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 TO 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 December 20, 2021, the entire contents of which are hereby incorporated by reference in their entirety for all purposes.

[0002] The present disclosure relates to solid electrolyte materials and, as such, relates to the fields of electronics, chemistry, and materials science. [Background technology]

[0003] The development of solid-state battery technology is being driven by the known shortcomings of liquid electrolyte-based batteries and at the same time by the explosive growth of battery-powered devices. Lithium-based solid-state electrolytes, including argyrodite-like materials such as Li6PS5Cl, have been widely studied due to their high ionic conductivity. However, electrolytes such as argyrodite-like materials are also highly reactive towards the cathode materials. Generally, sulfur in the electrolyte, when placed near a nickel cathode, reacts with the nickel to form nickel sulfide, degrading the surface of the cathode. This can result in a decrease in the ionic / electronic separation of the cathode material and a decrease in the electrochemical performance.

[0004] Due to the electrolyte precursors, the presence of water is avoided during the synthesis of electrolyte materials. Therefore, the production of electrolyte materials in the absence of water has been pursued to reduce degradation of the electrolyte precursors and thereby maximize ionic conductivity.

[0005] There is a need for solid electrolyte materials that have high ionic conductivity and low reactivity with cathode materials.With the above observations in mind, among others, various aspects of the present disclosure have been devised. Summary of the Invention

[0006] Disclosed herein is 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, 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; the electrolyte material has FT-IR peaks at about 975 cm -1 ±25 cm -1 , 690 cm -1 ±25 cm -1 , and 525 cm -1 ±25 cm -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 is represented by the formula Li 7-w-z PS 6-w-z-v O v X w Y z . In some aspects, 0 < v ≦ 1. In some embodiments, the solid electrolyte material can have an FT-IR spectrum as shown in Figure 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, comprising:

[0008] Further described herein is an electrochemical cell comprising 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 (wherein X and Y are each one or more of a halogen or a pseudohalogen, 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 with 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 In some embodiments, the electrochemical cell has a higher discharge capacity compared to a material having the general formula Li 7-w-z P.S. 6-w-z X w Y z In some embodiments, the electrochemical cell has a first cycle efficiency of at least about 88%. In some embodiments, the electrochemical cell has a first cycle efficiency of at least about 88%. 7-w-z P.S. 6-w-z X w Y z In some embodiments, the electrolyte material has a lower charging resistance compared to a material having a -4 mS / cm 2 The ionic conductivity may be

[0009] Further included herein is an electrochemical cell including a positive electrode and an electrolyte material disposed between the positive electrode and the negative electrode, the electrolyte material including Li, S, and P. In some embodiments, the electrolyte material further includes at least one of a halogen or pseudohalogen.

[0010] Further described herein is a method of making an electrolyte material, the method comprising milling a mixture comprising a plurality of electrolyte precursors, the electrolyte precursors 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 of a halide-containing material or a pseudohalide-containing material. In some embodiments, the method further comprises heating the mixture after milling. In some aspects, the heating can result in crystallization of the mixture to form the electrolyte material. In some embodiments, the mixture can include at least 100 ppm water, about 250 ppm water, about 500 ppm water, about 1000 ppm water, or about 100,000 ppm water. In some embodiments, water is added to the solvent prior to milling. In some embodiments, at least one of the plurality of electrolyte precursors is 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 aspects, the solvent may include an ether, an ester, a nitrile, a ketone, or an alcohol.

[0011] Further described herein is an electrochemical cell including 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 wherein the electrolyte material is manufactured by a process including milling a mixture including a plurality of electrolyte precursors, the electrolyte precursors including 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 description of the drawings]

[0012] [Figure 1] FIG. 1 shows a flow chart of a process for producing the solid electrolyte material of the present disclosure.

[0013] [Diagram 2] FIG. 2 shows FT-IR plots of electrolyte materials of the present disclosure having water contents of 0 ppm, 100 ppm, 250 ppm, 500 ppm, and 1000 ppm.

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

[0015] [Figure 4] FIG. 4 shows a plot of an X-ray diffraction measurement of a solid electrolyte material produced by the process of the present disclosure.

[0016] [Diagram 5] FIG. 5 shows a plot of an X-ray diffraction measurement of a solid electrolyte material produced by the process of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Before the present invention is disclosed and described, it is to be understood that the invention is not limited to the particular methods, compositions, or materials disclosed herein, but extends to equivalents thereof as would be recognized by one of ordinary skill in the art. It is also to be understood that the terminology used herein is used for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0018] Concentrations, amounts, and other numerical data may be expressed or presented in a range format herein. It is understood that such range formats are used merely for convenience and brevity, and should be interpreted flexibly to include not only the numerical values ​​explicitly recited as the limits of the range, but also all individual numerical values ​​or subranges subsumed within the range as if each numerical value and subrange were explicitly recited. By way of example, 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 the individual values ​​and subranges within the stated range. Thus, this numerical range includes individual values ​​such as 2, 2.4, 3, 3.7, 4, 5.5, 10, 10.1, 14, 15, 15.98, 20, 20.13, 23, 25.06, 30, 35.1, 38.0, 40, 44, 44.6, 45, 48, 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, etc. This same principle applies to ranges reciting only one numerical value as a minimum or maximum value. Moreover, such an interpretation should be applied regardless of the breadth of the range or feature being recited.

[0019] As used herein, the term "about" is used to provide flexibility to the endpoints of a numerical range by defining that a given value can be "a little above" or "a little below" the endpoint. For example, the endpoints can be within 10%, 8%, 5%, 3%, 2%, or 1% of the recited value. Furthermore, for convenience and brevity, a numerical range of "about 50 mg / mL to about 80 mg / mL" should be understood to also support a range of "50 mg / mL to 80 mg / mL". Endpoints can also be based on variability permitted by appropriate regulatory agencies, such as the FDA, USP, etc.

[0020] In this disclosure, the terms "including," "containing," and / or "having" are understood to mean including / including and are open-ended terms.

[0021] As used herein, "pseudohalogens" and "pseudohalides" refer to compounds whose chemical properties resemble elemental halogens and halide ions. The terms "pseudohalogens" and "pseudohalides" may be used interchangeably with "superhalogens" or "superhalides," respectively.

[0022] Described herein are solid electrolyte materials synthesized with a given amount of water that have superior performance characteristics as 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 in terms of discharge capacity, efficiency and charge resistance.

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

[0024] Generally, it is desirable to synthesize electrolyte materials, such as lithium argyrodite-like materials, in the absence of little or no water. Exposure to water during the manufacturing process introduces oxygen into the electrolyte material, which can replace 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 an ionic conductivity that is significantly lower, in some cases an order of magnitude lower (e.g., 1000 times lower), than oxygen-free electrolyte materials. Therefore, electrolyte materials are generally manufactured in dry, oxygen-free environments with highly controlled humidity and gas content.

[0025] Furthermore, the presence of oxygen reduces reactivity with 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, the nickel reacts with the sulfur to form nickel sulfide. As the reaction continues, the nickel sulfide and other by-products can ionically sequester the cathode material and reduce 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 including 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 initially found that the critical current density significantly decreases, but when the oxygen content of the electrolyte material is further increased, the ionic conductivity increases and approaches 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 forms a more stable interface between itself and the cathode material, and as a result, the degradation of the cathode material may be reduced. When 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] Accordingly, the electrolyte material of the present disclosure strikes a surprising and unexpected balance between maintaining high ionic conductivity and reducing the activity by cathode materials such as nickel.

[0028] I. Electrolyte Material The solid electrolyte material of the present disclosure contains lithium (Li), T, X, A, and oxygen (O). In some embodiments, the solid electrolyte material may also contain 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 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 a non-limiting example, T is phosphorus.

[0030] In some embodiments, X and, when present, Y, can be a halogen or pseudohalogen. In some embodiments, when 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, when X and / or Y are pseudohalogens, the pseudohalogens include borohydrides (BH4 - ), fluoroboric acid (BF4 - ), Azanide (NH2 - ), nitrogen trioxide (NO3 - ), cyanide (CN - ), hydroxide (OH - ), thiocyanic acid (SCN - ), hydrosulfide (SH - ) and other pseudohalogens known in the art and combinations thereof. In a non-limiting example, X is chlorine.

[0031] In some embodiments, A can 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 material of the present disclosure may have a unique FT-IR signal due to the presence of oxygen in the electrolyte material (see, for example, FIG. 2). In some embodiments, the FT-IR spectrum of the electrolyte material of the present disclosure has a peak at about 975 cm -1 ±25cm -1 , about 690cm -1 ±25cm -1 and approximately 525 cm -1 ±25cm -1In some non-limiting examples, the solid electrolyte material can have an FT-IR spectrum as shown in FIG.

[0033] The solid electrolyte material of the present disclosure may have a unique X-ray diffraction pattern (XRD). For example, Li 5.5 P.S. 4.5 A solid electrolyte material of the present disclosure that includes 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, a solid electrolyte material of the present disclosure that includes LiCl may have a peak at 2θ=34.8°±0.5°. As yet another example, a solid electrolyte material of the present disclosure that includes LiS may have a peak at 2θ=27.2°±0.5°.

[0034] As noted above, oxygen is incorporated into the electrolyte material during the synthesis process due to the presence of water. 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 embodiments, the amount of oxygen present in the solid electrolyte material may be based on exposure to 40 to 5000 ppm of water during the synthesis process. Thus, the amount of oxygen present in the solid electrolyte material may be about 40 ppm water to 100 ppm water, about 100 ppm water to about 200 ppm water, about 200 ppm water to about 300 ppm water, about 300 ppm water to about 400 ppm water, about 400 ppm water to about 500 ppm water, about 500 ppm water to about 600 ppm water, about 600 ppm water to about 700 ppm water. , from about 700 ppm water to about 800 ppm water, from about 800 ppm water to about 900 ppm water, from about 900 ppm water to about 1000 ppm water, from about 1000 ppm water to about 2000 ppm water, from about 2000 ppm water to about 3000 ppm water, from about 3000 ppm water to about 4000 ppm water, or from about 4000 ppm water to about 5000 ppm water. In some embodiments, the amount of oxygen present in the solid electrolyte material is from about 40 ppm water to about 200 ppm water, from about 40 ppm water to about 300 ppm water, from about 40 ppm water to about 400 ppm water, from about 40 ppm water to about 500 ppm water, from about 40 ppm water to about 600 ppm water, from about 40 ppm water to about 700 ppm water, from about 40 ppm water to about 800 ppm water, from about 40 ppm water to about 900 ppm water, from about 40 ppm water to about 1000 ppm water, from about 40 ppm water to about 2000 ppm water, from about 40 ppm water to about 3000 ppm water, from about 40 ppm water to about 4000 ppm water, from about The concentration of water may be based on exposure to about 5,000 ppm water to about 5,000 ppm water, about 2,000 ppm water to about 5,000 ppm water, about 1,000 ppm water to about 5,000 ppm water, about 900 ppm water to about 5,000 ppm water, about 800 ppm water to about 5,000 ppm water, about 700 ppm water to about 5,000 ppm water, about 600 ppm water to about 5,000 ppm water, about 500 ppm water to about 5,000 ppm water, about 400 ppm water to about 5,000 ppm water, about 300 ppm water to about 5,000 ppm water, about 200 ppm water to about 5,000 ppm water, or about 100 ppm water to about 5,000 ppm water.In yet another aspect, the amount of oxygen present in the solid electrolyte material may be based on exposure to 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 amount of oxygen present in the solid electrolyte material may be based on exposure to more than about 5000 ppm water. In some non-limiting examples, the amount of oxygen present in the solid electrolyte material may be based on exposure to about 100 ppm water, about 250 ppm water, about 500 ppm water, or about 1000 ppm water. In still further embodiments, the amount of oxygen present in the solid electrolyte material can be based on exposure to at least about 40 ppm water, at least about 100 ppm water, at least about 200 ppm water, at least about 300 ppm water, at least about 400 ppm water, at least about 500 ppm water, at least about 600 ppm water, at least about 700 ppm water, at least about 800 ppm water, at least about 900 ppm water, at least about 1000 ppm water, at least about 2000 ppm water, at least about 3000 ppm water, at least about 4000 ppm water, or at least about 5000 ppm water.

[0036] In some additional embodiments, the amount of oxygen present in the solid electrolyte material may be based on exposure to about 40 to about 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 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 additional embodiments, the amount of oxygen present in the solid electrolyte material is from about 100 ppm to about 500 ppm, from about 100 ppm to about 1,000 ppm, from about 100 ppm to about 5,000 ppm, from about 100 ppm to about 10,000 ppm, from about 100 ppm to about 25,000 ppm, from about 100 ppm to about 50,000 ppm, from about 100 ppm to about 75,000 ppm, from about 100 ppm to about 100,000 ppm, or The range may be based on an exposure of about 0 ppm, about 500 ppm to about 100,000 ppm, about 1,000 ppm to about 100,000 ppm, about 5,000 ppm to about 100,000 ppm, about 10,000 ppm to about 100,000 ppm, about 25,000 ppm to about 100,000 ppm, about 50,000 ppm to about 100,000 ppm, or about 75,000 ppm to about 100,000 ppm. In some examples, the amount of oxygen present in the solid electrolyte material can be based on an exposure of about 40 ppm, about 100 ppm, about 500 ppm, about 1,000 ppm, about 5,000 ppm, about 10,000 ppm, about 25,000 ppm, about 50,000 ppm, about 75,000 ppm, or about 100,000 ppm.

[0037] In some embodiments, the solid electrolyte material of the present disclosure has the general formula Li (7-w-z) P.S. (6-w-z) X w Y zwhere X and Y are each a halogen or pseudohalogen, and 0≦w≦2, 0≦z≦2, and w+z=2. In some additional embodiments, the solid electrolyte materials of the present disclosure may have improved performance compared to the same electrolyte material synthesized with 0 ppm HO and / or lacking an oxygen component. Metrics of improved performance include discharge capacity, first cycle efficiency, and lower charge resistance.

[0038] In some embodiments, the solid electrolyte materials of the present disclosure generally have the general formula Li (7-w-z) P.S. (6-w-z) X w Y z where X and Y are each a halogen or pseudohalogen, and 0≦w≦2, 0≦z≦2, and w+z=2. In some additional embodiments, the solid electrolyte material of the present disclosure may have a lower ionic conductivity compared to the same electrolyte material lacking the oxygen component, synthesized with 0 ppm HO. However, improvements in the other metrics discussed above outweigh this loss in ionic conductivity in many applications. In some embodiments, the ionic conductivity of the solid electrolyte of the present disclosure is at least about 1×10 -6 mS / cm 2 In some embodiments, the ionic conductivity of the solid electrolyte of the present disclosure can be at least about 1×10 -5 mS / cm 2 , at least about 1 x 10 -4 mS / cm 2 , or at least about 1×10 -3 mS / cm 2 It can be.

[0039] II. Method for producing solid electrolyte material The solid electrolyte materials described in Section I can be synthesized by mixing the reactants according to the following reactions: 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 T.A. 6-w-z-v O v X w Y z +ε Solvent In the formula, v=(α * a) + (β * b) + (γ * c) + (δ * d)+(ε * e) and a, b, c, d and e = ppm of water per mole α, β, γ, δ and ε = moles.

[0040] The species of reactants A, T, X, and Y can be those described in Section I above. In some preferred embodiments, the reactants may be anhydrous, i.e., the reactants may each or collectively have a water content of 0 ppm. In other embodiments, the reactants 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 "reactant species" may be used interchangeably with the terms "precursor" or "electrolyte precursor."

[0041] The solvent may be any aprotic solvent with low polarity. In some embodiments, the solvent may include one or more of 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 aspects, 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 during at least a portion of the milling process, or during the entire milling process (see Section III below). The solvent may have a water content of 0 ppm or greater. In some embodiments, water may be added to the solvent to achieve a desired oxygen content of the electrolyte material. In some additional embodiments, the reaction may include the use of one or more co-solvents selected from the solvents listed above.

[0042] The solvent may include an ether. 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 an ester. 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 comprise a ketone. 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 of water in each reactant and solvent can be controlled to produce an electrolyte material with high ionic conductivity and low reactivity towards cathodes, such as high nickel content cathodes.

[0048] In some embodiments, the total water content of the mixture (ie, reactants and solvent) can be between 40 and 5000 ppm water. Thus, the total water content of the mixture can be from about 40 ppm water to about 100 ppm water, from about 100 ppm water to about 200 ppm water, from about 200 ppm water to about 300 ppm water, from about 300 ppm water to about 400 ppm water, from about 400 ppm water to about 500 ppm water, from about 500 ppm water to about 600 ppm water, from about 600 ppm water to about 700 ppm water, from about 700 ppm water to about 800 ppm water, from about 800 ppm water to about 900 ppm water, from about 900 ppm water to about 1000 ppm water, from about 1000 ppm water to about 2000 ppm water, from about 2000 ppm water to about 3000 ppm water, from about 3000 ppm water to about 4000 ppm water, or from about 4000 ppm water to about 5000 ppm water. In some embodiments, the total water content of the mixture is from about 40 ppm water to about 200 ppm water, from about 40 ppm water to about 300 ppm water, from about 40 ppm water to about 400 ppm water, from about 40 ppm water to about 500 ppm water, from about 40 ppm water to about 600 ppm water, from about 40 ppm water to about 700 ppm water, from about 40 ppm water to about 800 ppm water, from about 40 ppm water to about 900 ppm water, from about 40 ppm water to about 1000 ppm water, from about 40 ppm water to about 2000 ppm water, from about 40 ppm water to about 3000 ppm water, from about 40 ppm water to about 4000 ppm water, from about 30 ...0 ppm water, from about 40 ppm water to about 500 ppm water, from about 40 ppm water to about 600 ppm water, from about 40 ppm water to about 700 ppm water, from about 40 ppm water to about 800 ppm water, from about 40 ppm water to about 900 ppm water, from about 40 ppm water to about 1000 ppm water, from about 40 ppm water to about 2000 ppm water, from about 40 ppm water to about 3000 ppm water, from about pm water to about 5000 ppm water, about 2000 ppm water to about 5000 ppm water, about 1000 ppm water to about 5000 ppm water, about 900 ppm water to about 5000 ppm water, about 800 ppm water to about 5000 ppm water, about 700 ppm water to about 5000 ppm water, about 600 ppm water to about 5000 ppm water, about 500 ppm water to about 5000 ppm water, about 400 ppm water to about 5000 ppm water, about 300 ppm water to about 5000 ppm water, about 200 ppm water to about 5000 ppm water, or about 100 ppm water to about 5000 ppm water.In yet another aspect, the total water content of the mixture can 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 can be greater than about 5000 ppm water. In some non-limiting examples, the total water content of the mixture can be about 100 ppm water, about 250 ppm water, about 500 ppm water, or about 1000 ppm water. In still further embodiments, the total water content of the mixture can be at least about 40 ppm water, at least about 100 ppm water, at least about 200 ppm water, at least about 300 ppm water, at least about 400 ppm water, at least about 500 ppm water, at least about 600 ppm water, at least about 700 ppm water, at least about 800 ppm water, at least about 900 ppm water, at least about 1000 ppm water, at least about 2000 ppm water, at least about 3000 ppm water, at least about 4000 ppm water, or at least about 5000 ppm water.

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

[0050] The reaction typically occurs in an inert atmosphere, which may include or consist of argon (Ar) or nitrogen (N2) gas. In some embodiments, the inert atmosphere may have a water content of 0 ppm. This helps control the amount of water added to the solid electrolyte material and prevents 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 may occur for about 6 seconds to about 200 hours. In some embodiments, the reaction may occur for 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. One of ordinary skill in the art will appreciate that the duration of the reaction may be affected by several variables, such as energy input, temperature, particle size of the reactants, solvent type, etc.

[0052] The final electrolyte material may include 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] Typically, 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 in 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 the reaction between the electrolyte and a high nickel-containing cathode. When the electrolyte contacts the surface of a cathode having 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 has been found that by replacing the sulfur atoms in the solid electrolyte material with oxygen, the reactivity of the electrolyte material and the cathode is reduced, and as a result, the degradation of both the electrolyte and the cathode is slowed.

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

[0056] III. Method for manufacturing electrolyte material FIG. 1 shows a flow chart of a process for making the solid electrolyte composition of the present disclosure. Process 100 begins with preparation step 110, where any preparatory operations such as precursor synthesis, purification, and equipment 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, may 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 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. The one or more solvents may be one or more low polarity aprotic solvents as described in Section II.

[0057] In some embodiments, materials containing lithium include lithium metal, lithium sulfide (LiS), lithium chloride (LiCl), lithium nitride (LiN), lithium borohydride (LiBH), lithium fluoroborate (LiBF), lithium amide (LiNH), lithium nitrate (LiNO), and mixtures thereof.

[0058] In some embodiments, sulfur-containing materials include elemental sulfur, phosphorus pentasulfide (P2S5), and phosphorus pentasulfide (P4S), which have the general chemical formula x Examples include phosphorus sulfides, such as phosphorus sulfide having the formula: where 3≦x≦10, 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. Some examples include phosphorus sulfide having the general chemical formula P4S x (wherein 3≦x≦10) include P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, P4S 10 or combinations thereof. In further examples, alkali metal sulfides include sodium sulfide (NaS), potassium sulfide (KS), rubidium sulfide (RbS), and cesium sulfide (CsS). In further examples, alkaline earth metal sulfides include beryllium sulfide (BeS), calcium sulfide (CaS), magnesium sulfide (MgS), strontium sulfide (SrS), and barium sulfide (BaS). In some embodiments, the phosphorus-containing material includes elemental phosphorus, phosphorus sulfides such as phosphorus pentasulfide (P2S5), phosphorus oxides such as phosphorus pentoxide (P2S5), and phosphorus oxides having the general chemical formula P4S x where 3≦x≦10, phosphorus chlorides such as phosphorus trichloride (PCl3) and phosphorus pentachloride (PCl5), phosphorus oxychloride (POCl3), and mixtures thereof.

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

[0060] The ratio and amount of the reacting compounds may not be particularly limited, so long as the water content of the reacting compounds and the one or more solvents is predetermined to achieve the desired oxygen content of the solid electrolyte material. The amount of the solvent added may be predetermined based on the water content of each of the reacting compounds and based on the water content of the solvent. Thus, the amount of the 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 the reacting compounds and the solvent to achieve the desired oxygen content of the electrolyte material. Additional materials, such as co-solvents and polymers, may be added during this step 120.

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

[0062] In some embodiments, adequate mixing can be achieved at temperatures of about -20°C to about 200°C for about 6 seconds to about 200 hours. One of skill in the art will appreciate that the time required for adequate mixing can be influenced by a variety of factors, such as energy input, temperature, precursor particle size, solvent type, etc. In some aspects, adequate mixing can be achieved in 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, adequate mixing can be achieved after about 10 minutes to about 48 hours. In some additional embodiments, suitable mixing can be accomplished at a temperature of about -20°C to about 0°C, about 0°C to about 25°C, about 25°C to about 50°C, about 50°C to about 75°C, about 75°C to about 100°C, about 100°C to about 125°C, about 125°C to about 150°C, about 150°C to about 175°C, or about 175°C to about 200°C.

[0063] By introducing water prior to step 130 and milling / mixing the composition with greater than 0 ppm water, the resulting electrolyte material contains oxygen evenly distributed throughout the composition, as opposed to a composition that contains 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 may be performed in either a static or preferably agitated drying operation. Following drying, a heat treatment may be performed in optional step 150. The temperature of the heat treatment is not particularly limited, as long as it is equal to or greater than the temperature required to produce the crystalline phase of the solid electrolyte material of the present disclosure, or to enhance the ionic conductivity or compatibility with lithium metal. The material resulting from the heat treatment step 150 may be single phase or may also contain other crystalline phases, glass phases, and small amounts of precursor phases.

[0065] Generally, the heat treatment time is not limited, so long as it allows for the production of the desired composition and phases. 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 can be carried out in an inert gas atmosphere (e.g., argon or nitrogen), in a reducing atmosphere (e.g., hydrogen), or under vacuum. The heat treatment step 150 may be omitted entirely if the desired composition and phases are achieved during the initial mixing and drying steps.

[0066] IV. Electrochemical Cell The solid electrolyte material described herein may be used in a solid electrochemical cell. The solid electrolyte material may be disposed between a positive electrode and a negative electrode in a solid electrolyte material layer. The solid electrolyte material layer may include the solid electrolyte material of the present disclosure at a concentration of about 10% to about 100% by volume. In some embodiments, the concentration of the solid electrolyte material of the present 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 the present disclosure in the solid electrolyte material layer can be about 10% by volume to about 30% by volume, about 10% by volume to about 40% by volume, about 10% by volume to about 50% by volume, about 10% by volume to about 60% by volume, about 10% by volume to about 70% by volume, about 10% by volume to about 80% by volume, about 10% by volume to about 90% by volume, about 20% by volume to about 100% by volume, about 30% by volume to about 10% by volume, about 40% by volume to about 100% by volume, about 50% by volume to about 100% by volume, about 60% by volume to about 100% by volume, about 70% by volume to about 100% by volume, or about 80% by volume to about 100% by volume. In still further embodiments, the concentration of the solid electrolyte material of the present disclosure in the solid electrolyte material layer can be about 10 vol%, 20 vol%, 30 vol%, 40 vol%, 50 vol%, 60 vol%, 70 vol%, 80 vol%, 90 vol%, or about 100 vol%.

[0067] In some embodiments, the solid electrolyte material layer can include a binder or other modifier. In some aspects, the binder can 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 about 1 μm to about 1000 μm. In some embodiments, the solid electrolyte material layer may have a thickness of about 1 μm to about 5 μm, about 5 μm to about 10 μm, about 10 μm to about 15 μm, about 15 μm to about 20 μm, about 20 μm to about 25 μm, about 25 μm to about 30 μm, about 30 μm to about 35 μm, about 35 μm to about 40 μm, about 40 μm to about 45 μm, about 45 μm to about 50 μm, about 50 μm to about 60 μm, about 60 μm to about 70 μm, about 70 μm to about 80 μm, about 80 μm to about 90 μm, about 90 μm to about 100 μm, about 100 μm to about 150 μm, about 150 μm to about 200 μm, about 200 μm to about 25 μm, about 25 μm to about 30 μm, about 30 μm to about 35 μm, about 35 μm to about 40 μm, about 40 μm to about 45 μm, about 45 μm to about 50 μm, about 5 ...50 μm, The thickness may be from about 100 μm to about 100 μm, from about 100 μm to about 200 μm, from about 200 μm to about 300 μm, from about 300 μm to about 400 μm, from about 400 μm to about 500 μm, from about 500 μm to about 600 μm, from about 600 μm to about 700 μm, from about 700 μm to about 800 μm, from about 800 μm to about 900 μm, or from about 900 μm to about 1000 μm. In some additional embodiments, the solid electrolyte material layer has a thickness of about 1 μm to about 10 μm, about 1 μm to about 15 μm, about 1 μm to about 20 μm, about 1 μm to about 25 μm, about 1 μm to about 30 μm, about 1 μm to about 35 μm, about 1 μm to about 40 μm, about 1 μm to about 45 μm, about 1 μm to about 50 μm, about 1 μm to about 100 μm, about 1 μm to about 200 μm, about 1 μm to about 300 μm, about 1 μm to about 400 μm, about 1 μm to about 500 μm, about 1 μm to about 600 μm, about 1 μm to about 700 μm, about 1 μm to about 800 μm, about 1 μm to about 900 μm, about 5 μm to about 1000 μm, about 10 ... The thickness of the film may be from about 1000 μm to about 1000 μm, from about 15 μm to about 1000 μm, from about 20 μm to about 1000 μm, from about 25 μm to about 1000 μm, from about 30 μm to about 1000 μm, from about 35 μm to about 1000 μm, from about 40 μm to about 1000 μm, from about 45 μm to about 1000 μm, from about 50 μm to about 1000 μm, from about 100 μm to about 1000 μm, from about 200 μm to about 1000 μm, from about 300 μm to about 1000 μm, from about 400 μm to about 1000 μm, from about 500 μm to about 1000 μm, from about 600 μm to about 1000 μm, from about 700 μm to about 1000 μm, or from about 800 μm to about 1000 μm. In yet other embodiments, the solid electrolyte material layer can 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] The electrochemical cell may include a positive electrode. The positive electrode may be formed from materials including aluminum, nickel, titanium, stainless steel, and carbon. In some embodiments, the positive electrode may include a positive 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 a metal oxide, a metal phosphate, a metal sulfide, 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 include a solid electrolyte material of the present disclosure at a concentration of about 5% to about 80% by volume. 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 yet additional 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] The electrochemical cell may include a negative electrode. The negative electrode may be formed from a material including copper, nickel, stainless steel, or carbon. The negative electrode may include a negative electrode active material, a binder, and a conductive additive. In some embodiments, the negative electrode active material may include lithium metal, lithium alloy, silicon, tin (Sn), graphitic carbon, hard carbon, and may further include a solid electrolyte composition such as the solid electrolyte composition described herein. The negative electrode active material may include the solid electrolyte material of the present 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 the binder used in the negative electrode include the same material used in the positive electrode. Examples of the conductive additive used in the negative electrode include the same material 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 a solid electrolyte material of the present disclosure has the general formula Li (7-w-z) P.S. (6-w-z) X w Y z where X and Y are each a halogen or pseudohalogen, and 0≦w≦2, 0≦z≦2, and w+z=2. In some additional embodiments, an electrochemical cell comprising a solid electrolyte material of the present disclosure has a higher discharge capacity compared to an electrochemical cell comprising the same electrolyte material lacking an oxygen component, synthesized with 0 ppm HO. In still further embodiments, the discharge capacity of an electrochemical cell comprising a solid electrolyte material of the present disclosure can be at least about 100 mAh / g. In some aspects, the discharge capacity can 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 from about 100 mAh / g to about 105 mAh / g, from about 105 mAh / g to about 110 mAh / g, from about 110 mAh / g to about 115 mAh / g, from about 115 mAh / g to about 120 mAh / g, from about 120 mAh / g to about 125 mAh / g, from about 125 mAh / g to about 130 mAh / g, or greater than about 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 including a solid electrolyte material of the present disclosure may have a higher first cycle efficiency compared to an electrochemical cell including a solid electrolyte material having the general formula Li6PS5Cl. In some additional embodiments, an electrochemical cell including a solid electrolyte material of the present disclosure may have a higher first cycle efficiency compared to an electrochemical cell including the same electrolyte material lacking an oxygen component, synthesized with 0 ppm HO. In further embodiments, the first cycle efficiency can 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 aspects, 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 exemplary embodiments, electrochemical cells including the solid electrolyte materials of the present disclosure have a first cycle efficiency of greater than 88%.

[0073] In some embodiments, electrochemical cells including the solid electrolyte material of the present disclosure have the general formula Li (7-w-z) P.S. (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] may have a higher charge resistance compared to an electrochemical cell having a solid electrolyte material. In some additional embodiments, an electrochemical cell comprising the solid electrolyte material of the present disclosure may have a higher charge resistance compared to the same electrolyte material lacking an oxygen component synthesized with 0 ppm of H2O. In still further embodiments, the charge resistance of an electrochemical cell comprising a solid electrolyte material can be from about 4 minutes to about 6 minutes. In some aspects, the charge resistance of an electrochemical cell comprising a 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 charge 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).

[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 P.S. 6-w-z X w Y z 4. The electrochemical cell according to any one of embodiments 1 to 3, having a higher discharge capacity compared to an electrochemical cell including an electrolyte material having the above formula:

[0078] Embodiment 5: An electrochemical cell comprising a compound having the general formula Li 7-w-z P.S. 6-w-z X w Y z 5. The electrochemical cell according to any one of embodiments 1 to 4, having a higher first cycle efficiency compared to an electrochemical cell comprising an electrolyte material having the formula:

[0079] Embodiment 6: The electrochemical cell of any one of embodiments 1-5, wherein the electrochemical cell has a first cycle efficiency of at least about 88%.

[0080] Embodiment 7: An electrochemical cell comprising a compound having the general formula Li 7-w-z P.S. 6-w-z X w Y z 7. The electrochemical cell according to any one of embodiments 1 to 6, having a lower charging resistance compared to an electrochemical cell comprising an electrolyte material having the formula:

[0081] Embodiment 8: A method of making an electrolyte material, comprising milling a mixture comprising: A plurality of electrolyte precursors, the plurality of electrolyte precursors 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]

[0023] Embodiment 9: The method of embodiment 8, wherein the electrolyte precursor further comprises a sulfur (S)-containing material.

[0083]

[0023] Embodiment 10: The method of embodiment 8 or embodiment 9, wherein the electrolyte precursor further comprises one or more of a halide-containing material or a pseudohalide-containing material.

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

[0085]

[0023] Embodiment 12: The method of embodiment 11, wherein heating causes the mixture to crystallize to form the electrolyte material.

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

[0087] Embodiment 14: The method of embodiment 13, wherein the mixture comprises about 250 ppm water.

[0088] Embodiment 15: The method of embodiment 13, wherein the mixture comprises about 500 ppm water.

[0089] Embodiment 16: The method of embodiment 13, wherein the mixture comprises 1000 ppm water.

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

[0091] Embodiment 18: The method of any one of embodiments 8-17, wherein water is added to the solvent prior to milling.

[0092] Embodiment 19: The method of any one of embodiments 8-18, wherein at least one of the plurality of electrolyte precursors is anhydrous.

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

[0094] Embodiment 21: The method of any one of embodiments 8 to 20, wherein the solvent is an aprotic solvent of low polarity.

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

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

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

[0098] Embodiment 25: 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, 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 has a solubility of about 975 cm -1 ±25cm -1 , 690cm -1 ±25cm -1 , and 525 cm -1 ±25cm -1 A solid electrolyte material with an FT-IR peak at

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

[0100] Embodiment 27: The solid electrolyte material of embodiment 25 or embodiment 26, wherein X is Cl.

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

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

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

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

[0105] Embodiment 32: The solid electrolyte material according to any one of Embodiments 29 to 31, wherein 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, wherein 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, wherein 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, wherein 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, wherein the electrolyte material has an ionic conductivity of at least 1×10 -4 mS / cm 2 .

[0110] Embodiment 37: A method for producing a solid electrolyte material, comprising: The 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) and A, B, C, and D = ppm of HO per unit mass, and Z, Y, Z and W = unit mass. The reactants were mixed according to the formula Li6PS 5-E O E forming a solid electrolyte material of Cl; Controlling the ppm of water in each precursor and solvent to produce an electrolyte material with high ionic conductivity and low reactivity towards high nickel content cathodes; A method comprising: EXAMPLES

[0111] Example 1: Characterization of electrolyte materials Solid electrolyte materials were produced 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 contents of 0 ppm, 100 ppm, 250 ppm, 500 ppm, and 1000 ppm. Fourier transform-infrared spectroscopy (FT-IR) was performed to characterize each of these samples (see FIG. 2). As can be seen in FIG. 2, as the water content of the electrolyte material increases, the peak at about 975 cm -1 , 690cm -1 and 525cm -1The magnitude of the peak at is increased. The peak's attribution is unknown, but the peak is characteristic of the materials described herein.

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

[0113] Example 2: Performance of electrolyte materials A performance test was carried out on the electrolyte material of Example 1. The results of the performance test are shown in Figures 3A to 3C.

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

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

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

[0117] FIG. 4 shows the XRD pattern of the electrolyte material synthesized using a precursor having 1000 ppm water. From the XRD pattern shown in FIG. 4, it can be seen that the electrolyte material contains Li 5.5 P.S. 4.5-x O x It can be confirmed that the electrolyte phase is a complex containing an electrolyte phase of Cl and an electrolyte phase of LiCl. 5.5 P.S. 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 with 100,000 ppm water An electrolyte material synthesized using a precursor and a solvent having 100,000 ppm water was prepared according to the method of the present disclosure. From the XRD pattern shown in FIG. 5, the electrolyte material contains Li 5.5 P.S. 4.5-x O x It can be confirmed that the electrolyte phase is a complex containing an electrolyte phase of Cl, an electrolyte phase of Li2S, and an electrolyte phase of LiCl. 5.5 P.S. 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°.

Claims

1. A positive electrode and an electrolyte material disposed between the positive electrode and the negative electrode; Including, The electrolyte material has the general formula: 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.) having Electrochemical cell.

2. X and Y are F, Cl, Br, I, BF, respectively. ４ , B.H. ４ , NO ２ and NO ３ 2. The electrochemical cell of claim 1 , wherein the at least one electrode is selected from the group consisting of:

3. The electrolyte material has a thickness of 975±25 cm －１ , 690±25cm －１ , and 525±25 cm －１ 3. The electrochemical cell according to claim 1, having an FT-IR spectrum with an absorption peak at

4. The electrochemical cell comprises a compound having the general formula Li ７－ｗ－ｚ P.S. ６－ｗ－ｚ X ｗ Y ｚ The electrochemical cell according to any one of claims 1 to 3, having a higher discharge capacity compared to an electrochemical cell comprising an electrolyte material having the formula:

5. The electrochemical cell comprises a compound having the general formula Li ７－ｗ－ｚ P.S. ６－ｗ－ｚ X ｗ Y ｚ 5. The electrochemical cell of claim 1, having a higher first cycle efficiency compared to an electrochemical cell comprising an electrolyte material having the formula:

6. 6. The electrochemical cell of any one of claims 1 to 5, wherein the electrochemical cell has a first cycle efficiency of at least about 88%.

7. The electrochemical cell comprises a compound having the general formula Li ７－ｗ－ｚ P.S. ６－ｗ－ｚ X ｗ Y ｚ 7. The electrochemical cell of claim 1, having a lower charging resistance compared to an electrochemical cell comprising an electrolyte material having the formula:

8. 1. A method of making an electrolyte material comprising milling a mixture comprising: a plurality of electrolyte precursors comprising one or more lithium (Li)-containing materials; one or more phosphorus (P)-containing materials; Halides or pseudohalides; One or more solvents; and water.

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

10. 10. The method of claim 8 or 9, wherein the electrolyte precursor further comprises one or more of a halide-containing material or a pseudohalide-containing material.

11. The method of any one of claims 8 to 10, further comprising heating the mixture after said milling.

12. The method of claim 11 , wherein the heating causes the mixture to crystallize to form the electrolyte material.

13. The method of any one of claims 8 to 12, wherein the mixture comprises at least 100 ppm water.

14. The method of claim 13, wherein the mixture comprises about 250 ppm water.

15. The method of claim 13, wherein the mixture comprises about 500 ppm water.

16. The method of claim 13, wherein the mixture comprises about 1000 ppm water.

17. 14. The method of claim 13, wherein the mixture comprises about 100,000 ppm water.

18. The method of any one of claims 8 to 17, wherein the water is added to the solvent prior to the milling.

19. The method of any one of claims 8 to 18, wherein at least one of the plurality of electrolyte precursors is anhydrous.

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

21. The method according to any one of claims 8 to 20, wherein the solvent is an aprotic solvent of low polarity.

22. 22. The method of claim 21, wherein the solvent is selected from the group consisting of xylene, toluene, benzene, heptane, and combinations thereof.

23. The method of any one of claims 8 to 20, wherein the solvent comprises an ether, an ester, a nitrile or an alcohol.

24. 1. An electrochemical cell comprising: Positive electrode; An electrolyte material; and Negative electrode; Including, Where: the electrolyte material is disposed between the positive electrode and the negative electrode; The electrolyte material is produced by the method according to any one of claims 8 to 23. Electrochemical cell.

25. A solid electrolyte material, 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 halogen or pseudohalogen; A is at least one element selected from the group consisting of S, Se, and N; The electrolyte material has a thickness of about 975 cm －１ ±25cm －１ , 690 cm －１ ±25cm －１ , and 525 cm －１ ±25cm －１ having an FT-IR peak at Solid electrolyte material.

26. 26. The solid electrolyte material of claim 25, wherein T is P.

27. 27. The solid electrolyte material according to claim 25 or 26, wherein X is Cl.

28. The solid electrolyte material according to any one of claims 25 to 27, wherein A is S.

29. The material has the formula Li ７－ｗ－ｚ P.S. ６－ｗ－ｚ－ｖ O ｖ X ｗ Y ｚ The solid electrolyte material according to any one of claims 25 to 27, represented by:

30. The solid electrolyte material according to claim 29, wherein 0<v≦1.

31. The solid electrolyte material according to claim 29, wherein the solid electrolyte material has an FT-IR spectrum shown in FIG.

32. 30. The solid electrolyte material of claim 29, wherein the amount of oxygen present is based on exposure to 40 ppm to 1000 ppm of water.

33. The electrochemical cell containing the electrolyte material has 0 ppm H ２ 33. The solid electrolyte material according to any one of claims 29 to 32, having a higher discharge capacity compared to an electrochemical cell comprising the same electrolyte material synthesized with O but lacking the oxygen component.

34. The electrochemical cell containing the electrolyte material has 0 ppm H ２ 34. The solid electrolyte material of any one of claims 29 to 33, having a higher first cycle efficiency (FCE) compared to an electrochemical cell comprising the same electrolyte material lacking an oxygen component exposed to O.

35. The electrochemical cell containing the electrolyte material has 0 ppm H ２ 35. The solid electrolyte material of any one of claims 29 to 34, having a lower resistance rise compared to an electrochemical cell comprising the same electrolyte material lacking the oxygen component exposed to O.

36. The electrolyte material is at least 1×10 －４ mS / cm ２ The solid electrolyte material according to any one of claims 25 to 35, having an ionic conductivity of

37. A method for producing a solid electrolyte material, comprising the steps of: The reaction: 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 [Where, 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 = unit mass. The reactants are mixed according to the formula Li ６ P.S. ５－Ｅ O Ｅ Producing a solid electrolyte material of Cl; Controlling the ppm of water in each precursor and solvent to produce an electrolyte material with high ionic conductivity and low reactivity towards high nickel content cathodes; A method comprising:

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