Negative electrode slurry, preparation method therefor, and electrode for all-solid-state battery, manufactured using same

Abstract

The present invention relates to a method for preparing a negative electrode slurry, a negative electrode slurry prepared thereby, and an electrode for an all-solid-state battery, manufactured by applying the negative electrode slurry. More specifically, the method for preparing a negative electrode slurry for an all-solid-state battery comprises the steps of: preparing a first mixture by mixing a negative electrode material and a binder solution containing a solvent and a first binder; preparing a dispersion by dispersing the first mixture; and preparing a second mixture by mixing a second binder with the dispersion.

Description

Negative electrode slurry, method for producing the same, and electrode for all-solid-state battery produced using the same

[0001] The present invention relates to a method for producing a negative electrode slurry for an all-solid-state battery, a negative electrode slurry produced thereby, and an electrode for an all-solid-state battery produced by applying the negative electrode slurry.

[0002] Recent industrial demands have led to the active development of batteries with high energy density and safety. For example, lithium-ion batteries are being used not only in information and communication devices, but also in the automotive sector. Safety is particularly important in the automotive sector, as it is directly related to life.

[0003] All-solid-state batteries are being proposed, replacing the electrolyte with a solid electrolyte. By eliminating the use of flammable organic dispersion media, all-solid-state batteries can significantly reduce the risk of fire or explosion in the event of a short circuit.

[0004] The problem to be solved by the present invention is to provide a cathode slurry having improved dispersion characteristics of a cathode material and a method for manufacturing the same.

[0005] Another problem to be solved by the present invention is to provide an electrode manufactured by applying the above-mentioned cathode slurry.

[0006] According to the concept of the present invention, a method for preparing a negative electrode slurry for an all-solid-state battery may include the steps of: preparing a first mixture by mixing a binder solution containing a solvent and a first binder and a negative electrode material; preparing a dispersion by dispersing the first mixture; and preparing a second mixture by mixing a second binder into the dispersion.

[0007] According to another concept of the present invention, an anode slurry for an all-solid-state battery can be manufactured by the above manufacturing method. In addition, the anode slurry for an all-solid-state battery can include one first peak in the particle size range of 0.01 μm to 0.1 μm and one second peak in the particle size range of 0.1 μm to 1 μm, as measured by a particle size analyzer.

[0008] According to another concept of the present invention, an electrode for an all-solid-state battery can be manufactured by applying the above negative electrode slurry.

[0009]

[0010] The present invention can realize an anode slurry for an all-solid-state battery with improved dispersibility and stability of metal particles contained in the anode material. The present invention can manufacture an electrode with excellent performance by applying the anode slurry described above. An all-solid-state battery using the electrode can have improved stability and cell characteristics.

[0011]

[0012] Figure 1 is a flowchart showing a method for manufacturing a negative electrode slurry for an all-solid-state battery according to one embodiment of the present invention.

[0013] Figure 2 is a flowchart showing a method for manufacturing a negative electrode slurry for an all-solid-state battery according to another embodiment of the present invention.

[0014] FIG. 3 is a 2D and 3D photographed image of a cathode slurry for an all-solid-state battery according to one embodiment and a comparative example of the present invention.

[0015] Figure 4 shows the results of particle size analysis of a negative electrode slurry for an all-solid-state battery according to one embodiment and a comparative example of the present invention.

[0016] FIG. 5 shows the viscosity change rate over time of a negative electrode slurry for an all-solid-state battery according to one embodiment and a comparative example of the present invention. FIG. 6 is a cross-sectional view of an all-solid-state battery according to one embodiment of the present invention.

[0017] Figures 7a to 7c are SEM images of negative electrode slurries for all-solid-state batteries according to one embodiment and a comparative example of the present invention. Figure 6a is an SEM image of the negative electrode slurry of Comparative Example 3, Figure 6b is an SEM image of Comparative Example 4, and Figure 6c is an SEM image of the negative electrode slurry of Example 1.

[0018] Figure 8 shows the results of particle size analysis of a negative electrode slurry for an all-solid-state battery according to one embodiment and a comparative example of the present invention.

[0019]

[0020] To fully understand the structure and effects of the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various forms and subject to various modifications. However, the description of these embodiments is provided solely to ensure a complete disclosure of the present invention and to fully inform those skilled in the art of the invention of the scope of the invention.

[0021] In this specification, when a component is referred to as being on another component, it means that it can be formed directly on the other component, or a third component may be interposed between them. Furthermore, in the drawings, the thicknesses of the components are exaggerated for the sake of clarity. Parts designated by the same reference numerals throughout the specification represent the same components.

[0022] The embodiments described herein will be described with reference to cross-sectional views, plan views, and / or perspective views, which are ideal illustrations of the present invention. Although terms such as "first," "second," and "third" are used to describe various components in various embodiments of this specification, these components should not be limited by these terms. These terms are used merely to distinguish one component from another. The embodiments described and illustrated herein also include complementary embodiments.

[0023] The terminology used herein is for the purpose of describing embodiments and is not intended to limit the present invention. In this specification, the singular also includes the plural unless specifically stated otherwise. As used herein, the words "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components.

[0024] The present invention relates to a method for producing an anode slurry for an all-solid-state battery having an effect of improving dispersibility and stability, a cathode slurry produced thereby, and an electrode for an all-solid-state battery produced by applying the anode slurry.

[0025]

[0026] Method for manufacturing cathode slurry

[0027] FIG. 1 and FIG. 2 are flowcharts showing a method for manufacturing a cathode slurry for an all-solid-state battery according to embodiments of the present invention.

[0028] Referring to FIG. 1, a method for manufacturing a negative electrode slurry for an all-solid-state battery according to one embodiment of the present invention includes a step (S100) of mixing a binder solution containing a solvent and a first binder and a negative electrode material to manufacture a first mixture; a step (S200) of dispersing the first mixture to manufacture a dispersion; and a step (S300) of mixing a second binder into the dispersion to manufacture a second mixture.

[0029]

[0030] The above first mixture preparation step (S100) includes adding a binder solution to the negative electrode material.

[0031] The above binder solution may include a solvent and a first binder.

[0032] The solvent may be an aqueous solvent or a non-aqueous solvent. In one embodiment, the solvent may be water.

[0033] As used herein, "aqueous solvent" refers to solvents containing water as a main component. For example, the aqueous solvent may include water. In addition, the aqueous solvent may further include at least one selected from the group consisting of methanol, ethanol, ethylene glycol, diethylene glycol, and glycerol.

[0034] The first binder may include at least one binder selected from the group consisting of an acrylate binder, a polyvinylidene fluoride binder, a polyvinylpyrrolidone binder, a polyvinyl alcohol binder, and a cellulose binder. In one embodiment, the first binder may be an aqueous binder.

[0035] The above acrylate binder may be, for example, polyacrylic acid (PAA), polymethylmethacrylate, polyisobutylmethacrylate, polyethylacrylate, polybutyl acrylate, or poly(2-ethylhexyl acrylate).

[0036] The above polyvinylidene fluoride-based binder is, for example, polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polyvinylidene fluoride-co-tetrafluoroethylene, polyvinylidene fluoride-co-trifluoroethylene, polyvinylidene fluoride-co-trifluorochloroethylene, polyvinylidene fluoride-co-hexafluoropropylene. It may be poly(vinylidene fluoride-co-ethylenefluoride-hexafluoropropylene) or polyvinylidene fluoride-co-trichloroethylene.

[0037] The above polyvinylpyrrolidone-based binder may be, for example, polyvinylpyrrolidone.

[0038] The above polyvinyl alcohol-based binder may be, for example, polyvinyl alcohol.

[0039] The cellulosic binder may be, for example, carboxymethylcellulose (CMC), methylcellulose (MC), hydroxypropylcellulose (HPC), methyl hydroxypropyl cellulose (MHPC), ethyl hydroxyethyl cellulose (EHEC), methyl ethyl hydroxyethyl cellulose (MEHEC), or cellulose gum. In one embodiment, the first binder may be carboxymethylcellulose (CMC).

[0040] The content of the first binder in the binder solution may be 0.5 wt% to 5 wt%. For example, the content of the first binder in the binder solution may be 0.5 wt% to 4 wt%, 0.8 wt% to 3.5 wt%, or 0.8 wt% to 3 wt%.

[0041] The viscosity of the above binder solution may be from 500 cps to 3000 cps. For example, it may be from 800 cps to 2500 cps, from 800 cps to 2300 cps, or from 1000 cps to 2000 cps.

[0042] The above negative electrode material may include carbon material and metal.

[0043] The carbon material may include at least one selected from the group consisting of carbon black, acetylene black, furnace black, carbon nanotubes, ketjen black, and graphene. In one embodiment, the carbon material may be carbon black.

[0044] The metal may include at least one selected from the group consisting of gold (Au), indium (In), germanium (Ge), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn). In one embodiment, the metal may be silver (Ag).

[0045] The weight ratio of the carbon material and the metal may be 1.2 to 4:1. For example, the weight ratio of the carbon material and the metal may be 1.2:1, 2:1, 3:1, or 4:1. By having the above weight ratio of the carbon material and the metal, sufficient ionic conductivity can be secured, and the catalytic activity of the metal can be smoothly achieved, thereby securing excellent output characteristics and capacity of the battery. In one embodiment, the weight ratio of the carbon material and the metal may be 3:1.

[0046] The above cathode material may further include additives. For example, it may further include at least one selected from the group consisting of fillers, coating agents, dispersants, and ion-conducting aids.

[0047] The binder solution may be added so that the content of the first binder in the first mixture is 1 wt% to 10 wt%. If the content of the first binder in the first mixture is less than the above range, the dispersion effect of the negative electrode material particles may be reduced in the dispersion process described below. If the content of the first binder exceeds the above range, the first binder may be excessively adsorbed on the surface of the carbon or metal particles, thereby hindering the movement of lithium ions. This may increase the internal resistance of the battery.

[0048] The first mixture preparation step (S100) may further include adding the binder solution to the negative electrode material and then mixing. The mixing method of the negative electrode material and the binder solution is not limited. In one embodiment, the mixing may be performed by adding the binder solution to the negative electrode material and then stirring the mixture at 20°C to 60°C for 20 to 200 minutes using a planetary mixer.

[0049] The first mixture manufactured in the first mixture manufacturing step (S100) may be in the form of a slurry. The first mixture may have a viscosity of 1000 cps to 4000 cps. For example, the viscosity may be 1000 cps to 3500 cps, 1500 cps to 3000 cps, 1500 cps to 2500 cps, or 2000 cps to 2500 cps.

[0050] The solids content in the first mixture may be from 15 wt% to 45 wt%. For example, the solids content in the first mixture may be from 15 wt% to 40 wt%, from 15 wt% to 35 wt%, from 20 wt% to 35 wt%, or from 20 wt% to 30 wt%.

[0051] If the solid content in the first mixture is outside the above range, the solid content in the first mixture can be adjusted by adding a solvent in the concentration adjustment step (S110) described below. The solvent is the same as that described in the first mixture preparation step (S100). In one embodiment, the solvent may be an aqueous solvent. For example, the solvent may include water. The dispersion preparation step (S200) includes dispersing the first mixture.

[0052] The dispersion of the first mixture can be performed by a disperser. The type of the disperser is not limited as long as it can apply a shear force or an impact force to the first mixture. For example, the disperser can be a bead mill, a ball mill, a spike mill, a basket mill, an attrition mill, an ultrasonic disperser, or a high-pressure homogenizer. More specifically, the disperser can be a “disperser including a grinding media.” As used herein, a “disperser including a grinding media” is a device that includes a grinding media such as a ball or a bead therein, and a device that can grind and disperse particles by the grinding media applying a physical impact to the material. For example, the disperser including the grinding media may be selected from the group consisting of a bead mill, a ball mill, a spike mill, a basket mill and an attrition mill.

[0053] By using a “disperser including a grinding media”, it is possible to prevent the first binder from being deformed or destroyed due to excessive grinding action, thereby increasing the dispersion effect.

[0054] In one embodiment, the average particle diameter (D50) of the grinding medium may be 0.5 mm or greater. Specifically, the average particle diameter (D50) of the grinding medium may be 0.6 mm or greater or 0.8 mm or greater. For example, the average particle diameter (D50) of the grinding medium may be 0.5 mm to 5 mm, 0.6 mm to 4 mm, 0.6 mm to 3 mm, or 0.8 mm to 2 mm. When the average particle diameter (D50) of the grinding medium is less than 0.5 mm, the battery performance may be degraded due to platelet formation of silver particles. In addition, when the average particle diameter (D50) of the grinding medium exceeds 5 mm, proper grinding may not be achieved, thereby reducing the dispersion effect of the first mixture.

[0055] In one embodiment of the present invention, dispersion of the first mixture can be performed by a bead mill.

[0056] The dispersion time of the first mixture can be appropriately selected depending on the type and operating conditions of the disperser used. For example, dispersion of the first mixture can be performed for 10 to 120 minutes.

[0057]

[0058] The second mixture preparation step (S300) includes adding a second binder to the dispersion.

[0059] The second binder may include at least one binder selected from the group consisting of a rubber-based binder, an imide-based binder, a nitrile-based binder, an acetate-based binder, and a cyano-based binder. In one embodiment, the second binder may be an aqueous binder.

[0060] The above imide binder may be, for example, polyimide or polyamide imide.

[0061] The above nitrile-based binder may be, for example, polyacrylonitrile or an acrylonitrile-styrene-butadiene copolymer.

[0062] The acetate-based binder may be, for example, polyvinylacetate, polyethylene-co-vinyl acetate, cellulose acetate, cellulose acetate butyrate, or cellulose acetate propionate.

[0063] The above cyano-based binder may be, for example, cyanoethyl sucrose.

[0064] In one embodiment of the present invention, the second binder may be styrene butadiene rubber (SBR). In another embodiment of the present invention, the second binder may be nitrile butadiene rubber (NBR).

[0065] The second binder may be added so that the content of the second binder in the second mixture is 0.5 wt% to 10 wt%. For example, the content of the second binder in the second mixture may be 1 wt% to 8 wt% or 1.5 wt% to 6 wt%. Within the above range, the second mixture (i.e., the negative electrode slurry) has appropriate adhesiveness and viscosity, so that the negative electrode slurry can be uniformly applied onto the current collector during electrode manufacturing.

[0066] The second mixture preparation step (S300) may further include adding the second binder to the dispersion and then mixing. The mixing method of the dispersion and the second binder is not limited, and may be, for example, stirring. In one embodiment, the mixing may be performed using a planetary mixer at a temperature of 20°C to 60°C for 10 to 120 minutes.

[0067]

[0068] The present invention can produce a dispersion by performing a dispersion process using physical force on a first mixture containing a first binder and an anode material. Since the first binder has excellent dispersibility, the constituent materials within the dispersion can be uniformly dispersed within the dispersion. After the high-pressure dispersion step (S200), the second binder can be added to the dispersion. The second binder can have excellent adhesive properties. The present invention can prevent the second binder from being destroyed and modified by the disperser, thereby reducing adhesive properties. Consequently, according to the present invention, an anode slurry for an all-solid-state battery with improved dispersibility and adhesive properties can be produced.

[0069]

[0070] Figure 2 is a flowchart of a method for preparing a negative electrode slurry for an all-solid-state battery according to another embodiment of the present invention. In the present invention, after the first mixture preparation step (S100), a concentration adjustment step (S110) of additionally adding a solvent to the first mixture may be additionally performed. The solvent is the same as that described above in the first mixture preparation step (S100). For example, the solvent may be an aqueous solvent. For example, the solvent may include water.

[0071] Referring to FIG. 2, the concentration control step (S110) may additionally add a solvent to the first mixture to form the solid content of the first mixture to 15 wt% to 45 wt%. For example, by additionally adding water to the first mixture, the solid content in the first mixture may be formed to 15 wt% to 45 wt%, 15 wt% to 40 wt%, 15 wt% to 35 wt%, 20 wt% to 35 wt%, or 20 wt% to 30 wt%.

[0072] The viscosity of the first mixture to which the solvent is additionally added may be 1000 cps to 4000 cps. For example, it may be 1000 cps to 3500 cps, 1300 cps to 3000 cps, 1300 cps to 2500 cps, or 1500 cps to 2500 cps.

[0073] When the solid content of the first mixture satisfies the above range, it has an appropriate viscosity, so that dispersibility can be effectively expressed in the above-described dispersion process.

[0074]

[0075] cathode slurry

[0076] An anode slurry for an all-solid-state battery according to one embodiment of the present invention can be manufactured by the anode slurry manufacturing method described above.

[0077] An anode slurry for an all-solid-state battery according to one embodiment of the present invention may include a solvent, a carbon material, a metal, a first binder, and a second binder. The solvent may be an aqueous solvent. For example, the solvent may include water.

[0078] The carbon material may include at least one selected from the group consisting of carbon black, acetylene black, furnace black, carbon nanotubes, ketjen black, and graphene. In one embodiment, the carbon material may be carbon black.

[0079] The metal may include at least one selected from the group consisting of gold (Au), indium (In), germanium (Ge), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn). In one embodiment, the metal may be silver (Ag). The first binder may include at least one binder selected from the group consisting of a polyvinylidene fluoride-based binder, a polyvinylpyrrolidone-based binder, a polyvinyl alcohol-based binder, and a cellulose-based binder. The polyvinylidene fluoride-based binder, the polyvinylpyrrolidone-based binder, the polyvinyl alcohol-based binder, and the cellulose-based binder are the same as those described above in the method for preparing a negative electrode slurry.

[0080] The second binder may include at least one binder selected from the group consisting of, for example, a rubber-based binder, an imide-based binder, a nitrile-based binder, an acetate-based binder, and a cyano-based binder. The rubber-based binder, the imide-based binder, the nitrile-based binder, the acetate-based binder, and the cyano-based binder are the same as those described above in the method for preparing a negative electrode slurry.

[0081] When the negative electrode slurry according to the present invention is measured using a particle size analyzer, an analysis result (i.e., a graph) can be obtained. The analysis result may include a first peak in a range of particle sizes from 0.01 μm to 0.1 μm, and a second peak in a range of 0.1 μm to 1 μm. More specifically, the second peak may exist in a range of 0.1 μm to 0.5 μm. The second peak may be larger than the first peak. The average particle diameter (D50) of the negative electrode slurry according to the analysis result may be from 0.1 μm to 0.5 μm.

[0082] The negative electrode slurry of the present invention may have an excellent viscosity maintenance effect. In one embodiment, the viscosity (cps) increase rate of the negative electrode slurry 1 day after preparation with respect to the viscosity (cps) of the negative electrode slurry immediately after preparation, as measured at a shear rate of shear 10, may be less than 90%. More specifically, the viscosity increase rate of the negative electrode slurry of the present invention may be less than 80%. For example, the viscosity increase rate (%) may be calculated as “((slurry viscosity 1 day after preparation - slurry viscosity immediately after preparation) ÷ slurry viscosity immediately after preparation) x 100”.

[0083] The cathode slurry of the present invention can have improved metal particle dispersibility. The cathode slurry of the present invention can have excellent viscosity maintenance effects. An electrode manufactured using the cathode slurry of the present invention can have improved electrical properties.

[0084]

[0085] All-solid-state batteries

[0086] FIG. 6 is a cross-sectional view illustrating an all-solid-state battery according to embodiments of the present invention. Referring to FIG. 6, the all-solid-state battery (10) may include a positive electrode layer (100), a negative electrode layer (200) facing the positive electrode layer (100), and a solid electrolyte layer (300) disposed between the positive electrode layer (100) and the negative electrode layer (200). However, the present invention is not limited thereto, and the all-solid-state battery (10) may further include an additional functional layer, such as an adhesion enhancing layer, disposed between the positive electrode layer (100) and the solid electrolyte layer (300) or between the negative electrode layer (200) and the solid electrolyte layer (300).

[0087] The positive electrode layer (100) may include a positive electrode current collector (110) and a positive electrode active material layer (120) disposed on the positive electrode current collector (110). The positive electrode active material layer (120) may include a positive electrode active material, a solid electrolyte, a conductive material, and a binder.

[0088] The positive electrode current collector (110) can provide a reference surface on which the positive electrode active material layer (120) is arranged. The positive electrode current collector (110) can have a plate or foil shape. For example, the positive electrode current collector (110) can include 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.

[0089] Unlike the one illustrated in FIG. 6, in one embodiment of the present invention, the positive electrode current collector (110) may be omitted. Although not illustrated, a carbon layer having a thickness of 0.1 μm to 4 μm may be additionally disposed between the positive electrode current collector (110) and the positive electrode active material layer (120) to increase the bonding strength between the positive electrode current collector (110) and the positive electrode active material layer (120).

[0090] The cathode active material may be a material that can reversibly absorb and desorb lithium ions. For example, the cathode active material may include, but is not limited to, lithium transition metal oxides such as lithium cobalt oxide (LCO), lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium manganate, and lithium iron phosphate, nickel sulfide, copper sulfide, lithium sulfide, iron oxide, or vanadium oxide. The cathode active materials may be used alone or as a mixture of two or more thereof.

[0091] Lithium transition metal oxides include, for example, Li a A 1-b B b D2(0.90≤a≤1, 0≤b≤0.5), Li a E 1-b B b O 2-c D c (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05), LiE 2-b B b O 4-c D c (0≤b≤0.5, 0≤c≤0.05), Li a Ni 1-b-c Co b B c D α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Ni 1-b-c Co b B c O 2-α F α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Ni 1-b-c Mn b B c D α(0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2), Li a Nor 1-b-c Mn b B c O 2-α F α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Nor b E c G d O2(0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1), Li a Nor b Co c Mn d GeO2(0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0.001≤e≤0.1), Li a NiG b O2(0.9≤a≤1, 0.001≤b≤0.1), Li a CoG b O2(0.90≤a≤1, 0.001≤b≤0.1), Li a MnG b O2(0.90≤a≤1, 0.001≤b≤0.1), Li a Mn2GbO4(0.90≤a≤1, 0.001≤b≤0.1), QO2, QS2, LiQS2, V2O5, LiV2O5, LiIO2, LiNiVO4, Li 3-f J2(PO4)3(0≤f≤2), Li 3-fIt may be a compound represented by any one of Fe2(PO4)3(0≤f≤2), LiFePO4. In these compounds, the capital letter “A” is Ni, Co, Mn, or a combination thereof, the capital letter “B” is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof, the capital letter “D” is O, F, S, P, or a combination thereof, the capital letter “E” is Co, Mn, or a combination thereof, the capital letter “F” is F, S, P, or a combination thereof, the capital letter “G” is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof, the capital letter “Q” is Ti, Mo, Mn, or a combination thereof, the capital letter “I” is Cr, V, Fe, Sc, Y, or a combination thereof, and the capital letter “J” is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.

[0092] The cathode active material may include, for example, a lithium salt of a transition metal oxide having a layered rock salt type structure among the lithium transition metal oxides described above. The "layered rock salt type structure" is, for example, a cubic rock salt type structure. <111> It is a structure in which oxygen atomic layers and metal atomic layers are alternately and regularly arranged in a direction, and thereby each atomic layer forms a two-dimensional plane. The "cubic rock salt structure" refers to the sodium chloride type (NaCl type) structure, which is a type of crystal structure, and specifically refers to a structure in which the face-centered cubic lattice (fcc) formed by each cation and anion is arranged with a displacement of half of the ridge of the unit lattice. Lithium transition metal oxides having this layered rock salt structure include, for example, LiNi x Co y Al z O2(NCA) or LiNi x Co y Mnz O2(NCM) (0 <x<1,0<y<1, 0<z<1, x+y+z=1) 등의 삼원계 리튬전이금속산화물일 수 있다. 양극 활물질이 층상암염형 구조를 갖는 삼원계 리튬전이금속산화물을 포함하는 경우, 전고체 전지(10)의 에너지 밀도가 커지고 열안정성이 향상될 수 있다.

[0093] The above-described compound included in the positive electrode active material may be covered by a coating layer (not shown). The positive electrode active material may also be a mixture of the above-described compound and a compound to which a coating layer is added. Meanwhile, the coating layer added to the surface of the positive electrode active material may include, for example, an oxide, a hydroxide, an oxyhydroxide, an oxycarbonate, or a hydroxycarbonate of the coating elements below. The compound forming the coating layer 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 may include, for example, Li2O-ZrO2 (LZO). The method for forming the coating layer may be selected within a range that does not adversely affect the physical properties of the positive electrode active material. The method for forming the coating layer may include, for example, a spray coating method or an immersion method.

[0094] When the positive electrode active material includes nickel (Ni) as a ternary lithium transition metal oxide such as NCA or NCM, for example, the capacity density of the all-solid-state battery (10) can be increased, and metal dissolution of the positive electrode active material in a charged state can be reduced. As a result, the cycle characteristics of the all-solid-state battery (10) in a charged state can be improved. Meanwhile, the “cycle characteristics” are characteristics indicating the degree to which the all-solid-state battery (10) is deteriorated due to charge / discharge of the all-solid-state battery (10). An all-solid-state battery (10) with high cycle characteristics can have a small degree of deterioration of the all-solid-state battery (10) due to charge / discharge, and an all-solid-state battery (10) with low cycle characteristics can have a large degree of deterioration of the all-solid-state battery (10) due to charge / discharge.

[0095] The shape of the positive electrode active material may include particle shapes such as a sphere or an ellipsoid, for example. The particle size and content of the positive electrode active material are not particularly limited.

[0096] The solid electrolyte may include a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics. Examples of the sulfide-based solid electrolyte include Li2S-P2S5, Li2S-P2S5-LiX (X is a halogen element), 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, n are positive numbers, capital letter “Z” represents Ge, Zn or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are positive numbers, capital letter “M” is one of P, Si, Ge, B, Al, Ga In), Li 7-x PS 6-x Cl x(0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may include at least one selected from (0≤x≤2).

[0097] Sulfide-based solid electrolytes include, for example, Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may be an argyrodite-type compound including at least one selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound including at least one selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0098] Alternatively, the sulfide-based solid electrolyte is Li 7-a M a PS 6-c X cIt may be an argyrodite-type compound containing X, wherein X may be F, Br, Cl, or a combination thereof. M is candium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), arsenic (As), antimony (Sb), bismuth (Bi), or a combination thereof. Can be.

[0099] The density of the argyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. Since the argyrodite-type solid electrolyte has a density of 1.5 g / cc or more, the internal resistance of the all-solid-state battery is reduced, and the defect of the solid electrolyte membrane being penetrated and short-circuited due to the formation of lithium dendrites can be prevented. The elastic modulus of the solid electrolyte may be, for example, 15 GPa to 35 GPa.

[0100] The solid electrolyte included in the positive electrode active material layer (120) may have a smaller median particle size (D50) than the solid electrolyte included in the solid electrolyte layer (300). For example, the median particle size (D50) of the solid electrolyte included in the positive electrode active material layer (120) may be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less of the median particle size (D50) of the solid electrolyte included in the solid electrolyte layer (300). Meanwhile, the median particle size (D50) may be a median diameter measured using a laser particle size distribution meter.

[0101] The positive electrode active material layer (120) may include a conductive material. The conductive material may have conductivity without causing a chemical change in the all-solid-state battery (10), thereby increasing the conductivity of the positive electrode active material and the solid electrolyte. The conductive material may include a carbon-based material. The conductive material may include, for example, one or more selected from graphite, carbon black, acetylene black, carbon nanofibers, and carbon nanotubes.

[0102] The positive electrode active material layer (120) may further include a binder. The binder may include a material for binding the positive electrode active material, solid electrolyte, and conductive material included in the positive electrode active material layer (120) and improving bonding strength with the positive electrode current collector (110). For example, the binder may include polyvinylidene fluoride, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, or polymethyl methacrylate.

[0103] When the total amount of the positive electrode active material, the solid electrolyte, the conductive material, and the binder is 100 parts by weight, the positive electrode active material layer (120) may include 85 parts by weight to 92 parts by weight of the positive electrode active material. The positive electrode active material layer (120) may include 0.5 parts by weight to 1.5 parts by weight of the binder.

[0104] Within the positive electrode active material layer (120), the conductive material may be present in an amount of 1 to 50 parts by weight relative to 100 parts by weight of the solid electrolyte. If the conductive material is present in an amount less than 1 part by weight relative to 100 parts by weight of the solid electrolyte, the electrical conductivity of the positive electrode active material layer (120) may be reduced. If the conductive material is present in an amount greater than 50 parts by weight relative to 100 parts by weight of the solid electrolyte, the conductive material ratio may be excessively high, and thus a covering layer covering the surface of the solid electrolyte may not be properly formed.

[0105] According to embodiments, the positive electrode active material layer (120) may further include at least one additive selected from the group consisting of a filler, a coating agent, a dispersant, and an ion conductive auxiliary agent in addition to the above-described positive electrode active material, solid electrolyte, conductive agent, and binder.

[0106] The solid electrolyte layer (300) is disposed between the positive electrode layer (100) and the negative electrode layer (200) and may include a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics. The solid electrolyte included in the solid electrolyte layer (300) may be the same as or different from any one of the materials that may be included in the solid electrolyte included in the positive electrode active material layer (120) described above.

[0107] The solid electrolyte layer (300) of one embodiment may include a sulfide-based solid electrolyte. The sulfide-based solid electrolyte may be manufactured by treating starting materials such as Li2S and P2S5 by a melting rapid cooling method or a mechanical milling method. In addition, a heat treatment may be performed after the treatment. The solid electrolyte may be amorphous, crystalline, or a mixture thereof. In addition, the solid electrolyte may include, for example, at least sulfur (S), phosphorus (P), and lithium (Li) as constituent elements among the above-described sulfide-based solid electrolyte materials. For example, the solid electrolyte may be a material including Li2S-P2S5. When using a sulfide-based solid electrolyte material including Li2S-P2S5 to form the solid electrolyte, the mixing molar ratio of Li2S and P2S5 is, for example, in the range of Li2S:P2S5=50:50 to 90:10.

[0108] Sulfide-based solid electrolytes include, for example, Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may be an argyrodite-type compound including at least one selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound including at least one selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0109] Alternatively, the sulfide-based solid electrolyte is Li 7-a M a PS 6-c X cIt may be an argyrodite-type compound containing X, wherein X may be F, Br, Cl, or a combination thereof. M is candium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), arsenic (As), antimony (Sb), bismuth (Bi), or a combination thereof. Can be.

[0110] The density of the argyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. When the argyrodite-type solid electrolyte has a density of 1.5 g / cc or more, the internal resistance of the all-solid-state battery is reduced, and the defect of the solid electrolyte membrane being penetrated and short-circuited due to the formation of lithium dendrites can be prevented. The elastic modulus of the solid electrolyte is, for example, 15 GPa to 35 GPa.

[0111] The solid electrolyte layer (300) may further include a binder. The binder in the solid electrolyte layer (300) may be, for example, styrene butadiene rubber (SBR), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PE), polymethacrylate (PMA), polyacrylic acid (PAA), etc., but is not limited thereto. The binder of the solid electrolyte layer (300) may be the same as or different from the binder included in the positive electrode active material layer (120) or the binder included in the negative electrode coating layer (220).

[0112] The negative electrode layer (200) may include a negative electrode current collector (210) and a negative electrode coating layer (220) on the negative electrode current collector (210). The negative electrode current collector (210) may provide a reference surface on which the negative electrode coating layer (220) is disposed. The negative electrode current collector (210) may include, for example, a material that does not react with lithium, i.e., does not form an alloy or a compound with lithium. For example, the negative electrode current collector (210) may include at least one metal selected from the group consisting of copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), and nickel (Ni). The thickness of the negative electrode current collector (210) may be 1 μm to 20 μm, more specifically 5 μm to 15 μm, and more specifically 7 μm to 10 μm.

[0113] The negative electrode current collector (210) may be composed of one of the above-described metals, or may include an alloy or coating material of two or more metals. The negative electrode current collector (210) may have, for example, a plate shape or a foil shape. Meanwhile, in one embodiment, the negative electrode current collector (210) may be omitted.

[0114] The negative electrode coating layer (220) can allow lithium metal to grow between it and the negative electrode current collector (210) when the all-solid-state battery (10) is charged. The negative electrode coating layer (220) can act as a protective layer for the lithium metal and simultaneously suppress the precipitation and growth of lithium dendrites.

[0115] The cathode coating layer (220) may include a metal and carbon. For example, the cathode coating layer (220) may include at least one metal selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn). The cathode coating layer (220) may include at least one carbon selected from the group consisting of carbon black, acetylene black, furnace black, carbon nanotubes, ketjen black, and graphene. In one embodiment, the cathode coating layer (220) may include a mixture of carbon black and silver (Ag).

[0116] The cathode coating layer (220) may further include additives other than metal and carbon. The cathode coating layer (220) may further include, for example, at least one additive selected from the group consisting of a binder, a filler, a coating agent, a dispersant, and an ion conductive additive.

[0117] The negative electrode coating layer (220) may have a smaller thickness than the positive electrode active material layer (120). The thickness of the negative electrode coating layer (220) may be, for example, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5% or less of the thickness of the positive electrode active material layer (120). The thickness of the negative electrode coating layer (220) may be, for example, 1 um to 20 um, 2 um to 10 um, or 3 um to 7 um. If the thickness of the negative electrode coating layer (220) is too thin, lithium dendrites formed between the negative electrode coating layer (220) and the negative electrode current collector (210) may cause the negative electrode coating layer (220) to collapse, thereby deteriorating the cycle characteristics of the all-solid-state battery (10). If the thickness of the cathode coating layer (220) increases excessively, the energy density of the all-solid-state battery (10) may decrease and the internal resistance of the all-solid-state battery (10) due to the cathode coating layer (220) may increase, thereby deteriorating the cycle characteristics of the all-solid-state battery (10).

[0118] Meanwhile, although not shown, a carbon layer may be further included to improve adhesion between the cathode coating layer (220) and the solid electrolyte layer (300).

[0119] The negative electrode layer (200) of the all-solid-state battery according to the present embodiment can be manufactured using the above-described negative electrode slurry. The negative electrode layer (200) can be manufactured using a conventional technique for manufacturing an electrode, and is not particularly limited. Specifically, the above-described negative electrode slurry can be applied and dried on a negative electrode current collector (210) using a doctor blade, spray, bar coating, slot die coating, or the like, and then pressed to manufacture an electrode. An negative electrode coating layer (220) can be formed from the negative electrode slurry.

[0120]

[0121] Hereinafter, embodiments of the present invention will be described in more detail. However, the following embodiments are provided merely to aid understanding of the present invention, and the scope of the present invention is not limited thereby.

[0122]

[0123] Example 1

[0124] 1) A cathode material was prepared by mixing silver (Ag) and carbon (C). The composition of the cathode material mixture was such that silver (Ag) and carbon were in a weight ratio of 25:75.

[0125] 2) A 1% solid content (1 wt%) carboxymethyl cellulose (CMC) aqueous solution was added to the above-mentioned negative electrode material, and then mixed at a temperature of 25°C for 120 minutes to prepare a first mixture in the form of a slurry. To control the viscosity, water was additionally added to the first mixture, and finally, a first mixture having a solid content concentration of 25% and a viscosity of 1865 cps was prepared.

[0126] 3) A bead mill containing beads with an average particle diameter (D50) of 0.8 mm was prepared. The first mixture was added to the bead mill, and a dispersion process was performed for 20 minutes to obtain a dispersion.

[0127] 4) After the dispersion process was completed, a styrene-butadiene rubber (SBR) aqueous dispersion was added to the dispersion, and stirred at a temperature of 25°C for 60 minutes to prepare a second mixture, a negative electrode slurry. 5) The prepared slurry was coated on a copper current collector to prepare an electrode plate.

[0128]

[0129] Example 2: Bead mill average particle size (D50) 2.0 mm

[0130] A cathode slurry and a plate containing the same were manufactured in the same manner as in Example 1, except that the dispersion process was performed using a bead mill containing beads having an average particle diameter (D50) of 2 mm.

[0131]

[0132] Comparative Example 1: Slurry manufactured without dispersion process

[0133] A negative electrode slurry was prepared in the same manner as in Example 1, except that dispersion was not performed. That is, a second mixture, a negative electrode slurry, was prepared by adding and stirring a styrene-butadiene rubber (SBR) aqueous dispersion to the first mixture. This was coated on a copper current collector to prepare an electrode plate.

[0134]

[0135] Comparative Example 2: Slurry subjected to dispersion process after second binder addition

[0136] 1) A first mixture having a solid concentration of [25%] and a viscosity of 1865 cps was prepared in the same manner as in Example 1.

[0137] 2) A second mixture was prepared by adding a styrene-butadiene rubber (SBR) aqueous dispersion to the first mixture and stirring at a temperature of 25°C for 60 minutes.

[0138] 3) A bead mill containing beads with an average particle diameter (D50) of 0.8 mm was prepared. The second mixture was added to the bead mill, and a dispersion process was performed for 30 minutes to prepare a cathode slurry.

[0139] 4) The manufactured slurry was coated on a copper current collector to manufacture an electrode plate.

[0140]

[0141] Comparative Example 3: Bead mill average particle diameter (D50) 0.2 mm

[0142] A cathode slurry and a plate containing the same were manufactured in the same manner as in Example 1, except that the dispersion process was performed using a bead mill containing beads having an average particle diameter (D50) of 0.2 mm.

[0143]

[0144] Comparative Example 4: Bead mill average particle diameter (D50) 0.3 mm

[0145] A cathode slurry and a plate containing the same were manufactured in the same manner as in Example 1, except that the dispersion process was performed using a bead mill containing beads having an average particle diameter (D50) of 0.3 mm.

[0146]

[0147]

[0148] Evaluation Example 1: Cathode Slurry Surface Image Analysis

[0149] The surface images of the negative electrode plate according to the examples and comparative examples were taken with a VK-X1100 microscope from KEYENCE, and 2D images and 3D images were obtained. Fig. 3 (a) is a 2D image of the surface of the negative electrode plate of Example 1, (b) is a 3D image of the surface of the negative electrode slurry of Example 1, (c) is a 2D image of the surface of the negative electrode plate of Comparative Example 1, and (d) is a 3D image of the surface of the negative electrode slurry of Comparative Example 1. Compared to Comparative Example 1, it was confirmed that the particle distribution on the surface of the negative electrode slurry of Example 1 was uniform.

[0150]

[0151] Evaluation Example 2: Particle Size Analysis

[0152] The particle size distribution of the negative electrode slurry according to the examples and comparative examples was measured using a Mastersizer 3000 particle size analyzer from Malvern, and the results are shown in Table 1 and Fig. 4. Fig. 4 is a graph showing the particle size analysis results of the negative electrode slurry according to the comparative examples and examples.

[0153] D10 represents the particle size that accounts for 10% of the volume from the largest particle size based on the total volume of the graph, D50 represents the particle size that accounts for 50% of the volume from the largest particle size based on the total volume of the graph, and D90 represents the particle size that accounts for 90% of the volume from the largest particle size based on the total volume of the graph. In other words, when the graph is divided into 10 equal parts based on the cumulative distribution of particle sizes, the sizes of the particles corresponding to the positions of 1 / 10, 5 / 10, and 9 / 10 are indicated.

[0154] Particle size distribution (μm) of cathode slurry Specific surface area SSA (m 2 / kg)D10D50D90Example 10.0230.292.380040Comparative Example 10.2581.888.515040

[0155] Referring to Table 1 and FIG. 4, it can be confirmed that the negative electrode slurry according to Example 1 of the present invention includes a first peak in the range of particle sizes from 0.01 μm to 0.1 μm in the particle size analysis results, and has a second peak in the range of particle sizes from 0.1 μm to 1 μm. In particular, it can be confirmed that the particle size in the first peak is 0.03 μm, and the particle size in the second peak is 0.33 μm. At this time, the second peak is larger than the first peak. On the other hand, it can be confirmed that Comparative Example 1 has a peak only in the range of 1 μm to 10 μm.

[0156] Through this, it can be confirmed that the cathode slurry according to the embodiment of the present invention has superior dispersibility compared to the comparative example.

[0157]

[0158] Evaluation Example 3: Analysis of Timeliness

[0159] The viscosity change rate of the cathode slurry according to the examples and comparative examples was analyzed.

[0160] The viscosity of the slurry according to the shear rate (1 / s) was measured immediately after (0 d) and after 1 day (1 d) of the negative electrode slurry of Example 1, Comparative Example 1, and Comparative Example 2, and the results are shown in Fig. 5. In addition, the viscosity and viscosity increase rate at Shear 10 immediately after (0 d) and after 1 day (1 d) of the slurry are shown in Table 2.

[0161] Immediately after manufacturing (0d) 1 day later (1d) Viscosity increase rate Shear 10 (cps) TI Shaer 10 (cps) TI Example 1 20 77.4 0.88 36 80 0.84 7 7.1% Comparative example 1 15 85.8 0.66 30 83.10 78 9 4.4% Comparative example 2 18 0 40.77 34 40.9 0.80 9 0.7% TI (Thixotropy Index): Viscosity at Shear 10 relative to viscosity at Shear 1

[0162] Referring to Table 2 and Fig. 5, it can be confirmed that the anode slurries of Comparative Examples 1 and 2 had viscosity increases of 94.4% and 90.7%, respectively, 1 day after production. That is, it can be confirmed that the viscosity change over time is large. On the other hand, the anode slurry of Example 1 had a viscosity increase rate of less than 80%, which means that the viscosity change over time is small. Through this, it can be confirmed that the anode slurry according to Example 1 of the present invention has superior viscosity stability compared to the anode slurries of Comparative Examples 1 and 2.

[0163]

[0164] Evaluation Example 4: Dispersibility Evaluation According to Grinding Medium Particle Size

[0165] In order to confirm the dispersion effect according to the particle size of the grinding medium, particle size distribution analysis and SEM image capturing of the negative electrode slurries of Comparative Example 3 (average bead particle size: 0.2 mm), Comparative Example 4 (average bead particle size: 0.3 mm), and Example 1 (average bead particle size: 0.8 mm) were performed. Figures 7a to 7c are SEM images of the negative electrode slurries of Comparative Example 3, Comparative Example 4, and Example 1, respectively, and Table 3 shows the results of the particle size distribution within the negative electrode slurry.

[0166] Particle size distribution of cathode slurry (μm) D10 D50 D90 Comparative example 30.0 69 0.72 35.5 Comparative example 40.0 30 8 0.35 18.02 Example 10.0 2 30.2 9 2.3 Example 20.0 2 15 0.2 8 1.4

[0167] Referring to Table 3, the D90 of the negative electrode slurry of Examples 1 and 2, which were dispersed using a bead mill having an average particle diameter (D50) of 0.8 mm and 2 mm, respectively, was 5 μm or less, confirming that most of the aggregates were disintegrated and dispersed. In addition, referring to FIGS. 7a to 7c, it can be confirmed that large plate-like aggregates were observed in the negative electrode slurry of Comparative Examples 3 and 4, which were dispersed using a bead mill having an average particle diameter of less than 0.5 mm, whereas such plate-like aggregates were not observed in the negative electrode slurry of Example 1.

[0168] That is, it can be confirmed that the dispersion effect can be maximized by performing the dispersion process using beads with an average particle diameter of 0.5 mm or more.

[0169] While embodiments of the present invention have been described with reference to the attached drawings, the present invention may be implemented in other specific forms without altering the technical spirit or essential features thereof. Therefore, it should be understood that the embodiments described above are exemplary in all respects and are not limiting.

Claims

1. A step of preparing a first mixture by mixing a binder solution containing a solvent and a first binder and a cathode material; A step of dispersing the first mixture to prepare a dispersion; and A method for producing a negative electrode slurry for an all-solid-state battery, comprising a step of producing a second mixture by mixing a second binder into the above dispersion.

2. In paragraph 1, the cathode material: Contains carbon materials and metals, The weight ratio of the carbon material and the metal is 1.2 to 4:1, Method for manufacturing a cathode slurry for an all-solid-state battery.

3. A method for producing a cathode slurry for an all-solid-state battery, wherein in the second paragraph, the metal comprises at least one selected from the group consisting of gold (Au), indium (In), germanium (Ge), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn).

4. A method for producing a cathode slurry for an all-solid-state battery, wherein the carbon material in the second paragraph includes at least one selected from the group consisting of carbon black, acetylene black, furnace black, carbon nanotubes, ketjen black, and graphene.

5. In the first paragraph, the first binder, A method for producing an anode slurry for an all-solid-state battery, comprising at least one selected from the group consisting of an acrylate binder, a polyvinylidene fluoride binder, a polyvinylpyrrolidone binder, a polyvinyl alcohol binder, and a cellulose binder.

6. A method for producing a negative electrode slurry for an all-solid-state battery, wherein the viscosity of the binder solution in the first paragraph is 500 cps to 3000 cps.

7. A method for producing a negative electrode slurry for an all-solid-state battery, wherein the content of the first binder in the first mixture is 1 wt% to 10 wt%.

8. A method for producing a negative electrode slurry for an all-solid-state battery, wherein the dispersion is performed by a disperser including a grinding media in the first paragraph.

9. A method for producing a negative electrode slurry for an all-solid-state battery, wherein the disperser is at least one selected from the group consisting of a bead mill, a ball mill, a spike mill, a basket mill, and an attrition mill.

10. A method for producing a negative electrode slurry for an all-solid-state battery, wherein the average particle diameter (D50) of the grinding medium in the 8th paragraph is 0.2 mm to 5 mm.

11. A method for producing a negative electrode slurry for an all-solid-state battery, wherein the dispersion is performed for 10 to 120 minutes in the first paragraph.

12. A method for producing a negative electrode slurry for an all-solid-state battery, wherein the second binder comprises at least one selected from the group consisting of a rubber-based binder, an imide-based binder, a nitrile-based binder, an acetate-based binder, and a cyano-based binder.

13. A method for producing a negative electrode slurry for an all-solid-state battery, wherein the content of the second binder in the second mixture is 0.5 wt% to 10 wt% in the first paragraph.

14. A method for producing a negative electrode slurry for an all-solid-state battery, further comprising a step of additionally adding a solvent to the first mixture before dispersion to form a solid content in the first mixture of 15 wt% to 45 wt%.

15. A method for producing a negative electrode slurry for an all-solid-state battery, wherein the viscosity of the first mixture in the first paragraph is 1000 cps to 4000 cps.

16. Contains water, carbon material, metal, first binder and second binder, From the analysis results measured by the Particle Size Analyzer, Contains one first peak in the particle size range of 0.01 μm to 0.1 μm, A cathode slurry for an all-solid-state battery, comprising one second peak in the particle size range of 0.1 μm to 1 μm.

17. In the 16th paragraph, at least one selected from the group consisting of gold (Au), indium (In), germanium (Ge), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn) is included. An anode slurry for an all-solid-state battery, wherein the carbon material comprises at least one selected from the group consisting of carbon black, acetylene black, furnace black, carbon nanotubes, ketjen black, and graphene.

18. In paragraph 16, The first binder comprises at least one selected from the group consisting of an acrylate binder, a polyvinylidene fluoride binder, a polyvinylpyrrolidone binder, a polyvinyl alcohol binder, and a cellulose binder, An all-solid-state battery negative electrode slurry, wherein the second binder comprises at least one selected from the group consisting of a rubber-based binder, an imide-based binder, a nitrile-based binder, an acetate-based binder, and a cyano-based binder.

19. In the 16th paragraph, the average particle diameter (D50) of the negative electrode slurry is 0.1 μm to 0.5 μm, the negative electrode slurry for an all-solid-state battery.

20. A negative electrode for an all-solid-state battery manufactured by applying the negative electrode slurry of Article 16.

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