All-solid-state battery and method for manufacturing same

Abstract

The present invention relates to an all-solid-state battery and a method for manufacturing same. More specifically, the all-solid-state battery according to the present invention has a positive electrode active material layer that is surrounded by a positive electrode current collector and a solid electrolyte layer, thus preventing the positive electrode active material layer from sagging during a pressing process, and ensuring the structural stability of the battery.

Description

All-solid-state battery and method for manufacturing the same

[0001] This application claims the benefit of priority from Korean Patent Application No. 10-2023-0166203, dated November 27, 2023, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to an all-solid-state battery and a method for manufacturing the same.

[0003] Various batteries are being studied to overcome the limitations of current lithium secondary batteries in terms of battery capacity, stability, output, large-scale development, and miniaturization.

[0004] Representative examples include metal-air batteries with much larger theoretical capacity than lithium secondary batteries, all-solid-state batteries with no risk of explosion in terms of safety, supercapacitors for output, NaS batteries or RFBs (redox flow batteries) for large-scale applications, and thin film batteries for miniaturization, all of which are being continuously researched in academia and industry.

[0005] All-solid-state batteries replace the liquid electrolytes used in conventional lithium secondary batteries with solid electrolytes. Because they do not use flammable solvents, they eliminate the risk of ignition or explosion caused by decomposition reactions of conventional electrolytes, significantly improving safety. Furthermore, because lithium metal or lithium alloys can be used as a cathode material, they offer the advantage of dramatically improving the battery's energy density relative to its mass and volume.

[0006] Typically, in order to manufacture an all-solid-state battery, the cell is manufactured through a process of sequentially stacking a cathode, a solid electrolyte layer, and an anode, and a process of arranging the stack and then pressing the outer body. The electrodes and solid electrolyte layers used in all-solid-state batteries are not all the same size. Therefore, cracks may occur at the ends due to the size difference between the electrodes or solid electrolyte layers during the pressing process. In addition, the cathode is not rigid and has a characteristic of being widely spreadable due to the binder contained therein. Therefore, when pressing in one direction during the pressing process, a part of the cathode may be pushed to a part where the force is not applied, causing it to stretch unevenly, which may deteriorate the performance of the cell.

[0007] Figure 1 is a schematic diagram showing a longitudinal cross-section of an all-solid-state battery according to the prior art.

[0008] A unit cell (100) of an all-solid-state battery according to the prior art has a structure in which a positive electrode collector (111), a positive electrode active material layer (112), a solid electrolyte layer (120), and a negative electrode layer (130) are sequentially stacked. A stack cell (200) is formed by stacking a plurality of unit cells (100), and may be, for example, a stack of two or more unit cells (100). When manufacturing a unit cell (100), the area of ​​the positive electrode layer (110) including the positive electrode collector (111) and the positive electrode active material layer (112) is smaller than that of the adjacent solid electrolyte layer (120), so that it is not easy to align the solid electrolyte layer (120) on the positive electrode layer (110), and thus a misalignment may occur. In addition, after stacking the components as described above, when pressurized, a crack (C) may occur in the solid electrolyte layer (120) due to a difference in the area of ​​the adjacent positive electrode active material layer (112) and the solid electrolyte layer (120), and if the stacked structure itself collapses (D), contact between the positive electrode layer and the negative electrode layer may occur.

[0009] Therefore, there is a need for technological development that can secure the structural stability of all-solid-state batteries to prevent cracks or stretching of the anode during the pressurization process during cell assembly.

[0010] [Prior Art Literature]

[0011] [Patent Document]

[0012] (Patent Document 1) Japanese Patent Publication No. 2022-186164

[0013] The present inventors have conducted various studies to solve the above problems and have confirmed that in an all-solid-state battery including a unit cell or a stack cell in which multiple unit cells are stacked, among the unit cells including a cathode current collector, a cathode active material layer, a solid electrolyte layer, and an anode layer, a cathode active material layer having a relatively small size is surrounded by the cathode current collector and the solid electrolyte layer, thereby preventing problems such as the occurrence of cracks or stretching of the cathode during the pressurizing process by ensuring structural stability by preventing size deviations among the components included in the unit cell.

[0014] Accordingly, the purpose of the present invention is to provide an all-solid-state battery with secured structural stability and a method for manufacturing the same.

[0015] To achieve the above purpose, the present invention provides an all-solid-state battery including a unit cell,

[0016] The above unit cell includes an anode layer, a solid electrolyte layer formed on the anode layer, and a cathode layer formed on the solid electrolyte layer.

[0017] The above positive electrode layer includes a positive electrode current collector having a receiving portion formed to receive a portion of the positive electrode active material layer, and a positive electrode active material layer received in the receiving portion.

[0018] An all-solid-state battery is provided, wherein the solid electrolyte layer is formed in contact with the positive electrode current collector and the positive electrode active material layer.

[0019] In one embodiment of the present invention, an all-solid-state battery is provided, wherein the height of the receiving portion is smaller than the height of the positive electrode active material layer.

[0020] In one embodiment of the present invention, a part of the side surface of the positive electrode active material layer is in contact with the positive electrode current collector, and a part of the side surface is in contact with the solid electrolyte layer.

[0021] An all-solid-state battery is provided, wherein a portion of the positive electrode active material layer in contact with the positive electrode current collector is smaller than a portion in contact with the solid electrolyte layer.

[0022] In one embodiment of the present invention, the negative electrode layer includes a negative electrode current collector; and a negative electrode active material layer formed on the negative electrode current collector,

[0023] An all-solid-state battery is provided, wherein the negative active material layer is laminated so as to be in contact with the solid electrolyte layer.

[0024] In one embodiment of the present invention, the negative electrode layer includes a negative electrode current collector; and a non-cathode coating layer formed on the negative electrode current collector,

[0025] An all-solid-state battery is provided, wherein the above-mentioned non-cathode coating layer is laminated so as to be in contact with the above-mentioned solid electrolyte layer.

[0026] In one embodiment of the present invention, an all-solid-state battery is provided, wherein two or more unit cells are stacked.

[0027]

[0028] The present invention also comprises the steps of: (S1) forming a positive electrode active material layer on a positive electrode current collector having a receiving portion formed to receive a portion of the positive electrode active material layer;

[0029] (S2) A step of forming a solid electrolyte layer on the positive electrode current collector and positive electrode active material layer excluding the above-mentioned receiving portion;

[0030] (S3) forming a cathode layer on the solid electrolyte layer; and

[0031] (S4) A method for manufacturing an all-solid-state battery is provided, including a unit cell manufacturing process including a step of bonding the positive electrode current collector, the positive electrode active material layer, the solid electrolyte layer, and the negative electrode layer by applying pressure in the direction in which they are laminated.

[0032] In one embodiment of the present invention, a method for manufacturing an all-solid-state battery is provided, wherein the pressure is 400 MPa to 700 MPa.

[0033] The unit cell included in the all-solid-state battery of the present invention has a structure in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are sequentially laminated, such that a relatively small positive electrode active material layer is surrounded by a positive electrode current collector and a solid electrolyte layer, so that the cross-sectional area of ​​the unit cell is constant and structurally stable, and thus has the effect of preventing the occurrence of cracks even during a pressurizing process.

[0034] In addition, a part of the positive electrode active material layer is accommodated and in contact with the positive electrode current collector, and another part of the positive electrode active material layer is surrounded by a solid electrolyte layer, which has the effect of preventing the problem of the positive electrode active material layer stretching during the pressurizing process.

[0035] Figure 1 is a schematic diagram showing a longitudinal cross-section of an all-solid-state battery according to the prior art.

[0036] Figure 2 is a schematic diagram showing a longitudinal cross-section of an all-solid-state battery according to one embodiment of the present invention.

[0037] Figures 3a to 3d are schematic diagrams showing the cross-sectional structure of all-solid-state batteries manufactured in examples and comparative examples.

[0038] Figure 4 is a graph showing the experimental results on the life characteristics of all-solid-state batteries manufactured in examples and comparative examples.

[0039] Figures 5a to 5c show scanning electron microscope (SEM) images of cross-sections of all-solid-state batteries manufactured in examples and comparative examples.

[0040] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0041] The terms and words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0042]

[0043] All-solid-state batteries

[0044] The present invention relates to an all-solid-state battery.

[0045] An all-solid-state battery according to the present invention includes a unit cell, wherein the unit cell includes a positive electrode layer, a solid electrolyte layer formed on the positive electrode layer, and a negative electrode layer formed on the solid electrolyte layer, wherein the positive electrode layer includes a positive electrode current collector having a receiving portion formed therein in which a portion of the positive electrode active material layer is received, and a positive electrode active material layer received in the receiving portion, and the solid electrolyte layer is formed in contact with the positive electrode current collector and the positive electrode active material layer.

[0046] The above unit cell has a rectangular parallelepiped shape, and the cross-sectional areas of the positive electrode layer, the solid electrolyte layer, and the negative electrode layer are equal. Here, the cross-sectional area of ​​the positive electrode layer may be the cross-sectional area of ​​the positive electrode current collector, the cross-sectional area of ​​a portion including the positive electrode active material layer and the positive electrode current collector in contact with the positive electrode active material layer, or the cross-sectional area of ​​the positive electrode active material layer and the solid electrolyte layer in contact with the positive electrode active material layer.

[0047] In addition, since the unit cell does not include any heterogeneous materials or empty spaces other than the positive electrode layer, the solid electrolyte layer, and the negative electrode layer, problems such as structural instability or deterioration of battery performance due to heterogeneous materials or empty spaces can be prevented. Accordingly, the unit cell of the all-solid-state battery may be composed of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer.

[0048]

[0049] In one embodiment of the present invention, two or more unit cells may be stacked.

[0050] In the case of a stack cell in which two or more of the above unit cells are stacked, it also does not contain any heterogeneous materials or empty spaces. The stack cell may also have a rectangular parallelepiped shape.

[0051]

[0052] Figure 2 is a schematic diagram showing a longitudinal cross-section of an all-solid-state battery according to one embodiment of the present invention.

[0053] Referring to Fig. 2, the all-solid-state battery (10) may be in the form of a stack cell (200) in which two unit cells (100) are stacked. The positive electrode active material layer (112) is relatively small in size compared to the solid electrolyte layer (120) and the negative electrode layer (130). By designing the periphery of the positive electrode active material layer (112) to be surrounded by the positive electrode current collector (111) and the solid electrolyte layer (120), the step caused by the size difference between the positive electrode active material layer (112), the solid electrolyte layer (120), and the negative electrode layer (130) can be compensated for.

[0054] The positive electrode current collector (111) includes a body portion (111a) and a receiving portion (111b) in which a positive electrode active material layer (112) is received. The receiving portion (111b) is formed in a negative shape on the body portion (111a). A portion of the positive electrode active material layer (112) is received in the receiving portion (111b). The positive electrode active material layer (112) received in the receiving portion (111b) is surrounded by the positive electrode current collector (111).

[0055] Among the side lengths (H1+H2) of the positive electrode active material layer (112), the length (H1) of the side in contact with the positive electrode current collector (111) may be smaller than the length (H2) of the side in contact with the solid electrolyte layer (120). If the length (H1) of the side in contact with the positive electrode current collector (111) is large, the possibility of contact with the negative electrode layer (130) increases, which may cause a short circuit.

[0056] Since a portion of the positive electrode active material layer (112) is accommodated in the receiving portion (111b), the remaining positive electrode active material layer (112) that is not accommodated in the receiving portion (111b) is surrounded by the solid electrolyte layer (120). The solid electrolyte layer (120) is formed on the positive electrode active material layer (112). The solid electrolyte layer (120) is formed in a form that surrounds the remaining positive electrode active material layer (112) that is not accommodated in the receiving portion (111b) among the positive electrode active material layers (112). Therefore, the solid electrolyte layer (120) is also formed on the body portion (111a) of the positive electrode current collector (111) excluding the receiving portion (111b).

[0057] Since the positive electrode active material layer (112), which is relatively smaller than the solid electrolyte layer (120) and the negative electrode layer (130), is wrapped by the positive electrode current collector (111) and the solid electrolyte layer (120), the step due to the size difference is compensated for, and thus the unit cell (100) becomes a rectangular parallelepiped shape. Accordingly, the stack cell (200) in which the unit cells (100) are stacked also becomes a rectangular parallelepiped shape.

[0058] When a pressurizing process is performed by applying pressure in a certain direction to a rectangular parallelepiped unit cell (100) or stack cell (110), problems such as cracks or stretching of the anode can be prevented, thereby ensuring structural stability. In addition, since the anode does not stretch in a uniform shape, but spreads out while exhibiting irregularities in the stretching shape, it is difficult to secure a desired shape and area. However, in the present invention, stretching of the anode can be prevented, so the anode can be controlled to a desired shape and area.

[0059] In one embodiment of the present invention, the height of the receiving portion may be smaller than the height of the positive electrode active material layer.

[0060] Since only a portion of the positive electrode active material layer is accommodated in the above-mentioned receiving portion, the height of the receiving portion may preferably be smaller than the height of the positive electrode active material layer. Since the positive electrode active material layer is accommodated in the above-mentioned receiving portion, the positive electrode active material layer is fixed by the positive electrode active material layer, thereby preventing the positive electrode from sagging during the pressurizing process.

[0061]

[0062] In one embodiment of the present invention, a part of the side surface of the positive electrode active material layer is in contact with the positive electrode current collector, and a part of the side surface is in contact with the solid electrolyte layer. However, the length of the side surface of the positive electrode active material layer that is in contact with the positive electrode current collector may be smaller than the length of the side surface that is in contact with the solid electrolyte layer.

[0063] Based on the side surface of the positive electrode active material layer, a portion of the side surface of the positive electrode active material layer is accommodated in the receiving portion of the positive electrode current collector and comes into contact with the positive electrode current collector, and the remaining portion comes into contact with the solid electrolyte layer. If the length of the side surface of the positive electrode active material layer in contact with the positive electrode current collector is longer than the length in contact with the solid electrolyte layer, the probability of the positive electrode current collector coming into contact with the negative electrode increases, which may cause a short circuit.

[0064]

[0065] In one embodiment of the present invention, the positive electrode layer includes a positive electrode current collector and a positive electrode active material layer formed on one surface of the positive electrode current collector.

[0066] The above positive electrode current collector supports the positive electrode active material layer and serves to transfer electrons between the external conductor and the positive electrode active material layer.

[0067] In addition, the positive electrode current collector is not particularly limited as long as it has high electronic conductivity without causing chemical changes in the all-solid-state battery. For example, the positive electrode current collector may be made of aluminum, nickel, titanium, palladium, calcined carbon, copper, stainless steel, copper or stainless steel surface-treated with carbon, nickel, silver, etc., or an aluminum-cadmium alloy.

[0068] In addition, the positive electrode current collector may have a finely irregular structure on its surface or may employ a three-dimensional porous structure to strengthen the bonding strength with the positive electrode active material layer. Accordingly, the positive electrode current collector may include various forms such as a film, sheet, foil, mesh, net, porous body, foam, or non-woven fabric.

[0069]

[0070] The above positive electrode active material layer may be formed with an area smaller than the positive electrode current collector and positioned on the positive electrode current collector.

[0071] The above positive electrode active material layer includes a positive electrode active material, a conductive material, and a binder. In addition, the positive electrode active material layer may further include a solid electrolyte.

[0072] In addition, the positive electrode active material is not particularly limited as long as it is a material capable of reversibly absorbing and releasing lithium ions, and examples thereof include lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), and Li[Ni x Co y Mn z M v ]O2 (wherein M is one or two or more elements selected from the group consisting of Al, Ga, and In; 0.3≤x<1.0, 0≤y, z≤0.5, 0≤v≤0.1, x+y+z+v=1), Li(Li a M b-a-b' M' b' )O 2-c A c(In the above formula, 0≤a≤0.2, 0.6≤b≤1, 0≤b'≤0.2, 0≤c≤0.2; M includes at least one selected from the group consisting of Mn and Ni, Co, Fe, Cr, V, Cu, Zn and Ti; M' is at least one selected from the group consisting of Al, Mg and B, and A is at least one selected from the group consisting of P, F, S and N.) layered compounds or compounds substituted with one or more transition metals; chemical formula Li 1+y Mn 2-y Lithium manganese oxides such as O4 (where y is 0 to 0.33), LiMnO3, LiMn2O3, LiMnO2; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, LiFe3O4, V2O5, Cu2V2O7; chemical formula LiNi 1-y Ni-site type lithium nickel oxide represented by MyO2 (wherein, M=Co, Mn, Al, Cu, Fe, Mg, B or Ga, and y is 0.01 to 0.3); chemical formula LiMn 2-y M y Lithium manganese composite oxides represented by O2 (wherein M is Co, Ni, Fe, Cr, Zn or Ta, and y is 0.01 to 0.1) or Li2Mn3MO8 (wherein M is Fe, Co, Ni, Cu or Zn); LiMn2O4 in which a portion of Li in the chemical formula is replaced by an alkaline earth metal ion; disulfide compounds; Fe2(MoO4)3, etc., but are not limited thereto.

[0073] In addition, the positive electrode active material may be included in an amount of 60 to 80 wt% based on the total weight of the positive electrode active material layer. Specifically, the content of the positive electrode active material may be 60 wt%, 65 wt% or more, or 68 wt% or more, and may be 72 wt% or less, 75 wt% or less, or 80 wt% or less. If the content of the positive electrode active material is less than 60 wt%, battery performance may deteriorate, and if it is more than 80 wt%, mass transfer resistance may increase.

[0074]

[0075] In addition, the solid electrolyte may have an argyrodite structure, and specifically, may include a sulfide-based solid electrolyte, a halide-based solid electrolyte, or an oxide-based solid electrolyte.

[0076] The above sulfide-based solid electrolyte may include a compound represented by the following chemical formula 1 or a mixture thereof:

[0077] <Chemical Formula 1>

[0078] Li a M b S c X d

[0079] In the above chemical formula 1, M is selected from P, Sn, Sb, As, and Ge;

[0080] The above X is selected from Cl, Br and I,

[0081] 5 ≤ a ≤ 7.5, 0.5 < b ≤ 1.5, 4 < c ≤ 6, and 0.5 < d ≤ 2.

[0082] The above halide-based solid electrolyte may be represented by the following chemical formula 2:

[0083] <Chemical Formula 2>

[0084] Li 6-3a M a Br b Cl c

[0085] In the above chemical formula 2, M is a metal other than Li, and a is 0 <a<2 이고, b는 0≤b≤6 이고, c는 0≤c≤6 이며, b+c=6 이다.

[0086] For example, the halide solid electrolyte may include at least one selected from the group consisting of Li3YBr6, Li3YCl6, and Li3YBr2Cl4.

[0087] The above oxide-based solid electrolyte is Li 3x La 2 / 3-x LLT system with perovskite structure such as TiO3, Li 14 LISICON, Li such as Zn(GeO4)4 1.3 Al 0.3 Ti 1.7 LATP series such as (PO4)3, (Li 1+x Ge 2-x Al x LAGP systems such as (PO4)3) and phosphate systems such as LiPON can be appropriately selected and used, but are not particularly limited thereto.

[0088]

[0089] In addition, the conductive material is not particularly limited as long as it prevents side reactions in the internal environment of the all-solid-state battery, does not cause chemical changes in the battery, and has excellent electrical conductivity. Representative examples thereof include graphite or conductive carbon, and examples thereof include graphite such as natural graphite and artificial graphite; carbon black such as carbon black, acetylene black, Ketjen black, Denka black, thermal black, channel black, furnace black, lamp black, and summer black; carbon-based materials having a crystal structure of graphene or graphite; conductive fibers such as carbon fiber and metal fiber; fluorinated carbon; metal powder such as aluminum powder and nickel powder; conductive whiskey such as zinc oxide and potassium titanate; conductive oxides such as titanium oxide; and conductive polymers such as polyphenylene derivatives; which may be used alone or in combination of two or more thereof, but are not necessarily limited thereto. Preferably, the conductive material may include vapor-grown carbon fiber (VGCF).

[0090] The conductive material may typically be included in an amount of 1 wt% to 5 wt% based on the total weight of the positive electrode active material layer, and specifically, the content of the conductive material may be 1 wt% or more, 1.5 wt% or more, or 2 wt% or more, and 4 wt% or less, 4.5 wt% or less, or 5 wt% or less. If the content of the conductive material is too low, such as less than 1 wt%, it may be difficult to expect an effect of improving electrical conductivity or the electrochemical characteristics of the battery may deteriorate, and if it exceeds 5 wt%, the amount of positive electrode active material may be relatively small, which may lower the capacity and energy density. The method of including the conductive material in the positive electrode is not particularly limited, and conventional methods known in the art, such as mixing or coating with the positive electrode active material, may be used.

[0091]

[0092] In addition, the binder is a component that assists in the bonding of the positive electrode active material and the conductive material and the bonding to the current collector, and includes styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile copolymer, acrylonitrile-butadiene rubber, nitrile butadiene rubber, acrylonitrile-styrene-butadiene copolymer, acrylic rubber, butyl rubber, fluorine rubber, polytetrafluoroethylene, polyethylene, polypropylene, ethylene / propylene copolymer, polybutadiene, polyethylene oxide, chlorosulfonated polyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyvinyl alcohol, polyvinyl acetate, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, polystyrene, latex, acrylic resin, phenol resin, epoxy resin, carboxymethylcellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate It may include at least one selected from the group consisting of butyrate, cellulose acetate propionate, cyanoethylcellulose, cyanoethylsucrose, polyester, polyamide, polyether, polyimide, polycarboxylate, polycarboxylic acid, polyacrylic acid, polyacrylate, lithium polyacrylate, polymethacrylic acid, polymethacrylate, polyacrylamide, polyurethane, polyvinylidene fluoride, and poly(vinylidene fluoride)-hexafluoropropene. Preferably, the binder may include polytetrafluoroethylene (PTFE).

[0093] In addition, the binder may be included in an amount of 0.5 wt% to 4 wt% based on the total weight of the positive electrode active material layer, and specifically, the content of the binder may be 0.5 wt% or more, 1 wt% or more, or 1.5 wt% or more, and 3 wt% or less, 3.5 wt% or less, or 4 wt% or less. If the content of the binder is less than 0.5 wt%, the adhesive strength between the positive electrode active material and the positive electrode current collector may be reduced, and if it exceeds 4 wt%, the adhesive strength may be improved, but the content of the positive electrode active material may be reduced, which may lower the battery capacity.

[0094]

[0095] In one embodiment of the present invention, the solid electrolyte layer may be wider than the area of ​​the positive electrode active material layer. Here, the area of ​​the solid electrolyte layer and the area of ​​the positive electrode active material layer refer to the areas when the solid electrolyte layer and the positive electrode active material layer are viewed from above.

[0096] Since the above solid electrolyte layer is formed to surround the positive electrode active material layer, the lithium ion transfer area increases, which can be advantageous in terms of ion conductivity.

[0097] Additionally, the solid electrolyte layer may include a sulfide-based solid electrolyte, a halide-based solid electrolyte, or an oxide-based solid electrolyte. In terms of lithium ion conductivity, the solid electrolyte layer may include a sulfide-based solid electrolyte having an argyrodite-type crystal structure.

[0098] The above sulfide-based solid electrolyte may include a compound represented by the following chemical formula 1 or a mixture thereof:

[0099] <Chemical Formula 1>

[0100] Li a M b A c X d

[0101] In the above chemical formula 1, M is selected from P, Sn, Sb, As, and Ge;

[0102] The above A is selected from S, Se and Te,

[0103] The above X is selected from Cl, Br and I,

[0104] 5 ≤ a ≤ 7.5, 0.5 < b ≤ 1.5, 4 < c ≤ 6, and 0.5 < d ≤ 2.

[0105] The above halide-based solid electrolyte may be represented by the following chemical formula 2:

[0106] <Chemical Formula 2>

[0107] Li 6-3a M a Br b Cl c

[0108] In the above chemical formula 1, M is a metal other than Li, and a is 0 <a<2 이고, b는 0≤b≤6 이고, c는 0≤c≤6 이며, b+c=6 이다.

[0109] For example, the halide solid electrolyte may include at least one selected from the group consisting of Li3YBr6, Li3YCl6, and Li3YBr2Cl4.

[0110] The above oxide-based solid electrolyte is Li 3x La 2 / 3-x LLT system with perovskite structure such as TiO3, Li 14 LISICON, Li such as Zn(GeO4)4 1.3 Al 0.3 Ti 1.7 LATP series such as (PO4)3, (Li 1+x Ge 2-x Al x LAGP systems such as (PO4)3) and phosphate systems such as LiPON can be appropriately selected and used, but are not particularly limited thereto.

[0111]

[0112] In one embodiment of the present invention, the negative electrode layer includes a negative electrode current collector; and a negative electrode active material layer formed on the negative electrode current collector, and the negative electrode active material layer may be laminated so as to be in contact with the solid electrolyte layer.

[0113] Alternatively, the cathode layer may include a cathode current collector; and a non-cathode coating layer formed on the cathode current collector, and the non-cathode coating layer may be laminated so as to be in contact with the solid electrolyte layer.

[0114]

[0115] The above negative electrode active material layer includes a negative electrode active material, a binder, and a conductive material.

[0116] The above negative active material is lithium (Li + ) can be reversibly intercalated or deintercalated, a material that can react with lithium ions to form a reversibly lithium-containing compound, or a lithium metal or a lithium alloy.

[0117] The above lithium ion (Li + ) can be reversibly inserted or de-inserted, for example, crystalline carbon, amorphous carbon, or a mixture thereof. The lithium ion (Li + ) can be, for example, tin oxide, titanium nitrate or silicon. The lithium alloy can be, for example, an alloy of lithium (Li) and a metal selected from the group consisting of indium (In), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), aluminum (Al) and tin (Sn).

[0118] Preferably, the negative electrode active material may be lithium metal or a lithium-indium alloy (Li-In), and specifically, may be in the form of a lithium metal or lithium and a thin film or a lithium-indium alloy thin film or powder.

[0119] The negative electrode active material may be included in an amount of 40 to 80 wt% based on the total weight of the negative electrode active material layer. Specifically, the content of the negative electrode active material may be 40 wt% or more or 50 wt% or more, and 70 wt% or less or 80 wt% or less. If the content of the negative electrode active material is less than 40 wt%, the connectivity between the wet negative electrode active material layer and the dry negative electrode active material layer may be insufficient, and if it exceeds 80 wt%, the material transfer resistance may increase.

[0120] In addition, the binder is a component that assists in the bonding of the negative electrode active material and the conductive material and the bonding to the negative electrode current collector, and includes styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile copolymer, acrylonitrile-butadiene rubber, nitrile butadiene rubber, acrylonitrile-styrene-butadiene copolymer, acrylic rubber, butyl rubber, fluorine rubber, polytetrafluoroethylene, polyethylene, polypropylene, ethylene / propylene copolymer, polybutadiene, polyethylene oxide, chlorosulfonated polyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyvinyl alcohol, polyvinyl acetate, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, polystyrene, latex, acrylic resin, phenol resin, epoxy resin, carboxymethylcellulose, hydroxypropyl cellulose, cellulose acetate, cellulose It may include at least one selected from the group consisting of acetate butyrate, cellulose acetate propionate, cyanoethylcellulose, cyanoethylsucrose, polyester, polyamide, polyether, polyimide, polycarboxylate, polycarboxylic acid, polyacrylic acid, polyacrylate, lithium polyacrylate, polymethacrylic acid, polymethacrylate, polyacrylamide, polyurethane, polyvinylidene fluoride, and poly(vinylidene fluoride)-hexafluoropropene. Preferably, the binder may include polytetrafluoroethylene (PTFE).

[0121] In addition, the binder may be included in an amount of 0.5 wt% to 4 wt% based on the total weight of the negative electrode active material layer, and specifically, the content of the binder may be 0.5 wt% or more, 1 wt% or more, or 1.5 wt% or more, and 3 wt% or less, 3.5 wt% or less, or 4 wt% or less. If the content of the binder is less than 0.5 wt%, the adhesive strength between the positive electrode active material and the negative electrode current collector may be reduced, and if it exceeds 4 wt%, the adhesive strength may be improved, but the content of the negative electrode active material may be reduced, which may lower the battery capacity.

[0122]

[0123] In addition, the conductive material is not particularly limited as long as it prevents side reactions in the internal environment of the all-solid-state battery, does not cause chemical changes in the battery, and has excellent electronic conductivity. Representative examples thereof include graphite or conductive carbon, and examples thereof include graphite such as natural graphite and artificial graphite; carbon black such as carbon black, acetylene black, Ketjen black, Denka black, thermal black, channel black, furnace black, lamp black, and summer black; carbon-based materials having a crystal structure of graphene or graphite; conductive fibers such as carbon fiber and metal fiber; fluorinated carbon; metal powder such as aluminum powder and nickel powder; conductive whiskey such as zinc oxide and potassium titanate; conductive oxides such as titanium oxide; and conductive polymers such as polyphenylene derivatives; which may be used alone or in combination of two or more thereof, but are not necessarily limited thereto. Preferably, the conductive material may include vapor-grown carbon fiber (VGCF).

[0124] The conductive material may typically be included in an amount of 1 wt% to 5 wt% based on the total weight of the negative electrode active material layer, and specifically, the content of the conductive material may be 1 wt% or more, 1.5 wt% or more, or 2 wt% or more, and 4 wt% or less, 4.5 wt% or less, or 5 wt% or less. If the content of the conductive material is too low, less than 1 wt%, it may be difficult to expect the effect of improving electronic conductivity or the electrochemical characteristics of the battery may deteriorate, and if it exceeds 5 wt%, the amount of the negative electrode active material may be relatively small, which may lower the capacity and energy density. The method of including the conductive material in the negative electrode is not particularly limited, and conventional methods known in the art, such as mixing with the negative electrode active material or coating, may be used.

[0125] In addition, the negative electrode current collector is not particularly limited as long as it is conductive and does not cause a chemical change in the battery. For example, the negative electrode current collector may be made of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, etc., an aluminum-cadmium alloy, etc. In addition, the negative electrode current collector, like the positive electrode current collector, may be made of various forms such as a film, sheet, foil, net, porous body, foam, non-woven fabric, etc. having fine irregularities formed on the surface.

[0126] The method for manufacturing the above negative electrode is not particularly limited, and can be manufactured by forming a negative electrode active material layer on the negative electrode current collector using a method for forming a layer or film commonly used in the art. For example, methods such as compression, coating, and deposition can be used. In addition, a case in which a battery is assembled on the negative electrode current collector without a lithium thin film and then a metallic lithium thin film is formed on the metal plate through initial charging is also included in the negative electrode of the present invention.

[0127]

[0128] In addition, the non-cathode coating layer does not contain a negative electrode active material, and a negative electrode active material may be formed in the non-cathode coating layer by charging. For example, when the battery is charged, lithium ions may move from the positive electrode and lithium metal may be precipitated from the negative electrode. In other words, the non-cathode coating layer may be a film that induces lithium precipitation.

[0129] The above-mentioned cathode-free coating layer may include metal particles and carbon material particles, and specifically, may include a carbon material-metal composite.

[0130] The above carbon material particles may be, for example, amorphous carbon material particles. However, the carbon material particles are not limited to amorphous particles. Specific examples of the amorphous carbon material include carbon black such as acetylene black, furnace black, and Ketjen black, graphene, or combinations thereof.

[0131] In addition, the metal particles may be particles that form an alloy with lithium, and the metal particles may be at least one type of particle selected from silver (Ag), gold, platinum, palladium, silicon, aluminum, bismuth, tin, indium, and zinc. The non-cathode coating layer may be formed as a very thin film with a micro-thickness, and may be formed with a thickness of, for example, 10 μm or less.

[0132] Preferably, the non-cathode coating layer may include an Ag-C composite as a carbon material-metal composite, and upon first charging, lithium may be precipitated between the negative electrode current collector and the coating layer including the Ag-C composite.

[0133]

[0134] In one embodiment of the present invention, the all-solid-state battery may be a pouch-type all-solid-state battery.

[0135]

[0136] Manufacturing method of all-solid-state battery

[0137] The present invention also relates to a method for manufacturing an all-solid-state battery.

[0138] The method for manufacturing an all-solid-state battery according to the present invention includes a unit cell manufacturing process including the following steps (S1) to (S4):

[0139] (S1) A step of forming a positive electrode active material layer on a positive electrode current collector having a receiving portion formed to receive a portion of the positive electrode active material layer;

[0140] (S2) A step of forming a solid electrolyte layer on the positive electrode current collector and positive electrode active material layer excluding the above-mentioned receiving portion;

[0141] (S3) forming a cathode layer on the solid electrolyte layer; and

[0142] (S4) A step of bonding the positive electrode current collector, positive electrode active material layer, solid electrolyte layer, and negative electrode layer by applying pressure in the direction in which they are laminated.

[0143] The constituent materials and shapes of the positive electrode current collector, positive electrode active material layer, solid electrolyte layer, and negative electrode layer are as described above.

[0144] Below, the method for manufacturing an all-solid-state battery according to the present invention is described in more detail step by step.

[0145]

[0146] In one embodiment of the present invention, in the step (S1), a positive electrode active material layer can be formed on a positive electrode current collector in which a receiving portion for receiving a portion of the positive electrode active material layer is formed.

[0147] The above positive electrode active material layer can be manufactured by a wet process or a dry process, respectively. The positive electrode manufactured according to the manufacturing process of the positive electrode active material layer may be referred to as a wet positive electrode and a dry positive electrode, respectively.

[0148] When the above wet process is performed, the positive electrode active material layer can be formed by applying a slurry for forming a positive electrode active material layer onto a positive electrode current collector. Specifically, the positive electrode active material layer can be prepared by applying and drying a slurry for forming a positive electrode active material layer prepared by mixing a positive electrode active material, a conductive material, and a binder in an organic solvent onto a receiving portion of a positive electrode current collector. At this time, it is preferable to use an organic solvent that can uniformly disperse the positive electrode active material, the binder, and the conductive material, and that is easily evaporated. Specifically, examples thereof include acetonitrile, methanol, ethanol, tetrahydrofuran, water, and isopropyl alcohol.

[0149] In addition, when the above dry process is performed, the positive electrode active material layer may be separately manufactured in the form of a sheet, then formed by punching it out to a size to be accommodated in the receiving portion of the positive electrode current collector and bonding it to the receiving portion of the positive electrode current collector. At this time, the sheet may be manufactured by a conventional method using the slurry for forming the positive electrode active material layer as described above.

[0150]

[0151] In one embodiment of the present invention, in the step (S2), a solid electrolyte layer can be formed on the positive electrode current collector and the positive electrode active material layer excluding the receiving portion.

[0152] The above-described positive electrode current collector includes a body portion and a receiving portion engraved on the body portion. A positive electrode active material layer is formed on the receiving portion. Therefore, when the solid electrolyte layer is formed on the positive electrode active material layer, a solid electrolyte layer can also be formed on the body portion of the positive electrode current collector, excluding the receiving portion.

[0153] The above solid electrolyte layer can be manufactured by applying a slurry obtained by mixing a solid electrolyte and a binder in a solvent onto the positive electrode active material layer and then drying it.

[0154] The above solid electrolyte may include at least one selected from the group consisting of a sulfide-based solid electrolyte, a halide-based solid electrolyte, and an oxide-based solid electrolyte, as described above. Preferably, the solid electrolyte may include a sulfide-based solid electrolyte having an argyrodite-type crystal structure.

[0155] In addition, the binder resin may include at least one selected from the group consisting of an acrylic copolymer, an acrylic block copolymer, and a random copolymer of an acrylic monomer or oligomer.

[0156] In addition, the binder may be included in an amount of 5 to 15 parts by weight based on 100 parts by weight of the solid electrolyte. Specifically, the content of the binder may be 5 parts by weight or more, 7 parts by weight or more, or 9 parts by weight or more, or 11 parts by weight or less, 13 parts by weight or less, or 15 parts by weight or less. If the content of the binder is less than 5 parts by weight, it may be difficult to form a solid electrolyte layer, and if it exceeds 15 parts by weight, ionic conductivity may decrease.

[0157] In addition, the solvent is not particularly limited as long as it is a solvent that can dissolve and / or disperse the solid electrolyte and / or binder to form a slurry. For example, the solvent may be at least one selected from the group consisting of dimethylsulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, xylene, dimethylformamide (N,N-Dimethylmethanamide (DMF), benzene, tetrahydrofuran (THF), and water. The amount of the solvent used may be adjusted in consideration of the coating thickness of the coating layer, the physical properties of the solid electrolyte to be manufactured, etc.

[0158] The above coating method may be bar coating, roll coating, spin coating, slit coating, die coating, blade coating, comma coating, slot die coating, lip coating, or solution casting, but is not limited thereto as long as it is a method capable of forming a layer by coating.

[0159] The drying method described above is not particularly limited as long as it can form a film (layer) by evaporating the solvent after application. For example, the drying may be performed at a temperature of 300°C or lower. Specifically, the drying temperature may be 300°C or lower, 200°C or lower, 150°C or lower, or 100°C or lower.

[0160]

[0161] In one embodiment of the present invention, in the step (S3), a cathode layer can be formed on the solid electrolyte layer.

[0162] The method for forming the cathode layer on the above solid electrolyte layer is not particularly limited as long as it is a method commonly practiced in the art, and a method such as lamination can be used.

[0163]

[0164] In one embodiment of the present invention, in the step (S4), the positive electrode current collector, the positive electrode active material layer, the solid electrolyte layer, and the negative electrode layer can be bonded by applying pressure in the direction in which they are laminated.

[0165] The above step (S4) represents a process of pressurizing after manufacturing a unit cell, but pressurizing may be performed after manufacturing a stack cell, or pressurizing may be performed after placing it in an outer material.

[0166] The above pressure may be 400 MPa to 700 MPa, and specifically, may be 400 MPa or more, 450 MPa or more, or 500 MPa or more, and 600 MPa or less, 650 MPa or less, or 700 MPa or less. If the pressure is less than 400 MPa, the pressure may be insufficient to manufacture an all-solid-state battery, or pores may remain inside the positive electrode, which may increase resistance, and if it exceeds 700 MPa, excessive pressure may be applied, which may cause breakage in a part of the battery.

[0167] Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0168]

[0169] Example 1

[0170] An all-solid-state battery (10) having a cross-sectional structure as shown in Fig. 3a was manufactured.

[0171] Aluminum foil was prepared as a cathode current collector (111). The aluminum foil includes a body portion and a receiving portion engraved on the body portion.

[0172] After attaching a dry sheet containing NMC (Ni, Co, Mn) O2 to the above-mentioned receiving portion, a positive electrode active material layer (112) was formed to manufacture a positive electrode layer (110).

[0173] After that, a slurry for forming a solid electrolyte was dip-coated on the body portion and the positive electrode active material layer (112), which are portions of the positive electrode current collector (111) excluding the receiving portion, and then dried to form a solid electrolyte layer (120). The slurry for forming a solid electrolyte was prepared by mixing a sulfide-based solid electrolyte having an argyrodite-based crystal structure and a rubber-based binder in a weight ratio of 1:1 and then adding the mixture to an N-methylpyrrolidone (NMP) solvent.

[0174] The above positive electrode active material layer (112) is formed to be surrounded by the positive electrode current collector (111) and the solid electrolyte layer (120). In terms of the positive electrode active material layer (112), the length in contact with the positive electrode current collector (111) is made shorter than the length in contact with the solid electrolyte layer (120).

[0175] Thereafter, a cathode layer (130) was laminated on the solid electrolyte layer (120) and pressurized at a pressure of 500 MPa to manufacture an all-solid-state battery (10) in the form of a unit cell. The cathode layer (130) was an anodeless one in which an Ag-C complex was formed on one surface of a Cu current collector.

[0176]

[0177] Example 2

[0178] An all-solid-state battery (10) having a cross-sectional structure as shown in Fig. 3b was manufactured.

[0179] Aluminum foil was prepared as a cathode current collector (111). The aluminum foil includes a body portion and a receiving portion engraved on the body portion.

[0180] A positive electrode (110) was manufactured by forming a positive electrode active material layer (112) by coating a slurry containing NMC (Ni, Co, Mn) O2 on the above-mentioned receiving portion.

[0181] After that, a slurry for forming a solid electrolyte was dip-coated on the body portion and the positive electrode active material layer (112), which are portions of the positive electrode current collector (111) excluding the receiving portion, and then dried to form a solid electrolyte layer (120). The slurry for forming a solid electrolyte was prepared by mixing a sulfide-based solid electrolyte having an argyrodite-based crystal structure and a rubber-based binder in a weight ratio of 1:1 and then adding the mixture to an N-methylpyrrolidone (NMP) solvent.

[0182] The above positive electrode active material layer (112) is formed to be surrounded by the positive electrode current collector (111) and the solid electrolyte layer (120). In terms of the positive electrode active material layer (112), the length in contact with the positive electrode current collector (111) is made shorter than the length in contact with the solid electrolyte layer (120).

[0183] Thereafter, a cathode layer (130) was laminated on the solid electrolyte layer (120) and pressurized at a pressure of 500 Mpa to manufacture a unit cell-type all-solid-state battery (10). The cathode layer was an anodeless one, in which an Ag-C complex was formed on one surface of a Cu current collector.

[0184]

[0185] Comparative Example 1

[0186] An all-solid-state battery having a cross-sectional structure as shown in Fig. 3c was manufactured.

[0187] After laminating the positive electrode layer (110), the solid electrolyte layer (120), and the negative electrode layer (130), a pressure of 500 MPa was applied to manufacture an all-solid-state battery (10). Here, the positive electrode layer (110), the solid electrolyte layer (120), and the negative electrode layer (130) were all in the form of sheets, and their sizes were arranged in the order of positive electrode layer (110) 〈negative electrode layer (130) 〈solid electrolyte layer (120). In addition, the constituent materials of the positive electrode layer (110), the solid electrolyte layer (120), and the negative electrode layer (130) were the same as in Example 2.

[0188]

[0189] Comparative Example 2

[0190] An all-solid-state battery having a cross-sectional structure as shown in Figure 3d was manufactured.

[0191] An all-solid-state battery was manufactured in the same manner as in Comparative Example 1, except that the sizes of the positive electrode layer (110), the solid electrolyte layer (120), and the negative electrode layer (130) were all the same.

[0192]

[0193] Experimental Example 1: All-solid-state battery performance evaluation experiment

[0194] Performance evaluation experiments were conducted on all-solid-state batteries.

[0195] In order to evaluate the performance of the above all-solid-state battery, the discharge capacity according to the cycle was measured under 0.33C / 0.33C conditions to evaluate the life characteristics.

[0196] As a result, as shown in Fig. 4, it can be seen that Examples 1 and 2 have significantly better life characteristics than Comparative Examples 1 and 2. It can be seen that these results are due to the structural stability of the all-solid-state battery.

[0197]

[0198] Experimental Example 2: Checking for Cracks

[0199] It was confirmed whether cracks occurred in the all-solid-state battery due to the pressurization process.

[0200] The cross-sections of the unit cells of Examples 1 and 2 and Comparative Examples 1 and 2 were observed using a scanning electron microscope (SEM).

[0201] Figures 5a to 5c show scanning electron microscope (SEM) images of cross-sections of all-solid-state batteries manufactured in examples and comparative examples.

[0202] Figure 5a shows that there is no damage overall, including cracks, in the cross-section of the battery.

[0203] In addition, referring to FIGS. 5b and 5c, it can be seen that the anode layer (110) stretches and cracks occur, and the cracks in that part extend to the solid electrolyte layer (130).

[0204]

[0205] Although the present invention has been described above with reference to limited embodiments and drawings, the present invention is not limited thereto, and it is obvious that various modifications and variations are possible within the scope of the technical idea of ​​the present invention and the equivalent scope of the patent claims to be described below by a person having ordinary skill in the art to which the present invention pertains.

[0206]

[0207] [Explanation of symbols]

[0208] 10: All-solid-state batteries

[0209] 100: Unit cell

[0210] 110: Bipolar layer

[0211] 111: Positive current collector,

[0212] 111a: Body, 111b: Receptacle

[0213] 112: Positive electrode active material layer

[0214] 120: Solid electrolyte layer

[0215] 130: Cathode layer

[0216] 131: Negative current collector, 132: Negative active material layer

[0217] 200: Stack Cell

[0218] C: Crack, D: Collapse

Claims

1. An all-solid-state battery comprising a unit cell, The above unit cell includes an anode layer, a solid electrolyte layer formed on the anode layer, and a cathode layer formed on the solid electrolyte layer. The above positive electrode layer comprises a positive electrode current collector having a receiving portion formed to receive a portion of the positive electrode active material layer, and a positive electrode active material layer received in the receiving portion. An all-solid-state battery, wherein the solid electrolyte layer is formed in contact with the positive electrode current collector and the positive electrode active material layer.

2. In paragraph 1, An all-solid-state battery, wherein the height of the receiving portion is smaller than the height of the positive electrode active material layer.

3. In paragraph 1, A part of the side surface of the above positive electrode active material layer is in contact with the positive electrode current collector, and the remaining part is in contact with the solid electrolyte layer. An all-solid-state battery, wherein a portion of the positive electrode active material layer in contact with the positive electrode current collector is smaller than a portion in contact with the solid electrolyte layer.

4. In paragraph 1, The above negative electrode layer includes a negative electrode current collector; and a negative electrode active material layer formed on the negative electrode current collector, An all-solid-state battery, wherein the negative active material layer is laminated so as to be in contact with the solid electrolyte layer.

5. In paragraph 1, The above cathode layer includes a cathode current collector; and a non-cathode coating layer formed on the cathode current collector, An all-solid-state battery, wherein the non-cathode coating layer is laminated so as to be in contact with the solid electrolyte layer.

6. In paragraph 1, An all-solid-state battery in which two or more of the above unit cells are stacked.

7. (S1) A step of forming a positive electrode active material layer on a positive electrode current collector having a receiving portion formed to receive a portion of the positive electrode active material layer; (S2) A step of forming a solid electrolyte layer on the positive electrode current collector and positive electrode active material layer excluding the above-mentioned receiving portion; (S3) a step of forming a cathode layer on the solid electrolyte layer; and (S4) A method for manufacturing an all-solid-state battery, including a unit cell manufacturing process, comprising the step of bonding the positive electrode current collector, the positive electrode active material layer, the solid electrolyte layer, and the negative electrode layer by applying pressure in the direction in which they are laminated.

8. In paragraph 7, A method for manufacturing an all-solid-state battery, wherein the pressure is 400 MPa to 700 MPa.

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