel, or carbon. The negative electrode may comprise a negative electrode active material, a binder, and a conductive additive. In some embodiments, the negative electrode active material may comprise lithium metal, lithium alloy, silicon, tin (Sn), graphite carbon, hard carbon, and may further comprise a solid electrolyte composition such as the solid electrolyte composition described herein. The negative electrode active material may contain the solid electrolyte material of this disclosure at a concentration of about 5% to about 80% by volume. The negative electrode active material may have a thickness of about 1 μm to about 1000 μm. Examples of binders used in the negative electrode include materials similar to those used in the positive electrode. Examples of conductive additives used in the negative electrode include materials similar to those used in the positive electrode.

[0071] The discharge capacity of an electrochemical cell refers to the amount of electricity discharged from the battery during a discharge cycle. In some embodiments, an electrochemical cell comprising the solid electrolyte material of the present disclosure is a cell of the general formula Li (7-w-z) PS (6-w-z) X w Y z Compared to electrochemical cells containing a solid electrolyte material having (wherein X and Y are halogens or pseudohalogens, respectively, and 0 ≤ w ≤ 2, 0 ≤ z ≤ 2, and w + z = 2), the electrochemical cell may have a higher discharge capacity. In some additional embodiments, an electrochemical cell containing the solid electrolyte material of the present disclosure has a higher discharge capacity compared to an electrochemical cell containing the same electrolyte material lacking an oxygen component, synthesized with 0 ppm H2O. In further embodiments, the discharge capacity of an electrochemical cell containing the solid electrolyte material of the present disclosure may be at least about 100 mAh / g. In some embodiments, the discharge capacity may be at least about 110 mAh / g, at least about 120 mAh / g, or at least about 130 mAh / g. In some additional embodiments, the discharge capacity can be approximately 100 mAh / g to approximately 105 mAh / g, approximately 105 mAh / g to approximately 110 mAh / g, approximately 110 mAh / g to approximately 115 mAh / g, approximately 115 mAh / g to approximately 120 mAh / g, approximately 120 mAh / g to approximately 125 mAh / g, approximately 125 mAh / g to approximately 130 mAh / g, or greater than approximately 130 mAh / g.

[0072] The first cycle efficiency of an electrochemical cell is defined as the ratio of the first discharge capacity to the first charge capacity. In some embodiments, an electrochemical cell comprising the solid electrolyte material of the Disclosure may have a higher first cycle efficiency compared to an electrochemical cell comprising a solid electrolyte material having the general formula Li6PS5Cl. In some additional embodiments, an electrochemical cell comprising the solid electrolyte material of the Disclosure may have a higher first cycle efficiency compared to an electrochemical cell comprising the same electrolyte material lacking an oxygen component, synthesized with 0 ppm H2O. In further embodiments, the first cycle efficiency may be greater than about 85%, greater than about 86%, greater than about 87%, greater than about 88%, greater than about 89%, greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, or greater than about 99%. In some embodiments, the first cycle efficiency can be about 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or about 99%. In an exemplary embodiment, an electrochemical cell comprising the solid electrolyte material of the Disclosure has a first cycle efficiency greater than 88%.

[0073] In some embodiments, an electrochemical cell comprising a solid electrolyte material of the present disclosure has the general formula Li (7-w-z) PS (6-w-z) X w Y z[Wherein, X and Y are each a halogen or a pseudohalogen, 0 ≦ w ≦ 2, 0 ≦ z ≦ 2, and w + z = 2], compared with an electrochemical cell having a solid electrolyte material, may have a higher charging resistance. In some additional embodiments, an electrochemical cell comprising the solid electrolyte material of the present disclosure may have a higher charging resistance compared to the same electrolyte material lacking an oxygen component synthesized with 0 ppm of H2O. In still further embodiments, the charging resistance of an electrochemical cell comprising the solid electrolyte material can be from about 4 minutes to about 6 minutes. In some aspects, the charging resistance of an electrochemical cell comprising the solid electrolyte material can be from about 4 Ω to about 4.5 Ω, from about 4.5 Ω to about 5 Ω, from about 5 Ω to about 5.5 Ω, or from about 5.5 Ω to about 6 Ω. In some additional aspects, the charging resistance can be about 4 Ω, 4.25 Ω, 4.5 Ω, 4.75 Ω, 5 Ω, 5.25 Ω, 5.5 Ω, 5.75 Ω, or 6 Ω.

[0074] Exemplary embodiments Embodiment 1: An electrochemical cell comprising a positive electrode and an electrolyte material disposed between the positive electrode and a negative electrode, wherein the electrolyte material has a general structure Li 7-w-z PS 6-w-z-v O v X w Y z (Wherein, X and Y are each one or more of a halogen and a pseudohalogen; 0 ≦ w ≦ 2; 0 ≦ z ≦ 2; and 0 < v ≦ 1), an electrochemical cell.

[0075] Embodiment 2: The electrochemical cell according to Embodiment 1, wherein X and Y are each selected from the group consisting of F, Cl, Br, I, BF4, BH4, NO2, and NO3.

[0076] Embodiment 3: The electrochemical cell according to Embodiment 1 or Embodiment 2, wherein the electrolyte material has an FT-IR spectrum having absorption peaks at 975 ± 25 cm -1 、690 ± 25 cm -1 、and 525 ± 25 cm -1 .

[0077] Embodiment 4: The electrochemical cell has a general formula Li7-w-z PS 6-w-z X w Y z An electrochemical cell according to any one of embodiments 1 to 3, having a higher discharge capacity compared to an electrochemical cell containing an electrolyte material having the above characteristics.

[0078] Embodiment 5: An electrochemical cell comprising Li 7-w-z PS 6-w-z X w Y z An electrochemical cell according to any one of embodiments 1 to 4, having a higher first-cycle efficiency compared to an electrochemical cell containing an electrolyte material having the above characteristics.

[0079] Embodiment 6: An electrochemical cell according to any one of Embodiments 1 to 5, wherein the electrochemical cell has a first cycle efficiency of at least about 88%.

[0080] Embodiment 7: An electrochemical cell comprising Li 7-w-z PS 6-w-z X w Y z An electrochemical cell according to any one of embodiments 1 to 6, having a lower charging resistance compared to an electrochemical cell containing an electrolyte material having the above characteristics.

[0081] Embodiment 8: A method for producing an electrolyte material, comprising milling a mixture containing the following: Multiple electrolyte precursors, each comprising one or more lithium (Li)-containing materials; One or more phosphorus (P)-containing materials; Halides or pseudohalides; One or more solvents; and water.

[0082] Embodiment 9: The method according to Embodiment 8, wherein the electrolyte precursor further comprises a sulfur (S)-containing material.

[0083] Embodiment 10: The method according to Embodiment 8 or Embodiment 9, wherein the electrolyte precursor further comprises one or more materials selected from halide-containing materials or pseudo-halide-containing materials.

[0084] Embodiment 11: The method according to any one of Embodiments 8 to 10, further comprising heating the mixture after milling.

[0085] Embodiment 12: The method according to Embodiment 11, wherein heating causes crystallization of the mixture to form an electrolyte material.

[0086] Embodiment 13: The method according to any one of Embodiments 8 to 12, wherein the mixture contains at least 100 ppm of water.

[0087] Embodiment 14: The method according to Embodiment 13, wherein the mixture contains about 250 ppm of water.

[0088] Embodiment 15: The method according to Embodiment 13, wherein the mixture contains about 500 ppm of water.

[0089] Embodiment 16: The method according to Embodiment 13, wherein the mixture contains 1000 ppm of water.

[0090] Embodiment 17: The method according to Embodiment 13, wherein the mixture contains about 100,000 ppm of water.

[0091] Embodiment 18: The method according to any one of Embodiments 8 to 17, wherein water is added to the solvent before milling.

[0092] Embodiment 19: The method according to any one of Embodiments 8 to 18, wherein at least one of the multiple electrolyte precursors is an anhydrous.

[0093] Embodiment 20: The method according to any one of Embodiments 8 to 19, wherein the amount of water to be added is predetermined based on the amount of water contained in a plurality of electrolyte precursors and the amount of water contained in the solvent.

[0094] Embodiment 21: The method according to any one of Embodiments 8 to 20, wherein the solvent is a low-polarity aprotic solvent.

[0095] Embodiment 22: The method according to Embodiment 21, wherein the solvent is selected from the group consisting of xylene, toluene, benzene, heptane, and combinations thereof.

[0096] Embodiment 23: The method according to any one of Embodiments 8 to 20, wherein the solvent comprises an ether, ester, nitrile, or alcohol.

[0097] Embodiment 24: An electrochemical cell comprising a positive electrode, an electrolyte material, and a negative electrode, wherein the electrolyte material is disposed between the positive electrode and the negative electrode, and the electrolyte material is manufactured by the method described in any one of Embodiments 8 to 23.

[0098] Embodiment 25: A solid electrolyte material comprising Li, T, X, A, O, and optionally Y, wherein T is at least one element selected from the group consisting of P, As, Si, Ge, Al, and B; X and, if present, Y are halogens or pseudohalogens; A is at least one element selected from the group consisting of S, Se, and N; the electrolyte material is approximately 975 cm³. -1 ±25cm -1 , 690cm -1 ±25cm -1 , and 525cm -1 ±25cm -1 A solid electrolyte material having an FT-IR peak.

[0099] Embodiment 26: The solid electrolyte material according to Embodiment 25, wherein T is P.

[0100] Embodiment 27: A solid electrolyte material according to Embodiment 25 or Embodiment 26, wherein X is Cl.

[0101] Embodiment 28: A solid electrolyte material according to any one of Embodiments 25 to 27, wherein A is S.

[0102] Embodiment 29: The material is a solid electrolyte material according to any one of Embodiments 25 to 28, represented by the formula Li 7-w-z PS 6-w-z-v O v X w Y z

[0103] Embodiment 30: The solid electrolyte material according to Embodiment 29, where 0 < v ≤ 1.

[0104] Embodiment 31: The solid electrolyte material according to Embodiment 29 or Embodiment 30, having FT-IR as shown in FIG. 2.

[0105] Embodiment 32: The solid electrolyte material according to any one of Embodiments 29 to 31, where the amount of oxygen present is based on exposure to water of 40 ppm to 1000 ppm.

[0106] Embodiment 33: The solid electrolyte material according to any one of Embodiments 29 to 32, where an electrochemical cell containing the electrolyte material has a higher discharge capacity compared to an electrochemical cell containing the same electrolyte material lacking an oxygen component, synthesized with 0 ppm of H2O.

[0107] Embodiment 34: The solid electrolyte material according to any one of Embodiments 29 to 33, where an electrochemical cell containing the electrolyte material has a higher first cycle efficiency (FCE) compared to an electrochemical cell containing the same electrolyte material lacking an oxygen component, exposed to 0 ppm of H2O.

[0108] Embodiment 35: The solid electrolyte material according to any one of Embodiments 29 to 34, where an electrochemical cell containing the electrolyte material has a lower resistance increase compared to an electrochemical cell containing the same electrolyte material lacking an oxygen component, exposed to 0 ppm of H2O.

[0109] Embodiment 36: The solid electrolyte material according to any one of Embodiments 25 to 35, where the electrolyte material has an ionic conductivity of at least 1×10 -4 mS / cm

[0110] ​​ Embodiment 37: A method for producing a solid electrolyte material, The following reactions: XLi2S (Appm H2O )+YP2S 5(Bppm H2O) + ZLi X(Cppm H2O) +W solvent (Dppm H2O) → Li6P S5-E O E Cl+W solvent [where E=(X * A) + (Y * B) + (Z * C)+(W * D) and A, B, C, and D = ppm of H2O per unit mass, and Z, Y, Z, and W are all unit masses. The reactants are mixed according to the formula Li6PS 5-E O E To produce a solid electrolyte material of Cl, To produce an electrolyte material that has high ionic conductivity and low reactivity to high nickel-content cathodes by controlling the ppm of each precursor and the solvent water, Methods that include... [Examples]

[0111] Example 1: Characterization of electrolyte materials Solid electrolyte materials were prepared according to the process described herein. The electrolyte materials contained phosphorus and sulfur among the electrolyte precursors. The electrolyte materials were synthesized using precursors with water content of 0 ppm, 100 ppm, 250 ppm, 500 ppm, and 1000 ppm. Each of these samples was characterized by Fourier transform infrared spectroscopy (FT-IR) (see Figure 2). As shown in Figure 2, the water content of the electrolyte material increased by approximately 975 cm³. -1 , 690cm -1 and 525cm -1The magnitude of the peak increases. The attribute of the peak is unknown, but the peak is characteristic of the material described herein.

[0112] As shown in Figure 2, the magnitude of the peaks corresponding to SO and PO bonds increases as the water content of the electrolyte material increases. As the water content of the electrolyte material increases, the presence of oxygen in the material also increases.

[0113] Example 2: Performance of Electrolyte Materials Performance tests were conducted on the electrolyte material of Example 1. The results of the performance tests are shown in Figures 3A to 3C.

[0114] Figure 3A shows the discharge capacity of the electrolyte material in mAh / g after charging cycles 1 to 12. Electrolyte materials with 100 ppm, 250 ppm, and 500 ppm of water had higher discharge capacities compared to the same electrolyte material with 0 ppm or 1000 ppm of water.

[0115] Figure 3B shows the efficiency of the electrolyte materials after charging cycles 1-5. Electrolyte materials with 500 ppm and 1000 ppm of water had higher first-cycle efficiency (FCE) compared to electrolyte materials with 0 ppm of water. All electrolyte materials tested had an FCE of at least 88%.

[0116] Figure 3C shows the charging resistance of the electrolyte material after charging cycles 1 to 15. The electrolyte material with 1000 ppm of water shows a slightly lower increase in resistance compared to the material with 0 ppm of water.

[0117] Figure 4 shows the XRD pattern of an electrolyte material synthesized using a precursor containing 1000 ppm of water. From the XRD pattern shown in Figure 4, it can be seen that the electrolyte material is Li 5.5 PS 4.5-x O x It can be confirmed that it is a complex containing both a Cl electrolyte phase and a LiCl electrolyte phase. 5.5 PS 4.5-x O xCl has peaks at 15.4°, 17.9°, 25.4°, 29.9°, and 31.4°. LiCl has a peak at 34.7°.

[0118] Example 3: Electrolyte material containing 100,000 ppm of water An electrolyte material synthesized using a precursor and a solvent containing 100,000 ppm of water was prepared according to the method of this disclosure. From the XRD pattern shown in Figure 5, the electrolyte material is Li 5.5 PS 4.5-x O x It can be confirmed that it is a complex containing an electrolyte phase of Cl, an electrolyte phase of Li2S, and an electrolyte phase of LiCl. 5.5 PS 4.5-x O x Cl has peaks at 15.7°, 18.1°, 25.6°, 29.8°, and 31.6°. Li2S has a peak at 27.2°. LiCl has a peak at 34.9°. Some embodiments of the present invention are shown below. [Embodiment 1] Positive electrode and, An electrolyte material disposed between the positive electrode and the negative electrode, Includes, The aforementioned electrolyte material has the general formula: Li 7-w-z PS 6-w-z-v O v X w Y z (In the formula, X and Y are each one or more of halogens and pseudohalogens; 0≦w≦2; 0≦z≦2; and 0 <v≦1である。) Having, Electrochemical cell. [Embodiment 2] X and Y are F, Cl, Br, I, and BF, respectively. 4 BH 4 NO 2 and NO 3 An electrochemical cell according to [Embodiment 1], selected from the group consisting of the following. [Embodiment 3] The aforementioned electrolyte material is 975±25cm -1 , 690±25cm -1 , and 525±25cm -1 An electrochemical cell according to [Embodiment 1] or [Embodiment 2], having an FT-IR spectrum with an absorption peak. [Embodiment 4] The aforementioned electrochemical cell has the general formula Li 7-w-z PS 6-w-z X w Y z An electrochemical cell according to any one of [Embodiment 1] to [Embodiment 3], having a higher discharge capacity compared to an electrochemical cell containing an electrolyte material having the above characteristics. [Embodiment 5] The electrochemical cell has the general formula Li 7-w-z PS 6-w-z X w Y z An electrochemical cell according to any one of [Embodiment 1] to [Embodiment 4] having a higher first cycle efficiency compared to an electrochemical cell containing an electrolyte material having the above. [Embodiment 6] The electrochemical cell according to any one of [Embodiment 1] to [Embodiment 5], wherein the electrochemical cell has a first cycle efficiency of at least about 88%. [Embodiment 7] The electrochemical cell has the general formula Li 7-w-z PS 6-w-z X w Y z An electrochemical cell according to any one of [Embodiment 1] to [Embodiment 6] having a lower charging resistance compared to an electrochemical cell containing an electrolyte material having the above. [Embodiment 8] A method for producing an electrolyte material, comprising milling a mixture containing the following: Multiple electrolyte precursors, each comprising one or more lithium (Li)-containing materials; One or more phosphorus (P)-containing materials; Halides or pseudohalides; One or more solvents; and water. [Embodiment 9] The method according to [Embodiment 8], wherein the electrolyte precursor further comprises a sulfur (S)-containing material. [Embodiment 10] The method according to [Embodiment 8] or [Embodiment 9], wherein the electrolyte precursor further comprises one or more materials selected from halide-containing materials or pseudo-halide-containing materials. [Embodiment 11] The method according to any one of [Embodiment 8] to [Embodiment 10], further comprising heating the mixture after the milling. [Embodiment 12] The method according to [Embodiment 11], wherein the heating brings about the crystallization of the mixture to form the electrolyte material. [Embodiment 13] The method according to any one of [Embodiment 8] to [Embodiment 12], wherein the mixture comprises at least 100 ppm of water. [Embodiment 14] The method according to [Embodiment 13], wherein the mixture comprises about 250 ppm of water. [Embodiment 15] The method according to [Embodiment 13], wherein the mixture comprises about 500 ppm of water. [Embodiment 16] The method according to [Embodiment 13], wherein the mixture comprises about 1000 ppm of water. [Embodiment 17] The method according to [Embodiment 13], wherein the mixture contains about 100,000 ppm of water. [Embodiment 18] The method according to any one of [Embodiment 8] to [Embodiment 17], wherein the water is added to the solvent before the milling. [Embodiment 19] The method according to any one of [Embodiment 8] to [Embodiment 18], wherein at least one of the plurality of electrolyte precursors is an anhydrous. [Embodiment 20] The method according to any one of [Embodiment 8] to [Embodiment 19], wherein the amount of water to be added is predetermined based on the amount of water contained in the plurality of electrolyte precursors and the amount of water contained in the solvent. [Embodiment 21] The method according to any one of [Embodiment 8] to [Embodiment 20], wherein the solvent is a low-polarity aprotic solvent. [Embodiment 22] The method according to [Embodiment 21], wherein the solvent is selected from the group consisting of xylene, toluene, benzene, heptane, and combinations thereof. [Embodiment 23] The method according to any one of [Embodiment 8] to [Embodiment 20], wherein the solvent comprises an ether, an ester, a nitrile, or an alcohol. [Embodiment 24] It is an electrochemical cell, positive electrode; Electrolyte materials; and negative electrode; Includes, Here, The electrolyte material is disposed between the positive electrode and the negative electrode. The electrolyte material is manufactured by the method described in any one of [Embodiment 8] to [Embodiment 23]. Electrochemical cell. [Embodiment 25] A solid electrolyte material, Includes Li, T, X, A, O, and optionally Y, Here, T is at least one element selected from the group consisting of P, As, Si, Ge, Al, and B; X, and when present, Y is a halogen or a pseudohalogen; A is at least one element selected from the group consisting of S, Se, and N; The electrolyte material has an FT-IR peak at about 975 cm -1 ±25 cm -1 , 690 cm -1 ±25 cm -1 , and 525 cm -1 ±25 cm -1 ; Solid electrolyte material. [Embodiment 26] The solid electrolyte material according to [Embodiment 25], wherein T is P. [Embodiment 27] The solid electrolyte material according to [Embodiment 25] or [Embodiment 26], wherein X is Cl. [Embodiment 28] The solid electrolyte material according to any one of [Embodiments 25] to [Embodiment 27], wherein A is S. [Embodiment 29] The solid electrolyte material according to any one of [Embodiments 25] to [Embodiment 27], wherein the material is represented by the formula Li 7-w-z PS 6-w-z-v O v X w Y z . [Embodiment 30] The solid electrolyte material according to [Embodiment 29], wherein 0 < v ≦ 1. [Embodiment 31] The solid electrolyte material according to [Embodiment 29], wherein the solid electrolyte material has the FT-IR shown in FIG. 2. [Embodiment 32] The solid electrolyte material according to [Embodiment 29], wherein the amount of oxygen present is based on exposure to 40 ppm to 1000 ppm of water. [Embodiment 33] The solid electrolyte material according to any one of [Embodiments 29] to [Embodiment 32], wherein the electrochemical cell containing the electrolyte material has a higher discharge capacity compared to an electrochemical cell containing the same electrolyte material lacking an oxygen component synthesized in 0 ppm of H 2 O. [Embodiment 34] The solid electrolyte material according to any one of [Embodiments 29] to [Embodiment 33], wherein the electrochemical cell containing the electrolyte material has a higher first cycle efficiency (FCE) compared to an electrochemical cell containing the same electrolyte material lacking an oxygen component exposed to 0 ppm of H 2 O. [Embodiment 35] The solid electrolyte material according to any one of [Embodiments 29] to [Embodiment 34], wherein the electrochemical cell containing the electrolyte material has a lower resistance increase compared to an electrochemical cell containing the same electrolyte material lacking an oxygen component exposed to 0 ppm of H 2 O. [Embodiment 36] The solid electrolyte material according to any one of [Embodiments 25] to [Embodiment 35], wherein the electrolyte material has an ionic conductivity of at least -4 ​2 ​ ​ ​ ​ ​ 2 S (Appm H2O ​ 2 S 5(Bppm H2O) + ​ X(Cppm H2O) ​ (Dppm H2O) → ​ 6 P S5-E O E ​ ​ * ​ * ​ * ​ * D) A, B, C, and D = H per unit mass 2 ppm of O, and Z, Y, Z, and W are all unit masses. The reactants are mixed according to the formula Li 6 PS 5-E O E To produce a solid electrolyte material of Cl, To produce an electrolyte material that has high ionic conductivity and low reactivity to high nickel-content cathodes by controlling the ppm of each precursor and the solvent water, Methods that include...

Claims

1. Positive electrode and, An electrolyte material disposed between the positive electrode and the negative electrode, Includes, The electrolyte material has the general formula: Li ７－ｗ－ｚ PS ６－ｗ－ｚ－ｖ O ｖ X ｗ Y ｚ (In the formula, X and Y are each one or more of halogens and pseudohalogens; 0 ≤ w ≤ 2; 0 ≤ z ≤ 2; and (0 < v ≤ 1.) It has, The aforementioned electrolyte material is 975 ± 25 cm －１ , 690±25cm －１ , and 525±25cm －１ It has an FT-IR spectrum with an absorption peak, Electrochemical cell.

2. X and Y are each F, Cl, Br, I, BF ４ , BH ４ , NO ２ and NO ３ The electrochemical cell according to claim 1, selected from the group consisting of

3. The electrochemical cell has the general formula Li ７－ｗ－ｚ PS ６－ｗ－ｚ X ｗ Y ｚ An electrochemical cell according to any one of claims 1 to 2, having a higher discharge capacity compared to an electrochemical cell containing an electrolyte material having the above characteristics.

4. The electrochemical cell has the general formula Li ７－ｗ－ｚ PS ６－ｗ－ｚ X ｗ Y ｚ An electrochemical cell according to claim 1 or 2, having a higher first cycle efficiency compared to an electrochemical cell containing an electrolyte material having the above.

5. The electrochemical cell according to claim 1 or 2, wherein the electrochemical cell has a first cycle efficiency of at least 88%.

6. The electrochemical cell has the general formula Li ７－ｗ－ｚ PS ６－ｗ－ｚ X ｗ Y ｚ An electrochemical cell according to claim 1 or 2, having a lower charging resistance compared to an electrochemical cell containing an electrolyte material having the above.

7. A method for producing an electrolyte material, comprising milling a mixture containing the following: Multiple electrolyte precursors, each comprising one or more lithium (Li)-containing materials; One or more phosphorus (P)-containing materials; Halides or pseudohalides; One or more solvents; and At least 100 ppm of water.

8. The method according to claim 7, wherein the electrolyte precursor further comprises a sulfur (S)-containing material.

9. The method according to claim 7 or 8, wherein the electrolyte precursor further comprises one or more materials selected from halide-containing materials or pseudo-halide-containing materials.

10. The method according to claim 7 or 8, further comprising heating the mixture after the milling.

11. The method according to claim 10, wherein the heating causes the mixture to crystallize and form the electrolyte material.

12. The method according to claim 7 or 8, wherein the water is added to the solvent before the milling.

13. The method according to claim 7 or 8, wherein at least one of the plurality of electrolyte precursors is an anhydrous.

14. The method according to claim 7 or 8, wherein the amount of water to be added is predetermined based on the amount of water contained in the plurality of electrolyte precursors and the amount of water contained in the solvent.

15. The method according to claim 7 or 8, wherein the solvent is a low-polarity aprotic solvent.

16. The method according to claim 15, wherein the solvent is selected from the group consisting of xylene, toluene, benzene, heptane, and combinations thereof.

17. The method according to claim 7 or 8, wherein the solvent comprises an ether, an ester, a nitrile, or an alcohol.

18. A solid electrolyte material, Includes Li, T, X, A, O, and optionally Y, Here, T is at least one element selected from the group consisting of P, As, Si, Ge, Al, and B; X and, if present, Y are halogens or pseudo-halogens; A is at least one element selected from the group consisting of S, Se, and N; The aforementioned solid electrolyte material is approximately 975 cm³ －１ ±25cm －１ 690cm －１ ±25cm －１ , and 525 cm －１ ±25cm －１ It has an FT-IR peak, Solid electrolyte material.

19. The solid electrolyte material according to claim 18, wherein T is P.

20. The solid electrolyte material according to claim 18 or 19, wherein X is Cl.

21. The solid electrolyte material according to claim 18 or 19, wherein A is S.

22. The solid electrolyte material is of the formula Li ７－ｗ－ｚ PS ６－ｗ－ｚ－ｖ O ｖ X ｗ Y ｚ The solid electrolyte material according to claim 18 or 19, as represented by...

23. The solid electrolyte material according to claim 22, wherein 0 < v ≤ 1.

24. The solid electrolyte material according to claim 22, wherein the solid electrolyte material has the FT-IR shown in Figure 2.

25. The solid electrolyte material according to claim 22, wherein the amount of oxygen present is based on exposure to water at a concentration of 40 ppm to 1000 ppm.

26. The electrochemical cell containing the solid electrolyte material has 0 ppm H ２ The solid electrolyte material according to claim 22, having a higher discharge capacity compared to an electrochemical cell containing the same solid electrolyte material lacking an oxygen component, synthesized with O.

27. The electrochemical cell containing the solid electrolyte material has 0 ppm H ２ The solid electrolyte material according to claim 22, having a higher first cycle efficiency (FCE) compared to an electrochemical cell containing the same solid electrolyte material lacking an oxygen component, which has been exposed to O.

28. The electrochemical cell containing the solid electrolyte material has 0 ppm H ２ The solid electrolyte material according to claim 22, having a lower resistance increase compared to an electrochemical cell containing the same solid electrolyte material lacking an oxygen component, which has been exposed to O.

29. The solid electrolyte material is at least 1 × 10 －４ A solid electrolyte material according to claim 18 or 19, having an ionic conductivity of mS / cm.

30. A method for producing a solid electrolyte material, The following reactions: XLi ２ S （Ａｐｐｍ Ｈ２Ｏ )+YP ２ S ５（Ｂｐｐｍ Ｈ２Ｏ） + ZLi Ｘ（Ｃｐｐｍ Ｈ２Ｏ） +W solvent （Ｄｐｐｍ Ｈ２Ｏ） → Li ６ P Ｓ５－Ｅ O Ｅ Cl + W solvent [In the formula, E = (X] ＊ A) + (Y) ＊ B) + (Z) ＊ C) + (W ＊ D) A, B, C, and D = H per unit mass ２ ppm of O, and Z, Y, Z, and W are all unit masses. The reactants are mixed according to the formula Li ６ PS ５－Ｅ O Ｅ To produce a solid electrolyte material of Cl, To produce an electrolyte material that has high ionic conductivity and low reactivity to high nickel-content cathodes by controlling the ppm of each precursor and the solvent water, Methods that include...

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