All-solid-state battery

Abstract

This all-solid-state battery comprises: a positive electrode that contains a positive electrode active material layer which includes a positive electrode active material, a positive electrode binder, and a solid electrolyte; a solid electrolyte layer; and a negative electrode that contains a negative electrode active material layer. The positive electrode active material contains single crystal particles (A) composed of a lithium-nickel-cobalt-manganese composite oxide, and the positive electrode binder contains a fluorine-based elastomer (B).

Description

All solid state battery

[0001] The present invention relates to an all-solid-state battery.

[0002] The all-solid-state battery includes, for example, a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order. Patent Document 1 describes a technique relating to the all-solid-state battery.

[0003] Patent Document 1 discloses a method for producing a positive electrode for a solid battery, the method comprising the steps of: mixing a positive electrode active material, a sulfide-based solid electrolyte, a binder, and a solvent to prepare a positive electrode slurry; applying the prepared positive electrode slurry; and drying the applied positive electrode slurry, the solvent being butyl butyrate; and the binder being a copolymer composed of vinylidene fluoride (VDF) monomer units and hexafluoropropylene (HFP) monomer units, wherein the molar ratio of the HFP monomer units to the total of the VDF monomer units and the HFP monomer units is 10% or more and 20% or less. This method aims to suppress deterioration of the sulfide-based solid electrolyte, ensure sufficient adhesive strength between the current collector and the positive electrode layer, and suppress a decrease in battery output due to rapid drying.

[0004] Japanese Patent Application Laid-Open No. 2016-25027

[0005] The present invention provides an all-solid-state battery with an improved performance balance between capacity and resistance value.

[0006] According to the present invention, the following all-solid-state battery is provided.

[0007] [1] An all-solid-state battery comprising: a positive electrode including a positive electrode active material layer including a positive electrode active material, a positive electrode binder, and a solid electrolyte; a solid electrolyte layer; and a negative electrode including a negative electrode active material layer, wherein the positive electrode active material includes single crystal particles (A) made of a lithium-nickel-cobalt-manganese composite oxide, and the positive electrode binder includes a fluorine-based elastomer (B). [2] The all-solid-state battery according to [1], wherein the lithium-nickel-cobalt-manganese composite oxide includes a composite oxide represented by the following formula (1): Li ａ Ni ｂ Co ｃ Mn ｄ Mｅ O ２ (1) (in the formula (1), M is one or more selected from the group consisting of Al, Mg, Na, Co, K, W, Cu, Fe, Ba, V, Cr, Ti, Zr, Zn, In, Ta, Y, In, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B, and Mo, and 0.5≦a≦1.5, 0.6≦b<1.0, 0<c<0.2, 0<d<0.2, 0≦e<1.0) [3] The all-solid-state battery according to [1] or [2], wherein a content of the single-crystal particles (A) in the positive electrode active material is 50 parts by mass or more and 100 parts by mass or less, when a content of the positive electrode active material in the positive electrode active material layer is 100 parts by mass. [4] An average particle diameter d of the positive electrode active material in a volume-based particle size distribution measured by a laser diffraction / scattering particle size distribution measurement method ５０The all-solid-state battery according to any one of [1] to [3], wherein the thickness of the fluorine-based elastomer (B) is 0.1 μm or more and 30 μm or less. [5] The all-solid-state battery according to any one of [1] to [4], wherein the fluorine-based elastomer (B) contains a structural unit derived from vinylidene fluoride (VdF). [6] The all-solid-state battery according to [5], wherein the fluorine-based elastomer (B) further contains one or more structural units selected from the group consisting of a structural unit derived from hexafluoropropylene (HFP), a structural unit derived from trifluoropropylene (TFP), a structural unit derived from tetrafluoroethylene (TFE), a structural unit derived from 2,3,3,3-tetrafluoropropylene, a structural unit derived from 1,3,3,3-tetrafluoropropylene, and a structural unit derived from perfluoroalkyl vinyl ether (PAVE). [7] The all-solid-state battery according to any one of [1] to [6], wherein the fluorine-based elastomer (B) comprises one or more selected from the group consisting of a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP) and a copolymer of vinylidene fluoride (VdF) and trifluoropropylene (TFP). [8] The all-solid-state battery according to any one of [1] to [7], wherein the fluorine-based elastomer (B) contains structural units derived from vinylidene fluoride (VdF) in an amount of 20 mol% or more. [9] The all-solid-state battery according to any one of [1] to [8], wherein the fluorine-based elastomer (B) has a mass average molecular weight (Mw) of 10,000 or more and 10,000,000 or less.

[10] The all-solid-state battery according to any one of [1] to [9], wherein the content of the positive electrode binder in the positive electrode active material layer is 0.5 parts by mass or more and 8.0 parts by mass or less, based on 100 parts by mass of the entire positive electrode active material layer.

[11] The all-solid-state battery according to any one of [1] to

[10] , wherein the content of the positive electrode active material in the positive electrode active material layer is 50.0 parts by mass or more and 90.0 parts by mass or less, based on 100 parts by mass of the entire positive electrode active material layer.

[12] The all-solid-state battery according to any one of [1] to

[11] , wherein the solid electrolyte in the positive electrode active material layer includes one or more solid electrolytes selected from the group consisting of a sulfide-based solid electrolyte, an oxide-based solid electrolyte, and a polymer-based solid electrolyte.

[13] The all-solid-state battery according to any one of [1] to

[12] , wherein the content of the solid electrolyte in the positive electrode active material layer is 5.0 parts by mass or more and 40.0 parts by mass or less, based on 100 parts by mass of the entire positive electrode active material layer.

[14] The all-solid-state battery according to any one of [1] to

[13] , wherein the positive electrode active material layer further contains a conductive additive.

[15] The all-solid-state battery according to

[14] , wherein the conductive additive contains one or more selected from the group consisting of carbon black, activated carbon, graphite, mesoporous carbon, fullerenes, carbon nanotubes, carbon nanofibers, and carbon brushes.

[16] The all-solid-state battery according to

[14] or

[15] , wherein the content of the conductive additive in the positive electrode active material layer is 0.1 parts by mass or more and 10.0 parts by mass or less, based on 100 parts by mass of the entire positive electrode active material layer.

[0008] According to the present invention, it is possible to provide an all-solid-state battery with an improved performance balance between capacity and resistance value.

[0009] FIG. 1 is a cross-sectional view showing an example of the structure of an all-solid-state battery according to an embodiment of the present invention.

[0010] The following describes an embodiment of the present invention. Note that the shapes, sizes, and layouts of the components in the drawings are merely schematic representations that allow the present invention to be understood, and are not to scale. Furthermore, unless otherwise specified, "to" in a numerical range indicates a range from above to below.

[0011] <All-Solid-State Battery> The all-solid-state battery of this embodiment includes a positive electrode including a positive electrode active material layer containing a positive electrode active material, a positive electrode binder, and a solid electrolyte, a solid electrolyte layer, and a negative electrode including a negative electrode active material layer, wherein the positive electrode active material includes single crystal particles (A) (hereinafter, may be abbreviated as "single crystal particles (A)") constituted by a lithium-nickel-cobalt-manganese composite oxide, and the positive electrode binder includes a fluorine-based elastomer (B).

[0012] As a result of investigations by the present inventors, it has become clear that by using a fluorine-based elastomer as a positive electrode binder, the performance balance between the capacity and resistance value of an all-solid-state battery can be improved even when single-crystal particles composed of a lithium-nickel-cobalt-manganese composite oxide are used as the positive electrode active material. In other words, according to this embodiment, an all-solid-state battery with an improved performance balance between the capacity and resistance value can be provided.

[0013] (Positive Electrode) The positive electrode of this embodiment includes a positive electrode active material layer. The positive electrode active material layer of this embodiment includes a positive electrode active material, a positive electrode binder, and a solid electrolyte.

[0014] The positive electrode active material of this embodiment includes single crystal particles (A) composed of a lithium-nickel-cobalt-manganese composite oxide. In this embodiment, single crystal particles are particles in which no grain boundaries are observed when observed under an electron microscope at 1000 to 5000 magnifications, and the particles are composed of a single crystal grain. Note that even when multiple single crystal particles are closely attached, this falls within the category of single crystal particles. On the other hand, in this embodiment, polycrystalline particles are particles in which multiple crystal grains with different crystal orientations and grain boundaries are observed within a solid when observed under an electron microscope at 1000 to 5000 magnifications.

[0015] The lithium-nickel-cobalt-manganese composite oxide of this embodiment preferably contains a composite oxide represented by the following formula (1):

[0016] Li ａ Ni ｂ Co ｃ Mn ｄ M ｅ O ２ (1) In the formula (1), M represents one or more elements selected from the group consisting of Al, Mg, Na, Co, K, W, Cu, Fe, Ba, V, Cr, Ti, Zr, Zn, In, Ta, Y, In, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B, and Mo, and 0.5≦a≦1.5, 0.6≦b<1.0, 0<c<0.2, 0<d<0.2, and 0≦e<1.0.

[0017] In the composite oxide of formula (1), 0.5≦a≦1.5, preferably 0.6≦a≦1.4, more preferably 0.7≦a≦1.3, even more preferably 0.8≦a≦1.2, even more preferably 0.9≦a≦1.1, and even more preferably a=1.0.

[0018] In addition, in the composite oxide of the formula (1), 0.6≦b<1.0 is satisfied, and from the viewpoint of further improving the capacity of the all-solid-state battery, 0.65≦b<1.0 is preferred, 0.7≦b<1.0 is more preferred, 0.75≦b<1.0 is even more preferred, and 0.8≦b≦0.95 is even more preferred.

[0019] In the composite oxide of the formula (1), 0<c<0.2, preferably 0.01≦c≦0.15, more preferably 0.02≦c≦0.15, and even more preferably 0.03≦c≦0.1.

[0020] In the composite oxide of the formula (1), 0<d<0.2, preferably 0.01≦d≦0.15, more preferably 0.02≦d≦0.15, and even more preferably 0.02≦d≦0.1.

[0021] In the composite oxide of the formula (1), 0≦e<1.0, preferably 0≦e≦0.5, more preferably 0≦e≦0.3, even more preferably 0≦e≦0.2, even more preferably 0≦e≦0.1, and even more preferably e=0.

[0022] The positive electrode active material of this embodiment may further contain a positive electrode active material other than the single crystal particles (A) composed of a lithium-nickel-cobalt-manganese composite oxide. The positive electrode active material other than the single crystal particles (A) is not particularly limited, and examples thereof include composite oxides of lithium and transition metals such as lithium-nickel composite oxide, lithium-cobalt composite oxide, lithium-manganese composite oxide, lithium-nickel-manganese composite oxide, lithium-nickel-cobalt composite oxide, lithium-nickel-aluminum composite oxide, lithium-nickel-cobalt-aluminum composite oxide, lithium-nickel-cobalt-manganese composite oxide other than the single crystal particles (A), lithium-nickel-manganese-aluminum composite oxide, and lithium-nickel-cobalt-manganese-aluminum composite oxide; TiS ２ , FeS, MoS ２ transition metal sulfides such as MnO, V ２ O ５ , V ６ O １３ , TiO ２ and olivine-type lithium phosphate, and from the viewpoint of improving working potential, capacity, durability, and energy density, preferably, the lithium-iron phosphate includes one or more elements selected from the group consisting of olivine-type lithium iron phosphate, lithium-nickel composite oxide, lithium-cobalt composite oxide, lithium-manganese composite oxide, lithium-nickel-manganese composite oxide, lithium-nickel-cobalt composite oxide, lithium-nickel-aluminum composite oxide, lithium-nickel-cobalt-aluminum composite oxide, lithium-nickel-manganese-cobalt composite oxide, lithium-nickel-manganese-aluminum composite oxide, and lithium-nickel-cobalt-manganese-aluminum composite oxide. Here, the olivine-type lithium phosphate includes, for example, at least one element selected from the group consisting of Mn, Cr, Co, Cu, Ni, V, Mo, Ti, Zn, Al, Ga, Mg, B, Nb, and Fe, as well as lithium, phosphorus, and oxygen.

[0023] When the content of the positive electrode active material in the positive electrode active material layer is taken as 100 parts by mass, from the viewpoint of further improving the performance balance between the capacity and the resistance value of the all-solid-state battery, the content of the single crystal particles (A) in the positive electrode active material of this embodiment is preferably 50 parts by mass or more and 100 parts by mass or less, more preferably 60 parts by mass or more and 100 parts by mass or less, even more preferably 70 parts by mass or more and 100 parts by mass or less, even more preferably 80 parts by mass or more and 100 parts by mass or less, even more preferably 90 parts by mass or more and 100 parts by mass or less, and even more preferably 95 parts by mass or more and 100 parts by mass or less.

[0024] The average particle diameter d of the positive electrode active material of this embodiment ５０ is preferably 0.1 μm or more and 30 μm or less, more preferably 0.3 μm or more and 20 μm or less, even more preferably 0.5 μm or more and 15 μm or less, and even more preferably 1.0 μm or more and 10.0 μm or less. ５０ means the particle size at 50% of the integrated value in the particle size distribution (volume basis) determined by the laser diffraction scattering method.

[0025] When the entire cathode active material layer is taken as 100 parts by mass, from the viewpoint of further improving the capacity of the all-solid-state battery, the content of the cathode active material in the cathode active material layer of the present embodiment is preferably 50.0 parts by mass or more and 90.0 parts by mass or less, more preferably 55.0 parts by mass or more and 90.0 parts by mass or less, even more preferably 60.0 parts by mass or more and 90.0 parts by mass or less, still more preferably 65.0 parts by mass or more and 90.0 parts by mass or less, still more preferably 70.0 parts by mass or more and 88.0 parts by mass or less, and still more preferably 75.0 parts by mass or more and 85.0 parts by mass or less.

[0026] The positive electrode binder of this embodiment contains a fluorine-based elastomer (B).

[0027] From the viewpoint of further improving the performance balance between the capacity and resistance value of the all-solid-state battery, the fluorine-based elastomer (B) preferably contains a constituent unit derived from vinylidene fluoride (VdF), and more preferably contains a constituent unit derived from vinylidene fluoride (VdF) and one or more constituent units selected from the group consisting of constituent units derived from hexafluoropropylene (HFP), constituent units derived from trifluoropropylene (TFP), constituent units derived from tetrafluoroethylene (TFE), constituent units derived from 2,3,3,3-tetrafluoropropylene, constituent units derived from 1,3,3,3-tetrafluoropropylene, and constituent units derived from perfluoroalkyl vinyl ether (PAVE). Furthermore, from the viewpoint of further improving the performance balance between the capacity and the resistance value of the all-solid-state battery, the fluorine-based elastomer (B) more preferably contains one or more selected from the group consisting of a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP) and a copolymer of vinylidene fluoride (VdF) and trifluoropropylene (TFP), and more preferably contains a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP).

[0028] The mass average molecular weight (Mw) of the fluorine-based elastomer (B) is preferably 10,000 or more and 10,000,000 or less, more preferably 30,000 or more and 5,000,000 or less, even more preferably 50,000 or more and 1,000,000 or less, even more preferably 80,000 or more and 800,000 or less, and even more preferably 100,000 or more and 500,000 or less.

[0029] The content of structural units derived from vinylidene fluoride (VdF) in the fluorine-based elastomer (B) is preferably 20 mol% or more, more preferably 20 mol% or more and 95 mol% or less, even more preferably 30 mol% or more and 90 mol% or less, even more preferably 40 mol% or more and 90 mol% or less, even more preferably 60 mol% or more and 85 mol% or less, and even more preferably 70 mol% or more and 85 mol% or less.

[0030] When the entire positive electrode active material layer is taken as 100 parts by mass, the content of the positive electrode binder in the positive electrode active material layer of the present embodiment is, from the viewpoint of further improving the performance balance between the capacity and the resistance value of the all-solid-state battery, preferably 0.5 parts by mass or more and 8.0 parts by mass or less, more preferably 0.8 parts by mass or more and 7.5 parts by mass or less, even more preferably 1.0 parts by mass or more and 7.0 parts by mass or less, and still more preferably 1.5 parts by mass or more and 6.5 parts by mass or less.

[0031] The solid electrolyte in the positive electrode active material layer of the present embodiment preferably includes one or more selected from the group consisting of a sulfide-based solid electrolyte, an oxide-based solid electrolyte, and a polymer-based solid electrolyte, and more preferably includes a sulfide-based solid electrolyte.

[0032] The oxide-based solid electrolyte is, for example, LiTi ２ (P.O. ４ ) ３ , LiZr ２ (P.O. ４ ) ３ , LiGe ２ (P.O. ４ ) ３ NASICON-type solid electrolyte materials such as (La ０．５＋ｘ Li ０．５－３ｘ ) TiO ３ Perovskite-type solid electrolyte materials such as Li ２ O-P ２ O ５ Material, Li ２ O-P ２ O ５ -Li ３ The material contains one or more selected from the group consisting of N materials and the like.

[0033] The sulfide-based solid electrolyte is, for example, Li ２ S-P ２ S ５ Material, Li ２ S-SiS ２ Material, Li ２ S-GeS ２ Material, Li ２ S-Al ２ S ３ Material, Li ２ S-SiS ２ -Li ３ P.O. ４Materials, Li ２ S-P ２ S ５ -GeS ２ Materials, Li ２ S-Li ２ O-P ２ S ５ -SiS ２ Materials, Li ２ S-GeS ２ -P ２ S ５ -SiS ２ Materials, Li ２ S-SnS ２ -P ２ S ５ -SiS ２ Materials, Li ２ S-P ２ S ５ -Li ３ N material, Li ２ S ２＋Ｘ -P ４ S ３ Materials, Li ２ S-P ２ S ５ -P ４ S ３ Materials, LiPO ４ -Li ２ S-SiS materials, Li ３ PS ４ 、Li ３ PO ４ -Li ２ S-Si ２ S material, Li ３ PO ４ -Li ２ S-SiS ２ Materials, LiI-Li ２ S-B ２ S ３ Materials, LiI-Li ２ S-SiS ２ Materials, LiI-Li ２ S-P ２ S ５ Materials, LiI-Li ２ S-P ２ O ５ Materials, LiI-Li ３ PO ４ -P ２ S ５ Li ２ S-P２ S ５ -LiCl material, Li ７－ｘ P.S. ６－ｘ Cl ｘ (where 0≦x≦2), Li ７－ｘ P.S. ６－ｘ Br ｘ (where 0≦x≦2), Li ７－ｘ P.S. ６－ｘ I ｘ (where 0≦x≦2), Li １０ GeP ２ S １２ , and Li ３．２５ Ge ０．２５ P ０．７５ S ４ More preferably, Li ７－ｘ P.S. ６－ｘ Cl ｘ (where 0≦x≦2), Li ７－ｘ P.S. ６－ｘ Br ｘ (where 0≦x≦2) and Li ７－ｘ P.S. ６－ｘ I ｘ (where 0≦x≦2), and more preferably Li ６ P.S. ５ Cl, Li ６ P.S. ５ Br and Li ６ P.S. ５ I, more preferably Li ６ P.S. ５ Contains Cl.

[0034] The polymer-based solid electrolyte material includes one or more selected from the group consisting of polyether-based electrolyte materials such as polyethylene oxide, polypropylene oxide, ethylene oxide-propylene copolymer, and dimethylsiloxane-ethylene oxide copolymer; gel polymer electrolyte materials such as polyacrylonitrile, polyvinylidene fluoride, and vinylidene fluoride-hexafluoropropylene polymer; and polymer solid electrolyte materials using hyperbranched polymers.

[0035] When the entire cathode active material layer is taken as 100 parts by mass, the content of the solid electrolyte in the cathode active material layer of the present embodiment is, from the viewpoint of further improving the performance balance between the capacity and the resistance value of the all-solid-state battery, preferably 5.0 parts by mass or more and 40.0 parts by mass or less, more preferably 8.0 parts by mass or more and 35.0 parts by mass or less, even more preferably 10.0 parts by mass or more and 33.0 parts by mass or less, even more preferably 12.0 parts by mass or more and 30.0 parts by mass or less, and still more preferably 14.0 parts by mass or more and 28.0 parts by mass or less.

[0036] The positive electrode active material layer of this embodiment preferably further contains a conductive additive, from the viewpoint of further reducing the resistance value of the all-solid-state battery. The conductive additive in the positive electrode active material layer of this embodiment preferably contains one or more selected from the group consisting of carbon black, activated carbon, graphite, mesoporous carbon, fullerenes, carbon nanotubes, carbon nanofibers, and carbon brushes, and more preferably contains carbon black, from the viewpoint of further reducing the resistance value of the all-solid-state battery.

[0037] When the entire positive electrode active material layer is taken as 100 parts by mass, the content of the conductive additive in the positive electrode active material layer of the present embodiment is, from the viewpoint of further improving the performance balance between the capacity and the resistance value of the all-solid-state battery, preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 0.3 parts by mass or more and 5.0 parts by mass or less, even more preferably 0.5 parts by mass or more and 4.0 parts by mass or less, even more preferably 0.8 parts by mass or more and 3.0 parts by mass or less, and still more preferably 1.0 parts by mass or more and 2.0 parts by mass or less.

[0038] The density of the positive electrode active material layer of this embodiment is preferably 1.0 g / cm ３ 5.0g / cm or more ３ or less, more preferably 2.0 g / cm ３ 4.0g / cm or more ３ The following is the result.

[0039] The thickness of the positive electrode active material layer is not particularly limited, but is, for example, preferably from 1 μm to 150 μm, more preferably from 5 μm to 100 μm, and even more preferably from 10 μm to 80 μm.

[0040] The positive electrode of this embodiment may further include a positive electrode current collector. The positive electrode current collector may include, for example, one or more selected from the group consisting of aluminum, stainless steel, nickel, titanium, and alloys thereof. The positive electrode current collector may be in the form of, for example, a foil, a flat plate, or a mesh. The thickness of the positive electrode current collector is, for example, 1 μm or more and 50 μm or less.

[0041] The positive electrode of this embodiment can be produced, for example, by dissolving or dispersing the components constituting the positive electrode active material layer in a solvent to produce a positive electrode slurry, applying the positive electrode slurry to at least one surface of a positive electrode current collector, drying, and rolling. Alternatively, the positive electrode of this embodiment can be produced, for example, by applying the positive electrode slurry to a support, drying it, peeling it from the support, and laminating the resulting film on the positive electrode current collector.

[0042] The negative electrode of the present embodiment includes a negative electrode active material layer. The negative electrode active material layer of the present embodiment includes, for example, a negative electrode active material and may further include one or more selected from the group consisting of a negative electrode binder, a solid electrolyte, and a conductive additive.

[0043] The negative electrode active material of this embodiment is not particularly limited, and examples thereof include carbon materials such as graphite, amorphous carbon, diamond-like carbon, fullerene, carbon nanotubes, and carbon nanohorns; lithium-based metal materials such as metallic lithium and lithium alloys; Si, SiO ２ , SiO ｘ (0<x≦2), Si-based materials such as Si-containing composite materials include one or more conductive polymers selected from the group consisting of polyacene, polyacetylene, polypyrrole, and the like, and more preferably include a lithium-based metal material.

[0044] The content of the negative electrode active material in the negative electrode active material layer of this embodiment is preferably 70 parts by mass or more and 100 parts by mass or less, more preferably 80 parts by mass or more and 100 parts by mass or less, and even more preferably 90 parts by mass or more and 100 parts by mass or less, when the total amount of the negative electrode active material layer is 100 parts by mass.

[0045] The negative electrode active material layer of this embodiment may contain one or more binder resins selected from the group consisting of rubber-based binders and acrylic-based binders. Such binder resins may be in the form of an emulsion. When water is used as the solvent, it is preferable to use an aqueous binder and a thickener such as CMC (carboxymethyl cellulose) in combination.

[0046] The content of the binder resin in the negative electrode active material layer of this embodiment may be, for example, 1 part by mass or more and 10 parts by mass or less, or 3 parts by mass or more and 6 parts by mass or less, when the total amount of the negative electrode active material layer is 100 parts by mass.

[0047] The solid electrolyte in the negative electrode active material layer of the present embodiment preferably includes one or more selected from the group consisting of a sulfide-based solid electrolyte, an oxide-based solid electrolyte, and a polymer-based solid electrolyte, and more preferably includes a sulfide-based solid electrolyte.

[0048] The oxide-based solid electrolyte is, for example, LiTi ２ (P.O. ４ ) ３ , LiZr ２ (P.O. ４ ) ３ , LiGe ２ (P.O. ４ ) ３ NASICON-type solid electrolyte materials such as (La ０．５＋ｘ Li ０．５－３ｘ ) TiO ３ Perovskite-type solid electrolyte materials such as Li ２ O-P ２ O ５ Material, Li ２ O-P ２ O ５ -Li ３ The material contains one or more selected from the group consisting of N materials and the like.

[0049] The sulfide-based solid electrolyte is, for example, Li ２ S-P ２ S ５ Material, Li ２ S-SiS ２ Material, Li ２ S-GeS ２ Material, Li ２ S-Al２ S ３ Materials, Li ２ S-SiS ２ -Li ３ PO ４ Materials, Li ２ S-P ２ S ５ -GeS ２ Materials, Li ２ S-Li ２ O-P ２ S ５ -SiS ２ Materials, Li ２ S-GeS ２ -P ２ S ５ -SiS ２ Materials, Li ２ S-SnS ２ -P ２ S ５ -SiS ２ Materials, Li ２ S-P ２ S ５ -Li ３ N material, Li ２ S ２＋Ｘ -P ４ S ３ Materials, Li ２ S-P ２ S ５ -P ４ S ３ Materials, LiPO ４ -Li ２ S-SiS materials, Li ３ PS ４ 、Li ３ PO ４ -Li ２ S-Si ２ S material, Li ３ PO ４ -Li ２ S-SiS ２ Materials, LiI-Li ２ S-B ２ S ３ Materials, LiI-Li ２ S-SiS ２ Materials, LiI-Li ２ S-P ２ S ５ Materials, LiI-Li ２ S-P ２ O５ Material, LiI-Li ３ P.O. ４ -P ２ S ５ Li ２ S-P ２ S ５ -LiCl material, Li ７－ｘ P.S. ６－ｘ Cl ｘ (where 0≦x≦2), Li ７－ｘ P.S. ６－ｘ Br ｘ (where 0≦x≦2), Li ７－ｘ P.S. ６－ｘ I ｘ (where 0≦x≦2), Li １０ GeP ２ S １２ , and Li ３．２５ Ge ０．２５ P ０．７５ S ４ More preferably, Li ７－ｘ P.S. ６－ｘ Cl ｘ (where 0≦x≦2), Li ７－ｘ P.S. ６－ｘ Br ｘ (where 0≦x≦2) and Li ７－ｘ P.S. ６－ｘ I ｘ (where 0≦x≦2), and more preferably Li ６ P.S. ５ Cl, Li ６ P.S. ５ Br and Li ６ P.S. ５ I, more preferably Li ６ P.S. ５ Contains Cl.

[0050] The polymer-based solid electrolyte material includes one or more selected from the group consisting of polyether-based electrolyte materials such as polyethylene oxide, polypropylene oxide, ethylene oxide-propylene copolymer, and dimethylsiloxane-ethylene oxide copolymer; gel polymer electrolyte materials such as polyacrylonitrile, polyvinylidene fluoride, and vinylidene fluoride-hexafluoropropylene polymer; and polymer solid electrolyte materials using hyperbranched polymers.

[0051] From the viewpoint of further reducing the resistance value of the all-solid-state battery, the conductive additive in the negative electrode active material layer of the present embodiment includes one or more selected from the group consisting of carbon black, activated carbon, graphite, mesoporous carbon, fullerenes, carbon nanotubes, carbon nanofibers, and carbon brushes, and more preferably includes carbon black.

[0052] The content of the conductive additive in the negative electrode active material layer of the present embodiment is preferably 0.05 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 5.0 parts by mass or less, from the viewpoint of further improving the performance balance between the capacity and the resistance value of the all-solid-state battery, when the entire negative electrode active material layer is taken as 100 parts by mass.

[0053] In the negative electrode active material layer, electrode additives generally used for forming electrodes, such as thickeners, dispersants, and stabilizers, can be used as appropriate.

[0054] The density of the negative electrode active material layer of this embodiment is preferably 0.5 g / cm ３ 3.0g / cm or more ３ or less, more preferably 1.2 g / cm ３ 2.0g / cm or more ３ The following is the result.

[0055] The thickness of the negative electrode active material layer of this embodiment is preferably 1 μm or more and 150 μm or less, more preferably 5 μm or more and 100 μm or less, and even more preferably 10 μm or more and 80 μm or less.

[0056] The negative electrode current collector includes, for example, one or more selected from the group consisting of copper, stainless steel, nickel, titanium, and alloys thereof. The negative electrode current collector may be in the form of, for example, a foil, a flat plate, or a mesh. The thickness of the negative electrode current collector is, for example, 1 μm or more and 50 μm or less.

[0057] (Solid Electrolyte Layer) The solid electrolyte layer of this embodiment includes a solid electrolyte.

[0058] The solid electrolyte in the solid electrolyte layer of the present embodiment preferably includes one or more selected from the group consisting of a sulfide-based solid electrolyte, an oxide-based solid electrolyte, and a polymer-based solid electrolyte, and more preferably includes a sulfide-based solid electrolyte.

[0059] The oxide-based solid electrolyte is, for example, LiTi ２ (P.O. ４ ) ３ , LiZr ２ (P.O. ４ ) ３ , LiGe ２ (P.O. ４ ) ３ NASICON-type solid electrolyte materials such as (La ０．５＋ｘ Li ０．５－３ｘ ) TiO ３ Perovskite-type solid electrolyte materials such as Li ２ O-P ２ O ５ Material, Li ２ O-P ２ O ５ -Li ３ The material contains one or more selected from the group consisting of N materials and the like.

[0060] The sulfide-based solid electrolyte is, for example, Li ２ S-P ２ S ５ Material, Li ２ S-SiS ２ Material, Li ２ S-GeS ２ Material, Li ２ S-Al ２ S ３ Material, Li ２ S-SiS ２ -Li ３ P.O. ４Materials, Li ２ S-P ２ S ５ -GeS ２ Materials, Li ２ S-Li ２ O-P ２ S ５ -SiS ２ Materials, Li ２ S-GeS ２ -P ２ S ５ -SiS ２ Materials, Li ２ S-SnS ２ -P ２ S ５ -SiS ２ Materials, Li ２ S-P ２ S ５ -Li ３ N material, Li ２ S ２＋Ｘ -P ４ S ３ Materials, Li ２ S-P ２ S ５ -P ４ S ３ Materials, LiPO ４ -Li ２ S-SiS materials, Li ３ PS ４ 、Li ３ PO ４ -Li ２ S-Si ２ S material, Li ３ PO ４ -Li ２ S-SiS ２ Materials, LiI-Li ２ S-B ２ S ３ Materials, LiI-Li ２ S-SiS ２ Materials, LiI-Li ２ S-P ２ S ５ Materials, LiI-Li ２ S-P ２ O ５ Materials, LiI-Li ３ PO ４ -P ２ S ５ Li ２ S-P２ S ５ -LiCl material, Li ７－ｘ P.S. ６－ｘ Cl ｘ (where 0≦x≦2), Li ７－ｘ P.S. ６－ｘ Br ｘ (where 0≦x≦2), Li ７－ｘ P.S. ６－ｘ I ｘ (where 0≦x≦2), Li １０ GeP ２ S １２ , and Li ３．２５ Ge ０．２５ P ０．７５ S ４ More preferably, Li ７－ｘ P.S. ６－ｘ Cl ｘ (where 0≦x≦2), Li ７－ｘ P.S. ６－ｘ Br ｘ (where 0≦x≦2) and Li ７－ｘ P.S. ６－ｘ I ｘ (where 0≦x≦2), and more preferably Li ６ P.S. ５ Cl, Li ６ P.S. ５ Br and Li ６ P.S. ５ I, more preferably Li ６ P.S. ５ Contains Cl.

[0061] The polymer-based solid electrolyte material includes one or more selected from the group consisting of polyether-based electrolyte materials such as polyethylene oxide, polypropylene oxide, ethylene oxide-propylene copolymer, and dimethylsiloxane-ethylene oxide copolymer; gel polymer electrolyte materials such as polyacrylonitrile, polyvinylidene fluoride, and vinylidene fluoride-hexafluoropropylene polymer; and polymer solid electrolyte materials using hyperbranched polymers.

[0062] The content of the solid electrolyte in the solid electrolyte layer of the present embodiment is preferably 80 parts by mass or more and 100 parts by mass or less, and more preferably 90 parts by mass or more and 100 parts by mass or less, when the total amount of the solid electrolyte layer is 100 parts by mass.

[0063] The thickness of the solid electrolyte layer of this embodiment is preferably 1 μm or more and 150 μm or less, more preferably 5 μm or more and 100 μm or less, and even more preferably 10 μm or more and 80 μm or less.

[0064] (Optional Configuration of All-Solid-State Battery) The all-solid-state battery of this embodiment may further include an exterior body. Examples of the exterior body include an aluminum laminate film, a strong aluminum can case, and a cylindrical aluminum exterior body.

[0065] The all-solid-state battery of this embodiment may further include a positive electrode terminal and a negative electrode terminal. Examples of the positive electrode terminal include a terminal made of aluminum or an aluminum alloy. Examples of the negative electrode terminal include a terminal made of copper, a copper alloy, or a nickel-plated copper or copper alloy.

[0066] (Method for manufacturing all-solid-state battery) The method for manufacturing an all-solid-state battery is not particularly limited, and known methods can be applied. First, the preparation of the negative electrode will be described. The negative electrode can be prepared by known methods. Regardless of the method used to prepare the negative electrode, it is preferably prepared in a low-moisture environment under dew point control in order to suppress adsorption of moisture into the solid electrolyte.

[0067] When using a negative electrode having a negative electrode active material layer formed on a negative electrode current collector, a slurry prepared by dispersing a negative electrode active material, a solid electrolyte, and a binder in a dehydrated organic solvent is applied to a portion or all of the surface of a negative electrode current collector such as copper foil, followed by drying to obtain a negative electrode precursor sheet. The obtained negative electrode precursor sheet can be compressed using a press molding method such as a roll press, a uniaxial press, a rubber press, or an isostatic pressing (CIP, WIP) to obtain a negative electrode sheet. The organic solvent preferably includes one or more solvents selected from the group consisting of acetonitrile, xylene, dimethoxyethane, dimethyl carbonate, triethylamine, and other tertiary amine solvents, heptane, hexane, tetrahydrofuran, toluene, N-methylpyrrolidone, as well as ether solvents, thiol solvents, and butyl butyrate, all of which are preferably dehydrated.

[0068] The negative electrode can be obtained by disposing a metallic lithium layer (negative electrode active material layer) such as lithium foil on part or all of a negative electrode current collector such as stainless steel foil, and then adhering them together by rolling or the like.

[0069] Next, a solid electrolyte layer is formed on the surface of the negative electrode. When a sulfide-based solid electrolyte is used, it is preferably formed in a low-moisture environment under dew point control to prevent moisture adsorption.

[0070] The solid electrolyte layer can be formed on the surface of the negative electrode by, for example, applying a slurry of a solid electrolyte dispersed in an organic solvent to the surface of a negative electrode active material layer formed on a negative electrode current collector, followed by drying. The organic solvent may include, for example, one or more selected from the group consisting of acetonitrile, xylene, dimethoxyethane, dimethyl carbonate, triethylamine, and other tertiary amine solvents, heptane, hexane, tetrahydrofuran, toluene, N-methylpyrrolidone, as well as ether solvents, thiol solvents, and butyl butyrate, and it is preferable that all of them have been dehydrated.

[0071] Next, the stacked negative electrode and solid electrolyte layer are compressed using a press molding method such as a vacuum laminator, roll press, uniaxial press, rubber press, or isostatic pressing (CIP, WIP), to obtain a negative electrode-solid electrolyte layer laminate. When the solid electrolyte layer is stacked together with a substrate layer such as a polyester sheet and pressurized, the substrate layer is peeled off from the solid electrolyte layer. In this case, it is also preferable to use a substrate layer whose surface is coated with a release agent such as silicone, so that the substrate layer can be easily peeled off from the solid electrolyte layer.

[0072] Next, the fabrication of the positive electrode will be described. Regardless of the method used to fabricate the positive electrode, it is preferable to fabricate the positive electrode in a low moisture environment under dew point control in order to suppress moisture adsorption.

[0073] The positive electrode of this embodiment can be produced, for example, by dissolving or dispersing the components constituting the positive electrode active material layer in a solvent to produce a positive electrode slurry, applying the positive electrode slurry to at least one surface of a positive electrode current collector, drying, and rolling. Alternatively, the positive electrode of this embodiment can be produced, for example, by applying the positive electrode slurry to a support, drying it, peeling it from the support, and laminating the resulting film on the positive electrode current collector. The solvent preferably includes one or more solvents selected from the group consisting of tertiary amine solvents such as acetonitrile, xylene, dimethoxyethane, dimethyl carbonate, and triethylamine, heptane, hexane, tetrahydrofuran, toluene, N-methylpyrrolidone, ether solvents, thiol solvents, and butyl butyrate, and each of these solvents is preferably dehydrated.

[0074] A positive electrode is laminated on the negative electrode-solid electrolyte layer laminate to obtain an electrode laminate precursor. When a sulfide-based solid electrolyte is used as the solid electrolyte, the ionic conductivity of the solid electrolyte may decrease due to exposure to moisture. Therefore, after obtaining the electrode laminate precursor, it is preferable to compress the electrode laminate precursor using a vacuum laminator, roll press, uniaxial press, rubber press, isostatic pressing (CIP, WIP), or the like to obtain an electrode laminate.

[0075] The resulting electrode laminate is preferably quickly sealed in an exterior housing. One end of a rectangular metal plate serving as a negative electrode terminal is attached to the negative electrode current collector, and one end of a rectangular metal terminal serving as a positive electrode terminal is attached to the positive electrode current collector, and then the electrode laminate is housed in an aluminum exterior housing. A resin layer such as polyolefin is preferably formed on at least the surface of the inner surface of the exterior housing facing the electrode laminate. The resin layer is heated to melt the resin and solidify it again, and the electrode laminate is sealed in the aluminum exterior housing. At this time, the other end of the positive electrode terminal and the other end of the negative electrode terminal are positioned so as to extend outside the exterior housing. A layer of resin of the same type or a different type from the resin used in the resin layer on the interior surface of the exterior housing can be provided in the areas where the positive electrode terminal and the negative electrode terminal contact the resin layer on the interior surface of the exterior housing.

[0076] The present invention is not limited to the above-described embodiment, and the present invention includes modifications and improvements within the scope of achieving the object of the present invention.

[0077] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0078] Example 1 An all-solid-state battery was fabricated by the following method.

[0079] [I] Preparation of a negative electrode-solid electrolyte layer laminate (1) A foil (manufactured by Honjo Metals Co., Ltd.) was prepared as a negative electrode, in which a metallic lithium layer of 20 μm was formed on the surface of a 10 μm thick stainless steel negative electrode current collector. (2) A solution of Li, a solid electrolyte, in xylene was added. ６ P.S. ５A slurry containing Cl dispersed therein was applied to the surface of a polyester film primarily composed of polyester, followed by drying to form a solid electrolyte layer on the polyester film. Next, the solid electrolyte layer was laminated on the negative electrode together with the polyester film so that the resulting solid electrolyte layer contacted the surface of the metallic lithium layer of the negative electrode, yielding a negative electrode-solid electrolyte layer laminate. (3) The negative electrode-solid electrolyte layer laminate obtained in (2) above was vacuum-sealed using a vacuum laminator and held at room temperature (25°C) under a pressure of 300 MPa for 1 minute. The negative electrode-solid electrolyte layer laminate was then removed from the vacuum laminator and compressed by an isostatic pressing method (CIP method) to obtain a negative electrode-solid electrolyte layer laminate with a porosity of 7%. The size of the negative electrode-solid electrolyte layer laminate was 50 mm x 70 mm. (4) The polyester film was peeled off from the solid electrolyte layer to obtain a negative electrode-solid electrolyte layer laminate.

[0080] [II] Lamination of Positive Electrode and Negative Electrolyte Layer Laminates (1) A slurry was obtained by dispersing a positive electrode active material, a solid electrolyte, a conductive additive, and a binder in butyl butyrate at the ratios (mass%) shown in Table 1. The obtained slurry was then applied to a 10 μm-thick aluminum foil and dried to form a positive electrode active material layer, thereby obtaining a positive electrode. (2) The positive electrode obtained in (1) above was cut to 45 mm × 65 mm, and the positive electrode and the negative electrode-solid electrolyte layer laminate were laminated such that the positive electrode active material layer was in contact with the solid electrolyte layer of the negative electrode-solid electrolyte layer laminate prepared in [I] above, thereby obtaining an electrode laminate precursor. The number of layers of the positive electrode and the negative electrode-solid electrolyte layer laminate was one each.

[0081] [III] Preparation of Electrode Laminate The electrode laminate precursor obtained in [II] above was vacuum-sealed using a vacuum laminator and held at room temperature (25° C.) under a pressure of 300 MPa for 1 minute. The electrode laminate precursor was then removed from the vacuum laminator and compressed by a CIP method to obtain an electrode laminate having a porosity of 5% in the positive electrode active material layer.

[0082] [IV] Encapsulation in an exterior body The electrode laminate obtained in [III] above was enclosed in an aluminum exterior body (manufactured by Dai Nippon Printing Co., Ltd.) by the method described in the embodiment, and an all-solid-state battery in which the positive electrode terminal and the negative electrode terminal were extended to the outside of the exterior body was obtained.

[0083] <Evaluation of Battery Characteristics> The all-solid-state battery obtained by the above method was evaluated by charging and discharging. The charging and discharging conditions were as follows. First, the all-solid-state battery was charged at a constant current up to 4.25 V at a charge rate of 0.05 C, then switched to constant voltage charging, and charging was cut off at 0.005 C. Next, it was discharged at a constant current down to 2.5 V at a discharge rate of 0.05 C. The initial discharge capacity was calculated from the above charge and discharge, and the obtained initial discharge capacity was defined as the initial capacity (mAh). In addition, a tester was applied to the positive and negative electrode terminals of the all-solid-state battery after charging, and the DC resistance between the positive and negative electrodes was measured at room temperature (25°C). The obtained results are shown in Table 1.

[0084] (Examples 2 to 8, Comparative Examples 1 to 3) All-solid-state batteries were fabricated and their battery characteristics were evaluated in the same manner as in Example 1, except that the types and ratios (mass%) of the positive electrode active material, solid electrolyte, conductive additive, and binder in the positive electrode active material were changed to the types and ratios shown in Table 1. The obtained results are shown in Table 1.

[0085]

[0086] The resistance value ratio in Table 1 means a resistance value when the DC resistance value of the all-solid-state battery after full charge in Example 1 is set to 1.00. The SC / PC blending ratio means the mass ratio of single crystal particles (SC) to polycrystalline particles (PC).

[0087] The details of each component in Table 1 are as follows: <Positive electrode active material> LiNi ０．８ Co ０．１ Mn ０．１ O ２ Single crystal particles (average particle diameter d ５０ : 4 μm, manufactured by MSE Supplies) LiNi ０．８ Co ０．１ Mn ０．１ O ２ Polycrystalline particles (average particle diameter d５０ : 4 μm, manufactured by MSE Supplies) LiNi ０．９ Co ０．０５ Mn ０．０５ O ２ Single crystal particles (average particle diameter d ５０ : 4 μm, manufactured by MSE Supplies)

[0088] <Solid electrolyte> Li ６ P.S. ５ Cl (average particle diameter d ５０ : 1 μm, manufactured by NEI) <Binder> VdF+HFP (copolymer of vinylidene fluoride and hexafluoropropylene, molecular weight: approximately 300,000, polymer composition: VdF is 75 mol % and HFP is 25 mol % of the entire polymer) PAA (polyacrylic acid, molecular weight: 450,000, manufactured by Sigma-Aldrich Japan) SBR (styrene-butadiene rubber, manufactured by Nippon Zeon Co., Ltd.) <Conductive additive> CB (carbon black, manufactured by Imerys)

[0089] This application claims priority based on Japanese Patent Application No. 2024-010301, filed January 26, 2024, the disclosure of which is incorporated herein by reference in its entirety.

[0090] 1 Positive electrode active material layer 2 Negative electrode active material layer 3 Positive electrode current collector 4 Negative electrode current collector 5 Solid electrolyte layer 6 Exterior body 7 Exterior body 8 Negative electrode terminal 9 Positive electrode terminal 10 All-solid-state battery

Claims

1. A solid-state battery comprising a positive electrode including a positive electrode active material layer containing a positive electrode active material, a binder for the positive electrode, and a solid electrolyte, a solid electrolyte layer, and a negative electrode including a negative electrode active material layer, wherein the positive electrode active material includes single crystal particles (A) composed of a lithium-nickel-cobalt-manganese composite oxide, and the binder for the positive electrode includes a fluorine-based elastomer (B).

2. The all-solid-state battery according to claim 1, wherein the lithium-nickel-cobalt-manganese composite oxide contains a composite oxide represented by the following formula (1). Li ａ Ni ｂ Co ｃ Mn ｄ M ｅ O ２ (1) (In the formula (1), M is one or more selected from the group consisting of Al, Mg, Na, Co, K, W, Cu, Fe, Ba, V, Cr, Ti, Zr, Zn, In, Ta, Y, In, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B and Mo, 0.5 ≦ a ≦ 1.5, 0.6 ≦ b < 1.0, 0 < c < 0.2, 0 < d < 0.2, 0 ≦ e < 1.0) 3. The solid-state battery according to claim 1 or 2, wherein the content of the single crystal particles (A) in the positive electrode active material is 50 parts by mass or more and 100 parts by mass or less when the content of the positive electrode active material in the positive electrode active material layer is 100 parts by mass.

4. The average particle diameter d of the positive electrode active material in the volume-based particle size distribution by the laser diffraction scattering method for particle size distribution measurement ５０ is 0.1 μm or more and 30 μm or less, and the all-solid-state battery according to any one of claims 1 to 3.

5. The solid-state battery according to any one of claims 1 to 4, wherein the fluorine-based elastomer (B) includes a structural unit derived from vinylidene fluoride (VdF).

6. The solid-state battery according to claim 5, wherein the fluorine-based elastomer (B) further includes one or more structural units selected from the group consisting of a structural unit derived from hexafluoropropylene (HFP), a structural unit derived from trifluoropropylene (TFP), a structural unit derived from tetrafluoroethylene (TFE), a structural unit derived from 2,3,3,3-tetrafluoropropylene, a structural unit derived from 1,3,3,3-tetrafluoropropylene, and a structural unit derived from perfluoroalkyl vinyl ether (PAVE).

7. The solid-state battery according to any one of claims 1 to 6, wherein the fluorine-based elastomer (B) includes one or more selected from the group consisting of a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP), and a copolymer of vinylidene fluoride (VdF) and trifluoropropylene (TFP).

8. The solid-state battery according to any one of claims 1 to 7, wherein the content of the structural unit derived from vinylidene fluoride (VdF) in the fluorine-based elastomer (B) is 20 mol% or more.

9. The solid-state battery according to any one of claims 1 to 8, wherein the mass average molecular weight (Mw) of the fluorine-based elastomer (B) is 10,000 or more and 10,000,000 or less.

10. The solid-state battery according to any one of claims 1 to 9, wherein the content of the binder for the positive electrode in the positive electrode active material layer is 0.5 parts by mass or more and 8.0 parts by mass or less when the entire positive electrode active material layer is 100 parts by mass.

11. The content of the positive electrode active material in the positive electrode active material layer is 50.0 parts by mass or more and 90.0 parts by mass or less when the entire positive electrode active material layer is 100 parts by mass. The all-solid-state battery according to any one of claims 1 to 10.

12. The solid electrolyte in the positive electrode active material layer contains one or more selected from the group consisting of sulfide-based solid electrolytes, oxide-based solid electrolytes, and polymer-based solid electrolytes. The all-solid-state battery according to any one of claims 1 to 11.

13. The content of the solid electrolyte in the positive electrode active material layer is 5.0 parts by mass or more and 40.0 parts by mass or less when the entire positive electrode active material layer is 100 parts by mass. The all-solid-state battery according to any one of claims 1 to 12.

14. The positive electrode active material layer further contains a conductive auxiliary agent. The all-solid-state battery according to any one of claims 1 to 13.

15. The conductive auxiliary agent contains one or more selected from the group consisting of carbon black, activated carbon, graphite, mesoporous carbon, fullerenes, carbon nanotubes, carbon nanofibers, and carbon brushes. The all-solid-state battery according to claim 14.

16. The content of the conductive auxiliary agent in the positive electrode active material layer is 0.1 parts by mass or more and 10.0 parts by mass or less when the entire positive electrode active material layer is 100 parts by mass. The all-solid-state battery according to claim 14 or 15.

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