Solid electrolyte material and solid-state battery manufactured therefrom

Abstract

A solid electrolyte material includes Li, T, X, and A, where T is at least one of Sb, P, As, Si, Ge, Al, and B; X is one or more halogens or N; and A is one or more of S or Se. In an X-ray diffraction measurement, the solid electrolyte material has peaks at 2θ = 14.5° ± 0.50°, 16.8° ± 0.50°, 23.9° ± 0.50°, 28.1° ± 0.50°, and 32.5° ± 0.50°, where 2θ is the Bragg angle, and can include glass-ceramics and / or mixed crystalline phases.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 082,146, filed on September 23, 2020, the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0003] The various embodiments described herein relate to the fields of solid-state primary and secondary electrochemical cell units, electrodes and electrode materials, electrolytes and electrolyte compositions, and their corresponding manufacturing and use methods. BACKGROUND OF THE INVENTION

[0004] From telephones and laptops to scooters and cars, the integration of rechargeable lithium-ion batteries with surrounding technologies has increased year by year. However, rechargeable lithium-ion batteries contain flammable liquid electrolytes, which not only pose safety risks but also limit the use of high-energy density anode materials such as lithium metal, thus restricting the performance potential of the batteries. To avoid these two problems, the flammable liquid electrolytes can be replaced with solid-state electrolytes.

[0005] Some of the most promising solid-state electrolytes are sulfide-based because they have high room-temperature conductivity and can be synthesized using light elements such as lithium (Li), phosphorus (P), and sulfur (S). One of the earliest sulfide solid electrolytes is lithium thiargillite (U.S. Patent: No. 8075865), which has the formula Li + (12-n-x) B n+ X 2- 6-x Y -x , where B n+ is selected from the group consisting of: P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb, and Ta; X 2- is selected from the group consisting of: S, Se, and Te; Y - is selected from the group consisting of: Cl, Br, I, F, CN, OCN, SCN, and N3; 0 ≤ x ≤ 2. Another member of the thiargillite family is a solid electrolyte material having a composition according to the formula Li 7+x-y M x Sb l-x S 6-y X y , where M is one or more selected from the group consisting of: Si, Ge, and Sn; 0 < x < 1; and X is one or more selected from the group consisting of: Cl, Br, and I; 0.05 < y < 2 (WO 2021013824). These materials of the thiargillite family exhibit high ionic conductivity.

[0006] However, one of the drawbacks of sulfide electrolytes is their poor air stability, as the PS bonds in their structure easily break and form PO bonds upon contact with oxygen and moisture. The formation of PO bonds reduces the electrolyte's ionic conductivity and promotes the release of hydrogen sulfide gas. One approach to circumvent this problem is to incorporate oxygen-containing species into sulfide electrolyte materials recognized in publications such as US2020 / 0087155 or WO2019 / 207951. In these documents, oxygen is incorporated into materials with a sulfogermanium sulfide structure to form Li6PS4OCl sulfogermanium sulfide or into Li3PS4 materials to produce Li3PS3O materials. Unfortunately, these materials tend to have low ionic conductivity and require very high temperatures to produce. To overcome these problems, a novel sulfide electrolyte has been synthesized and is disclosed herein, exhibiting a novel structure with appropriate stoichiometry, high conductivity, improved air stability, and suitability for cryogenic processing. Summary of the Invention

[0007] This application relates to a solid electrolyte material comprising Li, T, X, and A, wherein T comprises at least one element selected from the group consisting of Sb, P, As, Si, Ge, Al, B, and W; X comprises one or more halogens, pseudohalogens, or N; A comprises one or more of S or Se; and wherein, in X-ray diffraction measurements, the solid electrolyte material has peaks at 2θ = 14.5° ± 0.50°, 16.8° ± 0.50°, 23.9° ± 0.50°, 28.1° ± 0.50°, and 32.5° ± 0.50°.

[0008] In one embodiment, the solid electrolyte material includes the formula Li 1-a-b-c T a A b X c , of which 0.074 <a≤0.105,0.370<b≤0.421,0.074<c≤0.105。

[0009] In another embodiment of the solid electrolyte material, T comprises a blend of Sb and non-Sb elements selected from the group consisting of: Sb, P, As, Si, Ge, Al, B, and W.

[0010] In another embodiment of the solid electrolyte material, Sb accounts for 1% or more of the total elemental T.

[0011] In another embodiment of the solid electrolyte material, a = 0.1, b = 0.4, c = 0.1, T = Sb, A = S, and X = I.

[0012] In another embodiment of the solid electrolyte material, at least one of a glass-ceramic phase, a crystalline phase, and a mixed phase is included.

[0013] In another embodiment of the solid electrolyte material, the mixed phase includes other crystalline phases that, in X-ray diffraction measurements, contain peaks at 20.2°±0.50° and 23.6°±0.50°, and / or 21.0°±0.50° and 28.0°±0.50°, and / or 17.5°±0.50° and 18.2°±0.50° and / or 17.1° and 25.8°, wherein

[0014] In another embodiment of the solid electrolyte material, it comprises an ionic conductivity greater than about 0.500 mS / cm at room temperature.

[0015] In an alternative embodiment, this application relates to a lithium solid-state battery comprising: a positive electrode active material layer containing a positive electrode active material; a negative electrode active material layer containing a negative electrode active material; and a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer comprises a solid electrolyte material comprising Li, T, X, and A, wherein T comprises at least one element selected from the group consisting of: Sb, P, As, Si, Ge, Al, B, and W; X comprises one or more halogens, pseudohalogens, or N; A comprises one or more of S or Se; and wherein, in X-ray diffraction measurements, the solid electrolyte material has peaks at 2θ = 14.5° ± 0.50°, 16.8° ± 0.50°, 23.9° ± 0.50°, 28.1° ± 0.50°, and 32.5° ± 0.50°.

[0016] In another embodiment of a lithium solid-state battery, the solid electrolyte material includes the formula Li 1-a-b-c T a A b X c , of which 0.074 <a≤0.105,0.370<b≤0.421,0.074<c≤0.105。

[0017] In another embodiment of the lithium solid-state battery, T comprises a blend of Sb and non-Sb elements selected from the group consisting of: Sb, P, As, Si, Ge, Al, B, and W.

[0018] In another embodiment of the lithium solid-state battery, Sb accounts for 1% or more of the total element T.

[0019] In another embodiment of the lithium solid-state battery, formula Li 1-a-b-c T a A b X c It includes a = 0.1, b = 0.4, c = 0.1, T = Sb, A = S, and X = I.

[0020] In another embodiment of the lithium solid-state battery, at least one solid electrolyte material comprising a glass-ceramic phase, a crystalline phase, and a mixed phase is included.

[0021] In another embodiment of the lithium solid-state battery, the mixed phase includes other crystalline phases that, in X-ray diffraction measurements, contain peaks at 20.2°±0.50° and 23.6°±0.50°, and / or 21.0°±0.50° and 28.0°±0.50°, and / or 17.5°±0.50° and 18.2°±0.50°, and / or 17.1° and 25.8°, wherein...

[0022] In another embodiment of the lithium solid-state battery, a solid electrolyte material is included, said solid electrolyte material having a strength greater than about 0.500 mS / cm at room temperature. 2 ionic conductivity.

[0023] In another embodiment of the lithium solid-state battery, the positive electrode active material comprises one or more particles, wires, or filaments, wherein the one or more particles, wires, or filaments comprise at least one of the following: aluminum, nickel, titanium, stainless steel, magnesium, iron, zinc, indium, germanium, silver, platinum, gold, lithium, or alloys thereof.

[0024] In another embodiment of the lithium solid-state battery, the negative electrode active material includes: at least one of alkali metals, including lithium metal, lithium alloy, sodium metal, sodium alloy, potassium metal, and potassium alloy; or at least one of alkaline earth metals, including magnesium metal, magnesium alloy, calcium metal, and calcium alloy.

[0025] In another embodiment of the lithium solid-state battery, the negative electrode active material further includes silicon, tin, iron, germanium, or indium.

[0026] In another embodiment of the lithium solid-state battery, the positive electrode active material layer and the negative electrode active material layer each include one or more carbon-containing materials, including carbon fibers, graphite, graphene, carbon black, conductive carbon, amorphous carbon, VGCF, and carbon nanotubes.

[0027] In another embodiment of the lithium solid-state battery, the carbon-containing material is added in an amount of 2% to 50% by mass.

[0028] In another embodiment of the lithium solid-state battery, the carbon-containing material is added in an amount of 6% to 30% by mass.

[0029] In another embodiment of the lithium solid-state battery, the carbon-containing material is added in an amount of 8% to 25% by mass.

[0030] In another embodiment of the lithium solid-state battery, the carbon-containing material is added in an amount of 10% to 20% by mass.

[0031] In another embodiment of the lithium solid-state battery, the carbon-containing material is added in an amount of 12% to 18% by mass.

[0032] In another embodiment of the lithium solid-state battery, the carbon-containing material is added in an amount of 2% to 50% by mass.

[0033] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each comprise one or more of metal particles, filaments, or other structures.

[0034] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each include one or more adhesives or polymers, the one or more adhesives or polymers including fluoropolymers containing vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE) and derivatives thereof.

[0035] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each include one or more adhesives or polymers, the one or more adhesives or polymers including: homopolymers comprising polyvinylidene fluoride (PVdF), polyhexafluoropropylene (PHFP), or polytetrafluoroethylene (PTFE); or binary copolymers comprising copolymers of VdF and HFP, the binary copolymers including poly(vinylidene fluoride-hexafluoropropylene) copolymers (PVdF-HFP).

[0036] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each include one or more adhesives or polymers, the one or more adhesives or polymers including thermoplastic elastomers comprising styrene-butadiene rubber (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene block copolymer (SIS), styrene-ethylene-butene-styrene (SEBS), polyacrylonitrile (PAN), nitrile-butene rubber (NBR), polybutadiene, polyisoprene, or poly(methacrylate) nitrile-butadiene rubber (PMMA-NBR).

[0037] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each include one or more adhesives or polymers, the one or more adhesives or polymers including acrylic resins comprising poly(methyl methacrylate), poly(ethyl methacrylate), poly(isopropyl methacrylate), poly(isobutyl methacrylate), and poly(butyl methacrylate).

[0038] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each include one or more adhesives or polymers, the one or more adhesives or polymers including polycondensation polymers comprising polyurea, polyamide paper or polyimide, and polyester.

[0039] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each include one or more adhesives or polymers, the one or more adhesives or polymers including nitrile rubbers comprising acrylonitrile-butadiene rubber (ABR), polystyrene-nitrile-butadiene rubber (PS-NBR), or mixtures thereof.

[0040] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each comprise one or more adhesives or polymers, the one or more adhesives or polymers being present in an amount from 1% to 80% by mass.

[0041] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each comprise one or more adhesives or polymers, the one or more adhesives or polymers being present in an amount of 3% to 70% by mass.

[0042] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each comprise one or more adhesives or polymers, the one or more adhesives or polymers being present in an amount of 5% to 60% by mass.

[0043] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each comprise one or more adhesives or polymers, the one or more adhesives or polymers being present in an amount of 8% to 50% by mass.

[0044] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each comprise one or more adhesives or polymers, the one or more adhesives or polymers being present in an amount of 11% to 40% by mass.

[0045] In another embodiment of the lithium solid-state battery, the positive electrode layer and the negative electrode layer each comprise one or more adhesives or polymers, the one or more adhesives or polymers being present in an amount of 14% to 30% by mass.

[0046] In another embodiment of the lithium solid-state battery, the negative electrode active material has sufficient electronic activity and mechanical strength to act as the negative electrode, and wherein the negative electrode is absent.

[0047] In another embodiment of the lithium solid-state battery, the positive electrode active material layer comprises Li(Ni a Co b Mn c )O2, where 0 < a ≤ 1, 0 < b ≤ 1, 0 < c ≤ 1, and a + b + c = 1.

[0048] In another embodiment of the lithium solid-state battery, the positive electrode active material layer comprises Li(Ni 0.33 Co 0.33 Mn 0.33 )O2, Li(Ni 0.4 Co 0.3 Mn 0.3 )O2, Li(Ni 0.5 Co 0.2 Mn 0.3 )O2, Li(Ni 0.6 Co 0.2 Mn 0.2 )O2, Li(Ni 0.8 Co 0.1 Mn 0.1 )O2, or a combination thereof.

[0049] In another embodiment of the lithium solid-state battery, the positive electrode active material layer comprises one or more metal oxides including V2O5, V6O 13 , MoO3, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNi 1-Y Co Y O2, LiCo 1-Y Mn Y O2, LiNi 1-Y Mn Y O2(0 ≤ Y < 1), Li(Ni a Co b Mn c )O4(0 < a < 2, 0 < b < 2, 0 < c < 2, a + b + c = 2), LiMn2-ZNiZO4, LiMn 2-Z Co Z O4(0 < Z < 2), LiCoPO4, LiFePO4, CuO, Li(Ni a Co b Al c )O2(0 < a < 1, 0 < b < 1, 0 < c < 1, a + b + c = 1), or a combination thereof.

[0050] In another embodiment of the lithium solid-state battery, the positive electrode active material layer includes one or more metal sulfides, wherein the metal sulfides include titanium sulfide (TiS2), molybdenum sulfide (MoS2), iron sulfide (FeS, FeS2), copper sulfide (CuS), nickel sulfide (Ni3S2), and lithium sulfide (Li2S), or combinations thereof.

[0051] In another embodiment of the lithium solid-state battery, the positive electrode active material is present in an amount of 20% to 99% by mass.

[0052] In another embodiment of the lithium solid-state battery, the positive electrode active material is present in an amount of 30% to 95% by mass.

[0053] In another embodiment of the lithium solid-state battery, the positive electrode active material is present in an amount of 40% to 92.5% by mass.

[0054] In another embodiment of the lithium solid-state battery, the positive electrode active material is present in an amount of 50% to 90% by mass.

[0055] In another embodiment of the lithium solid-state battery, the positive electrode active material is present in an amount of 60% to 87.5% by mass.

[0056] In another embodiment of the lithium solid-state battery, the positive electrode active material is present in an amount of 65% to 85% by mass.

[0057] In another embodiment of the lithium solid-state battery, the negative electrode active material is present in an amount of 20% to 99% by mass.

[0058] In another embodiment of the lithium solid-state battery, the negative electrode active material is present in an amount of 30% to 95% by mass.

[0059] In another embodiment of the lithium solid-state battery, the negative electrode active material is present in an amount of 40% to 92.5% by mass.

[0060] In another embodiment of the lithium solid-state battery, the negative electrode active material is present in an amount of 50% to 90% by mass.

[0061] In another embodiment of the lithium solid-state battery, the negative electrode active material is present in an amount of 60% to 87.59% by mass.

[0062] In another embodiment of the lithium solid-state battery, the negative electrode active material is present in an amount of 65% to 85% by mass.

[0063] In another embodiment of the lithium solid-state battery, the positive electrode active material layer comprises one or more of the following: Li2S—P2S5, Li2S—P2S5—LiI, Li2S—P2S5—GeS2, Li2S—P2S5—Li2O, Li2S—P2S5—Li2O—LiI, Li2S-P2S5—LiI—LiBr, Li2S—SiS2, Li2S—SiS2—LiI, Li2S—SiS2—LiBr, Li2S—S—SiS2—LiCl, Li2S—S—SiS2—B2S3—LiI, Li2S—S—SiS2—P2S5—LiI, Li2S—B2S3, Li2S—P2S5—Z m S n (where m and n are positive numbers, and Z is Ge, Zn or Ga), Li2S—GeS2, Li2S—S—SiS2—Li3PO4 and Li2S—S—SiS2—Li x MO y (where x and y are positive numbers, and M is P, Si, Ge, B, Al, Ga or In).

[0064] In another embodiment of the lithium solid-state battery, the positive electrode active material layer comprises one or more of the following: Li3PS4, Li4P2S6, Li7P3S 11 、Li 10 GeP2S 12 、Li 10 SnP2S 12 。

[0065] In another embodiment of the lithium solid-state battery, the positive electrode active material layer comprises one or more of Li6PS5Cl, Li6PS5Br, Li6PS5I or is represented by the formula Li 7-y PS 6-y X y where X represents at least one halogen element and / or pseudohalogen, and where 0 < y ≤ 2.0, and where the halogen comprises one or more of F, Cl, Br, I, and the pseudohalogen comprises one or more of N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN and SCN.

[0066] In another embodiment of the lithium solid-state battery, the positive electrode active material layer comprises Li 8-y-z P2S 9-y-z X y W zOne or more of the following, wherein X and W represent at least one halogen element and / or pseudohalogen, and wherein 0 ≤ y ≤ 1 and 0 ≤ z ≤ 1, and wherein the halogen includes one or more of F, Cl, Br, I, and the pseudohalogen includes one or more of N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN.

[0067] In another embodiment of the lithium solid-state battery, the thickness of the positive electrode active material layer is in the range of 1 micrometer to 1000 micrometers.

[0068] In another embodiment of the lithium solid-state battery, the thickness of the positive electrode active material layer is in the range of 2 micrometers to 900 micrometers.

[0069] In another embodiment of the lithium solid-state battery, the thickness of the positive electrode active material layer is in the range of 1 micrometer to 100 micrometers.

[0070] In another embodiment of the lithium solid-state battery, the thickness of the positive electrode active material layer is in the range of 5 micrometers to 750 micrometers.

[0071] In another embodiment of the lithium solid-state battery, the thickness of the positive electrode active material layer is in the range of 10 micrometers to 500 micrometers.

[0072] In another embodiment of the lithium solid-state battery, the thickness of the positive electrode active material layer is in the range of 15 micrometers to 350 micrometers.

[0073] In another embodiment of the lithium solid-state battery, the thickness of the positive electrode active material layer is in the range of 20 micrometers to 200 micrometers.

[0074] In another embodiment of the lithium solid-state battery, the thickness of the positive electrode active material layer is in the range of 25 micrometers to 100 micrometers.

[0075] In another embodiment of the lithium solid-state battery, the thickness of the negative electrode active material layer is in the range of 500 nanometers to 1000 micrometers.

[0076] In another embodiment of the lithium solid-state battery, the thickness of the negative electrode active material layer is in the range of 1 micrometer to 900 micrometers.

[0077] In another embodiment of the lithium solid-state battery, the thickness of the negative electrode active material layer is in the range of 5 micrometers to 750 micrometers.

[0078] In another embodiment of the lithium solid-state battery, the thickness of the negative electrode active material layer is in the range of 10 micrometers to 500 micrometers.

[0079] In another embodiment of the lithium solid-state battery, the thickness of the negative electrode active material layer is in the range of 15 micrometers to 350 micrometers.

[0080] In another embodiment of the lithium solid-state battery, the thickness of the negative electrode active material layer is in the range of 20 micrometers to 200 micrometers.

[0081] In another embodiment of the lithium solid-state battery, the thickness of the negative electrode active material layer is in the range of 25 micrometers to 100 micrometers.

[0082] In another embodiment of the lithium solid-state battery, the thickness of the solid electrolyte layer is in the range of 500 nanometers to 1000 micrometers.

[0083] In another embodiment of the lithium solid-state battery, the thickness of the solid electrolyte layer is in the range of 1 micrometer to 900 micrometers.

[0084] In another embodiment of the lithium solid-state battery, the thickness of the solid electrolyte layer is in the range of 5 micrometers to 750 micrometers.

[0085] In another embodiment of the lithium solid-state battery, the thickness of the solid electrolyte layer is in the range of 10 micrometers to 500 micrometers.

[0086] In another embodiment of the lithium solid-state battery, the thickness of the solid electrolyte layer is in the range of 15 micrometers to 350 micrometers.

[0087] In another embodiment of the lithium solid-state battery, the thickness of the solid electrolyte layer is in the range of 20 micrometers to 200 micrometers.

[0088] In another embodiment of the lithium solid-state battery, the thickness of the solid electrolyte layer is in the range of 25 micrometers to 100 micrometers.

[0089] In another embodiment of the lithium solid-state battery, the amount of the solid electrolyte composition is from 5% to 80% by mass.

[0090] In another embodiment of the lithium solid-state battery, the amount of the solid electrolyte composition is from 7.5% to 70% by mass.

[0091] In another embodiment of the lithium solid-state battery, the amount of the solid electrolyte composition is from 10% to 60% by mass.

[0092] In another embodiment of the lithium solid-state battery, the amount of the solid electrolyte composition is from 12.5% ​​by mass to 50% by mass.

[0093] In another embodiment of the lithium solid-state battery, the amount of the solid electrolyte composition is 15% to 40% by mass.

[0094] In another embodiment of the lithium solid-state battery, the amount of the solid electrolyte composition is from 17.5% to 30% by mass.

[0095] In an alternative embodiment, this document discloses a method for producing a sulfide solid electrolyte material comprising a glass-ceramic, the sulfide solid electrolyte material comprising: Li, T, X, and A, wherein T is at least one selected from Sb, P, As, Si, Ge, Al, B, and W; X is one or more halogens, pseudohalogens, or N; and A is one or more selected from S or Se. The method comprises: mixing and grinding a raw material composition containing element A or compound Li₂A, element T or T, and compound LiX or Li₃N to amorphize the mixture under X-ray diffraction; and / or heating the sulfide glass at a heat treatment temperature equal to or greater than the crystallization temperature of the sulfide glass to synthesize the glass-ceramic, wherein, in X-ray diffraction measurements, the glass-ceramic has peaks at 2θ = 14.5° ± 0.50°, 16.8° ± 0.50°, 23.9° ± 0.50°, 28.1° ± 0.50°, and 32.5° ± 0.50°, where... Attached Figure Description

[0096] This disclosure can be understood by referring to the accompanying drawings, which are briefly described below, and the detailed embodiments described below. It should be noted that, for purposes of clarity, some elements in the drawings may not be drawn to scale.

[0097] Figure 1 This is a schematic cross-sectional view of an exemplary construction of a lithium solid-state electrochemical battery cell comprising a solid electrode composition according to an embodiment.

[0098] Figure 2 This is a flowchart of a method for generating a solid electrolyte composition according to an embodiment.

[0099] Figure 3 According to one embodiment Figure 2 The diagram shows X-ray diffraction measurements of the solid electrolyte composition produced by the method shown.

[0100] Figure 4 This is a graph showing the conductivity of a solid-state electrochemical cell using the solid electrolyte composition of this disclosure according to an embodiment. Detailed Implementation

[0101] In the following description, specific details are provided to give a thorough understanding of the various embodiments of this disclosure. However, upon reading and understanding this specification, claims, and drawings, those skilled in the art will understand that some embodiments of this disclosure can be practiced without being limited to some of the specific details set forth herein. Furthermore, to avoid obscuring this disclosure, the application of some well-known methods, processes, apparatuses, and systems in the various embodiments described herein is not disclosed in detail.

[0102] Figure 1 This is a schematic cross-sectional view of an exemplary configuration of a lithium solid-state electrochemical battery cell incorporating the electrode composition of this disclosure. The lithium solid-state battery 100 includes a positive electrode (current collector) 110, a positive electrode active material layer (cathode) 120, a solid electrolyte layer 130, a negative electrode active material layer (anode) 140, and a negative electrode (current collector) 150. The solid electrolyte layer 130 may be formed between the positive electrode active material layer 120 and the negative electrode active material layer 140. The positive electrode 110 is in electrical contact with the positive electrode active material layer 120, and the negative electrode 150 is in electrical contact with the negative electrode active material layer 140. The solid electrolyte composition described herein may form portions of the positive electrode active material layer 120, the negative electrode active material layer 140, and the solid electrolyte layer 130.

[0103] The positive electrode 110 may also be referred to as a "positive electrode current collector" and may be a foil or plate formed of, but not limited to, the following materials: aluminum (Al), nickel (Ni), titanium (Ti), stainless steel, magnesium (Mg), iron (Fe), zinc (Zn), indium (In), germanium (Ge), silver (Ag), platinum (Pt), gold (Au), lithium (Li), or alloys thereof. In some embodiments, the positive electrode layer 110 may be formed of one or more carbon-containing materials, such as carbon fibers, graphite, graphene, carbon black, conductive carbon, amorphous carbon, VGCF, and carbon nanotubes.

[0104] Similarly, the negative electrode 150, also known as the negative electrode current collector, can be formed from aluminum (Al), nickel (Ni), titanium (Ti), stainless steel, magnesium (Mg), iron (Fe), zinc (Zn), indium (In), germanium (Ge), silver (Ag), platinum (Pt), gold (Au), lithium (Li), or alloys thereof. If the negative electrode active material 140 has sufficient electronic conductivity and mechanical strength, the negative electrode 150 can be omitted entirely.

[0105] The positive electrode active material layer 120 may at least comprise a positive electrode active material, which includes, but is not limited to, metal oxides, metal phosphates, metal sulfides, sulfur, lithium sulfide, oxygen, or air. In some embodiments, the positive electrode active material layer 120 may comprise one or more NMC materials, which may be represented as Li(Ni) aCo b Mn c )O2 (0 < a < 1, 0 < b < 1, 0 < c < 1, a + b + c = 1) or, for example, NMC 111 (LiNi 0.33 Mn 0.33 Co 0.33 O2), NMC433 (LiNi 0.4 Mn 0.3 Co 0.3 O2), NMC 532 (LiNi 0.5 Mn 0.3 Co 0.2 O2), NMC 622 (LiNi 0.6 Mn 0.2 Co 0.2 O2), NMC811 (LiNi 0.8 Mn 0.1 Co 0.1 O2) or a combination thereof. In another embodiment, the positive electrode active material layer 120 may include one or more metal oxides, such as but not limited to V2O5, V6O 13 , MoO3, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNi 1-Y Co Y O2, LiCo 1-Y Mn Y O2, LiNi 1-Y Mn Y O2 (0 ≤ Y < 1), Li(Ni a Co b Mn c )O4 (0 < a < 2, 0 < b < 2, 0 < c < 2, a + b + c = 2), LiMn 2-Z Ni Z O4, LiMn 2-Z Co Z O4 (0 < Z < 2), LiCoPO4, LiFePO4, CuO, Li(Ni a Co b Al c )O2 (0 < a < 1, 0 < b < 1, 0 < c < 1, a + b + c = 1) or a combination thereof. In yet another embodiment, the positive electrode active material layer 120 may include one or more metal sulfides, and the metal sulfides include titanium sulfide (TiS2), molybdenum sulfide (MoS2), iron sulfide (FeS, FeS2), copper sulfide (CuS), nickel sulfide (Ni3S2), and lithium sulfide (Li2S) or a combination thereof.

[0106] The positive electrode active material can be added in an amount of 20% to 99% by mass; 30% to 95% by mass; 40% to 92.5% by mass; 50% to 90% by mass; 60% to 87.5% by mass; or 65% to 85% by mass.

[0107] The positive electrode active material layer 120 can further contain one or more solid electrolyte materials, such as one or more of the following: Li2S—P2S5, Li2S—P2S5—LiI, Li2S—P2S5—GeS2, Li2S—P2S5—Li2O, Li2S—P2S5—Li2O—LiI, Li2S-P2S5—LiI—LiBr, Li2S—SiS2, Li2S—SiS2—LiI, Li2S—SiS2—LiBr, Li2S—S—SiS2—LiCl, Li2S—S—SiS2—B2S3—LiI, Li2S—S—SiS2—P2S5—LiI, Li2S—B2S3, Li2S—P2S5—Z m S n (where m and n are positive numbers, and Z is Ge, Zn or Ga), Li2S—GeS2, Li2S—S—SiS2—Li3PO4 and Li2S—S—SiS2—Li x MO y (where x and y are positive numbers, and M is P, Si, Ge, B, Al, Ga or In). In another embodiment, one or more of the solid electrolyte materials can be Li3PS4, Li4P2S6, Li7P3S 11 、Li 10 GeP2S 12 、Li 10 SnP2S 12 。In a further embodiment, one or more of the solid electrolyte materials can be Li6PS5Cl, Li6PS5Br, Li6PS5I or expressed by the formula Li 7-y PS 6-y X y , where X represents at least one halogen element and / or pseudohalogen, and where 0 < y ≤ 2.0, and where the halogen can be one or more of F, Cl, Br, I, and the pseudohalogen can be one or N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN and SCN. In yet another embodiment, one or more of the solid electrolyte materials can be represented by the formula Li 8-y-z P2S 9-y-z X y W z(where X and W represent at least one halogen element and / or pseudohalogen, and where 0 ≤ y ≤ 1 and 0 ≤ z ≤ 1) is expressed, and where the halogen can be one or more of F, Cl, Br, I, and the pseudohalogen can be one or more of N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN. The solid electrolyte composition can be added in amounts from 5% to 80% by mass.

[0108] Solid electrolyte materials can be added in amounts of 7.5% to 70% by mass; 10% to 60% by mass; 12.5% ​​to 50% by mass; 15% to 40% by mass; or 17.5% to 30% by mass.

[0109] The positive electrode active material layer 120 may further contain one or more components with an electronic conductivity greater than or equal to 1 mS / cm 2 The carbon-containing species may consist of, but are not limited to, carbon black, graphite, graphene, carbon nanotubes, carbon fibers, VGCF, carbon black, or amorphous carbon. In another embodiment, the positive electrode active material layer 120 may further comprise one or more metal particles, filaments, or other structures.

[0110] Carbon-containing species can be added to the positive electrode active material layer in amounts of 2% to 50% by mass; 4% to 40% by mass; 6% to 30% by mass; 8% to 25% by mass; 10% to 20% by mass; or 12% to 18% by mass.

[0111] The positive electrode active material layer 120 may further comprise one or more adhesives or polymers, such as, but not limited to, fluoropolymers containing vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), or their derivatives as structural units. Specific examples include homopolymers such as polyvinylidene fluoride (PVdF), polyhexafluoropropylene (PHFP), and polytetrafluoroethylene (PTFE), and binary copolymers such as copolymers of VdF and HFP, such as poly(vinyl difluoropropylene-hexafluoropropylene) copolymer (PVdF-HFP). In another embodiment, the polymer or adhesive may be one or more thermoplastic elastomers, such as, but not limited to, styrene-butadiene rubber (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene block copolymer (SIS), styrene-ethylene-butene-styrene (SEBS), polyacrylonitrile (PAN), nitrile-butene rubber (NBR), polybutadiene, polyisoprene, and poly(methacrylate) nitrile-butadiene rubber (PMMA-NBR). In another embodiment, the polymer or adhesive may be one or more acrylic resins, such as, but not limited to, poly(methyl methacrylate), poly(ethyl methacrylate), poly(isopropyl methacrylate), poly(isobutyl methacrylate), poly(butyl methacrylate), etc. In yet another embodiment, the polymer or adhesive may be one or more condensation polymers, such as, but not limited to, polyurea, polyamide paper, polyimide, polyester, etc. In yet another embodiment, the polymer or adhesive may be one or more usable nitrile rubbers, such as, but not limited to, acrylonitrile-butadiene rubber (ABR), polystyrene-nitrile-butadiene rubber (PS-NBR), and mixtures thereof.

[0112] One or more of the adhesives or polymers may be added to the positive electrode active material layer in amounts of 1% to 80% by mass; 3% to 70% by mass; 5% to 60% by mass; 8% to 50% by mass; 11% to 40% by mass; or 14% to 30% by mass.

[0113] The thickness of the positive electrode active material layer 120 can, for example, range from 1 μm to 1000 μm. In another embodiment, the thickness can range from 2 μm to 900 μm. In yet another embodiment, the thickness can range from 5 μm to 750 μm. In yet another embodiment, the thickness can range from 10 μm to 500 μm. In yet another embodiment, the thickness can range from 15 μm to 350 μm. In another embodiment, the thickness can range from 20 μm to 200 μm. In yet another embodiment, the thickness can range from 25 μm to 100 μm.

[0114] The negative electrode active material layer 140 may be in the form of a plate, foil, or granules, and may contain at least one or more negative electrode active materials, including, but not limited to, alkali metals such as lithium metal, lithium alloys, sodium metal, sodium alloys, potassium metal, and potassium alloys. In other embodiments, the negative electrode active material layer 140 may contain one or more alkaline earth metals, such as magnesium metal, magnesium alloys, calcium metal, and calcium alloys. In yet another embodiment, the negative electrode active material layer 140 may contain materials with an electronic conductivity greater than or equal to 1 mS / cm. 2 One or more of the carbon-containing species. The carbon-containing species may consist of, but are not limited to, graphitic carbon, hard carbon, amorphous carbon, carbon black, vapor-grown carbon fiber (VGCF), carbon nanotubes, graphene, or combinations thereof. In yet another embodiment, the negative electrode active material layer 140 may contain one or more species containing silicon (Si), tin (Sn), iron (Fe), germanium (Ge), or indium (In).

[0115] The negative electrode active material can be added in amounts of 20% to 100% by mass; 30% to 95% by mass; 40% to 92.5% by mass; 50% to 90% by mass; 60% to 87.5% by mass; or 65% to 85% by mass.

[0116] The negative electrode active material layer 140 may further comprise a solid electrolyte material, such as one or more of the following: Li2S-P2S5, Li2S-P2S5-LiI, Li2S-P2S5-GeS2, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-P2S5-LiI-LiBr, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-S-SiS2-LiCl, Li2S-S-SiS2-B2S3-LiI, Li2S-S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (where m and n are positive numbers, and Z is Ge, Zn, or Ga), Li2S—GeS2, Li2S—S—SiS2—Li3PO4, and Li2S—S—SiS2—Li x MO y (Where x and y are positive numbers, and M is P, Si, Ge, B, Al, Ga, or In). In another embodiment, one or more of the solid electrolyte materials may be Li3PS4, Li4P2S6, or Li7P3S6. 11 Li 10 GeP2S 12 Li 10 SnP2S 12. In another embodiment, one or more of the solid electrolyte materials may be Li6PS5Cl, Li6PS5Br, Li6PS5I or represented by the formula Li 7-y PS 6-y X y where "X" represents at least one halogen element and / or pseudohalogen, and where 0 < y ≤ 2.0, and where the halogen may be one or more of F, Cl, Br, I, and the pseudohalogen may be one or N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN. In yet another embodiment, one or more of the solid electrolyte materials may be represented by the formula Li 8-y- z P2S 9-y-z X y W z (where "X" and "W" represent at least one halogen element and / or pseudohalogen, and where 0 ≤ y ≤ 1 and 0 ≤ z ≤ 1), and where the halogen may be one or more of F, Cl, Br, I, and the pseudohalogen may be one or N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN).

[0117] The solid electrolyte composition may be added to the negative electrode active material layer in an amount of 5% to 80% by mass; 7.5% to 70% by mass; 10% to 60% by mass; 12.5% to 50% by mass; 15% to 40% by mass; or 17.5% to 30% by mass.

[0118] The negative electrode active material layer 140 may include one or more carbon-containing species having an electronic conductivity greater than or equal to 1 mS / cm 2 . The carbon-containing species may consist of, but are not limited to, carbon black, graphite, graphene, carbon nanotubes, carbon fibers, VGCF, carbon black, or amorphous carbon. In another embodiment, the positive electrode active material layer 120 may further include one or more particles, wires, or filaments, including materials such as, but not limited to, gold (Au), silver (Ag), zinc (Zn), magnesium (Mg), aluminum (Al), silicon (Si), tin (Sn), or iron (Fe).

[0119] The carbon-containing species may be added to the negative electrode active material layer in an amount of 2% to 80% by mass; 5% to 70% by mass; 10% to 60% by mass; 15% to 50% by mass; 20% to 45% by mass; or 25% to 40% by mass.

[0120] The negative electrode active material layer 140 may further comprise a binder of one or more polymers, such as, but not limited to, fluoropolymers containing vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), and their derivatives as structural units. Specific examples include homopolymers such as polyvinylidene fluoride (PVdF), polyhexafluoropropylene (PHFP), and polytetrafluoroethylene (PTFE), and binary copolymers such as copolymers of VdF and HFP, such as poly(vinyl difluoropropylene-hexafluoropropylene) copolymer (PVdF-HFP). In another embodiment, the polymer or binder may be one or more thermoplastic elastomers, such as, but not limited to, styrene-butadiene rubber (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene block copolymer (SIS), styrene-ethylene-butene-styrene (SEBS), polyacrylonitrile (PAN), nitrile-butene rubber (NBR), polybutadiene, polyisoprene, and poly(methacrylate) nitrile-butadiene rubber (PMMA-NBR). In another embodiment, the polymer or adhesive may be one or more acrylic resins, such as, but not limited to, poly(methyl methacrylate), poly(ethyl methacrylate), poly(isopropyl methacrylate), poly(isobutyl methacrylate), poly(butyl methacrylate), etc. In yet another embodiment, the polymer or adhesive may be one or more condensation polymers, such as, but not limited to, polyurea, polyamide paper, polyimide, polyester, etc. In yet another embodiment, the polymer or adhesive may be one or more usable nitrile rubbers, such as, but not limited to, acrylonitrile-butadiene rubber (ABR), polystyrene-nitrile-butadiene rubber (PS-NBR), and mixtures thereof.

[0121] One or more of the adhesives or polymers may be added to the negative electrode active material in amounts of 1% to 80% by mass; 3% to 70% by mass; 5% to 60% by mass; 8% to 50% by mass; 11% to 40% by mass; or 14% to 30% by mass.

[0122] The thickness of the negative electrode active material layer 140 can be, for example, in the range of 500 nm to 1000 μm. In another embodiment, the thickness can be in the range of 1 μm to 900 μm. In yet another embodiment, the thickness can be in the range of 5 μm to 750 μm. In yet another embodiment, the thickness can be in the range of 10 μm to 500 μm. In yet another embodiment, the thickness can be in the range of 15 μm to 350 μm. In another embodiment, the thickness can be in the range of 20 μm to 200 μm. In yet another embodiment, the thickness can be in the range of 25 μm to 100 μm.

[0123] The solid electrolyte material contained within the solid electrolyte layer 130 is a solid electrolyte composition as described herein. In one embodiment, the solid electrolyte layer 130 may contain more than one solid electrolyte material, which may comprise one or more solid electrolyte materials described in the positive electrode active material 120 and the negative electrode active material 140. The solid electrolyte layer 130 may contain a solid electrolyte composition as described herein in the range of 1% to 100% by mass. In another embodiment, 20% to 97.5% by mass. In yet another embodiment, 40% to 95% by mass. In still another embodiment, 60% to 92.5% by mass. In yet another embodiment, 90% to 80% by mass.

[0124] Further, the solid electrolyte layer 130 may contain one or more binders as described in the positive electrode active material 120 and the negative electrode active material 140. Examples of binders may include those materials used for the positive electrode material layer, as well as additional self-healing polymers and poly(ethylene) oxide (PEO). The thickness of the solid electrolyte layer 130 is in the range of 500 nm to 1000 μm. In another embodiment, the thickness may be in the range of 1 μm to 900 μm. In yet another embodiment, the thickness may be in the range of 5 μm to 750 μm. In yet another embodiment, the thickness may be in the range of 10 μm to 500 μm. In yet another embodiment, the thickness may be in the range of 15 μm to 350 μm. In another embodiment, the thickness may be in the range of 20 μm to 200 μm. In yet another embodiment, the thickness may be in the range of 25 μm to 100 μm.

[0125] Despite Figure 1 While the structure is represented as layered, other shapes and configurations of solid-state electrochemical battery cells are also possible. Most generally, lithium solid-state batteries can be manufactured by providing a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer that are sequentially laminated and pressed between electrodes and provided within a housing.

[0126] Figure 2This is a flowchart of a method for producing a solid electrolyte composition that can be used to construct a secondary electrochemical battery cell. Method 200 begins with a preparation step 210, where any preparatory actions, such as precursor synthesis, purification, and equipment preparation, may be performed. After any initial preparation, method 200 proceeds to step 220, where sulfur compounds, lithium compounds, and other compounds as described herein may be combined with suitable solvents and / or other liquids. Exemplary sulfur compounds may include, for example, elemental sulfur, antimony sulfide (Sb₂S₃), and lithium sulfide (Li₂S), which are typically in powder form. Exemplary lithium compounds may include, for example, lithium metal (Li), lithium sulfide (Li₂S), and lithium nitride (Li₃N), which are typically in powder form. Exemplary halides may include LiCl, LiBr, and LiI, while exemplary pseudohalogens may include BH₄, BF₄, NO₃, CN, SO₃, OCN, SCN, and N₃. Exemplary solvents may include, but are not limited to, aprotic hydrocarbons such as heptane, aromatic hydrocarbons such as xylene, and other solvents with a low tendency to generate hydrogen sulfide gas upon contact with the precursor or final electrolyte composition. Solvents are not particularly limited, provided they remain partially or entirely liquid during the grinding process at the desired grinding temperature and do not participate in detrimental reactions with the solid electrolyte precursor or final solid electrolyte composition. There are no particular limitations on the ratios and amounts of various compounds, provided the combination allows for the synthesis of the desired composition and phase, as indicated by the presence of specific X-ray diffraction features. Ratios and amounts may also vary depending on the specific synthesis conditions. For example, the solvent volume to precursor mass ratio may need to be adjusted as the solid electrolyte composition is modified to ensure complete grinding of the precursor, thereby producing the desired solid electrolyte phase discussed herein.

[0127] The amount of solvent added to the composition is not limited, as long as it supports the synthesis of the desired solid electrolyte material composition. Various solvents can be mixed with the compound. Additional materials, such as co-solvents or polymers, may also be added during this step. Furthermore, the synthesis can be carried out without solvent.

[0128] Next, in step 230, the composition may be mixed and / or ground for a predetermined time period and temperature to produce a solid electrolyte as described above. The mixing time is not specifically limited, as long as it allows for proper homogenization and reaction of the precursors to produce the solid electrolyte. The mixing temperature is not specifically limited, as long as it allows for proper mixing and does not become so high that the precursors enter a gaseous state. For example, proper mixing can be completed over 10 minutes to 60 hours at temperatures between 20 and 120 degrees Celsius. Mixing can be performed using, for example, a planetary ball mill or a grinder.

[0129] Next, in step 240, the composition may be dried in an inert atmosphere such as argon or nitrogen or under vacuum for a predetermined time period and temperature. After drying, heat treatment may be performed during step 250 to crystallize the dried material. The temperature of the heat treatment is not particularly limited, as long as it is equal to or higher than the crystallization temperature required to produce the crystalline phase of this disclosure. The material produced by heat treatment step 250 may be single-phase and may also contain other crystalline phases and precursor phases with small fractions.

[0130] Typically, the heat treatment time is not limited, as long as it allows for the production of the desired composition and phase. The time can range from, for example, one minute to 24 hours. Furthermore, the heat treatment is performed in an inert gas atmosphere (e.g., argon) or under vacuum.

[0131] In the final step 260, the completed composition can be used to construct, for example... Figure 1 Electrochemical battery units, such as battery cells.

[0132] Other synthetic routes may also be used. For example, one method for synthesizing the solid electrolyte material discussed herein includes: mixing suitable precursors providing components Li, T, X, and A in a solvent capable of causing a reaction between the precursors, removing the solvent, and performing heat treatment at a temperature equal to or higher than the material's crystallization temperature.

[0133] Example

[0134] Preparation of solid electrolytes

[0135] Example 1

[0136] A precursor containing 4.26 g Li₂S (Lorad Chemical Corporation), 10.49 g Sb₂S₃ (Sigma-Aldrich Co.), 8.27 g LiI (Sigma-Aldrich Co.), and 2.08 g sulfur (Sigma-Aldrich Co.) was added to a 500 ml zirconia grinding jar containing zirconia grinding media and a compatible solvent (e.g., xylene or heptane). The mixture was ground in a Retsch PM 100 planetary mill at 400 RPM for 12 hours. The material was collected and dried at 70 °C in an inert (argon or nitrogen) atmosphere. The resulting solid electrolyte powder (Li₄SbS₄I) from Example 1 can then be used for positive electrode active material layers, solid electrolyte layers, and / or negative electrode active material layers.

[0137] Example 2

[0138] The solid electrolyte of Example 2 was prepared in the same manner as in Example 1, except that the masses of Li2S, Sb2S3, P2S5, sulfur powder, and LiI were selected stoichiometrically to synthesize Li4Sb 0.75 P 0.25 S4I.

[0139] Comparative Example 1

[0140] The solid electrolyte of Comparative Example 1 was prepared in the same manner as in Example 1, except that the masses of Li2S, P2S5, sulfur powder, and LiI were selected stoichiometrically to synthesize Li4SbS4I.

[0141] Air and moisture exposure

[0142] Air and moisture exposure tolerance tests were conducted by taking 1 g each of Examples 1-2 and Comparative Example 1 and exposing the materials to an atmosphere with an average dew point of -47 °C for 4 hours. After 4 hours had passed, the materials were collected and stored in an inert gas environment.

[0143] The sulfide solid electrolyte material obtained from the description of Example 1 includes Li, T, X, and A, and in X-ray diffraction (XRD) measurements, has peaks at 2θ = 14.5° ± 0.50°, 16.8° ± 0.50°, 23.9° ± 0.50°, 28.1° ± 0.50°, and 32.5° ± 0.50°, where the peaks can identify a novel crystalline phase. T is at least one of Sb, P, As, Si, Ge, Al, B, and W; A is at least one of S or Se; and X is one or more halogens or N. The chemical composition can be expressed as Li 1-a-b-c T a A b X c ; where the values of a, b, and c can be in the following ranges: 0.074 < a ≤ 0.105, 0.370 < b ≤ 0.421, 0.074 < c ≤ 0.105. The composition can be a mixed-phase material with other crystalline phases, the mixed-phase material being identified by XRD peaks at 2θ = 20.2° and 23.6°, and / or peaks at 2θ = 21.0° and 28.0°, and / or peaks at 17.5° and 18.2°, and / or peaks at 17.1° and 25.8°. The composition can contain a crystalline phase combined with one or more lithium halides or lithium sulfides.

[0144] Exemplary compositions are of the form Li 1-a-b-c T a A b X cDefined as follows, where a = c = 0.1, b = 0.4, T = Sb, A = S, and X = I. Such compositions, after applying appropriate synthesis and heat treatment conditions, produce the crystalline phase of this disclosure. The novel structure of this crystalline phase is advantageous for high ionic conductivity. The presence of halogen may contribute to the formation of a stable, low-resistivity interface with lithium metal and high-voltage cathode active materials. Furthermore, the presence of Sb can increase the air stability of said compounds compared to other Sb-free compounds.

[0145] Figure 3 Based on Examples 1 and 2, and comparing Example 1... Figure 2 The diagram shows X-ray diffraction measurements of the solid electrolyte compositions produced by the method illustrated. X-ray diffraction (XRD) measurements of Examples 1 and 2 reveal significant novel peaks indicating previously unknown crystalline phases at 2θ = 14.5° ± 0.50°, 16.8° ± 0.50°, 23.9° ± 0.50°, 28.1° ± 0.50°, and 32.5° ± 0.50°. In particular, the peak at 32.5° ± 0.50 was not observed in the comparative examples or any other compositions similar to those of the present invention and can be used to highlight the novel crystalline phase of this disclosure. Another exemplary example of peak positions is 2θ = 14.5° ± 0.20°, 16.8° ± 0.20°, 23.9° ± 0.20°, 28.1° ± 0.20°, and 32.5° ± 0.20, wherein... Other compositions may be mixed-phase materials with other crystalline phases, which are identified by XRD peaks at 2θ = 20.2° and 23.6°, and / or at 2θ = 21.0° and 28.0°, and / or at 17.5° and 18.2°, 17.1° and 25.8°, and / or by peaks associated with one or more lithium halides. However, the X-ray diffraction measurements of the material described in Comparative Example 1 lack peaks at 2θ = 14.5° ± 0.50°, 16.8° ± 0.50°, 23.9° ± 0.50°, 28.1° ± 0.50°, and 32.5° ± 0.50°, where Therefore, it does not conform to this disclosure. Furthermore, Comparative Example 1 shows X-ray diffraction results from a stoichiometry that does not involve antimony, and therefore does not conform to this disclosure.

[0146] Figure 4 This is a graph indicating the percentage of initial ionic conductivity remaining after 4 hours of exposure to an atmosphere with an average dew point of -47°C. According to... Figure 4It can be observed that the solid electrolyte materials described in Examples 1 and 2, after being exposed to the atmosphere, retain slightly more than 60% of their initial conductivity. However, the solid electrolyte material described in Comparative Example 1 exhibits a much lower conductivity retention rate, which is due to the lack of antimony in the composition.

[0147] For pure and mixed-phase electrolyte materials in pellets compressed at room temperature, measured examples of the composition provided approximately 0.525 mS / cm at room temperature. 2 The conductivity. Higher conductivity may be obtained by altering the stoichiometry and / or by compression or other processing methods and conditions at elevated temperatures.

[0148] Without departing from the scope of this document, the foregoing features and the following claimed features may be combined in various ways. Therefore, it should be noted that the contents contained in the above description and shown in the accompanying drawings should be interpreted illustratively rather than restrictively.

Claims

1. A solid electrolyte material comprising Li, T, X, and A, wherein T comprises Sb; X comprises one or more of a halogen, a pseudohalogen, or N, wherein the pseudohalogen is selected from the group consisting of NH, NH2, NO, NO2, NO3, N3, BF4, BH4, AlH4, CN, OCN, SCN, and SO3; A comprises one or more of S or Se; and wherein, in X-ray diffraction measurements, the solid electrolyte material has peaks at 2θ = 14.5° ± 0.50°, 16.8° ± 0.50°, 23.9° ± 0.50°, 28.1° ± 0.50°, and 32.5° ± 0.50°, wherein 2. The solid electrolyte material according to claim 1, comprising the formula: Li 1-a-b-c T a A b X c Of which 0.074 <a≤0.105,0.370<b≤0.421,0.074<c≤0.105。 3. The solid electrolyte material according to claim 1, wherein T comprises a blend of Sb and non-Sb elements, wherein the non-Sb elements are selected from the group consisting of: P, As, Si, Ge, Al, B and W.

4. The solid electrolyte material according to claim 1, wherein Sb accounts for 1% or more of the total elemental T.

5. The solid electrolyte material according to claim 2, wherein a = 0.1, b = 0.4, c = 0.1, T = Sb, A = S, and X = I.

6. The solid electrolyte material according to claim 1, comprising at least one of a glass-ceramic phase, a crystalline phase, and a mixed phase.

7. The solid electrolyte material according to claim 6, wherein the mixed phase comprises other crystalline phases, which, in X-ray diffraction measurements, contain peaks at 20.2°±0.50° and 23.6°±0.50°, and / or 21.0°±0.50° and 28.0°±0.50°, and / or 17.5°±0.50° and 18.2°±0.50° and / or 17.1° and 25.8°, wherein 8. A lithium solid-state battery, comprising: A positive electrode active material layer, wherein the positive electrode active material layer contains a positive electrode active material; A negative electrode active material layer, wherein the negative electrode active material layer contains a negative electrode active material; The material includes a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer comprises a solid electrolyte material containing Li, T, X, and A, wherein T comprises Sb; X comprises one or more of a halogen, a pseudohalogen, or N, wherein the pseudohalogen is selected from the group consisting of NH, NH2, NO, NO2, NO3, N3, BF4, BH4, AlH4, CN, OCN, SCN, and SO3; and A comprises one or more of S or Se; and wherein, in X-ray diffraction measurements, the solid electrolyte material has peaks at 2θ = 14.5°±0.50°, 16.8°±0.50°, 23.9°±0.50°, 28.1°±0.50°, and 32.5°±0.50°.

9. The lithium solid-state battery according to claim 8, wherein the solid electrolyte material comprises the formula Li 1-a-b-c T a A b X c , of which 0.074 <a≤0.105,0.370<b≤0.421,0.074<c≤0.105。 10. The lithium solid-state battery according to claim 8, wherein T comprises a blend of Sb and non-Sb elements, the non-Sb elements being selected from the group consisting of: P, As, Si, Ge, Al, B and W.

11. The lithium solid-state battery according to claim 8, wherein Sb accounts for 1% or more of the total element T.

12. The lithium solid-state battery according to claim 9, wherein a = 0.1, b = 0.4, c = 0.1, T = Sb, A = S, and X = I.

13. The lithium solid-state battery according to claim 8, wherein the solid electrolyte material comprises at least one of a glass phase, a ceramic phase, a crystalline phase, or a mixed phase.

14. The lithium solid-state battery of claim 13, wherein the mixed phase comprises other crystalline phases, which, in X-ray diffraction measurements, contain peaks at 20.2°±0.50° and 23.6°±0.50°, and / or 21.0°±0.50° and 28.0°±0.50°, and / or 17.5°±0.50° and 18.2°±0.50° and / or 17.1° and 25.8°, wherein 15. The lithium solid-state battery according to claim 8, wherein the positive electrode active material comprises one or more particles, wires or filaments, and the one or more particles, wires or filaments comprise at least one of the following: aluminum, nickel, titanium, stainless steel, magnesium, iron, zinc, indium, germanium, silver, platinum, gold, lithium or alloys thereof.

16. The lithium solid-state battery according to claim 8, wherein the negative electrode active material comprises: The alkaline metal includes at least one of the alkali metals or at least one of the alkaline earth metals, wherein the alkali metals include lithium metal, lithium alloys, sodium metal, sodium alloys, potassium metal, and potassium alloys; and the alkaline earth metals include magnesium metal, magnesium alloys, calcium metal, and calcium alloys.

17. The lithium solid-state battery according to claim 8, wherein the positive electrode active material layer and the negative electrode active material layer each comprise one or more carbon-containing materials, wherein the one or more carbon-containing materials include carbon fiber, graphite, graphene, carbon black, conductive carbon, amorphous carbon, VGCF, and carbon nanotubes.

18. The lithium solid-state battery according to claim 8, wherein the positive electrode active material layer and the negative electrode active material layer each comprise one or more of metal particles, filaments, or other structures; The positive electrode active material layer and the negative electrode active material layer each include one or more adhesives or polymers, and the one or more adhesives or polymers include fluoropolymers containing vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene and its derivatives. The positive electrode active material layer and the negative electrode active material layer each comprise one or more adhesives or polymers, wherein the one or more adhesives or polymers include: Homopolymers comprising polyvinylidene fluoride, polyhexafluoropropylene, or polytetrafluoroethylene; or binary copolymers comprising copolymers of VdF and HFP, said binary copolymers including poly(vinyl difluoropropylene-hexafluoropropylene) copolymers (PVdF-HFP); The positive electrode active material layer and the negative electrode active material layer each include one or more adhesives or polymers, and the one or more adhesives or polymers include thermoplastic elastomers comprising styrene-butadiene rubber, styrene-butadiene-styrene copolymer, styrene-isoprene block copolymer, styrene-ethylene-butene-styrene, polyacrylonitrile, nitrile-butene rubber, polybutadiene, polyisoprene, or poly(methacrylate) nitrile-butadiene rubber; The positive electrode active material layer and the negative electrode active material layer each include one or more adhesives or polymers, and the one or more adhesives or polymers include acrylic resins comprising poly(methyl)methacrylate, poly(ethyl)methacrylate, poly(isopropyl)methacrylate, poly(isobutyl)methacrylate, and poly(butyl)methacrylate. The positive electrode active material layer and the negative electrode active material layer each comprise one or more adhesives or polymers, wherein the one or more adhesives or polymers comprise condensation polymers containing polyurea, polyamide paper, or polyimide, or polyester; or The positive electrode active material layer and the negative electrode active material layer each include one or more adhesives or polymers, and the one or more adhesives or polymers include nitrile rubbers containing acrylonitrile-butadiene rubber, polystyrene-nitrile-butadiene rubber, or mixtures thereof.

19. The lithium solid-state battery of claim 8, wherein the positive electrode active material layer and the negative electrode active material layer each comprise one or more adhesives or polymers, wherein the one or more adhesives or polymers are present in an amount of 1% to 80% by mass, in an amount of 3% to 70% by mass, in an amount of 5% to 60% by mass, in an amount of 8% to 50% by mass, in an amount of 11% to 40% by mass, or in an amount of 14% to 30% by mass.

20. The lithium solid-state battery of claim 8, wherein the negative electrode active material has sufficient electronic activity and mechanical strength to serve as a negative electrode, and wherein the negative electrode is absent.

21. The lithium solid-state battery according to claim 8, wherein the positive electrode active material layer comprises Li(Ni) a Co b Mn c O2 Among them 0 <a≤1,0<b≤1,0<c≤1,a+b+c=1; The positive electrode active material layer includes Li(Ni) 0.33 Co 0.33 Mn 0.33 O2, Li(Ni) 0.4 Co 0.3 Mn 0.3 O2, Li(Ni) 0.5 Co 0.2 Mn 0.3 O2, Li(Ni) 0.6 Co 0.2 Mn 0.2 O2, Li(Ni) 0.8 Co 0.1 Mn 0.1 O2 or combinations thereof; where the positive electrode active material layer includes one or more metal oxides containing V2O5, V6O 13 , MoO3, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNi 1-Y Co Y O2, LiCo 1-Y Mn Y O2, LiNi 1-Y Mn Y O2(0≤Y<1), Li(Ni a Co b Mn c )O4(0<a<2, 0<b<2, 0<c<2, a + b + c = 2), LiMn 2-Z Ni Z O4, LiMn 2-Z Co Z O4(0<Z<2), LiCoPO4, LiFePO4, CuO, Li(Ni a Co b Al c )O2(0<a<1, 0<b<1, 0<c<1, a + b + c = 1) or a combination thereof; or The positive electrode active material layer comprises one or more metal sulfides, including titanium sulfide (TiS2), molybdenum sulfide (MoS2), iron sulfide (FeS, FeS2), copper sulfide (CuS), nickel sulfide (Ni3S2), and lithium sulfide (Li2S), or combinations thereof.

22. The lithium solid-state battery according to claim 8, wherein the positive electrode active material is present in an amount of 20% to 99% by mass, in an amount of 30% to 95% by mass, in an amount of 40% to 92.5% by mass, in an amount of 50% to 90% by mass, in an amount of 60% to 87.5% by mass, or in an amount of 65% to 85% by mass.

23. The lithium solid-state battery according to claim 8, wherein the negative electrode active material is present in an amount of 20% to 99% by mass, in an amount of 30% to 95% by mass, in an amount of 40% to 92.5% by mass, in an amount of 50% to 90% by mass, in an amount of 60% to 87.59% by mass, or in an amount of 65% to 85% by mass.

24. The lithium solid-state battery according to claim 8, wherein the positive electrode active material layer comprises one or more of the following: Li2S-P2S5, Li2S-P2S5-LiI, Li2S-P2S5-GeS2, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-P2S5-LiI-LiBr, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-S-SiS2-LiCl, Li2S-S-SiS2-B2S3-LiI, Li2S-S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (where m and n are positive numbers, and Z is Ge, Zn, or Ga), Li2S—GeS2, Li2S—S—SiS2—Li3PO4, and Li2S—S—SiS2—Li x MO y (where x and y are positive numbers, and M is P, Si, Ge, B, Al, Ga, or In); The positive electrode active material layer includes one or more of the following: Li3PS4, Li4P2S6, and Li7P3S6. 11 Li 10 GeP2S 12 Li 10 SnP2S 12 ; where the positive electrode active material layer includes one or more of Li6PS5Cl, Li6PS5Br, Li6PS5I or is represented by the formula Li 7-y PS 6-y X y where X represents at least one halogen element and / or pseudohalogen, and where 0 < y ≤ 2.0, and where the halogen includes one or more of F, Cl, Br, I, and the pseudohalogen includes one or more of N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN; or The positive electrode active material layer includes Li 8-y-z P2S 9-y-z X y W z One or more of the following, wherein X and W represent at least one halogen element and / or pseudohalogen, and wherein 0≤y≤1 and 0≤z≤1, and wherein the halogen includes one or more of F, Cl, Br, and I, and the pseudohalogen includes one or more of N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN.

25. The lithium solid-state battery according to claim 8, wherein the thickness of the positive electrode active material layer is in the range of 1 micrometer to 1000 micrometers, in the range of 2 micrometers to 900 micrometers, in the range of 1 micrometer to 100 micrometers, in the range of 5 micrometers to 750 micrometers, in the range of 10 micrometers to 500 micrometers, in the range of 15 micrometers to 350 micrometers, in the range of 20 micrometers to 200 micrometers, or in the range of 25 micrometers to 100 micrometers.

26. The lithium solid-state battery according to claim 8, wherein the thickness of the negative electrode active material layer is in the range of 500 nanometers to 1000 micrometers, in the range of 1 micrometer to 900 micrometers, in the range of 5 micrometers to 750 micrometers, in the range of 10 micrometers to 500 micrometers, in the range of 15 micrometers to 350 micrometers, in the range of 20 micrometers to 200 micrometers, or in the range of 25 micrometers to 100 micrometers.

27. The lithium solid-state battery of claim 8, wherein the thickness of the solid electrolyte layer is in the range of 500 nanometers to 1000 micrometers, in the range of 1 micrometer to 900 micrometers, in the range of 5 micrometers to 750 micrometers, in the range of 10 micrometers to 500 micrometers, in the range of 15 micrometers to 350 micrometers, in the range of 20 micrometers to 200 micrometers, or in the range of 25 micrometers to 100 micrometers.

28. The lithium solid-state battery according to claim 8, wherein the amount of the solid electrolyte composition is from 5% to 80% by mass, from 7.5% to 70% by mass, from 10% to 60% by mass, from 12.5% ​​to 50% by mass, from 15% to 40% by mass, or from 17.5% to 30% by mass.

29. A method for producing a sulfide solid electrolyte material comprising glass ceramic, the sulfide solid electrolyte material comprising: The method comprises: Li, T, X, and A, wherein T includes Sb; X is one or more of a halogen, pseudohalogen, or N, wherein the pseudohalogen is selected from the group consisting of NH, NH2, NO, NO2, NO3, N3, BF4, BH4, AlH4, CN, OCN, SCN, and SO3; A is one or more of S or Se; the method includes: mixing and grinding a raw material composition containing element A or compound Li2A, element T or T, and compound LiX or Li3N to make the mixture amorphous under X-ray diffraction; and heating the sulfide glass at a heat treatment temperature equal to or greater than the crystallization temperature of the sulfide glass to synthesize the glass-ceramic, wherein, in X-ray diffraction measurements, the glass-ceramic has peaks at 2θ = 14.5° ± 0.50°, 16.8° ± 0.50°, 23.9° ± 0.50°, 28.1° ± 0.50°, and 32.5° ± 0.50, wherein...

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