# US 2019/0356019 A1 · Solid electrolyte-containing sheet, solid electrolyte composition, all-solid state secondary battery, and methods for manufacturing solid electrolyte-containing sheet and all-solid state secondary battery > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0356019 A1 - Document ID: US20190356019A1 - Status: Published application - Kind: A1 - Application number: 16/531,234 - Filed: 2019-08-05 - Published: 2019-11-21 - Earliest claimed: 2017-03-08 - Assignees: FUJIFILM Corporation - Applicants: FUJIFILM Corporation - Inventors: Tomonori MIMURA; Hiroaki MOCHIZUKI; Masaomi MAKINO - Web page: https://patentgrep.com/patent/US20190356019A1 ## CPC - H01M 10/052: Li-accumulators - H01M 10/0562: Solid materials - H01B 1/06: mainly consisting of other non-metallic substances - H01B 1/10: sulfides - H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries - H01M 10/4235: {Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence)} - H01M 10/0585: of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators - H01M 2300/0071: Oxides - H01M 2300/0094: in the form of layered products, e.g. coatings - Y02E 60/10: Energy storage using batteries - Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K}) - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract Provided are a solid electrolyte-containing sheet containing an inorganic solid electrolyte (A) having a conductivity of an ion of a metal belonging to Group I or II of the periodic table and an inorganic compound (C) having a film on a surface, in which the film contains a solid electrolyte (B) and has a conductivity of an ion of a metal belonging to Group I or II of the periodic table, a solid electrolyte composition, an all-solid state secondary battery, and methods for manufacturing a solid electrolyte-containing sheet and an all-solid state secondary battery. ## Claims ### Claim 1 A solid electrolyte-containing sheet comprising: an inorganic solid electrolyte (A) having a conductivity of an ion of a metal belonging to Group I or II of the periodic table; and an inorganic compound (C) having a film on a surface, wherein the film contains a solid electrolyte (B) and has a conductivity of an ion of a metal belonging to Group I or II of the periodic table, and wherein the inorganic solid electrolyte (A) and the solid electrolyte (B) are compounds represented by Formula (1), La1Mb1Pc1Sd1Ae1 Formula (1) in the formula, L represents an element selected from Li, Na, and K, M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge, A represents an element selected from I, Br, Cl, and F, al to el represent compositional ratios of the respective elements, and a1:b1:c1:d1:e1 satisfies 1 to 12:0 to 5:1:2 to 12:0 to 10. ### Claim 2 (depends on 1) The solid electrolyte-containing sheet according to claim 1, wherein the inorganic compound (C) is a compound represented by any of Formulae (c-1) to (c-13), LixaLayaTiO3 Formula (c-1) in the formula, xa and ya represent compositional ratios, xa satisfies 0.3≤xa≤0.7, and ya satisfies 0.3≤ya≤0.7, LixbLaybZrzbMbbmbOnb Formula (c-2) in the formula, Mbb represents Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, Sn, or a combination of two or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn, xb, yb, zb, mb, and nb represent compositional ratios, xb satisfies 5≤x≤xb≤10, yb satisfies 1≤yb≤4, zb satisfies 1≤zb≤4, mb satisfies 0≤mb≤2, and nb satisfies 5≤nb≤20. Li3.5Zn0.25GeO4 Formula (c-3) LiTi2P3O12 Formula (c-4) Li1+xh+yh(Al, Ga),xh(Ti, Ge)2−xhSiyhP3−yhO12 Formula (c-5) in the formula, xh satisfies 0≤xh≤1, and yh satisfies 0≤yh≤1. Li3PO4 Formula (c-6) LiPON Formula (c-7) LiPOD1 Formula (c-8) in the formula, D1 represents Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, Au, or a combination of two or more elements selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au, LiA1ON Formula (c-9) in the formula, A1 represents Si, B, Ge, Al, C, Ga, or a combination of two or more elements selected from Si, B, Ge, Al, C, and Ga, LixcBycMcczcOnc Formula (c-10) in the formula, Mcc represents C, S, Al, Si, Ga, Ge, In, Sn, or a combination of two or more elements selected from C, S, Al, Si, Ga, Ge, In, and Sn, xc, yc, zc, and nc represent compositional ratios, xc satisfies 0≤xc≤5, yc satisfies 0 a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, a hydroxy group, a sulfanyl group, an isocyanate group, an oxetanyl group, an epoxy group, a dicarboxylic anhydride group, a carboxylic halide group, a silyl group, and an amino group. ### Claim 4 (depends on 1) The solid electrolyte-containing sheet according to claim 1, wherein the inorganic compound (C) has at least one functional group of functional groups belonging to the following group of functional groups (II), a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, a hydroxy group, an epoxy group, and an amino group. ### Claim 5 (depends on 1) The solid electrolyte-containing sheet according to claim 1, wherein the inorganic compound (C) is surface-treated. ### Claim 6 (depends on 1) The solid electrolyte-containing sheet according to claim 1, further comprising: a binder (D). ### Claim 7 (depends on 6) The solid electrolyte-containing sheet according to claim 6, wherein the binder (D) is an acrylic resin and/or a polyurethane resin. ### Claim 8 (depends on 1) The solid electrolyte-containing sheet according to claim 1, further comprising: an active material (E). ### Claim 9 A solid electrolyte composition comprising: an inorganic solid electrolyte (A) having a conductivity of an ion of a metal belonging to Group I or II of the periodic table; an inorganic compound (C) having a film on a surface; and a dispersion medium (F), wherein the film contains a solid electrolyte (B) and has a conductivity of an ion of a metal belonging to Group I or II of the periodic table, and wherein the inorganic solid electrolyte (A) and the solid electrolyte (B) are compounds represented by Formula (I), La1Mb1Pc1Sd1Ae1 Formula (1) in the formula, L represents an element selected from Li, Na, and K, M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge, A represents an element selected from I, Br, Cl, and F, al to el represent compositional ratios of the respective elements, and a1:b:1:c1:d1:e1 satisfies 1 to 12:0 to 5:1:2 to 12:0 to 10. ### Claim 10 (depends on 9) The solid electrolyte composition according to claim 9, wherein the inorganic compound (C) has at least one functional group of functional groups belonging to the following group of functional groups (I), a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, a hydroxy group, a sulfanyl group, an isocyanate group, an oxetanyl group, an epoxy group, a dicarboxylic anhydride group, a carboxylic halide group, a silyl group, and an amino group. ### Claim 11 (depends on 9) The solid electrolyte composition according to claim 9, further comprising: a binder (D). ### Claim 12 (depends on 1) An all-solid state secondary battery comprising: a positive electrode active material layer; a negative electrode active material layer; and a solid electrolyte layer, wherein at least any of the positive electrode active material layer, the negative electrode active material layer, or the solid electrolyte layer is the solid electrolyte-containing sheet according to claim 1. ### Claim 13 (depends on 1) A method for manufacturing the solid electrolyte-containing sheet according to claim 1, the method comprising: a step of applying a solid electrolyte composition onto a base material; and a step of drying the applied solid electrolyte composition, wherein the solid electrolyte composition comprises: an inorganic solid electrolyte (A) having a conductivity of an ion of a metal belonging to Group I or II of the periodic table; an inorganic compound (C) having a film on a surface; and a dispersion medium (F), in which the film contains a solid electrolyte (B) and has a conductivity of an ion of a metal belonging to Group I or II of the periodic table, and in which the inorganic solid electrolyte (A) and the solid electrolyte (B) are compounds represented by Formula (1), La1Mb1Pc1Sd1Ae1 Formula (1) in the formula, L represents an element selected from Li, Na, and K, M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge, A represents an element selected from I, Br, Cl, and F, al to el represent compositional ratios of the respective elements, and a1:b1:c1:d1:e1 satisfies 1 to 12:0 to 5:1:2 to 12:0 to 10. ### Claim 14 (depends on 13) A method for manufacturing an all-solid state secondary battery, wherein an all-solid state secondary battery is manufactured through the manufacturing method according to claim 13.