A negative electrode for all-solid-state batteries and all-solid-state batteries containing the same

Abstract

The present invention relates to a negative electrode for an all-solid-state battery and an all-solid-state battery containing the same, wherein the negative electrode for the all-solid-state battery includes a current collector and a negative electrode catalyst layer located on the current collector, comprising amorphous carbon, metal, and clay.

Description

[Technical Field]

[0001] This relates to a negative electrode for all-solid-state batteries and all-solid-state batteries containing the same. [Background technology]

[0002] Recently, with the rapid proliferation of electronic devices that use batteries, such as mobile phones, laptops, and electric vehicles, the demand for rechargeable batteries that are small, lightweight, and yet relatively high-capacity has been rapidly increasing. In particular, lithium-ion batteries are attracting attention as a power source for portable devices due to their light weight and high energy density. As a result, research and development to improve the performance of lithium-ion batteries is being actively pursued.

[0003] Among lithium-ion secondary batteries, all-solid-state batteries are batteries in which all materials are solid, and in particular, batteries that use a solid electrolyte. One way to increase the energy density of such all-solid-state batteries is to use lithium metal as the negative electrode. However, this method has problems due to the volume expansion of lithium and irreversible dendrite growth during charging and discharging.

[0004] To address these problems, research is being conducted on a method of constructing the negative electrode by forming a layer of lithium deposited on the negative electrode current collector during charging and discharging, without using lithium metal itself. However, this method is unsuitable because it results in low output characteristics and excessive short-circuit phenomena. [Overview of the project] [Problems that the invention aims to solve]

[0005] In one embodiment, a negative electrode for an all-solid-state battery exhibiting excellent battery chemical properties is provided.

[0006] In another embodiment, an all-solid-state battery including the negative electrode is provided. [Means for solving the problem]

[0007] In one embodiment, a current collector and a negative electrode for an all-solid-state battery are provided, comprising a negative electrode catalyst layer located on the current collector and containing amorphous carbon, metal, and clay.

[0008] The clay content may be 1% to 30% by weight or 10% to 25% by weight relative to 100% by weight of the entire negative electrode catalyst layer.

[0009] The clay may be montmorillonite (MMT), halloysite, bentonite, kaolinite, saponite, surface-modified clay, pyrophylite-talc, fluorohectorite, vermiculite, illite, mica, brittle mica, or a combination thereof.

[0010] The metal may be Ag, Au, Sn, Zn, Al, Mg, Ge, Cu, In, Ni, Bi, Pt, Pd, or a combination thereof.

[0011] Amorphous carbon may be carbon black, acetylene black, Denka black, Ketjen black, furnace black, activated carbon, or a combination thereof.

[0012] The BET specific surface area of ​​clay is 5 m². 2 / g~500m 2 / g is also acceptable.

[0013] The metal content may be 1% to 50% by weight relative to 100% by weight of the entire negative electrode catalyst layer.

[0014] The amorphous carbon content may be 20% to 98% by weight relative to 100% by weight of the entire negative electrode catalyst layer.

[0015] In another embodiment, an all-solid-state battery is provided, comprising a negative electrode; a positive electrode; and a solid electrolyte layer located between the negative and positive electrodes.

[0016] The negative electrode may further include a lithium-containing layer between the current collector and the negative electrode catalyst layer. [Effects of the Invention]

[0017] A negative electrode for an all-solid-state battery according to one embodiment can exhibit excellent electrochemical properties. [Brief explanation of the drawing]

[0018] [Figure 1] This is a schematic diagram illustrating an all-solid-state battery according to one embodiment. [Figure 2] This is a schematic diagram illustrating an all-solid-state battery according to another embodiment. [Figure 3] This is a cross-sectional FE-SEM image of the negative electrode manufactured according to Example 1. [Figure 4] These are photographs and graphs showing the EDAX results of the negative electrode manufactured according to Example 1. [Figure 5] These are photographs and graphs showing the EDAX results of the negative electrode manufactured by Comparative Example 1. [Figure 6] This graph shows the overvoltage results of all-solid-state semi-cells manufactured according to Examples 3 and 4 and Comparative Examples 2 and 3. [Figure 7] This graph shows the discharge characteristics of Examples 1-5 after two cycles. [Figure 8] This graph shows the charging characteristics during two cycles for Examples 1 to 5. [Modes for carrying out the invention]

[0019] Embodiments of the present invention will be described in detail below. However, these are presented as examples only and are not limited thereto, and the present invention is defined solely by the scope of the claims described below.

[0020] The terms used herein are for illustrative purposes only and are not intended to limit the invention. Unless otherwise clearly stated in the context, singular expressions include plural expressions.

[0021] Here, “these combinations” refers to mixtures of constituents, laminates, composites, copolymers, alloys, blends, reaction products, etc.

[0022] Here, terms such as “include,” “equip,” or “possess” are intended to specify the existence of a particular feature, number, stage, component, or combination thereof, and should be understood not to preemptively exclude the existence or possibility of adding one or more other features, numbers, stages, components, or combinations thereof.

[0023] To clearly represent various layers and regions in the drawings, thicknesses are shown enlarged, and similar parts are given the same drawing reference numerals throughout the specification. When a layer, film, region, plate, or other part is said to be "on top of" or "on" another part, this includes not only when it is "directly on top of" another part, but also when there is another part in between. Conversely, when a part is said to be "directly on top of" another part, it means that there is no other part in between.

[0024] Furthermore, in this context, "layer" includes not only the shapes formed on the entire surface when observed in a plan view, but also the shapes formed on some of the surfaces.

[0025] Here, "or" is not interpreted as having an exclusive meaning; for example, "A or B" is interpreted as including A, B, A+B, etc.

[0026] Unless otherwise defined herein, particle size or size may refer to average particle size. This average particle size refers to the average particle size (D50), which means the diameter of a particle whose cumulative volume in the particle size distribution is 50% by volume. Average particle size (D50) can be measured by methods widely known to those skilled in the art, such as using a particle size analyzer, or by using a transmission electron microscope or scanning electron microscope. Alternatively, it can be measured using a dynamic light-scattering device, and after performing data analysis to count the number of particles for each particle size range, the average particle size (D50) value can be calculated from this count.

[0027] A negative electrode for an all-solid-state battery according to one embodiment includes a current collector; and a negative electrode catalyst layer located on the current collector, comprising amorphous carbon, metal, and clay.

[0028] In one embodiment, the negative electrode catalyst 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 to the negative electrode side and deposit well on the surface of the current collector. That is, a lithium deposition layer is formed between the current collector and the negative electrode catalyst layer by the deposition of lithium ions, and this lithium deposition layer plays the role of the negative electrode active material. Such a negative electrode is generally called a deposition-type negative electrode.

[0029] When the negative electrode catalyst layer, which contains amorphous carbon and metal, also contains clay, the clay can improve lithium ion mobility, form stable pathways, enable the formation of a uniform lithium layer, and suppress lithium dendrite formation. Generally, during charging and discharging of all-solid-state batteries, overvoltage can occur at the negative electrode, causing excessive lithium dendrite formation on the negative electrode surface. These dendrites can penetrate the electrolyte and come into contact with the positive electrode, leading to a deterioration of the battery's lifespan. However, the negative electrode according to one embodiment can effectively prevent this. Furthermore, when the negative electrode catalyst layer contains clay, the charge and discharge efficiency can be improved.

[0030] In one embodiment, the clay content may be 1% to 30% by weight, 5% to 30% by weight, or 10% to 25% by weight, based on 100% by weight of the entire negative electrode catalyst layer. When the clay content falls within these ranges, the lithium dendrite prevention effect and the charge / discharge improvement effect due to the use of clay can be obtained even more effectively.

[0031] The clay may be montmorillonite (MMT), halloysite, bentonite, kaolinite, saponite, surface-modified clay, pyrophylite-talc, fluorohectorite, vermiculite, illite, mica, brittle mica, or a combination thereof. Surface-modified clay can be any surface-modified clay known in the art, such as clay whose surface has been modified by plasma treatment, clay with hydroxyl groups bonded to its surface, or clay modified with tetravalent ammonium salts.

[0032] The BET specific surface area of ​​clay is 5 m². 2 / g~500m 2 It may also be / g, or 25m2 / g to 300 m 2 It may be / g, and 50 m 2 / g to 250 m 2 It may be / g. When the specific surface area of the clay is included in the above range, the role of the clay can be more appropriately fulfilled, and uniform lithium can be formed. When the specific surface area of the clay is less than 5 m 2 / g, the surface area acting on lithium ions is small, and the role of the clay cannot be well exerted. When it exceeds 500 m 2 / g, during the production of the negative electrode slurry, the specific surface area is excessively high, inducing slurry non-uniformity, lengthening the surface area path of lithium ions, and the overvoltage may become slightly higher.

[0033] The effect obtained by including such clay can be achieved when used in a negative electrode catalyst layer containing both amorphous carbon and metal. When clay is used in a negative electrode catalyst layer containing only amorphous carbon, short-circuiting occurs during charge and discharge, so it is not appropriate.

[0034] In one embodiment, the metal contained in the negative electrode catalyst layer may be Ag, Au, Sn, Zn, Al, Mg, Ge, Cu, In, Ni, Bi, Pt, Pd, or a combination thereof. According to one embodiment, the metal may be Ag. Since the negative electrode catalyst layer contains such a metal together with clay, the electrical conductivity of the negative electrode can be further improved without causing a short circuit during charge and discharge.

[0035] The metal may be nanoparticles, and the size of the metal nanoparticles may be, for example, an average size of 5 nm to 80 nm, but as long as it is in the nanometer size, it can be appropriately used. By using metal nanoparticles having such a nano size, the battery characteristics (for example, life characteristics) of the all-solid-state battery can be further improved. When the size of the metal particles increases in micrometer units, the uniformity of the metal particles in the negative electrode catalyst layer decreases, the current density in a specific region increases, and the cycle life characteristics may deteriorate, so it is not appropriate.

[0036] Amorphous carbon may be carbon black, acetylene black, Denka black, Ketjen black, furnace black, activated carbon, or a combination thereof. An example of carbon black is Super P (Timcal). Amorphous carbon may be carbon black, acetylene black, Denka black, Ketjen black, or a combination thereof.

[0037] In one embodiment of the negative electrode catalyst layer, the metal content may be 1% to 50% by weight, 3% to 30% by weight, 4% to 25% by weight, 5% to 20% by weight, or 5% to 15% by weight, based on 100% by weight of the negative electrode catalyst layer.

[0038] Furthermore, the carbon-based material may be 20% to 98% by weight, 40% to 95% by weight, 60% to 95% by weight, 80% to 95% by weight, or 85% to 95% by weight based on 100% by weight of the total weight of the negative electrode catalyst layer.

[0039] When the content of metal or carbon-based material falls within the aforementioned range, the metal can be uniformly dispersed in the carbon-based material. Furthermore, when the content of metal and carbon-based material falls within the aforementioned range, a lithium deposition layer is substantially formed between the current collector and the negative electrode layer when lithium ions released from the positive electrode active material during charging move to the negative electrode side. Therefore, when lithium deposition occurs on the surface of the negative electrode layer, problems such as short circuits, problems due to side reactions with the electrolyte, or problems of crack formation on the negative electrode side can be effectively suppressed.

[0040] Amorphous carbon may be a single particle or an assembly having a secondary particle form in which primary particles are assembled. When amorphous carbon is a single particle, it may be amorphous carbon particles having an average particle size of 100 nm or less, for example, nano-sized particles of 10 nm to 100 nm.

[0041] Furthermore, when amorphous carbon is used as 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.

[0042] In one embodiment, the particle size of the primary particles may be 20 nm or more, 30 nm or more, 40 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, or 90 nm or more, and may also be 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, or 30 nm or less.

[0043] In one embodiment, the particle size of the secondary particles may be 1 μm or more, 3 μm or more, 5 μm or more, 7 μm or more, 10 μm or more, or 15 μm or more, and may be 20 μm or less, 15 μm or less, 10 μm or less, 7 μm or less, 5 μm or less, or 3 μm or less.

[0044] The morphology of the primary particles may be spherical, elliptical, plate-like, or a combination thereof, and in one embodiment, the morphology of the primary particles may be spherical, elliptical, or a combination thereof.

[0045] The negative electrode catalyst layer may further contain a binder.

[0046] The binder may include a non-aqueous binder, an aqueous binder, or a combination thereof.

[0047] Non-aqueous binders may include, for example, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, ethylene propylene copolymers, polystyrene, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamide-imide, polyimide, polyacrylate, or combinations thereof.

[0048] Examples of water-based binders include rubber-based binders and polymer resin binders. Rubber-based binders may be selected from styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, fluororubber, and combinations thereof. Polymer resin binders may be selected from polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, ethylene propylene diene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, and combinations thereof.

[0049] When using an aqueous binder as the negative electrode binder, a thickening agent that can impart viscosity may be used together, and the thickening agent may include, for example, a cellulosic compound. Cellulosic compounds may include carboxymethylcellulose, hydroxypropylmethylcellulose, methylcellulose, alkali metal salts thereof, or combinations thereof. As the alkali metal, Na, K, or Li can be used. The amount of such thickening agent used may be 0.1 to 3 parts by weight per 100 parts by weight of the negative electrode active material. The cellulosic compound can also act as a binder.

[0050] The binder is not limited to these, but any binder used in the relevant technical field is acceptable, and their content can be appropriately adjusted.

[0051] The binder may be present in amounts of 1 to 15% by weight relative to 100% by weight of the entire negative electrode catalyst layer. For example, the binder may be present in amounts of 1% or more by weight, 2% or more by weight, 3% or more by weight, 4% or more by weight, 5% or more by weight, 6% or more by weight, 7% or more by weight, 8% or more by weight, 9% or more by weight, 10% or more by weight, 11% or more by weight, 12% or more by weight, 13% or more by weight, or 14% or more by weight, and 15% or less by weight, 14% or less by weight, 13% or less by weight, 12% or less by weight, 11% or less by weight, 10% or less by weight, 9% or less by weight, 8% or less by weight, 7% or less by weight, 6% or less by weight, 5% or less by weight, 4% or less by weight, 3% or less by weight, or 2% or less by weight, relative to 100% by weight of the entire negative electrode layer.

[0052] When the binder is included in the negative electrode catalyst layer of the all-solid-state battery within the aforementioned content range, the electrical resistance and adhesive strength are improved, thereby enhancing the characteristics of the all-solid-state battery (battery capacity and output characteristics).

[0053] The negative electrode catalyst layer may further contain additives such as fillers, dispersants, and ion conductive materials. Generally, known materials used in all-solid-state batteries can be used as fillers, dispersants, and ion conductive materials that can be included in the negative electrode catalyst layer.

[0054] In one embodiment, the negative electrode may further include a lithium-containing layer between the current collector and the negative electrode catalyst layer.

[0055] Since the lithium-containing layer is a metallic layer containing lithium, it can function, for example, as a lithium reservoir.

[0056] The lithium-containing layer may also be a lithium-deposited layer formed when lithium ions released from the positive electrode active material during charging move to the negative electrode side and are deposited on the surface of the current collector. In this case, the lithium-containing layer can be called a lithium-deposited layer.

[0057] The lithium-containing layer may be a layer containing lithium or a lithium alloy.

[0058] Lithium alloys contain lithium and may also contain metals that can alloy with lithium. Metals that can alloy with lithium may include Ag, Au, Mg, In, Si, Sn, Al, Ge, Pb, Bi, Sb, Si-Y alloys (where Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth element, or a combination thereof, and not Si), Sn-Y alloys (where Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth element, or a combination thereof, and not Sn), etc. Element Y may be Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or combinations thereof.

[0059] The thickness of the lithium-containing layer may be between 1 μm and 1000 μm, or between 1 μm and 500 μm, 1 μm and 200 μm, 1 μm and 150 μm, 1 μm and 100 μm, or 1 μm and 50 μm. When the thickness of the lithium-containing layer falls within the above range, it can adequately perform its role as a lithium storage facility and may have the advantage of further improving its lifespan.

[0060] If the lithium-containing layer is a lithium-deposited layer, this lithium-deposited layer can be formed after the all-solid-state battery is manufactured. During charging, lithium ions are released from the positive electrode active material, pass through the solid electrolyte, and move to the negative electrode side. As a result, lithium is deposited and vapor-deposited onto the negative electrode current collector.

[0061] The charging process may also be a chemical conversion process carried out one to three times at approximately 25°C to 50°C and 0.05C to 1C. During discharge, the lithium contained in the lithium-containing layer is ionized and moves toward the positive electrode, so this lithium can be used as the negative electrode active material.

[0062] In one embodiment, since the lithium-containing layer is located between the current collector and the negative electrode active material layer, the negative electrode catalyst layer can act as a protective layer for the lithium-containing layer, thereby suppressing the deposition and growth of lithium dendrites. This suppresses short circuits and capacity degradation in the all-solid-state battery, and consequently improves the cycle life of the all-solid-state battery.

[0063] 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 alloys thereof, and may be in foil or sheet form. 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.

[0064] The current collector may have a metal substrate and further include a thin film formed on this substrate. The thin film may contain an element that can form an alloy with lithium, such as gold, silver, zinc, tin, indium, silicon, aluminum, bismuth, or a combination thereof, but is not limited to any element that can form an alloy with lithium in the art. If the current collector further includes a thin film, and the lithium-containing layer is deposited and formed during charging, a more planar lithium-containing layer can be formed, further improving the cycle life of the all-solid-state battery.

[0065] The thin film thickness may be between 1 nm and 800 nm, or between 10 nm and 700 nm, 50 nm and 600 nm, or 100 nm and 500 nm. When the thin film thickness falls within these ranges, the cycle lifetime characteristics can be further improved.

[0066] Another embodiment provides an all-solid-state battery comprising a negative electrode, a positive electrode, and a solid electrolyte layer located between the negative and positive electrodes.

[0067] The solid electrolyte contained in the solid electrolyte layer may be an inorganic solid electrolyte such as a sulfide-based solid electrolyte, an oxide-based solid electrolyte, or a halide-based solid electrolyte, or it may be a solid polymer electrolyte.

[0068] In one embodiment, the sulfide-based solid electrolytes are Li2S-P2S5, Li2S-P2S5-LiX (where X is a halogen element, e.g., 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, and Li2S-P2S5-Z. m S n (m and n are integers between 0 and 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 between 0 and 12, respectively; M is one of P, Si, Ge, B, Al, Ga, or In), Li a M b P c S d A e (a, b, c, d, and e are integers between 0 and 12, M is Ge, Sn, Si, or a combination thereof, and A is one of F, Cl, Br, or I) For example, Li 7-x PS 6-x F x (0≦x≦2), Li 7-x PS 6-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) is also acceptable. Specifically, Li3PS4, Li7P3S 11 , Li7PS6, Li6PS5Cl, Li6PS5Cl, Li6PS5I, Li6PS5Br, Li5.8 PS 4.8 Cl 1.2 Li 6.2 PS 5.2 Br 0.8 You can also use these.

[0069] For example, the sulfide-based solid electrolyte may be an argyrodite-type sulfide-based solid electrolyte. A 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 between 0 and 12, M is Ge, Sn, Si or a combination thereof, and A is one of F, Cl, Br, or I) which specifically include Li3PS4, Li7P3S 11 , Li7PS6, Li6PS5Cl, Li6PS5Br, Li6PS5I, Li 5.8 PS 4.8 Cl 1.2 Li 6.2 PS 5.2 Br 0.8 You can also use these.

[0070] Sulfide-based solid electrolytes may be amorphous, crystalline, or a mixture of both. For example, a sulfide-based solid electrolyte may be obtained by mixing Li2S and P2S5 in a molar ratio of 50:50 to 90:10, or 50:50 to 80:20. Within this mixing ratio range, a sulfide-based solid electrolyte with excellent ionic conductivity can be produced. Further ionic conductivity can be improved by adding other components such as SiS2, GeS2, and B2S3. Mixing methods include mechanical milling and solution milling. Mechanical milling involves placing the starting materials in a reactor and vigorously stirring them with a ball mill or similar device to atomize and mix the starting materials. When using the solution milling method, the starting materials are mixed in a solvent to obtain the solid electrolyte as a precipitate. Furthermore, additional calcination can be performed after mixing. Additional calcination can further strengthen the crystals of the solid electrolyte.

[0071] Of course, a sulfide-based solid electrolyte can also use a commercially available solid electrolyte.

[0072] Oxide-based solid electrolytes include, 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-x Si 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 - GeO2 - based ceramics, garnet (Garnet) - based ceramics Li 3+x La3M2O 12 (M = Te, Nb, or Zr, x is an integer from 1 to 10), or a mixture thereof can be included.

[0073] Solid polymer electrolytes include, for example, polyethylene oxide, poly(diallyldimethylammonium) trifluoromethanesulfonylimide (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, etc.), Li5ZrP3O 12 , Li5TiP3O 12 , Li3Fe2P3O 12 , Li4NbP3O 12 , Li 1+x (M,Al,Ga) x (Ge 1-y Ti y ) 2-x (PO4)3(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 is Al or Ga), Li6BaLa2Ta2O 12 , Li7La3Zr2O 12 , Li5La3Nb2O 12 , Li5La3M2O 12 (M is Nb, Ta), and Li 7+x Ax La 3-x Zr2O 12 (0 < x < 3, A can be one or more selected from Zn).

[0074] The halide-based solid electrolyte can contain a Li element, an M element (M is a metal other than Li), and an X element (X is a halogen). Examples of X include F, Cl, Br, and I. In particular, for the halide-based solid electrolyte, at least one of Br and Cl is suitable as X. Examples of M include metal elements such as Sc, Y, B, Al, Ga, and In.

[0075] The composition of the halide-based solid electrolyte is not particularly limited, but Li 6-3a M a Br b Cl c (where M is a metal other than Li, 0 < a < 2, 0 ≤ b ≤ 6, 0 ≤ c ≤ 6, b + c = 6). At this time, a may be 0.75 or more, may be 1 or more, and a may be 1.5 or less. b may be 1 or more, may be 2 or more. Also, c may be 3 or more, may be 4 or more. Specific examples of the halide-based solid electrolyte include Li3YBr6, Li3YCl6, or Li3YBr2Cl4.

[0076] The solid electrolyte is in particle form, and the average particle size (D50) may be 5.0 μm or less, for example, 0.1 μm to 5.0 μm, 0.5 μm to 5.0 μm, 0.5 μm to 4.0 μm, 0.5 μm to 3.0 μm, 0.5 μm to 2.0 μm, or 0.5 μm to 1.0 μm.

[0077] The solid electrolyte layer may further contain a binder. In this case, the binder may be styrene-butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, acrylate polymers, or a combination thereof, but is not limited thereto, and any binder used in the art may be used. The acrylate polymer may be butyl acrylate, polyacrylate, polymethacrylate, or a combination thereof.

[0078] A solid electrolyte layer can be formed by adding a solid electrolyte to a binder solution, coating a substrate film with this solution, and drying it. The solvent for 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 is omitted herein.

[0079] The positive electrode includes a current collector and a positive electrode active material layer located on one surface of the current collector. The positive electrode active material layer may contain a positive electrode active material. The positive electrode active material may be a lithiated compound capable of reversibly intercalating and releasing lithium ions, or it may be a sulfur-based compound.

[0080] Lithirsted compounds can be made from one or more composite oxides of metals selected from, for example, cobalt, manganese, nickel, and combinations thereof, and lithium. Specific examples of lithirsted compounds include 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);Lia HAVE BEEN 2-b B 1 b O 4-c D 1 c (0.90≦a≦1.8、0≦b≦0.5、0≦c≦0.5);Li a Ni 1-b-c Co 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 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 cG 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 e O2(0.90≦a≦1.8, 0≦b≦0.9, 0≦c≦0.5, 0≦d≦0.5, 0.001≦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) Examples include Fe2(PO4)3 (0≦f≦2) or LiFePO4.

[0081] In the above chemical formula, A is Ni, Co, Mn, or a combination thereof; B 1 These are Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements, or combinations thereof; D 1 is O, F, S, P, or a combination thereof, and 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 J is Cr, V, Fe, Sc, Y, or a combination of these; J is V, Cr, Mn, Co, Ni, Cu, or a combination of these; L 1 It is Mn, Al, or a combination of these.

[0082] According to one embodiment, as the positive electrode active material, LiNi x Co y Al z O2 (NCA), LiNi x Co y Mn z O2 (NCM) (where 0 < x < 1, 0 < y < 1, 0 < z < 1, x + y + z = 1), and other ternary lithium transition metal oxides can be mentioned.

[0083] Of course, those having a coating layer on the surface of this compound can also be used, or a compound having a coating layer and the compound can be mixed and used. This coating layer can contain 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. As the coating element contained in the coating layer, Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof can be used. The coating layer formation step can use any coating method as long as such an element is used for the compound and it does not adversely affect the physical properties of the positive electrode active material (for example, spray coating, dipping method, etc.). Since this is well understood by those skilled in the art, a detailed description is omitted.

[0084] In addition, as the coating layer, any known coating layer for the positive electrode active material of all-solid-state batteries can be applied. Examples thereof include Li2O-ZrO2 (LZO).

[0085] Furthermore, if the positive electrode active material contains nickel, cobalt, and manganese, or nickel, cobalt, and aluminum, the capacity density of the all-solid-state battery can be further improved, and metal leaching of the positive electrode active material can be further reduced in the charged state. This allows the all-solid-state battery to have further improved long-term reliability and cycle characteristics in the charged state.

[0086] Sulfur compounds include elemental sulfur (S8) and solid Li2S n (n≧1), Li2S n (n≧1) dissolved catholite, organosulfur compounds, carbon-sulfur polymer [(C2S x ) n [x = 2.5 to 50, n ≥ 2], or any combination thereof.

[0087] Here, the shape of the positive electrode active material can be, for example, spherical or ellipsoidal particle shapes. Furthermore, the average particle size of the positive electrode active material is not particularly limited and should be within a range applicable to the positive electrode active material of existing all-solid-state secondary batteries. Similarly, the content of the positive electrode active material in the positive electrode active material layer is not particularly limited and should be within a range applicable to the positive electrode layer of existing all-solid-state secondary batteries.

[0088] The positive electrode active material layer may additionally contain a solid electrolyte. The solid electrolyte contained in the positive electrode active material layer may be the aforementioned solid electrolyte, and in this case, it may be the same as or different from the solid electrolyte contained in the solid electrolyte layer. The solid electrolyte may be contained in an amount of 10% to 30% by weight based on the total weight of the positive electrode active material layer.

[0089] The current collector may include, 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 alloys thereof, and may be in the form of foil or sheet.

[0090] The positive electrode active material layer may further include a binder and / or a conductive material.

[0091] Examples of binders include, but are not limited to, polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, and nylon.

[0092] The binder may be included in an amount of 0.1% to 5% by weight, or 0.1% to 3% by weight, relative to the total weight of each component of the positive electrode for the all-solid-state battery, or relative to the total weight of the positive electrode active material layer. Within this content range, the binder can exhibit sufficient adhesive ability without degrading battery performance.

[0093] Conductive materials are used to impart conductivity to electrodes, and any electronically conductive material that does not cause chemical changes can be used in the battery that is constructed from them. Examples include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjenblack, carbon fibers, and carbon nanotubes; metallic 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 containing mixtures thereof.

[0094] The conductive material may be included in an amount of 0.1% to 5% by weight, or 0.1% to 3% by weight, relative to the total weight of each component of the positive electrode for the all-solid-state battery, or relative to the total weight of the positive electrode active material layer. Within this content range, the conductive material can improve electrical conductivity without degrading battery performance.

[0095] The thickness of the positive electrode active material layer may be 90 μm to 200 μm. For example, the thickness of the positive electrode active material layer may be 90 μm or more, 100 μm or more, 110 μm or more, 120 μm or more, 130 μm or more, 140 μm or more, 150 μm or more, 160 μm or more, 170 μm or more, 180 μm or more, or 190 μm or more, and may be 200 μm or less, 190 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, 150 μm or less, 140 μm or less, 130 μm or less, 120 μm or less, or 110 μm or less. As described above, since the thickness of the positive electrode active material layer is greater than the thickness of the negative electrode active material layer, the capacitance of the positive electrode is greater than the capacitance of the negative electrode.

[0096] The positive electrode can be manufactured by forming a positive electrode active material layer on the positive electrode current collector using a dry or wet coating method.

[0097] In one embodiment, a buffer material is additionally included to cushion the thickness changes that occur during charging and discharging of the all-solid-state battery. The buffer material can be placed between the negative electrode and the case, and if the battery is made up of one or more stacked electrode assemblies, it can be placed between different electrode assemblies.

[0098] Examples of cushioning materials include substances with an elastic recovery rate of 50% or more and insulating properties, specifically including silicone rubber, acrylic rubber, fluorocarbon rubber, nylon, synthetic rubber, or combinations thereof. Cushioning materials may exist in the form of polymer sheets.

[0099] Figure 1 is a cross-sectional view of an all-solid-state battery according to one embodiment. Referring to Figure 1, the all-solid-state battery 100 may have a structure in which an electrode assembly is constructed by stacking a negative electrode 400 including a negative electrode current collector 401 and a negative electrode catalyst layer 403, a solid electrolyte layer 300, and a positive electrode 200 including a positive electrode active material layer 203 and a positive electrode current collector 201, and this assembly is housed in a case such as a pouch. The all-solid-state battery 100 may further include an elastic layer 500 on the outside of at least one of the positive electrode 200 and the negative electrode 400. Although Figure 1 shows one electrode assembly including a negative electrode 400, a solid electrolyte layer 300, and a positive electrode 200, an all-solid-state battery can also be manufactured by stacking two or more electrode assemblies.

[0100] Figure 2 schematically shows the structure of a fully charged all-solid-state battery. The all-solid-state battery 100 includes a positive electrode 200 containing a positive electrode current collector 201 and a positive electrode active material layer 203, a negative electrode 400' containing a negative electrode current collector 401' and a negative electrode catalyst layer 403', and a solid electrolyte layer 300 located between the positive electrode 200 and the negative electrode 400', and includes a battery case 500 in which these are housed.

[0101] Furthermore, lithium ions are released from the positive electrode active material and deposited onto the negative electrode current collector 401', resulting in the lithium-containing layer 405' being positioned between the current collector 401' and the negative electrode catalyst layer 403'.

[0102] An all-solid-state battery according to one embodiment can be manufactured by preparing a laminate by positioning a negative electrode, a positive electrode, and a solid electrolyte layer between the negative and positive electrodes, and then pressing the laminate.

[0103] The pressurization process can be carried out in the range of 25°C to 90°C. Furthermore, the pressurization process can be carried out by applying pressure of 550 MPa or less, for example, 500 MPa or less, for example, in the range of 1 MPa to 500 MPa. The pressurization time varies depending on the temperature and pressure, and may be less than 30 minutes, for example. The pressurization process may be, for example, isostatic press, roll press, or plate press.

[0104] Examples and comparative examples of the present invention are described below. Such examples described below are merely one embodiment of the present invention, and the present invention is not limited to these examples. [Examples]

[0105] (Example 1) (1) Manufacturing of the negative electrode Carbon black 86.1% by weight, Ag 4.6% by weight with an average size of 60nm, montmorillonite (specific surface area: 250m²) 2 A negative electrode catalyst layer slurry was prepared by mixing 1.0 wt% of (1 / g), 2.8 wt% of carboxymethylcellulose, and 5.5 wt% of styrene-butadiene rubber with water.

[0106] The manufactured slurry was coated onto a stainless steel foil current collector, and then vacuum-dried at 80°C to produce a negative electrode containing a 12 μm thick negative electrode catalyst layer and a 10 μm thick current collector.

[0107] (2) Manufacturing of the solid electrolyte layer An isobutylyl isobutylate binder solution (solid content: 50% by weight), which contains butyl acrylate (an acrylate-based polymer), was added to an argyrodite-type solid electrolyte, Li6PS5Cl, and mixed. At this time, the mixing ratio of the solid electrolyte to the binder was 98.7:1.3 by weight.

[0108] The mixing process was carried out using a Thinky mixer. A 2 mm zirconia ball was added to the resulting mixture and stirred again in the Thinky mixer to produce a slurry. The slurry was cast onto a release polytetrafluoroethylene film and dried at room temperature to produce a solid electrolyte with a solid electrolyte layer thickness of 100 μm.

[0109] (3) Manufacturing of all-solid-state batteries The manufactured negative electrode, solid electrolyte, and lithium metal counter electrode were sequentially stacked, and a torque half-cell was fabricated by applying a pressure of 8 MPa.

[0110] (Example 2) The negative electrode was manufactured in the same manner as in Example 1, except that 82.1% by weight of carbon black, 4.6% by weight of Ag with an average size of 60 nm, 5.0% by weight of montmorillonite, 2.8% by weight of carboxymethylcellulose, and 5.5% by weight of styrene-butadiene rubber were mixed with water.

[0111] An all-solid-state half-cell was manufactured using the negative electrode, the solid electrolyte layer manufactured in Example 1, and the lithium metal counter electrode.

[0112] (Example 3) The negative electrode was manufactured in the same manner as in Example 1, except that 77.1% by weight of carbon black, 4.6% by weight of Ag with an average size of 60 nm, 10.0% by weight of montmorillonite, 2.8% by weight of carboxymethylcellulose, and 5.5% by weight of styrene-butadiene rubber were mixed with water.

[0113] An all-solid-state half-cell was manufactured using the negative electrode, the solid electrolyte layer manufactured in Example 1, and the lithium metal counter electrode.

[0114] (Example 4) The negative electrode was manufactured in the same manner as in Example 1, except that 68.0 wt% carbon black, 3.7 wt% Ag with an average size of 60 nm, 20.0 wt% montmorillonite, 2.8 wt% carboxymethylcellulose, and 5.5 wt% styrene-butadiene rubber were mixed with water.

[0115] An all-solid-state half-cell was manufactured using the negative electrode, the solid electrolyte layer manufactured in Example 1, and the lithium metal counter electrode.

[0116] (Example 5) The negative electrode was manufactured in the same manner as in Example 1, except that 58.0 wt% carbon black, 3.7 wt% Ag with an average size of 60 nm, 30.0 wt% montmorillonite, 2.8 wt% carboxymethylcellulose, and 5.5 wt% styrene-butadiene rubber were mixed with water.

[0117] An all-solid-state half-cell was manufactured using the negative electrode, the solid electrolyte layer manufactured in Example 1, and the lithium metal counter electrode.

[0118] (Example 6) Carbon black 68.0 wt%, Ag 3.7 wt% with an average size of 60 nm, halloysite (specific surface area: 50 m²) 2 The negative electrode was manufactured in the same manner as in Example 1, except that 20.0% by weight of (1 / g), 2.8% by weight of carboxymethylcellulose, and 5.5% by weight of styrene-butadiene rubber were mixed with water.

[0119] An all-solid-state half-cell was manufactured using the negative electrode, the solid electrolyte layer manufactured in Example 1, and the lithium metal counter electrode.

[0120] (Comparative Example 1) The negative electrode was manufactured in the same manner as in Example 1, except that 87.1% by weight of carbon black, 4.6% by weight of Ag with an average size of 60 nm, 2.8% by weight of carboxymethylcellulose, and 5.5% by weight of styrene-butadiene rubber were mixed with water.

[0121] An all-solid-state half-cell was manufactured using the negative electrode, the solid electrolyte layer manufactured in Example 1, and the lithium metal counter electrode.

[0122] (Comparative Example 2) The negative electrode was manufactured in the same manner as in Example 1, except that 81.7% by weight of carbon black, 10.0% by weight of montmorillonite, 2.8% by weight of carboxymethylcellulose, and 5.5% by weight of styrene-butadiene rubber were mixed with water.

[0123] An all-solid-state half-cell was manufactured using the negative electrode, the solid electrolyte layer manufactured in Example 1, and the lithium metal counter electrode.

[0124] (Comparative Example 3) The negative electrode was manufactured in the same manner as in Example 1, except that 71.7% by weight of carbon black, 20.0% by weight of montmorillonite, 2.8% by weight of carboxymethylcellulose, and 5.5% by weight of styrene-butadiene rubber were mixed with water.

[0125] An all-solid-state half-cell was manufactured using the negative electrode, the solid electrolyte layer manufactured in Example 1, and the lithium metal counter electrode.

[0126] (Reference example 1) The negative electrode was manufactured in the same manner as in Example 1, except that 53.0 wt% carbon black, 3.7 wt% Ag with an average size of 60 nm, 35.0 wt% montmorillonite, 2.8 wt% carboxymethylcellulose, and 5.5 wt% styrene-butadiene rubber were mixed with water.

[0127] An all-solid-state half-cell was manufactured using the negative electrode, the solid electrolyte layer manufactured in Example 1, and the lithium metal counter electrode.

[0128] (Reference example 2) The negative electrode was manufactured in the same manner as in Example 1, except that 38.0 wt% carbon black, 3.7 wt% Ag with an average size of 60 nm, 50.0 wt% montmorillonite, 2.8 wt% carboxymethylcellulose, and 5.5 wt% styrene-butadiene rubber were mixed with water.

[0129] An all-solid-state half-cell was manufactured using the negative electrode, the solid electrolyte layer manufactured in Example 1, and the lithium metal counter electrode.

[0130] Experimental Example 1) FE-SEM (field era Furthermore electron (microscope) measurement Figure 3 shows a cross-sectional FE-SEM image of the negative electrode manufactured in Example 1. As shown in Figure 3, montmorillonite can be seen in the negative electrode catalyst layer of the negative electrode.

[0131] Experimental Example 2) EDAX (Energy-dispersive X-ray spectroscopy measurement The negative electrode manufactured according to Example 1 was cross-sectioned using a focused ion beam (FIB), and energy dispersive x-ray spectroscopy (EDAX) analysis was performed to analyze the cross-sectional shape and elemental distribution. The results are shown in Figures 4(a) and 4(b), respectively.

[0132] Furthermore, the cross-sectional shape and elemental distribution of the negative electrode active material produced by Comparative Example 1 were analyzed by energy dispersion spectroscopy, and the results are shown in Figures 5(a) and (b), respectively.

[0133] As shown in Figure 4(a), the negative electrode of Example 1 contains montmorillonite (MMT) and silver, which is clearly evident from the elemental analysis shown in Figure 4(b), in which O, Na, Mg, Al, Si, and Ag were detected.

[0134] On the other hand, the negative electrode of Comparative Example 1, as shown in Figure 5(a), contained only silver, which is clearly evident from the elemental analysis shown in Figure 5(b), which detected only Al, Si, and Ag. In the results of Figure 5(b), Al and Si are impurities.

[0135] Experimental Example 3) Coulomb Efficiency Efficiency, CE (Computer Efficiency) Evaluation The all-solid-state half-cells of Examples 1-5 and Comparative Examples 2 and 3 were charged three times at 0.05C. The percentage of discharge capacity relative to charge capacity was calculated for each cycle. The results are shown in Table 1 below as CE.

[0136] Experimental Example 4) Overvoltage Evaluation The all-solid-state semi-batteries of Examples 1-5 and Comparative Examples 2 and 3 were subjected to three charge-discharge cycles under the conditions of 0.05C (0.27mA), a 20-hour cutoff (SOC100, the state where the battery is charged to 100% capacity when the total battery charge capacity is 100%), and a 0.27mA (0.05C) cutoff 1.5V discharge. The voltage was measured from the point where the voltage drop began at OCV (Open circuit voltage, approximately 2.5V) until the inflection point occurred around 0mV. The results for each cycle are shown as overvoltage in Table 1 below.

[0137] The results for the first charge were shown in Table 1 below, and the results for the second charge were shown in Table 1 below, representing two cycles. The results are shown in Table 1 below. Furthermore, the results for Examples 3 and 4 and Comparative Examples 2 and 3 are shown in Figure 6.

[0138] [Table 1]

[0139] As shown in Table 1 above, the all-solid-state semi-cells of Examples 1 to 5 exhibit excellent Coulomb efficiency and overvoltage characteristics.

[0140] Even though the negative electrode catalyst layer contained MMT, Comparative Examples 2 and 3, which did not contain Ag, showed overvoltage during the first charge cycle, but subsequently short-circuits occurred, making it impossible to measure the Coulomb efficiency. Therefore, it can be seen that the all-solid-state semi-cells of Comparative Examples 2 and 3 are not practical for actual use. Furthermore, as shown in Figure 6, the occurrence of short circuits is clearly visible in Comparative Examples 2 and 3.

[0141] Furthermore, Figure 7 shows the discharge characteristics and Figure 8 shows the charging characteristics for two cycles of Examples 1-5. Figure 7 shows that the examples generally have low overvoltages of approximately 20mV or less, indicating excellent electrochemical properties. Similarly, Figure 8 shows that the efficiency characteristics are inversely proportional to the overvoltage magnitude. In particular, Example 4, which used 20% by weight of clay, showed the best effect. These results demonstrate that the addition of clay improves electrochemical performance during charging and discharging.

[0142] While preferred embodiments of the present invention have been described above, the present invention is not limited thereto and can be implemented in various ways within the scope of the claims, detailed description of the invention, and attached drawings, and these also naturally fall within the scope of the present invention.

Claims

1. Current collector; and A negative electrode catalyst layer located on the current collector, comprising amorphous carbon, metal, and clay. A negative electrode for all-solid-state batteries, including a component for this purpose.

2. The negative electrode for an all-solid-state battery according to claim 1, wherein the clay content is 1% to 30% by weight relative to 100% by weight of the entire negative electrode catalyst layer.

3. The negative electrode for an all-solid-state battery according to claim 1, wherein the clay content is 10% to 25% by weight relative to 100% by weight of the entire negative electrode catalyst layer.

4. The negative electrode for an all-solid-state battery according to claim 1, wherein the clay is montmorillonite (MMT), halloysite, bentonite, kaolinite, saponite, surface-modified clay, pyrophyllite-talc, fluorohectorite, vermiculite, illite, mica, brittle mica, or a combination thereof.

5. The negative electrode for an all-solid-state battery according to claim 1, wherein the metal is Ag, Au, Sn, Zn, Al, Mg, Ge, Cu, In, Ni, Bi, Pt, Pd, or a combination thereof.

6. The amorphous carbon is carbon black, acetylene black, denka black, ketjen black, furnace black, activated carbon, or a combination thereof, as described in claim 1, for a negative electrode for an all-solid-state battery.

7. The anode for an all-solid-state battery according to claim 1, wherein the amorphous carbon is carbon black, acetylene black, denka black, ketjen black, or a combination thereof.

8. The BET specific surface area of ​​the aforementioned clay is 5 m². 2 / g to 500m 2 A negative electrode for an all-solid-state battery according to claim 1, wherein the value is / g.

9. The anode for an all-solid-state battery according to claim 1, wherein the content of the metal is 1% to 50% by weight based on 100% by weight of the total weight of the anode catalyst layer.

10. The negative electrode for an all-solid-state battery according to claim 1, wherein the content of amorphous carbon is 20% to 98% by weight based on 100% by weight of the total weight of the negative electrode catalyst layer.

11. The negative electrode according to any one of claims 1 to 10; Positive electrode; and Solid electrolyte layer located between the negative electrode and the positive electrode All-solid-state batteries, including those mentioned above.

12. The all-solid-state battery according to claim 11, wherein the negative electrode further includes a lithium-containing layer between the current collector and the negative electrode catalyst layer.

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