Negative electrode for all solid-state battery and all solid-state battery including same

Abstract

The present invention relates to a negative electrode for an all solid-state battery and an all solid-state battery including same, the negative electrode comprising a negative electrode-coating layer comprising carbon-based material, metal, and a binder containing polyacrylic acid and styrene-butadiene rubber in 5:4-5:2 weight ratio.

Description

Anode for an all-solid-state battery and an all-solid-state battery comprising the same

[0001] It's about all-solid-state batteries.

[0002] Recently, rapid developments have been made in electronic devices that use batteries, such as cell phones, laptop computers, and electric vehicles.

[0003] Development of all-solid-state batteries using lithium metal as the cathode is underway. All-solid-state batteries are composed entirely of solid materials, specifically those using solid electrolytes. Because the electrolyte is solid, all-solid-state batteries are structurally robust, reducing the risk of fire or explosion due to leakage from external impacts. Furthermore, they can be shaped into a variety of battery shapes.

[0004] One embodiment provides a cathode for an all-solid-state battery that exhibits low resistance, thus exhibiting excellent coulombic efficiency and excellent lifespan characteristics.

[0005] Another embodiment provides an all-solid-state battery comprising the above negative electrode.

[0006] One embodiment provides an anode for an all-solid-state battery, comprising a binder comprising polyacrylic acid and styrene-butadiene rubber in a weight ratio of 5:4 to 5:2; a carbon-based material; and a cathode coating layer comprising a metal.

[0007] Another embodiment provides an all-solid-state battery comprising the cathode, the anode, and a solid electrolyte positioned between the cathode and the anode.

[0008] An all-solid-state battery negative electrode according to one embodiment includes an aqueous binder and thus can exhibit low resistance, excellent initial efficiency, and excellent cycle life characteristics.

[0009] Figure 1 is a schematic drawing of an all-solid-state battery negative electrode according to one embodiment.

[0010] Figure 2 is a cross-sectional view schematically showing an all-solid-state battery according to one embodiment.

[0011] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention. The present invention is defined solely by the scope of the claims set forth below.

[0012] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

[0013] “Combination of these” means a mixture, laminate, composite, copolymer, alloy, blend, reaction product, etc. of the components.

[0014] It should be understood that terms such as "include," "comprise," or "have" are intended to specify the presence of a feature, number, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0015] Throughout this specification, when it is said that a part "includes" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0016] In addition, the terms "about", "substantially", etc. used throughout this specification are used in the sense of numerical values ​​or near numerical values ​​when manufacturing and material tolerances inherent to the meanings stated are presented, and are used to prevent unscrupulous infringers from unfairly exploiting disclosures that mention exact or absolute values ​​to aid understanding of this specification.

[0017] Throughout this specification, the description of “A and / or B” means “A or B or both.”

[0018] Unless otherwise specified herein, when a part such as a layer, film, region, plate, etc. is said to be “on” another part, this includes not only cases where it is “directly on” the other part, but also cases where there is another part in between.

[0019] In the present invention, "particle size" or "particle diameter" may be an average particle diameter. In addition, the average particle diameter may be defined as the average particle diameter (D50) based on 50% of the cumulative volume in a particle diameter distribution curve. The particle diameter may be measured by a method widely known to those skilled in the art, for example, by measuring with a particle size analyzer, or by measuring with a transmission electron microscope, a scanning electron microscope, or a field emission scanning electron microscope (FE-SEM). Alternatively, the average particle diameter (D50) may be obtained by measuring with a measuring device that utilizes dynamic light-scattering, performing data analysis to count the number of particles for each particle size range, and calculating from this. Alternatively, the average particle diameter (D50) may be measured using a laser diffraction method. When measuring by laser diffraction, more specifically, after the particles to be measured are dispersed in a dispersion medium, they are introduced into a commercially available laser diffraction particle size measuring device (e.g., Microtrac MT 3000) and irradiated with ultrasonic waves of approximately 28 kHz at an output of 60 W, and the average particle diameter (D50) based on 50% of the particle diameter distribution in the measuring device can be calculated.

[0020] "Thickness" may be measured, for example, from photographs taken with an optical microscope such as a scanning electron microscope.

[0021] An anode for an all-solid-state battery according to one embodiment includes a binder comprising polyacrylic acid and styrene-butadiene rubber in a weight ratio of 5:4 to 5:2; a carbon-based material; and a cathode coating layer comprising a metal.

[0022] Since water-based binders such as polyacrylic acid and styrene-butadiene rubber are used as binders in the cathode coating layer, it can be environmentally friendly.

[0023] Additionally, resistance can be reduced by using polyacrylic acid, and improved adhesion can be provided by using styrene-butadiene rubber.

[0024] The effect of using polyacrylic acid and styrene-butadiene rubber together can be obtained when the polyacrylic acid and styrene-butadiene rubber are included in a weight ratio of 5:4 to 5:2.

[0025] When polyacrylic acid is used, resistance is reduced, but adhesive strength may also be reduced. However, this reduction in adhesive strength can be prevented by using styrene-butadiene rubber together, particularly by using polyacrylic acid and styrene-butadiene rubber in a weight ratio of 5:4 to 5:2. In this way, when polyacrylic acid and styrene-butadiene rubber are used in a weight ratio of 5:4 to 5:2, the adhesive strength is maintained at the same level as when styrene-butadiene rubber is used alone, while the resistance can be effectively reduced. As a result, the capacity and life characteristics can be improved.

[0026] If the weight ratio of polyacrylic acid and styrene-butadiene rubber is outside the above range, for example, if the weight ratio of polyacrylic acid / styrene-butadiene rubber is less than 5 / 4, the resistance may decrease, and if it is greater than 5 / 2, the adhesive strength may decrease, which is not suitable.

[0027] In one embodiment, the content of the binder may be 6 wt% to 10 wt%, or 6.5 wt% to 8.5 wt%, based on 100 wt% of the total weight of the cathode coating layer. When the content of the binder is within the above range, the composition has excellent phase stability and excellent dispersibility of the carbon-based material and the metal when preparing the cathode coating layer composition, which is suitable.

[0028] In the above cathode coating layer, the carbon-based material and the metal may be mixed and present, or the metal may be present supported on the carbon-based material.

[0029] The carbonaceous material may be, for example, crystalline carbon, amorphous carbon, or a combination thereof, or may be amorphous carbon. The crystalline carbon may be, for example, natural graphite, artificial graphite, mesophase carbon microbeads, carbon nanotubes, graphene, or a combination thereof. The crystalline carbon may be in the form of amorphous, plate-like, flake-like, spherical, or fibrous particles. The amorphous carbon may be, for example, carbon black, acetylene black, Denka black, Ketjen black, furnace black, activated carbon, graphene, or a combination thereof. An example of the carbon black is Super P (Timcal). The amorphous carbon is not limited thereto, and any material classified as amorphous carbon in the relevant field may be used.

[0030] In one embodiment, the carbonaceous material may be a single particle, or may be an assembly having a secondary particle form in which primary particles are assembled. When the carbonaceous material is a single particle, the size of the carbonaceous material may be a nano-size with an average particle diameter of 100 nm or less, for example, 10 nm to 100 nm.

[0031] Additionally, when the carbon-based material is an assembly, the particle size of the primary particles may be 20 nm to 100 nm, and the particle size of the secondary particles may be 1 μm to 20 μm.

[0032] In one embodiment, the particle size of the primary particles may be 20 nm to 100 nm, 20 nm to 90 nm, 20 nm to 80 nm, or 30 nm to 70 nm.

[0033] In one embodiment, the particle size of the secondary particles may be 1 μm to 20 μm, 2 μm to 15 μm, or 3 μm to 10 μm.

[0034] The shape of the primary particles may be spherical, elliptical, plate-shaped, or a combination thereof, and in one embodiment, the shape of the primary particles may be spherical, elliptical, or a combination thereof.

[0035] The above metal may be Ag, Au, Sn, Zn, Al, Mg, Ge, Cu, In, Ni, Bi, Pt, Pd or a combination thereof, and may be Ag. Since the above cathode coating layer includes such a metal, it may exhibit improved electrical conductivity.

[0036] The metal may be a nanoparticle, and the size of the metal nanoparticle may be, for example, an average size of 5 nm to 800 nm, 5 nm to 700 nm, 5 nm to 500 nm, or 5 nm to 300 nm, but is not limited thereto, and any nanometer-sized particle may be appropriately used. When the metal nanoparticle having such a nanosize is used, the battery characteristics (e.g., life characteristics) of the all-solid-state battery can be improved. When the metal particle size increases to the micrometer level, the uniformity of the metal particles in the negative electrode coating layer decreases, so that the current density in a specific region increases and the cycle life characteristics may deteriorate, which is not appropriate.

[0037] In one embodiment, the content of the metal may be 14 wt% to 35 wt%, 18 wt% to 25 wt%, or 20 wt% to 24 wt% with respect to 100 wt% of the total weight of the cathode coating layer.

[0038] Additionally, the carbon-based material may be 55 wt% to 80 wt%, 60 wt% to 75 wt%, or 65 wt% to 70 wt% with respect to 100 wt% of the entire cathode coating layer.

[0039] In one embodiment, the cathode coating layer may further include a solid electrolyte. The solid electrolyte may be an inorganic solid electrolyte such as a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a halide-based solid electrolyte, or a solid polymer electrolyte.

[0040] In one embodiment, the sulfide-based solid electrolyte is Li2S-P2S5, Li2S-P2S5-LiX (X is a halogen element, for example, I or Cl), Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (m and n are integers greater than or equal to 0 and less than or equal to 12, respectively, and Z is one of Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p and q are integers greater than or equal to 0 and less than or equal to 12, respectively; M is one of P, Si, Ge, B, Al, Ga In), Li a M b P c S d A e (a, b, c, d and e are each integers greater than or equal to 0 and less than or equal to 12, M is Ge, Sn, Si or a combination thereof, and A is one of F, Cl, Br, or I). The sulfide-based solid electrolyte may be, for example, Li 7-x PS 6-x F x (0≤x≤2), Li 7-x PS6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2) or Li 7-x PS 6-x I x (0≤x≤2) can be. Also, specifically, Li3PS4, Li7P3S 11 , Li7PS6, Li6PS5Cl, Li6PS5Cl, Li6PS5I, Li6PS5Br, Li 5.8 PS 4.8 Cl 1.2 , Li 6.2 PS 5.2 Br 0.8 It could be the back.

[0041] In one embodiment, the sulfide-based solid electrolyte may be an argyrodite-type sulfide-based solid electrolyte. The argyrodite-type sulfide-based solid electrolyte may be, for example, Li a M b P c S d A e (a, b, c, d, and e are all 0 or greater and 12 or less, M is Ge, Sn, Si, or a combination thereof, and A is one of F, Cl, Br, or I).

[0042] As specific examples, Li3PS4, Li7P3S 11 , Li7PS6, Li6PS5Cl, Li6PS5Br, Li 5.8 PS 4.8 Cl 1.2 , Li 6.2 PS 5.2 Br 0.8 , Li6PS5I, Li 5.75 PS 4.75 Cl 1.25 , (Li 5.69 Cu 0.06 )PS 4.75 Cl 1.25 , (Li 5.72 Cu 0.03 )PS 4.75 Cl 1.25 , (Li5.69 Cu 0.06 )P(S 4.70 (SO4) 0.05 )Cl 1.25 , (Li 5.69 Cu 0.06 )P(S 4.60 (SO4) 0.15 )Cl 1.25 , (Li 5.72 Cu 0.03 )P(S 4.725 (SO4) 0.025 )Cl 1.25 , (Li 5.72 Na 0.03 )P(S 4.725 (SO4) 0.025 )Cl 1.25 , Li 5.75 P(S 4.725 (SO4) 0.025 )Cl 1.25 , or combinations thereof, but are not limited thereto.

[0043] The sulfide-based solid electrolyte may be amorphous, crystalline, or a mixture thereof. For example, the sulfide-based solid electrolyte may be obtained by mixing Li2S and P2S5 in a molar ratio of 50:50 to 90:10, or in a molar ratio of 50:50 to 80:20. Within the above mixing ratio range, a sulfide-based solid electrolyte having excellent ionic conductivity can be produced. Here, the ionic conductivity can be further improved by further including other components such as SiS2, GeS2, and B2S3.

[0044] Methods for mixing sulfur-containing raw materials for manufacturing sulfide-based solid electrolytes include mechanical milling and solution methods. Mechanical milling involves placing the starting raw materials in a reactor and vigorously stirring them with a ball mill, thereby finely agitating the starting raw materials and mixing them. Using the solution method, the starting raw materials are mixed in a solvent to obtain a solid electrolyte as a precipitate. Furthermore, heat treatment after mixing can solidify the crystals of the solid electrolyte and improve ionic conductivity. For example, a sulfide-based solid electrolyte can be manufactured by mixing sulfur-containing raw materials and heat-treating them twice or more, in which case a sulfide-based solid electrolyte with high ionic conductivity and robustness can be manufactured.

[0045] Of course, a commercially available solid electrolyte can be used as the sulfide-based solid electrolyte.

[0046] The above oxide-based solid electrolyte is, for example, Li 1+x Ti 2-x Al(PO4)3(LTAP)(0≤x≤4), Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (0 <x<2, 0≤y<3), BaTiO3, Pb(Zr,Ti)O3(PZT), Pb 1-x La x Zr 1-y Ti y O3(PLZT)(0≤x<1, 0≤y<1), Pb(Mg3Nb 2 / 3 )O3-PbTiO3(PMN-PT), HfO2, SrTiO3, SnO2, CeO2, Na2O, MgO, NiO, CaO, BaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, SiO2, lithium phosphate (Li3PO4), lithium titanium phosphate (Li x Ti y (PO4)3, 0 <x<2, 0<y<3), Li 1+x+y (Al, Ga) x (Ti, Ge) 2-xSi y P 3-y O 12 (0≤x≤1, 0≤y≤1), lithium lanthanum titanate (Li x La y TiO3, 0 <x<2, 0<y<3), Li2O, LiAlO2, Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2계 세라믹스, 가넷(Garnet)계 세라믹스 Li 3+x La3M2O 12 (M= Te, Nb, or Zr, x is an integer from 1 to 10), or a mixture thereof.

[0047] The above solid polymer electrolytes include, for example, polyethylene oxide, poly(diallyldimethylammonium)trifluoromethanesulfonyl imide (poly(diallyldimethylammonium)TFSI), Cu3N, Li3N, LiPON, Li3PO4.Li2S.SiS2, Li2S·GeS2·Ga2S3, Li2O·11Al2O3, Na2O·11Al2O3, (Na,Li) 1+x Ti 2-x Al x (PO4)3(0.1≤x≤0.9), Li 1+x Hf 2-x Al x (PO4)3(0.1≤x≤0.9), Na3Zr2Si2PO 12 , Li3Zr2Si2PO 12 , Na5ZrP3O 12 , Na5TiP3O 12 , Na3Fe2P3O 12 , Na4NbP3O 12 , Na-Silicates, Li 0.3 La 0.5 TiO3, Na5MSi4O 12 (M is a rare earth element such as Nd, Gd, Dy) Li5ZrP3O 12 , Li5TiP3O 12 , Li3Fe2P3O 12 , Li4NbP3O 12 , Li 1+x (M,Al,Ga) x (Ge1-y Ti y ) 2-x (PO4)3(0≤x≤0.8, 0≤y≤1.0, M is Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), Li 1+x+y Q x Ti 2-x Si y P 3-y O 12 (0 <x≤0.4, 0<y≤0.6, Q 는 Al 또는 Ga), Li6BaLa2Ta2O 12 , Li7La3Zr2O 12 , Li5La3Nb2O 12 , Li5La3M2O 12 (M is Nb, Ta) and Li 7+x A x La 3-x Zr2O 12 (0 <x<3, A는 Zn) 중에서 선택된 하나 이상을 포함할 수 있다.

[0048] The above halide-based solid electrolyte may include a Li element, an M element (M is a metal other than Li), and an X element (X is a halogen). As X, for example, F, Cl, Br, and I may be mentioned. In particular, in the halide-based solid electrolyte, at least one of Br and Cl is suitable as X. In addition, as the M, for example, a metal element such as Sc, Y, B, Al, Ga, or In may be mentioned.

[0049] The composition of the above halide-based solid electrolyte is not particularly limited, but Li 6-3a M a Br b Cl c(In the formula, M is a metal other than Li, and 0 <a<2, 0≤b≤6, 0≤c≤6, b+c=6)로 표현될 수 있다. 이때, 상기 a는 0.75 이상일 수 있고, 1 이상일 수 있고, a는, 1.5 이하일 수 있다. 상기 b는 1 이상일 수 있고, 2 이상일 수 있다. 또한, 상기 c는, 3 이상일 수 있고, 4 이상일 수도 있다. 상기 할라이드계 고체 전해질의 구체적인 예로는 Li3YBr6, Li3YCl6또는 Li3YBr2Cl4를 들 수 있다.

[0050] The above-described cathode coating layer may further include additives such as fillers, dispersants, and ionic conductive agents. In addition, known materials generally used in all-solid-state batteries may be used as fillers, dispersants, and ionic conductive agents that can be included in the cathode coating layer.

[0051] The thickness of the cathode coating layer may be, for example, 1 µm to 500 µm, 1 µm to 200 µm, 1 µm to 100 µm, or 1 µm to 50 µm, but is not limited thereto.

[0052] According to one embodiment, the cathode may further include a current collector supporting the cathode coating layer.

[0053] The current collector may be, for example, indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li) or an alloy thereof, and may be in the form of a foil or sheet. The thickness of the negative electrode current collector may be 1 μm to 20 μm, 5 μm to 15 μm, or 7 μm to 10 μm.

[0054] The current collector may be formed of the metal as a substrate and may further include a thin film formed on the substrate. The thin film may include an element capable of forming an alloy with lithium, and may be, for example, gold, silver, zinc, tin, indium, silicon, aluminum, bismuth, or a combination thereof, but is not limited thereto, and any element capable of forming an alloy with lithium in the art may be used. When the current collector further includes a thin film, when the lithium-containing layer is formed by precipitation during charging, a more planarized lithium-containing layer may be formed, thereby further improving the cycle life of the all-solid-state battery.

[0055] The thickness of the above thin film may be 1 nm to 800 nm, 10 nm to 700 nm, 50 nm to 600 nm, or 100 nm to 500 nm. When the thin film thickness is within the above range, the cycle life characteristics can be further improved.

[0056] In one embodiment, the negative electrode coating layer refers to a layer that helps lithium ions released from the positive electrode active material during charging and discharging of an all-solid-state battery to move toward the negative electrode and be deposited on the surface of the current collector. That is, a lithium-containing layer, for example, a lithium deposition layer, is formed between the current collector and the negative electrode coating layer due to the deposition of lithium ions, and the lithium deposition layer functions as the negative electrode active material. Such a negative electrode is generally referred to as a deposition-type negative electrode.

[0057] The metal and carbon-based materials included in the above-described negative electrode coating layer do not function as negative electrode active materials that directly participate in charge-discharge reactions. This precipitation-type negative electrode refers to a negative electrode that does not contain negative electrode active materials when assembling a battery, but in which the lithium-containing layer functions as a negative electrode active material.

[0058] According to one embodiment, the negative electrode may further include a lithium-containing layer formed during initial charging after battery manufacturing, between the current collector and the negative electrode coating layer. The thickness of the lithium-containing layer may be 1 µm to 1000 µm, 1 µm to 500 µm, 1 µm to 200 µm, 1 µm to 150 µm, 1 µm to 100 µm, or 1 µm to 50 µm. When the thickness of the lithium-containing layer is within the above range, the lithium storage function may be appropriately performed, and there may be an advantage of further improving the lifespan.

[0059] The lithium-containing layer can be formed when lithium ions are released from the positive electrode active material during charging after the battery is manufactured, pass through the solid electrolyte, and move toward the negative electrode, resulting in lithium being precipitated and deposited on the negative electrode current collector.

[0060] The above charging process may be a chemical reaction process performed once to three times at 0.05C to 1C at about 25°C to 50°C. When lithium is precipitated and deposited to form a lithium-containing layer, the lithium contained in the lithium-containing layer is ionized and moves toward the positive electrode during discharge, so that the lithium can be used as an anode active material.

[0061] In one embodiment, since the lithium-containing layer is positioned between the current collector and the negative electrode coating layer, the negative electrode coating layer can serve as a protective layer for the lithium-containing layer, thereby inhibiting the precipitation and growth of lithium dendrites. This can suppress short-circuiting and capacity degradation of the all-solid-state battery, and consequently improve the cycle life of the all-solid-state battery.

[0062] All-solid-state battery

[0063] An all-solid-state battery according to one embodiment includes the cathode, the anode, and a solid electrolyte layer positioned between the cathode and the anode.

[0064] Solid electrolyte layer

[0065] In one embodiment, the solid electrolyte layer may include a solid electrolyte. It may be an inorganic solid electrolyte such as a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a halide-based solid electrolyte, or a solid polymer electrolyte.

[0066] In one embodiment, the solid electrolyte may be a sulfide-based solid electrolyte. Such sulfide-based solid electrolytes are suitable because they have superior ionic conductivity compared to other solid electrolytes, such as oxide-based solid electrolytes, and can exhibit superior life characteristics over a wider operating range.

[0067] The above sulfide-based solid electrolyte, oxide-based solid electrolyte, halide-based solid electrolyte, and solid polymer electrolyte are as described above. In addition, the solid electrolyte included in the solid electrolyte layer may be the same as or different from the solid electrolyte included in the cathode coating layer.

[0068] The above solid electrolyte may be in the form of particles. At this time, the average particle diameter (D50) of the solid electrolyte may be 5.0 ㎛ or less, for example, 0.1 ㎛ to 5.0 ㎛, 0.5 ㎛ to 5.0 ㎛, 0.5 ㎛ to 4.0 ㎛, 0.5 ㎛ to 3.0 ㎛, 0.5 ㎛ to 2.0 ㎛, or 0.5 ㎛ to 1.0 ㎛.

[0069] The above solid electrolyte layer may further include a binder. At this time, the binder may be styrene butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, an acrylate polymer, or a combination thereof, but is not limited thereto, and any binder used in the relevant technical field may be used. The acrylate polymer may be butyl acrylate, polyacrylate, polymethacrylate, or a combination thereof.

[0070] The binder content in the solid electrolyte layer can be appropriately controlled and does not need to be limited.

[0071] The above solid electrolyte layer can be formed by adding a solid electrolyte to a binder solution, coating the same on a base film, and drying the same. The solvent of the binder solution may be isobutyryl isobutyrate, xylene, toluene, benzene, hexane, or a combination thereof. Since the solid electrolyte layer formation process is widely known in the art, a detailed description thereof will be omitted herein.

[0072] The thickness of the solid electrolyte layer may be, for example, 10 μm to 150 μm.

[0073] The solid electrolyte layer may further include an alkali metal salt, and / or an ionic liquid, and / or a conductive polymer.

[0074] The above alkali metal salt may be, for example, a lithium salt. The content of the lithium salt in the solid electrolyte layer may be 1 M or more, for example, 1 M to 4 M. In this case, the lithium salt may improve ion conductivity by enhancing the lithium ion mobility of the solid electrolyte layer.

[0075] The above lithium salts include, for example, LiSCN, LiN(CN)2, Li(CF3SO2)3C, LiC4F9SO3, LiN(SO2CF2CF3)2, LiCl, LiF, LiBr, LiI, LiB(C2O4)2, LiBF4, LiBF3(C2F5), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LIODFB), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(trifluoro methanesulfonyl)imide (LiTFSI, LiN(SO2CF3)2), lithium bis(fluorosulfonyl)imide (LiFSI, It may include LiN(SO2F)2), LiCF3SO3, LiAsF6, LiSbF6, LiClO4 or mixtures thereof.

[0076] In addition, the lithium salt may be an imide-based one, and for example, the imide-based lithium salt may include lithium bis(trifluoro methanesulfonyl)imide (LiTFSI, LiN(SO2CF3)2), lithium bis(fluorosulfonyl)imide (LiFSI, LiN(SO2F)2). The lithium salt may maintain or improve ionic conductivity by appropriately maintaining chemical reactivity with an ionic liquid.

[0077] The above ionic liquid has a melting point below room temperature and is a salt or room-temperature molten salt that is liquid at room temperature and consists only of ions.

[0078] The above ionic liquid comprises a) one or more cations selected from ammonium, pyrrolidinium, pyridinium, pyrimidinium, imidazolium, piperidinium, pyrazolium, oxazolium, pyridazinium, phosphonium, sulfonium, triazolium, and mixtures thereof, and b) BF4. - , PF6 - , AsF6 - , SbF6 - , AlCl4 - , HSO4 - , ClO4 - , CH3SO3 - , CF3CO2 - , Cl - , Br - , I - , BF4 - , SO4 - , CF3SO3 - , (FSO2)2N - , (C2F5SO2)2N - , (C2F5SO2)(CF3SO2)N - , and (CF3SO2)2N - It may be a compound containing one or more anions selected from among.

[0079] The ionic liquid may be at least one selected from the group consisting of, for example, N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidinium bis(3-trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide.

[0080] In the above solid electrolyte layer, the weight ratio of the solid electrolyte and the ionic liquid may be 0.1:99.9 to 90:10, for example, 10:90 to 90:10, 20:80 to 90:10, 30:70 to 90:10, 40:60 to 90:10, or 50:50 to 90:10. A solid electrolyte layer satisfying the above range can maintain or improve ionic conductivity by improving the electrochemical contact area with the electrode. Accordingly, the energy density, discharge capacity, rate characteristics, etc. of the all-solid-state secondary battery can be improved.

[0081] Bipolar

[0082] According to one embodiment, a positive electrode of an all-solid-state battery includes a positive electrode current collector and a positive electrode active material layer positioned on one surface of the positive electrode current collector.

[0083] The above-described positive electrode active material layer may include a positive electrode active material. The positive electrode active material may be a positive electrode active material capable of reversibly absorbing and releasing lithium ions. For example, the positive electrode active material may use at least one of a composite oxide of lithium and a metal selected from cobalt, manganese, nickel, and combinations thereof. A specific example of the positive electrode active material is Li. a A 1-b B 1 b D 1 2(0.90≤a≤1.8, 0≤b≤0.5); Li a E 1-b B 1 b O 2-c D 1 c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5); Li a E 2-b B 1 b O 4-c D 1 c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤05); Li a Ni 1-b-c Co b B1 c D 1 α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α≤2); Li a Ni 1-b-c Co b B 1 c O 2-α F 1 α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni 1-b-c Co b B 1 c O 2-α F 1 2(0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni 1-b-c Mr b B 1 c D 1 α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α≤2); Li a Ni 1-b-c Mr b B 1 c O 2-α F 1 α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni 1-b-c Mr b B 1 c O 2-α F 1 2(0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni b HAVE BEEN c G d O2(0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1); Li a Ni b Co c L 1 d G eO2(0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0≤e≤0.1); Li a NiG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a CoG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a MnG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn2G b O4(0.90≤a≤1.8, 0.001≤b≤0.1); QO2; QS2; LiQS2; V2O5; LiV2O5; LiI 1 O2; LiNiVO4; Li (3-f) J2(PO4)3(0≤f≤2); Li (3-f) Fe2(PO4)3(0≤f≤2); or LiFePO4.

[0084] In the above chemical formula, A is Ni, Co, Mn, or a combination thereof; B 1 is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements or a combination thereof; D 1 is O, F, S, P, or a combination thereof; E is Co, Mn, or a combination thereof; F 1 is F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; Q is Ti, Mo, Mn, or a combination thereof; I 1 is Cr, V, Fe, Sc, Y, or a combination thereof; J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof; L 1 is Mn, Al or a combination thereof.

[0085] According to one implementation example, LiNi is used as the positive electrode active material. x Co y Al z O2(NCA), LiNi x Coy Mn z O2(NCM)(but, 0 <x<1, 0<y<1, 0<z<1, x+y+z=1) 등의 삼성분계 리튬 전이 금속 산화물을 들 수 있다.

[0086] Of course, it is also possible to use a compound having a coating layer on the surface of the compound, or it is also possible to use a mixture of the compound and a compound having a coating layer. The coating layer may include at least one coating element compound selected from the group consisting of an oxide of the coating element, a hydroxide of the coating element, an oxyhydroxide of the coating element, an oxycarbonate of the coating element, and a hydroxycarbonate of the coating element. The compounds forming these coating layers may be amorphous or crystalline. The coating elements included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof. The coating layer forming process may use any coating method as long as it can coat the compound with these elements in a method that does not adversely affect the properties of the positive electrode active material (for example, spray coating, dipping, etc.), and since this is well understood by those working in the relevant field, a detailed description thereof will be omitted.

[0087] In addition, as the above coating layer, any known coating layer for the positive electrode active material of an all-solid-state battery can be applied. For example, it can be a buffer layer that plays a role in lowering the interfacial resistance between the positive electrode active material and the solid electrolyte. For example, the buffer layer can include a lithium-metal-oxide, wherein the metal can be one or more elements selected from the group consisting of Al, B, Ca, Ce, Cr, Fe, Mg, Mo, Nb, Si, Sn, Sr, Ta, V, W, and Zr. Specific examples of the buffer layer include Li2O-ZrO2 (LZO), LiNbO2, etc.

[0088] Furthermore, when the cathode active material is a ternary compound containing nickel, cobalt, and manganese, or nickel, cobalt, and aluminum, the capacity density of the all-solid-state battery can be further improved and metal dissolution from the cathode active material can be further reduced in a charged state. Consequently, the all-solid-state battery can exhibit improved long-term reliability and cycle performance in a charged state.

[0089] The average particle size of the positive electrode active material may be 1 μm to 25 μm, for example, 3 μm to 25 μm, 1 μm to 20 μm, 1 μm to 18 μm, 3 μm to 15 μm, or 5 μm to 15 μm. For example, the positive electrode active material may include small particles having an average particle size (D50) of 1 μm to 9 μm and large particles having an average particle size (D50) of 10 μm to 25 μm. A positive electrode active material having such a particle size range can be harmoniously mixed with other components within a positive electrode active material layer and can realize high capacity and high energy density.

[0090] The above-mentioned positive electrode active material may be in the form of a secondary particle formed by agglomeration of a plurality of primary particles, or may be in the form of a single crystal. In addition, the above-mentioned positive electrode active material may be in the form of a spherical or nearly spherical shape, or may be polyhedral or irregular.

[0091] In addition, the content of the positive electrode active material in the positive electrode active material layer is not particularly limited, and may be within a range applicable to the positive electrode layer of a conventional all-solid-state secondary battery. For example, with respect to the total 100 wt% of the positive electrode active material layer, the positive electrode active material may be included in an amount of 55 wt% to 99.5 wt%, for example, 65 wt% to 95 wt%, or 75 wt% to 91 wt%.

[0092] The above positive electrode active material layer may further include a binder and / or a conductive material.

[0093] The above binder may include, but is not limited to, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polyethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc.

[0094] The above binder may be included in an amount of 0.1 wt% to 5 wt%, or 0.1 wt% to 3 wt%, based on 100 wt% of the total positive electrode active material layer. Within the above content range, the binder can sufficiently exhibit adhesive ability without deteriorating battery performance.

[0095] The conductive material is used to provide conductivity to the electrode, and any material that does not cause chemical changes and is electronically conductive can be used in the battery. Examples of the conductive material include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanofiber, and carbon nanotubes; metal-based materials containing copper, nickel, aluminum, silver, etc. in the form of metal powder or metal fiber; conductive polymers such as polyphenylene derivatives; or conductive materials including mixtures thereof.

[0096] The conductive material may be included in an amount of 0.1 wt% to 5 wt%, or 0.1 wt% to 3 wt%, based on 100 wt% of the total weight of the positive electrode active material layer. Within the above content range, the conductive material can improve electrical conductivity without degrading battery performance.

[0097] The above-described positive electrode active material layer may additionally include a solid electrolyte. The solid electrolyte included in the positive electrode active material layer may be an inorganic solid electrolyte such as a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a halide-based solid electrolyte, or a solid polymer electrolyte. The solid electrolyte is as described in the above-described solid electrolyte, and may be the same as or different from the solid electrolyte included in the solid electrolyte.

[0098] With respect to the total weight of the positive electrode active material layer, the solid electrolyte may be included in an amount of 0.1 wt% to 35 wt%, for example, 1 wt% to 35 wt%, 5 wt% to 30 wt%, 8 wt% to 25 wt%, or 10 wt% to 20 wt%. In addition, with respect to the total weight of the positive electrode active material and the solid electrolyte in the positive electrode active material layer, 65 wt% to 99 wt% of the positive electrode active material and 1 wt% to 35 wt% of the solid electrolyte may be included, for example, 80 wt% to 90 wt% of the positive electrode active material and 10 wt% to 20 wt% of the solid electrolyte may be included. When the solid electrolyte is included in the positive electrode in such an amount, the efficiency and life characteristics of the all-solid-state battery can be improved without reducing the capacity. The above solid electrolyte may be included in an amount of 0.1 to 10 wt% to 30 wt% based on 100 wt% of the total positive electrode active material layer.

[0099] Elastic layer

[0100] An all-solid-state battery according to one embodiment may further include an elastic layer for buffering thickness changes that occur during charging and discharging. The elastic layer may be positioned between the negative electrode and the case.

[0101] The above elastic layer may be a material having an elastic recovery rate of 50% or more and an insulating function, and specifically may be silicone rubber, acrylic rubber, fluorine rubber, nylon, synthetic rubber, or a combination thereof. The above cushioning material may be in the form of a polymer sheet.

[0102] <Method for manufacturing an all-solid-state battery>

[0103] An all-solid-state battery according to one embodiment can be manufactured by a step of preparing a laminate by positioning a cathode, an anode, and a solid electrolyte layer between the cathode and the anode, and pressing the laminate.

[0104] The pressurizing process can be performed at a temperature ranging from 25°C to 90°C. In addition, the pressurizing process can be performed by pressurizing at a pressure of 550 MPa or less, for example, 500 MPa or less, for example, 1 MPa to 500 MPa. The pressurizing time can vary depending on the temperature and pressure, and can be, for example, less than 30 minutes. The pressurizing process can be, for example, isostatic pressing, roll pressing, plate pressing, or warm isostatic pressing.

[0105] The above-mentioned all-solid-state secondary battery may be a unit cell having a structure of positive electrode / solid electrolyte layer / negative electrode, a bi-cell having a structure of positive electrode / solid electrolyte layer / negative electrode / solid electrolyte layer / positive electrode, or a laminated battery in which the structure of the unit cell is repeated.

[0106] The shape of the above-mentioned all-solid-state secondary battery is not particularly limited, and may be, for example, coin-shaped, button-shaped, sheet-shaped, stacked, cylindrical, flat, etc. In addition, the above-mentioned all-solid-state secondary battery can be applied to large-scale batteries used in electric vehicles, etc. For example, the above-mentioned all-solid-state secondary battery can be used in hybrid vehicles such as plug-in hybrid electric vehicles (PHEVs). In addition, it can be used in fields requiring a large amount of power storage, and for example, it can be used in electric bicycles or power tools, etc. In addition, the above-mentioned all-solid-state secondary battery can be used in various fields such as portable electronic devices.

[0107] Fig. 1 is a cross-sectional view of an all-solid-state battery according to an embodiment. Referring to Fig. 1, the all-solid-state battery (100) may have a structure in which an electrode assembly in which a negative electrode (400) including a negative electrode collector (401) and a negative electrode coating layer (405), a solid electrolyte layer (300), and a positive electrode (200) including a positive electrode active material layer (203) and a positive electrode collector (201) are laminated is housed in a case such as a pouch. The all-solid-state battery (100) may further include an elastic layer (500) on the outer side of at least one of the positive electrode (200) and the negative electrode (400).

[0108] Additionally, when the all-solid-state battery is charged, lithium ions may be released from the positive electrode active material and deposited on the negative electrode current collector (401), thereby forming a lithium-containing layer (lithium deposition layer).

[0109] Although one electrode assembly including a cathode (400), a solid electrolyte layer (300), and a cathode (200) is illustrated in FIG. 1, an all-solid-state battery may be manufactured by stacking two or more electrode assemblies. For example, 2 to 100, 3 to 50, 4 to 20, etc. may be stacked.

[0110] Fig. 2 schematically illustrates an all-solid-state battery according to another embodiment. The all-solid-state battery (100) illustrated in Fig. 2 includes a positive electrode (200) including a positive electrode current collector (201) and a positive electrode active material layer (203), a negative electrode (400) including a negative electrode current collector (401), a negative electrode coating layer (403), and a solid electrolyte (300) positioned between the positive electrode (200) and the negative electrode (400), and includes a battery case (500) in which these are housed, and further includes a lithium precipitation layer (405') between the negative electrode current collector (401) and the negative electrode coating layer (403).

[0111] Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are merely examples of the present invention, and the present invention is not limited to the following examples.

[0112] (Example 1)

[0113] 1) Cathode manufacturing

[0114] A binder solution was prepared by adding a binder containing polyacrylic acid and styrene-butadiene rubber mixed in a weight ratio of 5:4 to an N-methyl pyrrolidone solvent.

[0115] Carbon black having a primary particle size (D50) of approximately 30 nm and silver (Ag) having an average particle size (D50) of approximately 60 nm were added to the above binder solution and mixed to prepare a cathode coating layer composition. At this time, the binder, carbon black, and silver were used in a weight ratio of 9:75:25.

[0116] The above negative electrode coating layer composition was applied to a nickel foil current collector using a bar coater and vacuum dried to manufacture a negative electrode.

[0117] LiNi 0.8 Co 0.15 Mn 0.05A cathode composition was prepared by mixing 85 wt% of O2 cathode active material, 13.5 wt% of lithium argyrodite-type solid electrolyte Li6PS5Cl, 1.0 wt% of polyvinylidene fluoride binder, and 0.5 wt% of carbon nanotube conductive material in an N-methyl pyrrolidone solvent.

[0118] The manufactured positive electrode composition was coated on an aluminum positive electrode current collector using a bar coater, dried, and rolled to manufacture a positive electrode.

[0119] (3) Manufacturing of solid electrolyte layer

[0120] An isobutyl isobutylate binder solution (solid content: 50 wt%) containing butyl acrylate, an acrylate polymer, was added to an argyrodite-type solid electrolyte Li6PS5Cl and mixed. At this time, the mixing ratio of the solid electrolyte and the binder was set to a weight ratio of 98.7:1.3.

[0121] The above mixing process was performed using a sinky mixer. 2 mm zirconia balls were added to the resulting mixture and stirred again using the sinky mixer to produce a slurry. The slurry was cast onto a polytetrafluoroethylene film and dried at room temperature to produce a solid electrolyte layer with a thickness of 100 μm.

[0122] (4) All-solid-state battery manufacturing

[0123] After sequentially stacking the above-mentioned negative electrode, the above-mentioned solid electrolyte layer, and the above-mentioned positive electrode, an all-solid-state battery was manufactured by applying hydrostatic pressure of 380 MPa.

[0124] (Example 2)

[0125] An all-solid-state battery was manufactured in the same manner as in Example 1, except that a binder containing polyacrylic acid and styrene-butadiene rubber mixed in a weight ratio of 5:3 was used, and the contents of the binder, carbon black, and silver were changed to a weight ratio of 8:75:25.

[0126] (Example 3)

[0127] An all-solid-state battery was manufactured in the same manner as in Example 1, except that a binder containing polyacrylic acid and styrene-butadiene rubber mixed in a weight ratio of 5:2 was used, and the contents of the binder, carbon black, and silver were changed to a weight ratio of 7:75:25.

[0128] (Comparative Example 1)

[0129] An all-solid-state battery was manufactured in the same manner as in Example 1, except that a binder solution prepared by adding a styrene-butadiene rubber binder to an N-methyl pyrrolidone solvent was used.

[0130] (Comparative Example 2)

[0131] An all-solid-state battery was manufactured in the same manner as in Example 1, except that a binder containing polyacrylic acid and styrene-butadiene rubber mixed in a weight ratio of 5:1 was used, and the contents of the binder, carbon black, and silver were changed to a weight ratio of 6:75:25.

[0132] (Comparative Example 3)

[0133] An all-solid-state battery was manufactured in the same manner as in Example 1, except that a binder containing polyacrylic acid and styrene-butadiene rubber mixed in a weight ratio of 5:5 was used, and the contents of the binder, carbon black, and silver were changed to a weight ratio of 10:75:25.

[0134] (Comparative Example 4)

[0135] An all-solid-state battery was manufactured in the same manner as in Example 1, except that a binder containing a copolymer of polyvinyl alcohol and polyacrylic acid and styrene-butadiene rubber mixed in a weight ratio of 5:4 was used.

[0136] The total content of the binder included in the cathode coating layer of Examples 1 to 3 and Comparative Examples 1 to 4 is shown in Table 1 below.

[0137] Experimental Example 1) Electrical Resistance Evaluation

[0138] The electrical resistance (surface resistance) of the cathodes manufactured in Examples 1 to 3 and Comparative Examples 1 to 3 was measured by probing 46 pins using a 4-probe method (XF057, manufactured by HIOKI), and the results are shown in Table 2 below.

[0139] Experimental Example 2) Measurement of initial Coulomb efficiency

[0140] The all-solid-state batteries manufactured in Examples 1 to 3 and Comparative Examples 1 to 4 were charged and discharged once at 0.1 C at 45°C. The discharge capacity / charge capacity ratio was obtained, and the results are shown in Table 1 below as the initial coulombic efficiency.

[0141] Experimental Example 3) Measurement of capacity retention rate

[0142] The all-solid-state batteries manufactured in Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to 100 charge-discharge cycles at 0.1 C at 45°C. The ratio of the 100-cycle discharge capacity to the 1-cycle discharge capacity was determined. The results are presented in Table 1 below as capacity retention rates.

[0143] Total binder content (wt%) PAA;SBR Weight resistivity (Ω) Initial coulombic efficiency (%) Capacity retention (%) Example 18.26 5:42.79 1.68 7.0 Example 27.415:32.59 1.48 6.1 Example 36.545:22.39 0.68 6.2 Comparative example 18.26 CMC:SBR = 1:24.0 8 5.28 4.5 Comparative example 25.665:11.89 0.88 3.3 Comparative example 39.095:53.28 8.18 3.0 Comparative example 48.26 PVA-PAA:SBR Weight ratio = 5:42.8 8 9.0 8 5.5

[0144] As shown in Table 1 above, it can be seen that the all-solid-state batteries of Examples 1 to 3 containing polyacrylic acid and styrene-butadiene rubber in a weight ratio of 5:2 to 5:4 exhibit low resistance, high initial coulombic efficiency, and excellent capacity retention.

[0145] On the other hand, in the case of Comparative Example 1, which only included styrene-butadiene rubber, it can be seen that the resistance was high, and both the initial coulombic efficiency and capacity retention rate were reduced.

[0146] The all-solid-state battery of Comparative Example 2 containing polyacrylic acid and styrene-butadiene rubber in a weight ratio of 5:1 had low resistance and high initial coulombic efficiency, but exhibited deteriorated life characteristics.

[0147] The all-solid-state battery of Comparative Example 3 containing polyacrylic acid and styrene-butadiene rubber in a weight ratio of 5:5 showed somewhat improved life characteristics, but high resistance and low initial Coulombic efficiency.

[0148] In Comparative Example 4, where a copolymer of polyvinyl alcohol-polyacrylic acid, rather than polyacrylic acid, was used together with styrene-butadiene rubber, the resistance did not increase significantly compared to Example 1, but a decrease in coulombic efficiency and capacity retention rate was observed.

[0149] Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the patent claims, the detailed description of the invention, and the attached drawings, and it is obvious that this also falls within the scope of the present invention.

Claims

1. A binder comprising polyacrylic acid and styrene-butadiene rubber in a weight ratio of 5:4 to 5:2; a carbon-based material; and a cathode coating layer comprising a metal. A cathode for an all-solid-state battery comprising:

2. In paragraph 1, An all-solid-state battery negative electrode having a binder content of 6 to 10 wt% based on 100 wt% of the total negative electrode coating layer.

3. In paragraph 1, The above carbon-based material is an all-solid-state battery negative electrode which is crystalline carbon, amorphous carbon or a combination thereof.

4. In paragraph 1, The above carbon-based material is an amorphous carbon negative electrode for an all-solid-state battery.

5. In paragraph 4, The above amorphous carbon is a cathode for an all-solid-state battery, which is carbon black, acetylene black, Denka black, Ketjen black, furnace black, activated carbon, graphene or a combination thereof.

6. In paragraph 1, The above metal is Ag, Au, Sn, Zn, Al, Mg, Ge, Cu, In, Ni, Bi, Pt, Pd or a combination thereof, and is a negative electrode for an all-solid-state battery.

7. In paragraph 1, The above metal is Ag, an all-solid-state battery negative electrode.

8. In paragraph 1, An all-solid-state battery negative electrode, wherein the metal is supported on the carbon-based material in the negative electrode coating layer.

9. In paragraph 1, An all-solid-state battery negative electrode, wherein the content of the carbon-based material is 55 to 80 wt% with respect to 100 wt% of the entire negative electrode coating layer.

10. In paragraph 1, An all-solid-state battery negative electrode having a content of the metal of 14 to 35 wt% based on 100 wt% of the entire negative electrode coating layer.

11. In paragraph 1, An all-solid-state battery negative electrode, wherein the metal has a size of 5 nm to 800 nm.

12. The cathode of any one of clauses 1 to 11; Bipolar; and A solid electrolyte layer positioned between the cathode and the anode An all-solid-state battery comprising:

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