Solid electrolyte material and solid-state battery manufactured using the same

Abstract

The solid electrolyte material comprises 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. 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° when measured by X-ray diffraction using Cu-Kα(1,2)=1.54064 Å, and may contain glass-ceramic and / or mixed crystalline phases.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to pending U.S. Provisional Patent Application No. 63 / 082,146, filed September 23, 2020, the entire contents of which are incorporated by reference.

[0002] Technical Field Various embodiments described in this disclosure relate to the fields of solid state primary and secondary electrochemical cells, electrodes and electrode materials, electrolytes and electrolyte compositions, and corresponding methods of making and using the same. [Background technology]

[0003] The incorporation of rechargeable lithium-ion batteries into the technology around us, from phones and laptop computers to scooters and cars, is increasing year by year. However, rechargeable lithium-ion batteries contain flammable liquid electrolytes that not only pose safety risks but also limit the use of high energy density anode materials such as lithium metal, thereby limiting the performance potential of the battery. To avoid both of these issues, the flammable liquid electrolyte can be replaced with a solid electrolyte.

[0004] Some of the most promising solid electrolytes are sulfide-based due to their high room temperature conductivity and can be synthesized using light elements such as lithium (Li), phosphorus (P), and sulfur (S), among others. One of the earliest sulfide solid electrolytes has the formula Li + (12-n-x) B n+ X 2- 6-x Y -x Lithium argyrodite (U.S. Pat. No. 8,075,865) having the formula: n+ is selected from the group consisting of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb and Ta, and 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, and 0 ≦ x ≦ 2. A member of another group of all-diodites is the formula Li 7+x-y M x Sb 1-x S 6-y X y is a solid electrolyte material having a composition according to, where M is one or more selected from the group consisting of Si, Ge and Sn, 0 < x < 1, X is one or more selected from the group consisting of Cl, Br and I, and 0.05 < y < 2 (WO2021013824). The materials of these all-diodite groups showed high ionic conductivity.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0005] However, one drawback of sulfide electrolytes is that when they come into contact with oxygen or moisture, the P-S bonds in their structures are easily broken and P-O bonds are formed, so they are inferior in air stability. The formation of P-O bonds reduces the ionic conductivity of the electrolyte and promotes the release of hydrogen sulfide gas. One way to avoid this problem was to incorporate oxygen-containing species into sulfide electrolytes as described in US Patent Application Publication No. US2020 / 0087155 or WO2019 / 207951. In these documents, oxygen is incorporated into materials having an all-diodite structure that forms Li6PS4OCl all-diodite or into Li3PS4 materials that yield Li3PS3O materials. Unfortunately, these materials tend to have low ionic conductivity and require very high temperatures to manufacture. To overcome these problems, a novel sulfide electrolyte is synthesized that exhibits a novel structure with appropriate stoichiometry, high conductivity, improved air stability, and low-temperature processing requirements, and is disclosed herein.

MEANS FOR SOLVING THE PROBLEM

[0006] The present application is directed to a solid electrolyte material comprising Li, T, X and A, where 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, and A comprises one or more of S or Se, the solid electrolyte material having peaks at 2θ=14.5°±0.50°, 16.8°±0.50°, 23.9°±0.50°, 28.1°±0.50° and 32.5°±0.50° as measured by X-ray diffraction using Cu-Kα(1,2)=1.54064Å.

[0007] In one embodiment, the solid electrolyte material has the formula Li 1-a-b-c T a A b X c where 0.074 <a≦0.105、0.370<b≦0.421、0.074<c≦0.105である。

[0008] 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.

[0009] In another embodiment of the solid electrolyte material, the ratio of Sb to all elements T is 1% or more.

[0010] In another embodiment of the solid electrolyte material, a=0.1, b=0.4, c=0.1, T=Sb, A=S, and X=I.

[0011] Another embodiment of the solid electrolyte material includes at least one of a glass-ceramic phase, a crystalline phase, and a mixed phase.

[0012] In another embodiment of the solid electrolyte material, the mixed phase comprises other crystalline phases having 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° as measured by X-ray diffraction with Cu-Kα(1,2)=1.5418 Å.

[0013] Another embodiment of the solid electrolyte material includes an ionic conductivity of greater than about 0.500 mS / cm at room temperature.

[0014] In an alternative embodiment, the present application provides a lithium solid-state battery including a positive electrode active layer including a positive electrode active material, a negative electrode active layer including a negative electrode active material, and a solid electrolyte layer disposed between the positive electrode active layer and the negative electrode active layer, wherein at least one of the positive electrode active layer, the negative electrode active layer, and the solid electrolyte layer includes a solid electrolyte material including Li, T, X, and A, where T is selected from the group consisting of Sb, P, As, Si, Ge, Al, B, and W. wherein X includes one or more halogens, pseudohalogens, or N, A includes one or more of S or Se, and 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° in X-ray diffraction measurement using Cu-Kα(1,2)=1.54064 Å.

[0015] In another embodiment of the lithium solid-state battery, the solid electrolyte material has the formula Li 1-a-b-c T a A b X c where 0.074 <a≦0.105、0.370<b≦0.421、0.074<c≦0.105である。

[0016] 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.

[0017] In another embodiment of the lithium solid state battery of the present invention, the proportion of Sb in the total elements T is 1% or more.

[0018] In another embodiment of the lithium solid state battery, 1-a-b-c T a A b X cincludes a=0.1, b=0.4, c=0.1, T=Sb, A=S, and X=I.

[0019] Another embodiment of the lithium solid-state battery includes at least one solid electrolyte material that includes a glass-ceramic phase, a crystalline phase, and a mixed phase.

[0020] In another embodiment of the lithium solid state battery, the mixed phase comprises other crystalline phases comprising 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° as measured by X-ray diffraction with Cu-Kα(1,2)=1.5418 Å.

[0021] In another embodiment of the lithium solid-state battery, the capacity of the battery is about 0.500 mS / cm The present invention includes solid electrolyte materials having ionic conductivities greater than 1000 ppm.

[0022] In another embodiment of the lithium solid-state battery, the active cathode material comprises one or more particles, wires, or filaments comprising at least one of aluminum, nickel, titanium, stainless steel, magnesium, iron, zinc, indium, germanium, silver, platinum, gold, lithium, or alloys thereof.

[0023] In another embodiment of the lithium solid-state battery, the negative electrode active material comprises at least one alkali metal, including lithium metal, lithium alloy, sodium metal, sodium alloy, potassium metal, potassium alloy, or at least one alkaline earth metal, including magnesium metal, magnesium alloy, calcium metal, calcium alloy.

[0024] In another embodiment of the lithium solid-state battery, the negative electrode active material further comprises silicon, tin, iron, germanium, or indium.

[0025] In another embodiment of the lithium solid-state battery, the positive and negative active electrode layers each comprise one or more carbon-containing materials, including carbon fiber, graphite, graphene, carbon black, conductive carbon, amorphous carbon, VGCF, and carbon nanotubes.

[0026] In another embodiment of the lithium solid state battery, the carbon-containing material is added in an amount of 2% to 50% by weight.

[0027] In another embodiment of the lithium solid state battery, the carbon-containing material is added in an amount of 6% to 30% by weight.

[0028] In another embodiment of the lithium solid state battery, the carbon-containing material is added in an amount of 8% to 25% by weight.

[0029] In another embodiment of the lithium solid state battery, the carbon-containing material is added in an amount of 10% to 20% by weight.

[0030] In another embodiment of the lithium solid state battery, the carbon-containing material is added in an amount of 12% to 18% by weight.

[0031] In another embodiment of the lithium solid state battery, the carbon-containing material is added in an amount of 2% to 50% by weight.

[0032] In another embodiment of the lithium solid-state battery, the positive and negative electrode layers each include one or more of metal particles, filaments, or other structures.

[0033] In another embodiment of the lithium solid-state battery, the positive and negative electrode layers each comprise one or more binders or polymers including fluororesins including vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE) and derivatives thereof.

[0034] In another embodiment of the lithium solid-state battery, the positive and negative electrode layers each comprise one or more binders or polymers including homopolymers including polyvinylidene fluoride (PVdF), polyhexafluoropropylene (PHFP) or polytetrafluoroethylene (PTFE), or binary copolymers including copolymers of VdF and HFP, including poly(vinylene difluoride-hexafluoropropylene) copolymer (PVdF-HFP).

[0035] In another embodiment of the lithium solid-state battery, the positive and negative electrode layers each comprise one or more binders or polymers including thermoplastic elastomers including styrene-butadiene rubber (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene block copolymer (SIS), styrene-ethylene-butylene-styrene (SEBS), polyacrylonitrile (PAN), nitrile-butylene rubber (NBR), polybutadiene, polyisoprene, or poly(methacrylate)nitrile-butadiene rubber (PMMA-NBR).

[0036] In another embodiment of the lithium solid state battery of the present invention, the positive electrode layer and the negative electrode layer each comprise one or more binders or polymers including acrylic resins including polymethyl(meth)acrylate, polyethyl(meth)acrylate, polyisopropyl(meth)acrylate, polyisobutyl(meth)acrylate, polybutyl(meth)acrylate.

[0037] In another embodiment of the lithium solid state battery, the positive and negative electrode layers each comprise one or more binders or polymers including polyurea, polyamide paper, or polyimide, polycondensation polymers including polyesters.

[0038] In another embodiment of the lithium solid-state battery, the positive and negative electrode layers each include one or more binders or polymers including nitrile rubbers, including acrylonitrile-butadiene rubber (ABR), polystyrene nitrile-butadiene rubber (PS-NBR), or mixtures thereof.

[0039] In another embodiment of the lithium solid state battery, the positive and negative electrode layers each include one or more binders or polymers present in an amount between 1% and 80% by weight.

[0040] In another embodiment of the lithium solid state battery, the positive and negative electrode layers each include one or more binders or polymers present in an amount between 3% and 70% by weight.

[0041] In another embodiment of the lithium solid state battery, the positive and negative electrode layers each include one or more binders or polymers present in an amount between 5% and 60% by weight.

[0042] In another embodiment of the lithium solid state battery, the positive and negative electrode layers each include one or more binders or polymers present in an amount between 8% and 50% by weight.

[0043] In another embodiment of the lithium solid state battery, the positive and negative electrode layers each include one or more binders or polymers present in an amount between 11% and 40% by weight.

[0044] In another embodiment of the lithium solid state battery, the positive and negative electrode layers each include one or more binders or polymers present in an amount between 14% and 30% by weight.

[0045] In another embodiment of a lithium solid-state battery, the negative electrode active material has sufficient electronic activity and mechanical strength to function as a negative electrode, and no negative electrode is present.

[0046] In another embodiment of the lithium solid state battery, the positive electrode active material layer is Li(Ni a Co b Mn c )O2, where 0 <a≦1、0<b≦1、0<c≦1、a+b+c=1である。

[0047] In another embodiment of the lithium solid state battery, the positive electrode active material layer is 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.

[0048] In another embodiment of the lithium solid battery, the positive electrode active material layer is V2O5, V6O 13 , MoO3, LiCoO2, LiNiO2, LiMnO 2 、 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 combinations thereof, including one or more metal oxides.

[0049] In another embodiment of the lithium solid battery, the positive electrode active material layer includes one or more of 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.

[0050] In another embodiment of the lithium solid state battery, the positive electrode active material is present in an amount of 20% to 99% by weight.

[0051] In another embodiment of the lithium solid state battery, the positive electrode active material is present in an amount of 30% to 95% by weight.

[0052] In another embodiment of the lithium solid state battery, the positive electrode active material is present in an amount between 40% and 92.5% by weight.

[0053] In another embodiment of the lithium solid state battery, the positive electrode active material is present in an amount of 50% to 90% by weight.

[0054] In another embodiment of the lithium solid state battery, the positive electrode active material is present in an amount between 60% and 87.5% by weight.

[0055] In another embodiment of the lithium solid state battery, the positive electrode active material is present in an amount of 65% to 85% by weight.

[0056] In another embodiment of the lithium solid state battery, the negative electrode active material is present in an amount of 20% to 99% by weight.

[0057] In another embodiment of the lithium solid state battery, the negative electrode active material is present in an amount of 30% to 95% by weight.

[0058] In another embodiment of the lithium solid state battery, the negative electrode active material is present in an amount between 40% and 92.5% by weight.

[0059] In another embodiment of the lithium solid state battery, the negative electrode active material is present in an amount of 50% to 90% by weight.

[0060] In another embodiment of the lithium solid state battery, the negative electrode active material is present in an amount between 60% and 87.59% by weight.

[0061] In another embodiment of the lithium solid state battery, the negative electrode active material is present in an amount of 65% to 85% by weight.

[0062] In another embodiment of the lithium solid battery, the positive electrode active material layer is 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.).

[0063] In another embodiment of the lithium solid battery, the positive electrode active material layer is Li3PS4, Li4P2S6, Li7P3S 11 , Li 10 GeP2S 12 , Li 10 SnP2S 12 including one or more of them.

[0064] In another embodiment of the lithium solid battery of the present invention, the positive electrode active material layer is Li6PS5Cl, Li6PS5Br, Li6PS5I, or a compound represented by the formula Li 7-y PS 6-y X y where X represents at least one halogen element and / or pseudohalogen, 0 < y ≦ 2.0, 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.

[0065] In another embodiment of the lithium solid battery of the present invention, the positive electrode active material layer is Li 8-y-z P2S 9-y-z Xy W z wherein X and W represent at least one halogen element and / or pseudohalogen, with 0≦y≦1 and 0≦z≦1; 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.

[0066] In another embodiment of the lithium solid state battery, the positive electrode active material layer has a thickness in the range of 1 micron to 1000 microns.

[0067] In another embodiment of the lithium solid state battery, the positive electrode active material layer has a thickness in the range of 2 microns to 900 microns.

[0068] In another embodiment of the lithium solid state battery, the positive electrode active material layer has a thickness in the range of 1 micron to 100 microns.

[0069] In another embodiment of the lithium solid state battery, the positive electrode active material layer has a thickness in the range of 5 microns to 750 microns.

[0070] In another embodiment of the lithium solid state battery, the positive electrode active material layer has a thickness in the range of 10 microns to 500 microns.

[0071] In another embodiment of the lithium solid state battery, the positive electrode active material layer has a thickness in the range of 15 microns to 350 microns.

[0072] In another embodiment of the lithium solid state battery, the positive electrode active material layer has a thickness in the range of 20 microns to 200 microns.

[0073] In another embodiment of the lithium solid state battery, the positive electrode active material layer has a thickness in the range of 25 microns to 100 microns.

[0074] In another embodiment of the lithium solid state battery, the negative electrode active material layer has a thickness in the range of 500 nanometers to 1000 microns.

[0075] In another embodiment of the lithium solid state battery, the negative electrode active material layer has a thickness in the range of 1 micron to 900 microns.

[0076] In another embodiment of the lithium solid state battery, the negative electrode active material layer has a thickness in the range of 5 microns to 750 microns.

[0077] In another embodiment of the lithium solid state battery, the negative electrode active material layer has a thickness in the range of 10 microns to 500 microns.

[0078] In another embodiment of the lithium solid state battery, the negative electrode active material layer has a thickness in the range of 15 microns to 350 microns.

[0079] In another embodiment of the lithium solid state battery, the negative electrode active material layer has a thickness in the range of 20 microns to 200 microns.

[0080] In another embodiment of the lithium solid state battery, the negative electrode active material layer has a thickness in the range of 25 microns to 100 microns.

[0081] In another embodiment of the lithium solid state battery, the solid electrolyte layer has a thickness in the range of 500 nanometers to 1000 microns.

[0082] In another embodiment of the lithium solid state battery, the solid electrolyte layer has a thickness in the range of 1 micron to 900 microns.

[0083] In another embodiment of the lithium solid-state battery, the solid electrolyte layer has a thickness in the range of 5 microns to 750 microns.

[0084] In another embodiment of the lithium solid state battery, the solid electrolyte layer has a thickness in the range of 10 microns to 500 microns.

[0085] In another embodiment of the lithium solid-state battery, the solid electrolyte layer has a thickness in the range of 15 microns to 350 microns.

[0086] In another embodiment of the lithium solid state battery, the solid electrolyte layer has a thickness in the range of 20 microns to 200 microns.

[0087] In another embodiment of the lithium solid-state battery, the solid electrolyte layer has a thickness in the range of 25 microns to 100 microns.

[0088] In another embodiment of the lithium solid state battery, the solid electrolyte composition is present in an amount of 5% to 80% by weight.

[0089] In another embodiment of the lithium solid state battery, the solid electrolyte composition is present in an amount between 7.5% and 70% by weight.

[0090] In another embodiment of the lithium solid state battery, the solid electrolyte composition is present in an amount of 10% to 60% by weight.

[0091] In another embodiment of the lithium solid-state battery, the solid electrolyte composition is present in an amount between 12.5% ​​and 50% by weight.

[0092] In another embodiment of the lithium solid-state battery, the solid electrolyte composition is present in an amount of 15% to 40% by weight.

[0093] In another embodiment of the lithium solid-state battery, the solid electrolyte composition is present in an amount between 17.5% and 30% by weight.

[0094] In another embodiment, disclosed herein is a method for producing a sulfide solid electrolyte material comprising a glass-ceramic comprising Li, T, X, and A, where T is at least one of Sb, P, As, Si, Ge, Al, B, and W, X is one or more halogens, pseudohalogens, or N, and A is one or more of S or Se, the method comprising producing a sulfide solid electrolyte material comprising element A or compound Li2A, element T or a sulfide of T, and compound LiX or Li3N. The method includes mixing and milling the raw material composition to render the mixture amorphous under X-ray diffraction, and / or heating the sulfide glass at a heat treatment temperature equal to or higher than the crystallization temperature of the sulfide glass to synthesize a glass-ceramic having peaks at 2θ=14.5°±0.50°, 16.8°±0.50°, 23.9°±0.50°, 28.1°±0.50°, and 32.5°±0.50° as measured by X-ray diffraction using Cu-Kα(1,2)=1.54064 Å.

[0095] The present disclosure will be understood by reference to the following detailed description in conjunction with the drawings, which are briefly described below. It should be noted that for illustrative clarity, certain elements in the drawings may not be drawn to scale. [Brief description of the drawings]

[0096] [Figure 1] FIG. 1 is a schematic cross-sectional view of an exemplary structure of a lithium solid-state electrochemical cell including a solid electrode composition, according to one embodiment.

[0097] [Diagram 2] FIG. 2 is a flow chart of a process for producing a solid electrolyte composition, according to one embodiment.

[0098] [Diagram 3] FIG. 3 is a plot of an X-ray diffraction measurement of a solid electrolyte composition produced by the process shown in FIG. 2, according to one embodiment.

[0099] [Figure 4]FIG. 4 is a plot showing the conductivity of a solid-state electrochemical cell using a solid electrolyte composition of the present disclosure, according to one embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0100] DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS In the following description, specific details are provided to provide a thorough understanding of various embodiments of the present disclosure. However, upon reading and understanding the specification, claims and drawings of the present application, those skilled in the art will understand that some embodiments of the present disclosure may be implemented without following some of the specific details described in the present disclosure. Furthermore, in order to avoid obscuring the present disclosure, some well-known methods, processes, devices and systems that are expected to be applied to the various embodiments described in the present disclosure are not disclosed in detail.

[0101] FIG. 1 is a schematic cross-sectional view showing an exemplary structure of a lithium solid-state electrochemical battery including an electrode composition of the present disclosure. The lithium solid-state battery 100 includes a positive electrode (current collector) 110, a positive electrode active material layer (positive electrode) 120, a solid electrolyte layer 130, a negative electrode active material layer (negative electrode) 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 in the present disclosure may form part of the positive electrode active material layer 120, the negative electrode active material layer 140, and the solid electrolyte layer 130.

[0102] The positive electrode 110, which may also be referred to as the "positive current collector", can be a foil or plate formed from materials such as 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 (not limited to these). In some embodiments, the positive electrode layer 110 can be formed from one or more carbon-containing materials, such as carbon fiber, graphite, graphene, carbon black, conductive carbon, amorphous carbon, VGCF, and carbon nanotubes.

[0103] Similarly, the negative electrode 150, also known as the negative 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 electron conductivity and mechanical strength, the negative electrode 150 can be completely omitted.

[0104] The positive electrode active material layer 120 can include at least a positive electrode active material such as metal oxide, metal phosphate, metal sulfide, sulfur, lithium sulfide, oxygen, or air (not limited to these). In some embodiments, the positive electrode active material layer 120 can be an NMC material represented as Li(Ni a Co 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), NMC 433 (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 Mn0.2 Co 0.2 O2), NMC 811 (LiNi 0.8 Mn 0.1 Co 0.1 O2), or may contain one or more of these combinations. In another embodiment, the positive electrode active material layer 120 is, for example, 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 one or more metal oxides such as these combinations (not limited to these). In yet another embodiment, the positive electrode active material layer 120 can include one or more metal sulfides such as titanium sulfide (TiS2), molybdenum sulfide (MoS2), iron sulfide (FeS, FeS2), copper sulfide (CuS), nickel sulfide (Ni3S2), and lithium sulfide (Li2S), or combinations thereof.

[0105] 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.

[0106] The positive electrode active material layer 120 further includes one or more solid electrolyte materials, such as 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 are Li3PS4, Li4P2S6, Li7P3S 11 、Li 10 GeP2S 12 、Li 10 SnP2S 12 It can be. In a further embodiment, one or more of the solid electrolyte materials are Li6PS5Cl, Li6PS5Br, Li6PS5I, or of the formula Li 7-y PS 6-y X y represented by, where X represents at least one halogen element and / or pseudohalogen, 0 < y ≤ 2.0, 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. In yet another embodiment, one or more of the solid electrolyte materials are of the formula Li 8-y-z P2S 9-y-z X y W z(X and W represent at least one halogen element and / or pseudohalogen, 0≦y≦1 and 0≦z≦1), the halogen can be one or more of F, Cl, Br, and 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 an amount of 5% to 80% by mass.

[0107] The solid electrolyte material may be added in an amount 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.

[0108] The positive electrode active material layer 120 has a capacitance of 1 mS / cm The cathode active material layer 120 may further include one or more carbon-containing species having an electronic conductivity of 1000 nm or more. The carbon-containing species may be, but is not limited to, carbon black, graphite, graphene, carbon nanotubes, carbon fibers, VGCF, carbon black, or amorphous carbon. In another embodiment, the cathode active material layer 120 may further include one or more metal particles, filaments, or other structures.

[0109] The carbon-containing species can be added to the positive electrode active material layer in an amount of 2% to 50%, 4% to 40%, 6% to 30%, 8% to 25%, 10% to 20%, or 12% to 18% by weight.

[0110] The positive electrode active material layer 120 may further include one or more binders or polymers, such as (but not limited to) fluororesins containing vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), or derivatives thereof as structural units. Specific examples thereof 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(vinylenedifluoride-hexafluoropropylene) copolymer (PVdF-HFP). In another embodiment, the polymer or binder can 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-butylene-styrene (SEBS), polyacrylonitrile (PAN), nitrile-butylene rubber (NBR), polybutadiene, polyisoprene, poly(methacrylate)nitrile-butadiene rubber (PMMA-NBR), etc. In a further embodiment, the polymer or binder can be one or more acrylic resins, such as, but not limited to, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polyisopropyl (meth)acrylate, polyisobutyl (meth)acrylate, polybutyl (meth)acrylate, etc. In yet another embodiment, the polymer or binder can be one or more polycondensation polymers, such as, but not limited to, polyurea, polyamide paper, polyimide, polyester, etc. In yet another embodiment, the polymer or binder can be one or more nitrile rubbers, such as, but not limited to, acrylonitrile-butadiene rubber (ABR), polystyrene nitrile-butadiene rubber (PS-NBR), and mixtures thereof.

[0111] One or more of the binders or polymers can be added to the positive electrode active material layer in an amount of 1 mass % to 80 mass %, 3 mass % to 70 mass %, 5 mass % to 60 mass %, 8 mass % to 50 mass %, 11 mass % to 40 mass %, or 14 mass % to 30 mass %.

[0112] The positive electrode active material layer 120 can have a thickness in the range of, for example, 1 μm to 1000 μm. In another embodiment, the thickness may be in the range of 2 μm to 900 μm. In yet another embodiment, the thickness may be in the range of 5 μm to 750 μm. In a further embodiment, the thickness may be in the range of 10 μm to 500 μm. In a further 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 a further embodiment, the thickness may be in the range of 25 μm to 100 μm.

[0113] Anode active material layer 140 can be in the form of a plate, foil, or particles and includes at least one or more anode active materials including, but not limited to, an alkali metal, such as lithium metal, lithium alloy, sodium metal, sodium alloy, potassium metal, potassium alloy, etc. In other embodiments, anode active material layer 140 may include one or more alkaline earth metals, such as magnesium metal, magnesium alloy, calcium metal, calcium alloy, etc. In further embodiments, anode active material layer 140 has a conductivity of 1 mS / cm The negative electrode active material layer 140 may include one or more carbon-containing species having an electronic conductivity of 1000 nm or more. The carbon-containing species may be, but is 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 include one or more species including silicon (Si), tin (Sn), iron (Fe), germanium (Ge), or indium (In).

[0114] The negative electrode active material can be added in an amount of 20% by mass to 100% by mass, 30% by mass to 95% by mass, 40% by mass to 92.5% by mass, 50% by mass to 90% by mass, 60% by mass to 87.5% by mass, or 65% by mass to 85% by mass.

[0115] The negative electrode active material layer 140 may further contain a solid electrolyte material, for example, 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, Li7P3S 11 、Li 10 GeP2S 12 、Li 10 SnP2S 12 . In a further embodiment, one or more of the solid electrolyte materials may be Li6PS5Cl, Li6PS5Br, Li6PS5I, or of the formula Li 7-y PS 6-y X y , where "X" represents at least one halogen element and / or pseudohalogen, 0 < y ≤ 2.0, 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. In yet another embodiment, one or more of the solid electrolyte materials may be of the formula Li 8-y-z P2S9-y-z X y W z (wherein "X" and "W" represent at least one halogen element and / or pseudohalogen, with 0≦y≦1 and 0≦z≦1), 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.

[0116] The solid electrolyte composition can be added to the negative electrode active material layer in an amount of 5 mass% to 80 mass%, 7.5 mass% to 70 mass%, 10 mass% to 60 mass%, 12.5 mass% to 50 mass%, 15 mass% to 40 mass%, or 17.5 mass% to 30 mass%.

[0117] The negative electrode active material layer 140 has a capacitance of 1 mS / cm The cathode active material layer 120 may further include one or more carbon-containing species having an electronic conductivity of 1000 nm or more. The carbon-containing species may be, but is not limited to, carbon black, graphite, graphene, carbon nanotubes, carbon fibers, VGCF, carbon black, or amorphous carbon. In another embodiment, the cathode active material layer 120 may further include one or more particles, wires, or filaments including a material such as, but not limited to, gold (Au), silver (Ag), zinc (Zn), magnesium (Mg), aluminum (Al), silicon (Si), tin (Sn), or iron (Fe).

[0118] The carbon-containing species can be added to the negative electrode active material layer in an amount of 2% to 80% by weight, 5% to 70% by weight, 10% to 60% by weight, 15% to 50% by weight, 20% to 45% by weight, or 25% to 40% by weight.

[0119] The negative electrode active material layer 140 may further include one or more binders or polymers, such as (but not limited to) fluororesins containing vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), or derivatives thereof as structural units. Specific examples thereof 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(vinylenedifluoride-hexafluoropropylene) copolymer (PVdF-HFP). In another embodiment, the polymer or binder can 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-butylene-styrene (SEBS), polyacrylonitrile (PAN), nitrile-butylene rubber (NBR), polybutadiene, polyisoprene, poly(methacrylate)nitrile-butadiene rubber (PMMA-NBR), etc. In a further embodiment, the polymer or binder can be one or more acrylic resins, such as, but not limited to, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polyisopropyl (meth)acrylate, polyisobutyl (meth)acrylate, polybutyl (meth)acrylate, etc. In yet another embodiment, the polymer or binder can be one or more polycondensation polymers, such as, but not limited to, polyurea, polyamide paper, polyimide, polyester, etc. In yet another embodiment, the polymer or binder can be one or more nitrile rubbers, such as, but not limited to, acrylonitrile-butadiene rubber (ABR), polystyrene nitrile-butadiene rubber (PS-NBR), and mixtures thereof.

[0120] One or more of the binders or polymers can be added to the negative electrode active material in an amount of 1 mass % to 80 mass %, 3 mass % to 70 mass %, 5 mass % to 60 mass %, 8 mass % to 50 mass %, 11 mass % to 40 mass %, or 14 mass % to 30 mass %.

[0121] 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 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 a further embodiment, the thickness may be in the range of 10 μm to 500 μm. In a further 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 a further embodiment, the thickness may be in the range of 25 μm to 100 μm.

[0122] The solid electrolyte material included in the solid electrolyte layer 130 is a solid electrolyte composition as described herein. In some embodiments, there may be more than one solid electrolyte material included in the solid electrolyte layer 130, which may include one or more commercially available electrolyte materials described in the positive electrode active material 120 and the negative electrode active material 140. The solid electrolyte layer 130 may include a solid electrolyte composition described herein in a range of 1% to 100% by weight. In another embodiment, 20% to 97.5% by weight. In yet another embodiment, 40% to 95% by weight. In a further embodiment, 60% to 92.5% by weight. In yet another embodiment, 90% to 80% by weight.

[0123] Additionally, the solid electrolyte layer 130 may include one or more binders as described for the positive electrode active material 120 and the negative electrode active material 140. Examples of binders include additional self-healing polymers and poly(ethylene)oxide (PEO) in addition to the materials used in the positive electrode material layer. 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 a further embodiment, the thickness may be in the range of 10 μm to 500 μm. In a further 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 a further embodiment, the thickness may be in the range of 25 μm to 100 μm.

[0124] Although shown as a lamellar structure in Figure 1, other shapes and configurations of solid-state electrochemical cells are possible. Most commonly, lithium solid-state batteries can be fabricated by providing a layer of positive electrode active material, a layer of solid electrolyte, and a layer of negative electrode active material that are sequentially stacked between the electrodes, pressed, and then disposed within a housing.

[0125] FIG. 2 is a flow chart of a process for producing a solid electrolyte composition useful in the construction of secondary electrochemical cells. Process 200 begins with a preparation step 210 where any preparation operations such as precursor synthesis, purification, and device preparation may be performed. After any initial preparation, process 200 proceeds to step 220 where sulfur compounds, lithium compounds, and other compounds as described herein may be combined with appropriate solvents and / or other liquids. Exemplary sulfur compounds include, for example, elemental sulfur, antimony sulfide (Sb2S3), and lithium sulfide (Li2S), typically in powder form. Exemplary lithium compounds include, for example, lithium metal (Li), lithium sulfide (Li2S), and lithium nitride (Li3N), typically in powder form. Exemplary halides include LiCl, LiBr, and LiI, and exemplary pseudohalogens include BH4, BF4, NO3, CN, SO3, OCN, SCN, and N3. Exemplary solvents include, but are not limited to, aprotic linear hydrocarbons such as heptane, aromatic hydrocarbons such as xylene, and other solvents that have a low tendency to generate hydrogen sulfide gas in contact with the precursor or final electrolyte composition. The solvent is not particularly limited as long as it remains partially or completely liquid during the milling process at the desired milling temperature and does not participate in adverse reactions with the solid electrolyte precursor or final solid electrolyte composition. The ratios and amounts of the various compounds are not particularly limited as long as the combination allows for the synthesis of the desired composition and phase as indicated by the presence of a specific X-ray diffraction feature. The ratios and amounts may also vary depending on the specific synthesis conditions. For example, the ratio of the solvent mass to the precursor mass may need to be adjusted depending on the composition of the solid electrolyte being adjusted to ensure complete milling of the precursor to produce the desired solid electrolyte discussed herein.

[0126] The amount of solvent added to the above combination is not limited, as long as it is an amount that supports the synthesis of the desired composition of solid electrolyte material. Multiple solvents may be mixed together with the mentioned compounds. Additional materials such as co-solvents or polymers may be added during this step. Furthermore, the synthesis can be performed without solvent.

[0127] Next, in step 230, the composition can be mixed and / or milled for a predetermined time and temperature to produce a solid electrolyte as described above. The mixing time is not particularly limited, so long as it allows for proper precursor homogenization and reaction to produce a solid electrolyte. The mixing temperature is not particularly limited, so long as it allows for proper mixing and is not high enough to cause the precursors to become gaseous. For example, proper mixing can be achieved at a temperature of 20-120°C for 10 minutes to 60 hours. Mixing can be achieved, for example, using a planetary ball mill or an attritor mill.

[0128] The composition may then be dried in step 240 for a predetermined time and temperature in an inert atmosphere, such as argon or nitrogen, or under vacuum. After drying, a 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 phases of the present disclosure. The material resulting from the heat treatment step 250 may be single phase or may contain other crystalline phases and only small amounts of precursor phases.

[0129] Generally, the heat treatment time is not limited as long as it allows the production of the desired composition and phase. The time can be, for example, within the range of 1 minute to 24 hours. Furthermore, the heat treatment is carried out in an inert gas atmosphere (e.g., argon) or under vacuum.

[0130] In a final step 260, the completed composition can be utilized in the construction of an electrochemical cell, such as the cell of FIG.

[0131] Other synthetic routes can be used as well. For example, the solid electrolyte materials described in the present disclosure can be synthesized using a method that includes mixing appropriate precursors providing the components Li, T, X, and A in a solvent capable of causing a reaction between the precursors, removing the solvent, and heat treating at a temperature equal to or higher than the crystallization temperature of the material. EXAMPLES

[0132] Preparation of solid electrolyte

[0133] Example 1

[0134] To a 500 ml zirconia milling jar containing zirconia milling media and a compatible solvent (e.g., xylene or heptane), 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. The mixture was milled in a Retsch PM 100 planetary mill at 400 RPM for 12 hours. The material was collected and dried at 70° C. under an inert (argon or nitrogen) environment. The resulting solid electrolyte powder of Example 1 (Li4SbS4I) can then be used for the positive electrode active layer, the solid electrolyte layer, and / or the negative electrode active layer.

[0135] Example 2

[0136] The masses of Li2S, Sb2S3, P2S5, sulfur powder and LiI were stoichiometrically selected to produce Li4Sb 0.75 P 0.25 A solid electrolyte of Example 2 was prepared in the same manner as in Example 1, except that S4I was synthesized.

[0137] Comparative Example 1

[0138] A solid electrolyte of Comparative Example 1 was prepared in the same manner as in Example 1, except that Li4SbS4I was synthesized by stoichiometrically selecting the masses of Li2S, P2S5, sulfur powder, and LiI.

[0139] Air and moisture exposure

[0140] 1 g each of Examples 1 to 2 and Comparative Example 1 was collected and exposed to an atmosphere with an average dew point of -47°C for 4 hours to conduct an air and moisture exposure resistance test. After 4 hours, the materials were recovered and stored in an inert gas environment.

[0141] The sulfide solid electrolyte material obtained from Example 1 contains Li, T, X, and A, and in X-ray diffraction (XRD) measurement using Cu-Kα(1,2) = 1.54064 Å, it 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°. These peaks identify a novel crystal 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 is Li 1-a-b-c T a A b X c which can be represented as, where the values of a, b, and c can be within the ranges of 0.074 < a ≤ 0.105, 0.370 < b ≤ 0.421, and 0.074 < c ≤ 0.105. The composition may be a mixed-phase material with other crystal phases 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 may contain crystal phases related to one or more lithium halides or lithium sulfides.

[0142] Exemplary compositions are Li 1-a-b-c T a A b X c(a=c=0.1, b=0.4, T=Sb, A=S, and X=I). Such a composition results in the crystalline phase of the present disclosure after application of appropriate synthesis and heat treatment conditions. The novel structure of this crystalline phase contributes to high ionic conductivity. The presence of halogen can aid in the formation of a stable, low resistance interface to lithium metal and high voltage cathode active material. Furthermore, the presence of Sb can increase the air stability of the compound compared to other compounds that do not contain Sb.

[0143] 3 is a plot of X-ray diffraction measurements of solid electrolyte compositions produced by the process shown in FIG. 2 according to Examples 1 and 2 and Comparative Example 1. X-ray diffraction (XRD) measurements of Examples 1 and 2 showed major new peaks indicative of 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° using Cu-Kα(1,2)=1.54064Å. In particular, the peak at 32.5°±0.50° has not been observed in the Comparative Examples or other compositions similar to the present composition, and may serve to highlight the novel crystalline phase of the present disclosure. Further illustrative examples of peak positions are 2θ=14.5°±0.20°, 16.8°±0.20°, 23.9°±0.20°, 28.1°±0.20°, and 32.5°±0.20°, using Cu-Kα(1,2)=1.54064 Å. Other compositions may be mixed phase materials having other crystalline phases 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°, 17.1° and 25.8°, and / or peaks associated with one or more lithium halides. However, the X-ray diffraction measurement of the material described in Comparative Example 1 lacks peaks at 2θ=14.5°±0.50°, 16.8°±0.50°, 23.9°±0.50°, 28.1°±0.50°, and 32.5°±0.50° with Cu-Kα(1,2)=1.54064 Å, and therefore does not conform to the present disclosure. Furthermore, Comparative Example 1 shows X-ray diffraction results from a stoichiometry that does not contain antimony, and therefore does not conform to the present disclosure.

[0144] 4 is a plot showing the percentage of initial ionic conductivity remaining after 4 hours of exposure to an atmosphere with an average dew point of −47° C. From FIG. 4, it is observed that after exposure to the atmosphere, the solid electrolyte materials described in Examples 1 and 2 all retained slightly more than 60% of their initial conductivity. However, the solid electrolyte material described in Comparative Example 1 shows a significantly lower conductivity retention due to the lack of antimony in the composition.

[0145] An example of the composition is a pellet compressed at room temperature, with a measured impedance of about 0.525 mS / mol / L at room temperature for the pure and mixed phase electrolyte materials. cm Higher conductivities could be achieved by modification of the stoichiometry and / or by compression at elevated temperatures or other processing methods and conditions.

[0146] The features described above and in the following claims can be combined in various ways without departing from their scope. It should therefore be noted that the matter contained in the above description or shown in the accompanying drawings should be interpreted as illustrative and not in a limiting sense. Some of the embodiments of the invention related to the present invention are shown below. [Aspect 1] 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, and A comprises one or more of S or Se, wherein 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° in X-ray diffraction measurement using Cu-Kα(1,2)=1.54064Å. [Aspect 2] formula: Li 1-a-b-c T a A b X c (In the formula, 0.074 <a≦0.105、0.370<b≦0.421、0.074<c≦0.105である。) The solid electrolyte material of embodiment 1, comprising: [Aspect 3] 2. The solid electrolyte material of embodiment 1, wherein 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. [Aspect 4] 2. The solid electrolyte material according to embodiment 1, wherein a ratio of Sb to all elements T is 1% or more. [Aspect 5] 3. The solid electrolyte material of embodiment 2, wherein a=0.1, b=0.4, c=0.1, T=Sb, A=S, and X=I. [Aspect 6] 2. The solid electrolyte material of embodiment 1, comprising at least one of a glass-ceramic phase, a crystalline phase, and a mixed phase. [Aspect 7] 7. The solid electrolyte material of embodiment 6, wherein the mixed phase comprises other crystalline phases having 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°, as measured by X-ray diffraction with Cu-Kα(1,2)=1.5418 Å. [Aspect 8] 2. The solid electrolyte material of embodiment 1, having an ionic conductivity of greater than about 0.500 mS / cm at room temperature. [Aspect 9] A lithium solid 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 contains a solid electrolyte material containing Li, T, X, and A, where T contains at least one element selected from the group consisting of Sb, P, As, Si, Ge, Al, B, and W, X contains one or more halogens, pseudohalogens, or N, A contains one or more of S or Se, and 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° in X-ray diffraction measurement using Cu-Kα(1,2) = 1.54064 Å. [Aspect 10] The solid electrolyte material has the formula: Li 1-a-b-c T a A b X c (where 0.074 < a ≤ 0.105, 0.370 < b ≤ 0.421, 0.074 < c ≤ 0.105). The lithium solid battery according to Aspect 9. [Aspect 11] The lithium solid battery according to Aspect 9, wherein T contains a blend of Sb and non-Sb elements selected from the group consisting of Sb, P, As, Si, Ge, Al, B, and W. [Aspect 12] The lithium solid battery according to Aspect 9, wherein the proportion of Sb in all elements T is 1% or more. [Aspect 13] a = 0.1, b = 0.4, c = 0.1, T = Sb, A = S, X = I. The lithium solid battery according to Aspect 10. [Aspect 14] The lithium solid battery according to Aspect 9, wherein the solid electrolyte material contains at least one of glass, ceramic phase, crystal phase, or mixed phase. [Aspect 15] The lithium solid battery according to Aspect 14, wherein the mixed phase contains other crystal phases having 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° in X-ray diffraction measurement using Cu-Kα(1,2) = 1.5418 Å. [Aspect 16] The lithium solid battery according to Aspect 9, containing a solid electrolyte material having an ionic conductivity exceeding about 0.500 mS / cm at room temperature. [Aspect 17] 10. A lithium solid state battery as described in embodiment 9, wherein the active cathode material comprises one or more particles, wires, or filaments comprising at least one of aluminum, nickel, titanium, stainless steel, magnesium, iron, zinc, indium, germanium, silver, platinum, gold, lithium, or alloys thereof. [Aspect 18] 10. The lithium solid state battery of embodiment 9, wherein the anode active material comprises at least one of an alkali metal, including lithium metal, lithium alloy, sodium metal, sodium alloy, potassium metal, potassium alloy, or at least one of an alkaline earth metal, including magnesium metal, magnesium alloy, calcium metal, calcium alloy. [Aspect 19] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material further comprises silicon, tin, iron, germanium, or indium. [Aspect 20] 10. A lithium solid state battery as described in embodiment 9, wherein the positive electrode active material layer and the negative electrode active material layer each comprise one or more carbon-containing materials including carbon fiber, graphite, graphene, carbon black, conductive carbon, amorphous carbon, VGCF, and carbon nanotubes. [Aspect 21] 21. The lithium solid state battery of embodiment 20, wherein the carbon-containing material is added in an amount of 2% by weight to 50% by weight. [Aspect 22] 21. The lithium solid state battery of embodiment 20, wherein the carbon-containing material is added in an amount of 6% by weight to 30% by weight. [Aspect 23] 21. The lithium solid state battery of embodiment 20, wherein the carbon-containing material is added in an amount of 8% by weight to 25% by weight. [Aspect 24] 21. The lithium solid state battery of embodiment 20, wherein the carbon-containing material is added in an amount of 10% by weight to 20% by weight. [Aspect 25] 21. The lithium solid state battery of embodiment 20, wherein the carbon-containing material is added in an amount of 12% to 18% by weight. [Aspect 26] 21. The lithium solid state battery of embodiment 20, wherein the carbon-containing material is added in an amount of 2% by weight to 50% by weight. [Aspect 27] 10. The lithium solid-state battery of embodiment 9, wherein the positive and negative electrode layers each comprise one or more of metal particles, filaments, or other structures. [Aspect 28] 10. The lithium solid state battery of embodiment 9, wherein the positive and negative electrode layers each comprise one or more binders or polymers comprising fluororesins including vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), and derivatives thereof. [Aspect 29] 10. The lithium solid-state battery of embodiment 9, wherein the positive and negative electrode layers each comprise one or more binders or polymers comprising a homopolymer comprising polyvinylidene fluoride (PVdF), polyhexafluoropropylene (PHFP) or polytetrafluoroethylene (PTFE), or a binary copolymer comprising a copolymer of VdF and HFP, including poly(vinylene difluoride-hexafluoropropylene) copolymer (PVdF-HFP). [Aspect 30] 10. The lithium solid-state battery of embodiment 9, wherein the positive and negative electrode layers each comprise one or more binders or polymers comprising a thermoplastic elastomer comprising styrene-butadiene rubber (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene block copolymer (SIS), styrene-ethylene-butylene-styrene (SEBS), polyacrylonitrile (PAN), nitrile-butylene rubber (NBR), polybutadiene, polyisoprene, or poly(methacrylate)nitrile-butadiene rubber (PMMA-NBR). [Aspect 31] 10. The lithium solid state battery of embodiment 9, wherein the positive and negative electrode layers each comprise one or more binders or polymers comprising acrylic resins including polymethyl(meth)acrylate, polyethyl(meth)acrylate, polyisopropyl(meth)acrylate, polyisobutyl(meth)acrylate, polybutyl(meth)acrylate. [Aspect 32] 10. The lithium solid state battery of embodiment 9, wherein the positive and negative electrode layers each comprise one or more binders or polymers including polyurea, polyamide paper, or polyimide, polycondensation polymers including polyester. [Aspect 33] 10. The lithium solid state battery of embodiment 9, wherein the positive and negative electrode layers each comprise one or more binders or polymers comprising a nitrile rubber, including acrylonitrile-butadiene rubber (ABR), polystyrene nitrile-butadiene rubber (PS-NBR), or a mixture thereof. [Aspect 34] 10. The lithium solid state battery of embodiment 9, wherein the positive and negative electrode layers each comprise one or more binders or polymers present in an amount between 1% and 80% by weight. [Aspect 35] 10. The lithium solid state battery of embodiment 9, wherein the positive and negative electrode layers each comprise one or more binders or polymers present in an amount between 3% and 70% by weight. [Aspect 36] The lithium solid-state battery according to Aspect 9, wherein the positive electrode layer and the negative electrode layer each contain one or more binders or polymers present in an amount of 5% by mass to 60% by mass. [Aspect 37] The lithium solid-state battery according to Aspect 9, wherein the positive electrode layer and the negative electrode layer each contain one or more binders or polymers present in an amount of 8% by mass to 50% by mass. [Aspect 38] The lithium solid-state battery according to Aspect 9, wherein the positive electrode layer and the negative electrode layer each contain one or more binders or polymers present in an amount of 11% by mass to 40% by mass. [Aspect 39] The lithium solid-state battery according to Aspect 9, wherein the positive electrode layer and the negative electrode layer each contain one or more binders or polymers present in an amount of 14% by mass to 30% by mass. [Aspect 40] The lithium solid-state battery according to Aspect 9, wherein the negative electrode active material has sufficient electronic activity and mechanical strength to function as the negative electrode, and the negative electrode is absent. [Aspect 41] The lithium solid-state battery according to Aspect 9, wherein the positive electrode active material layer contains Li(Ni a Co b Mn c )O 2 where 0 < a ≤ 1, 0 < b ≤ 1, 0 < c ≤ 1, and a + b + c = 1. [Aspect 42] The lithium solid-state battery according to Aspect 9, wherein the positive electrode active material layer contains Li(Ni 0.33 Co 0.33 Mn 0.33 )O 2 , Li(Ni 0.4 Co 0.3 Mn 0.3 )O 2 , Li(Ni 0.5 Co 0.2 Mn 0.3 )O 2 , Li(Ni 0.6 Co 0.2 Mn 0.2 )O 2 , Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 , or a combination thereof. [Aspect 43] The lithium solid-state battery according to Aspect 9, wherein the positive electrode active material layer contains one or more metal oxides including V 2 O 5 、V 6 O 13 , MoO 3 , LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiNi 1-Y Co Y O 2 , LiCo 1-Y Mn Y O 2 , LiNi 1-Y Mn Y O2 (0 ≤ Y < 1), Li(Ni a Co b Mn c )O 4 (0 < a < 2, 0 < b < 2, 0 < c < 2, a + b + c = 2), LiMn 2-Z Ni Z O 4 , LiMn 2-Z Co Z O 4 (0 < Z < 2), LiCoPO 4 , LiFePO 4 , CuO, Li(Ni a Co b Al c )O 2 (0 < a < 1, 0 < b < 1, 0 < c < 1, a + b + c = 1), or a combination thereof. [Aspect 44] The lithium solid-state battery according to Aspect 9, wherein the positive electrode active material layer contains one or more of metal sulfides including titanium sulfide (TiS 2 ), molybdenum sulfide (MoS 2 ), iron sulfide (FeS, FeS 2 ), copper sulfide (CuS), nickel sulfide (Ni 3 S 2 ), and lithium sulfide (Li 2 S), or a combination thereof. [Aspect 45] The lithium solid-state battery according to Aspect 9, wherein the positive electrode active material is present in an amount of 20% by mass to 99% by mass. [Aspect 46] 10. The lithium solid state battery of embodiment 9, wherein the positive electrode active material is present in an amount of 30% to 95% by weight. [Aspect 47] 10. The lithium solid state battery of embodiment 9, wherein the positive electrode active material is present in an amount of 40% to 92.5% by weight. [Aspect 48] 10. The lithium solid state battery of embodiment 9, wherein the positive electrode active material is present in an amount of 50% to 90% by weight. [Aspect 49] 10. The lithium solid state battery of embodiment 9, wherein the positive electrode active material is present in an amount of 60% to 87.5% by weight. [Aspect 50] 10. The lithium solid state battery of embodiment 9, wherein the positive electrode active material is present in an amount of 65% to 85% by weight. [Aspect 51] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material is present in an amount of 20% to 99% by weight. [Aspect 52] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material is present in an amount of 30% to 95% by weight. [Aspect 53] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material is present in an amount of 40% to 92.5% by weight. [Aspect 54] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material is present in an amount of 50% to 90% by weight. [Aspect 55] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material is present in an amount of 60% to 87.59% by weight. [Aspect 56] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material is present in an amount of 65% to 85% by weight. [Aspect 57] The positive electrode active material layer is Li 2 SP 2 S 5 , Li 2 SP 2 S 5 - LiI, Li 2 SP 2 S 5 -GeS 2 , Li 2 SP 2 S 5 -Li 2 O, Li 2 SP 2 S 5 -Li 2 O-LiI, Li 2 SP 2 S 5 -LiI-LiBr, Li 2 S-SiS 2 , Li 2 S-SiS 2 - LiI, Li 2 S-SiS 2 -LiBr, Li 2 SS-SiS 2 -LiCl, Li 2 SS-SiS 2 -B 2 S 3 - LiI, Li 2 SS-SiS 2 -P 2 S 5 - LiI, Li 2 S.B. 2 S 3 , Li 2 SP 2 S 5 -Z m S n (m and n are positive numbers, and Z is Ge, Zn, or Ga), Li 2 S-GeS 2 , Li 2 SS-SiS 2 -Li 3 PO 4 , and Li 2 SS-SiS 2 -Li x MO y (x and y are positive numbers, and M is P, Si, Ge, B, Al, Ga, or In). [Aspect 58] The positive electrode active material layer is Li 3 P.S. 4 , Li 4 P 2 S 6 , Li 7 P 3 S 11 , Li 10 GeP 2 S 12 , Li 10 SnP 2 S 12 10. The lithium solid-state battery of embodiment 9, comprising one or more of: [Aspect 59] The positive electrode active material layer is Li 6 P.S. 5 Cl, Li 6 P.S. 5 Br, Li 6 P.S. 5 I, or formula Li 7-y P.S. 6-y X y including one or more of those represented by, where X represents at least one halogen element and / or pseudohalogen, 0 < y ≦ 2.0, the halogen includes one or more of F, Cl, Br, and I, and the pseudohalogen includes N, NH, NH 2 , NO, NO 2 , BF 4 , BH 4 , AlH 4 , CN and SCN, the lithium solid battery according to Embodiment 9. [Embodiment 60] wherein the positive electrode active material layer contains one or more of Li 8-y-z P 2 S 9-y-z X y W z , where X and W represent at least one halogen element and / or pseudohalogen, 0 ≦ y ≦ 1 and 0 ≦ z ≦ 1, the halogen includes one or more of F, Cl, Br, and I, and the pseudohalogen includes N, NH, NH 2 , NO, NO 2 , BF 4 , BH 4 , AlH 4 , CN and SCN, the lithium solid battery according to Embodiment 9. [Embodiment 61] The lithium solid battery according to Embodiment 9, wherein the positive electrode active material layer has a thickness in the range of 1 micron to 1000 microns. [Embodiment 62] The lithium solid battery according to Embodiment 9, wherein the positive electrode active material layer has a thickness in the range of 2 microns to 900 microns. [Embodiment 63] The lithium solid battery according to Embodiment 9, wherein the positive electrode active material layer has a thickness in the range of 1 micron to 100 microns. [Embodiment 64] The lithium solid battery according to Embodiment 9, wherein the positive electrode active material layer has a thickness in the range of 5 microns to 750 microns. [Embodiment 65] The lithium solid battery according to Embodiment 9, wherein the positive electrode active material layer has a thickness in the range of 10 microns to 500 microns. [Embodiment 66] The lithium solid battery according to Embodiment 9, wherein the positive electrode active material layer has a thickness in the range of 15 microns to 350 microns. [Embodiment 67] The lithium solid battery according to Embodiment 9, wherein the positive electrode active material layer has a thickness in the range of 20 microns to 200 microns. [Embodiment 68] The lithium solid battery according to Embodiment 9, wherein the positive electrode active material layer has a thickness in the range of 25 microns to 100 microns. [Embodiment 69] The lithium solid battery according to Embodiment 9, wherein the negative electrode active material layer has a thickness in the range of 500 nanometers to 1000 microns. [Embodiment 70] The lithium solid battery according to Embodiment 9, wherein the negative electrode active material layer has a thickness in the range of 1 micron to 900 microns. [Embodiment 71] The lithium solid battery according to Embodiment 9, wherein the negative electrode active material layer has a thickness in the range of 5 microns to 750 microns. [Embodiment 72] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material layer has a thickness in the range of 10 microns to 500 microns. [Aspect 73] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material layer has a thickness in the range of 15 microns to 350 microns. [Aspect 74] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material layer has a thickness in the range of 20 microns to 200 microns. [Aspect 75] 10. The lithium solid state battery of embodiment 9, wherein the negative electrode active material layer has a thickness in the range of 25 microns to 100 microns. [Aspect 76] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte layer has a thickness in the range of 500 nanometers to 1000 microns. [Aspect 77] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte layer has a thickness in the range of 1 micron to 900 microns. [Aspect 78] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte layer has a thickness in the range of 5 microns to 750 microns. [Aspect 79] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte layer has a thickness in the range of 10 microns to 500 microns. [Aspect 80] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte layer has a thickness in the range of 15 microns to 350 microns. [Aspect 81] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte layer has a thickness in the range of 20 microns to 200 microns. [Aspect 82] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte layer has a thickness in the range of 25 microns to 100 microns. [Aspect 83] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte composition is present in an amount of 5% to 80% by weight. [Aspect 84] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte composition is present in an amount of 7.5% to 70% by weight. [Aspect 85] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte composition is present in an amount of 10% to 60% by weight. [Aspect 86] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte composition is present in an amount of 12.5% ​​to 50% by weight. [Aspect 87] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte composition is present in an amount of 15% to 40% by weight. [Aspect 88] 10. The lithium solid state battery of embodiment 9, wherein the solid electrolyte composition is present in an amount of 17.5% to 30% by weight. [Aspect 89] 1. A method for producing a sulfide solid electrolyte material comprising a glass ceramic comprising Li, T, X and A, wherein T is at least one of Sb, P, As, Si, Ge, Al, B and W, X is one or more halogens, pseudohalogens or N, and A is one or more of S or Se, the method comprising the steps of: 2 A, element T or sulfide of T, and compound LiX or Li 3 1. A method for producing a sulfide solid electrolyte material, comprising: mixing and milling a raw material composition containing N to render the mixture amorphous under X-ray diffraction; and / or heating the sulfide glass at a heat treatment temperature that is equal to or higher than the crystallization temperature of the sulfide glass to synthesize a glass ceramic having peaks at 2θ=14.5°±0.50°, 16.8°±0.50°, 23.9°±0.50°, 28.1°±0.50°, and 32.5°±0.50° in X-ray diffraction measurement using Cu-Kα(1,2)=1.54064 Å.

Claims

1. A solid electrolyte material comprising Li, T, X and A, wherein T comprises Sb, X comprises one or more halogens, pseudohalogens or N, and A comprises one or more of S or Se, wherein 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° in X-ray diffraction measurement using Cu-Kα(1,2)=1.54064 Å.

2. formula: Li １－ａ－ｂ－ｃ T ａ A ｂ X ｃ (Wherein, 0.074<a≦0.105, 0.370<b≦0.421, and 0.074<c≦0.105.) The solid electrolyte material of claim 1 , comprising:

3. 2. The solid electrolyte material of claim 1, wherein T comprises a blend of Sb and a non-Sb element selected from the group consisting of P, As, Si, Ge, Al, B, and W.

4. The solid electrolyte material according to claim 1 , wherein the ratio of Sb to all elements T is 1% or more.

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

6. 10. The solid electrolyte material of claim 1, comprising at least one of a glass-ceramic phase, a crystalline phase, and a mixed phase, or having an ionic conductivity greater than 0.500 mS / cm at room temperature.

7. 7. The solid electrolyte material according to claim 6, wherein the mixed phase includes other crystalline phases having 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° in X-ray diffraction measurement using Cu-Kα(1,2)=1.5418 Å.

8. A lithium solid-state battery including: a positive electrode active material layer including a positive electrode active material; a negative electrode active material layer including 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 includes a solid electrolyte material including Li, T, X, and A, wherein T includes Sb, X includes one or more types of halogen, pseudohalogen, or N, and A includes one or more types of S or Se, and 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° in X-ray diffraction measurement using Cu-Kα(1,2)=1.54064 Å.

9. The solid electrolyte material has the formula: Li １－ａ－ｂ－ｃ T ａ A ｂ X ｃ 9. The lithium solid state battery of claim 8, comprising: (wherein 0.074<a≦0.105, 0.370<b≦0.421, and 0.074<c≦0.105).

10. 9. The lithium solid state battery of claim 8, wherein T comprises a blend of Sb and a non-Sb element 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 the ratio of Sb to all elements T is 1% or more.

12. 10. 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. 9. The lithium solid-state battery of claim 8, wherein the solid electrolyte material comprises at least one of a glass-ceramic phase, a crystalline phase, or a mixed phase, or the solid electrolyte material has an ionic conductivity greater than 0.500 mS / cm at room temperature.

14. 14. The lithium solid state battery according to claim 13, wherein the mixed phase contains other crystalline phases having 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° in X-ray diffraction measurement using Cu-Kα(1,2)=1.5418 Å.

15. 9. The lithium solid state battery of claim 8, wherein the active cathode material comprises one or more particles, wires or filaments comprising at least one of aluminum, nickel, titanium, stainless steel, magnesium, iron, zinc, indium, germanium, silver, platinum, gold, lithium or alloys thereof.

16. 9. The lithium solid state battery according to claim 8, wherein the negative electrode active material comprises at least one of an alkali metal including lithium metal, a lithium alloy, a sodium metal, a sodium alloy, a potassium metal, and a potassium alloy, or at least one of an alkaline earth metal including magnesium metal, a magnesium alloy, a calcium metal, and a calcium alloy, or the negative electrode active material further comprises silicon, tin, iron, germanium, or indium.

17. The positive electrode active material layer and the negative electrode active material layer each contain one or more carbon-containing materials including carbon fiber, graphite, graphene, carbon black, conductive carbon, amorphous carbon, VGCF, and carbon nanotubes, and the carbon-containing material is added in an amount of 2% by mass to 50% by mass, 6% by mass to 30% by mass, 8% by mass to 25% by mass, 10% by mass to 20% by mass, 12% by mass to 18% by mass, or 2% by mass to 50% by mass. The lithium solid state battery according to claim 8.

18. The positive electrode active material layer and the negative electrode active material layer each contain at least one of metal particles or filaments, The positive electrode active material layer and the negative electrode active material layer each contain one or more binders or polymers including fluororesins including vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), and derivatives thereof; The positive electrode active material layer and the negative electrode active material layer each contain one or more binders or polymers including a homopolymer including polyvinylidene fluoride (PVdF), polyhexafluoropropylene (PHFP) or polytetrafluoroethylene (PTFE), or a binary copolymer including a copolymer of VdF and HFP including poly(vinylene difluoride-hexafluoropropylene) copolymer (PVdF-HFP); The positive electrode active material layer and the negative electrode active material layer each include one or more binders or polymers including a thermoplastic elastomer including styrene-butadiene rubber (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene block copolymer (SIS), styrene-ethylene-butylene-styrene (SEBS), polyacrylonitrile (PAN), nitrile-butylene rubber (NBR), polybutadiene, polyisoprene, or poly(methacrylate)nitrile-butadiene rubber (PMMA-NBR); The positive electrode active material layer and the negative electrode active material layer each contain one or more binders or polymers including an acrylic resin including polymethyl (meth)acrylate, polyethyl (meth)acrylate, polyisopropyl (meth)acrylate, polyisobutyl (meth)acrylate, or polybutyl (meth)acrylate; The positive electrode active material layer and the negative electrode active material layer each contain one or more binders or polymers including polyurea, polyamide paper, or polyimide, a polycondensation polymer including polyester; The positive electrode active material layer and the negative electrode active material layer each contain one or more binders or polymers including nitrile rubber including acrylonitrile-butadiene rubber (ABR), polystyrene nitrile-butadiene rubber (PS-NBR), or a mixture thereof; The lithium solid state battery according to claim 8.

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

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

21. The positive electrode active material layer is Li(Ni ａ Co ｂ Mn ｃ ) O ２ where 0<a≦1, 0<b≦1, 0<c≦1, and a+b+c=1; The positive electrode active material layer is Li(Ni ０．３３ Co ０．３３ Mn ０．３３ ) O ２ , Li(Ni ０．４ Co ０．３ Mn ０．３ ) O ２ , Li(Ni ０．５ Co ０．２ Mn ０．３ ) O ２ , Li(Ni ０．６ Co ０．２ Mn ０．２ ) O ２ , Li(Ni ０．８ Co ０．１ Mn ０．１ ) O ２ or a combination thereof, The positive electrode active material layer is V ２ O ５ , V ６ O １３ , MoO ３ , LiCoO ２ , LiNiO ２ , LiMnO ２ , LiMn ２ O ４ , LiNi １－Ｙ Co Ｙ O ２ , LiCo １－Ｙ Mn Ｙ O ２ , LiNi １－Ｙ Mn Ｙ O ２ (0≦Y<1), Li(Ni ａ Co ｂ Mn ｃ ) O ４ (0<a<2, 0<b<2, 0<c<2, a+b+c=2), LiMn ２－Ｚ Ni Ｚ O ４ , LiMn ２－Ｚ Co Ｚ O ４ (0<Z<2), LiCoPO ４ , LiFePO ４ , CuO, Li(Ni ａ Co ｂ A ｃ ) O ２ (0<a<1, 0<b<1, 0<c<1, a+b+c=1) or a combination thereof; The positive electrode active material layer is made of titanium sulfide (TiS ２ ), molybdenum sulfide (MoS ２ ), iron sulfide (FeS, FeS ２ ), copper sulfide (CuS), nickel sulfide (Ni ３ S ２ ) and lithium sulfide (Li ２ S) or combinations thereof; The lithium solid state battery according to claim 8.

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

23. 9. The lithium solid state battery of claim 8, wherein the negative electrode active material is present in an amount of 20% to 99% by weight, 30% to 95% by weight, 40% to 92.5% by weight, 50% to 90% by weight, 60% to 87.5% by weight, or 65% to 85% by weight of the negative electrode active material layer.

24. The positive electrode active material layer contains Li ２ S - P ２ S ５ 、Li ２ S - P ２ S ５ -LiI, Li ２ S - P ２ S ５ -GeS ２ 、Li ２ S - P ２ S ５ -Li ２ O, Li ２ S - P ２ S ５ -Li ２ O - LiI, Li ２ S - P ２ S ５ -LiI - LiBr, Li ２ S - SiS ２ 、Li ２ S - SiS ２ -LiI, Li ２ S - SiS ２ -LiBr, Li ２ S - S - SiS ２ -LiCl, Li ２ S - S - SiS ２ -B ２ S ３ -LiI, Li ２ S - S - SiS ２ -P ２ S ５ -LiI, Li ２ S - B ２ S ３ 、Li ２ S - P ２ S ５ -Z ｍ S ｎ (m and n are positive numbers, and Z is Ge, Zn or Ga.), Li ２ S - GeS ２ 、Li ２ S - S - SiS ２ -Li ３ PO ４ 、and Li ２ S - S - SiS ２ -Li ｘ MO ｙ (x and y are positive numbers, and M is P, Si, Ge, B, Al, Ga, or In), The positive electrode active material layer is ３ P.S. ４ , Li ４ P ２ S ６ , Li ７ P ３ S １１ , Li １０ GeP ２ S １２ , Li １０ SnP ２ S １２ One or more of the following are included: The positive electrode active material layer is ６ P.S. ５ Cl, Li ６ P.S. ５ Br, Li ６ P.S. ５ I, or formula Li ７－ｙ P.S. ６－ｙ X ｙ wherein X represents at least one halogen element and / or pseudohalogen, 0<y≦2.0, the halogen includes one or more of F, Cl, Br, and I, and the pseudohalogen includes N, NH, NH ２ , NO, NO ２ , B.F. ４ , B.H. ４ , AlH ４ , CN and SCN, The positive electrode active material layer is ８－ｙ－ｚ P ２ S ９－ｙ－ｚ X ｙ W ｚ wherein X and W represent at least one halogen element and / or pseudohalogen, 0≦y≦1 and 0≦z≦1, the halogen includes one or more of F, Cl, Br, I, and the pseudohalogen includes N, NH, NH ２ , NO, NO ２ , B.F. ４ , B.H. ４ , AlH ４ , CN and SCN, The lithium solid state battery according to claim 8.

25. 9. The lithium solid state battery of claim 8, wherein the positive electrode active material layer has a thickness in the range of 1 micron to 1000 microns, 2 microns to 900 microns, 1 micron to 100 microns, 5 microns to 750 microns, 10 microns to 500 microns, 15 microns to 350 microns, 20 microns to 200 microns, or 25 microns to 100 microns.

26. 9. The lithium solid state battery of claim 8, wherein the negative electrode active material layer has a thickness in the range of 500 nanometers to 1000 microns, 1 micron to 900 microns, 5 microns to 750 microns, 10 microns to 500 microns, 15 microns to 350 microns, 20 microns to 200 microns, or 25 microns to 100 microns.

27. 9. The lithium solid state battery of claim 8, wherein the solid electrolyte layer has a thickness in the range of 500 nanometers to 1000 microns, 1 micron to 900 microns, 5 microns to 750 microns, 10 microns to 500 microns, 15 microns to 350 microns, 20 microns to 200 microns, or 25 microns to 100 microns.

28. The lithium solid state battery according to claim 8, wherein the lithium solid state battery comprises a solid electrolyte material in one or both of the positive electrode active material layer and the negative electrode active material layer, and the solid electrolyte material is present 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 of each layer comprising the solid electrolyte material.

29. A method for producing a sulfide solid electrolyte material comprising a glass ceramic comprising Li, T, X and A, wherein T is Sb, X is one or more halogens, pseudohalogens or N, and A is one or more of S or Se, the method comprising: ２ A, element T or a sulfide of T, and the compound LiX or Li ３ A method for producing a sulfide solid electrolyte material, comprising: mixing and milling a raw material composition containing N to obtain a sulfide glass; and heating the sulfide solid electrolyte material at a heat treatment temperature that is equal to or higher than the crystallization temperature of the sulfide solid electrolyte material to synthesize a glass ceramic having peaks at 2θ=14.5°±0.50°, 16.8°±0.50°, 23.9°±0.50°, 28.1°±0.50°, and 32.5°±0.50° in X-ray diffraction measurement using Cu-Kα(1,2)=1.54064 Å.

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