All-solid-state battery and method for producing same

Abstract

The present invention relates to a positive electrode for an all-solid-state battery, an all-solid-state battery comprising same, and a method for producing the all-solid-state battery. More specifically, the positive electrode comprises a positive electrode current collector, and a positive electrode active material layer provided thereon, wherein the positive electrode active material of the positive electrode active material layer comprises large and small particles of differing average particle diameter, and the positive electrode active material layer comprises a plurality of engraved patterns thereon, the maximum depth in a third direction of each of the plurality of engraved patterns being smaller than the average particle diameter of the large particles and larger than the average particle diameter of the small particles.

Description

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

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

[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] Recently, all-solid-state batteries have been proposed, replacing the electrolyte in lithium-ion batteries with a solid electrolyte. By eliminating the use of flammable organic dispersion media, all-solid-state batteries significantly reduce the risk of fire or explosion in the event of a short circuit. Therefore, these all-solid-state batteries can offer superior safety.

[0004] The problem to be solved by the present invention is to provide an all-solid-state battery having excellent battery capacity and rapid charging characteristics.

[0005] Another problem to be solved by the present invention is to provide a method for manufacturing an all-solid-state battery having excellent battery capacity and rapid charging characteristics.

[0006] A positive electrode for an all-solid-state battery according to the concept of the present invention comprises: a positive electrode current collector; and a positive electrode active material layer provided on the positive electrode current collector, wherein the positive electrode active material of the positive electrode active material layer includes large and small particles having different average particle diameters, and the positive electrode active material layer may include a plurality of negative patterns provided thereon. A maximum depth of each of the plurality of negative patterns in a third direction may be smaller than the average particle diameter of the large particles and larger than the average particle diameter of the small particles.

[0007] An all-solid-state battery according to another concept of the present invention comprises a cathode layer, the cathode layer including a cathode current collector and a cathode active material layer on the cathode current collector;

[0008] A cathode layer; and a solid electrolyte layer provided between the cathode layer and the cathode layer, wherein the cathode active material of the cathode active material layer includes large and small particles having different average particle diameters, and the cathode active material layer may include a plurality of negative patterns provided thereon. The solid electrolyte particles of the solid electrolyte layer may fill each of the plurality of negative patterns. The maximum depth of each of the plurality of negative patterns in the third direction may be smaller than the average particle diameter of the large particles and larger than the average particle diameter of the small particles.

[0009] Another method for manufacturing an all-solid-state battery according to the present invention may include: forming a positive electrode layer having a plurality of negative patterns by pressing a positive electrode active material layer with a first pressure using a pressurizer having a plurality of positive patterns formed thereon; forming a positive electrode laminate by laminating the positive electrode layer and a first solid electrolyte layer and then applying a second pressure; forming a negative electrode laminate by laminating a negative electrode layer and a second solid electrolyte layer and then applying a third pressure; and combining the positive electrode laminate and the negative electrode laminate so that the first solid electrolyte layer and the second solid electrolyte layer are in contact with each other. The maximum depth of each of the plurality of negative patterns in the third direction may be smaller than the average particle diameter of the large particles and larger than the average particle diameter of the small particles.

[0010] The positive electrode and the all-solid-state battery including the same according to embodiments of the present invention have low internal resistance and excellent battery capacity by including a positive electrode active material layer having a predetermined pattern formed therein.

[0011] In addition, the all-solid-state battery according to embodiments of the present invention has excellent structural stability and life characteristics by making the thickness and area of ​​the second solid electrolyte layer adjacent to the cathode layer larger than the thickness and area of ​​the first solid electrolyte layer adjacent to the cathode layer.

[0012] Figure 1 is a cross-sectional view of an all-solid-state battery according to one embodiment of the present invention.

[0013] Figure 2 is a plan view of an all-solid-state battery according to one embodiment of the present invention.

[0014] Figure 3 is a cross-sectional view of an all-solid-state battery according to another embodiment of the present invention.

[0015] Figure 4 is a cross-sectional view of an all-solid-state battery according to another embodiment of the present invention.

[0016] Figure 5 is a cross-sectional view of an all-solid-state battery according to another embodiment of the present invention.

[0017] Figure 6 is a cross-sectional view of an all-solid-state battery according to another embodiment of the present invention.

[0018] Figure 7 is a cross-sectional view of a positive electrode and a first solid electrolyte layer according to one embodiment of the present invention.

[0019] Figure 8 is an enlarged view of a positive electrode active material layer and a first solid electrolyte layer according to one embodiment of the present invention.

[0020] Figures 9a to 9c are enlarged views of the positive electrode active material layer according to embodiments of the present invention.

[0021] Figures 10 and 11 are plan views of pattern layers according to embodiments of the present invention.

[0022] FIG. 12, FIG. 13a to FIG. 13d, and FIG. 14 are conceptual diagrams illustrating a method for manufacturing an all-solid-state battery according to one embodiment of the present invention.

[0023] Figure 15 is a conceptual diagram illustrating a method for manufacturing an all-solid-state battery according to another embodiment of the present invention.

[0024]

[0025] 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.

[0026] 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.

[0027] Embodiments described herein will be described with reference to cross-sectional and / or plan views, which are ideal illustrations of the present invention. In the drawings, the thicknesses of films and regions are exaggerated for the purpose of effectively explaining the technical contents. Accordingly, the regions illustrated in the drawings have a schematic nature, and the shapes of the regions illustrated in the drawings are intended to illustrate specific shapes of regions of the device and are not intended to limit the scope of the invention. Although terms such as first, second, and third are used to describe various components in various embodiments of the present specification, these components should not be limited by such terms. These terms are used only to distinguish one component from another. The embodiments described and illustrated herein also include complementary embodiments thereof.

[0028] Unless otherwise specified herein, the singular may also include the plural. Furthermore, unless otherwise specified, "A or B" may mean "including A, including B, or including A and B." As used herein, "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components.

[0029] As used herein, “combination thereof” may mean mixtures, laminates, composites, copolymers, alloys, blends, and reaction products of the components.

[0030] Unless otherwise defined herein, the particle size may be the average particle size. In addition, the particle size refers to the average particle size (D50), which means the diameter of particles with a cumulative volume of 50% by volume in a particle size distribution. The average particle size (D50) can be measured by a method well known to those skilled in the art, for example, by measuring with a particle size analyzer, or by measuring with a transmission electron microscope (TEM) photograph or a scanning electron microscope (SEM) photograph. Alternatively, the average particle size (D50) value can be obtained by measuring with a measuring device that utilizes dynamic light-scattering, performing data analysis to count the number of particles for each particle size range, and calculating from the counted number. Alternatively, the average particle size (D50) value can be obtained by measuring with a laser diffraction method. When measuring by laser diffraction, more specifically, after the particles to be measured are dispersed in a dispersion medium, they are introduced into a commercially available laser diffraction particle size measuring device (e.g., Microtrac MT 3000) and irradiated with ultrasonic waves of approximately 28 kHz at an output of 60 W, and the average particle size (D50) based on 50% of the particle size distribution in the measuring device can be calculated.

[0031]

[0032] Fig. 1 is a cross-sectional view of an all-solid-state battery according to one embodiment of the present invention. Fig. 2 is a plan view of an all-solid-state battery according to one embodiment of the present invention.

[0033] Referring to FIG. 1, an all-solid-state battery (10) according to one embodiment 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).

[0034] The positive electrode layer (100) of one embodiment may include a positive electrode current collector (110) and a positive electrode active material layer (120) disposed on the positive electrode current collector (110). Although not shown, the positive electrode active material layer (120) may include a positive electrode active material, a solid electrolyte, a conductive material, and a binder.

[0035] 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 include a plate or foil including, for example, indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof.

[0036] Meanwhile, unlike that illustrated in FIG. 1, 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).

[0037] The cathode active material may include a material that can reversibly absorb and desorb lithium ions. The cathode active material may include a plurality of particles. The cathode active material may include, but is not necessarily 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.

[0038] 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 bB 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-fA 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.

[0039] 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 Mn zO2(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.

[0040] 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 is 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 is 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 includes, for example, spray coating, dipping, etc.

[0041] 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, thereby reducing metal dissolution of the positive electrode active material in a charged state. As a result, the cycle characteristics of the all-solid-state battery (10) in a charged state are improved. Meanwhile, the "cycle characteristics" are characteristics indicating the degree to which the all-solid-state battery (10) is deteriorated by charge / discharge of the all-solid-state battery (10). An all-solid-state battery (10) with high cycle characteristics may 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 may have a large degree of deterioration of the all-solid-state battery (10) due to charge / discharge.

[0042] The cathode active material may have a particle shape such as a sphere or an ellipsoid, for example. The particle size and content of the cathode active material are not particularly limited. In one embodiment, the cathode active material may be in a polycrystal form and may include secondary particles in which at least two or more primary particles are aggregated. In other words, one first particle may include multiple primary particles (NNPs) aggregated together. The first particle may have a spherical or ellipsoidal shape.

[0043] A solid electrolyte may be dispersed between the positive electrode active materials. The solid electrolyte dispersed between the positive electrode active materials may have a particle shape. The solid electrolyte dispersed between the positive electrode active materials 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 xIt may include at least one selected from (0≤x≤2).

[0044] 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 (0≤x≤2) may be an argyrodite-type compound including at least one selected from. In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound including at least one selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I. 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.

[0045] The solid electrolyte in the positive electrode active material layer (120) may have a smaller median particle size (D50) than the solid electrolyte in the solid electrolyte layer (300) described later. 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.

[0046] 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.

[0047] The positive electrode active material layer (120) may further include a binder. The binder may bind the positive electrode active material, the solid electrolyte, and the conductive material within the positive electrode active material layer (120) to each other. The binder may include a material for improving the bonding strength between the positive electrode active material layer (120) and the positive electrode current collector (110). The binder may include, for example, polyvinylidene fluoride, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, and polymethyl methacrylate.

[0048] Based on 100 parts by weight of the total of the positive electrode active material, the solid electrolyte, the conductive material, and the binder, the positive electrode active material layer (120) may include 85 parts by weight or more and 92 parts by weight or less of the positive electrode active material. Based on 100 parts by weight of the total of the positive electrode active material, the solid electrolyte, the conductive material, and the binder, the positive electrode active material layer (120) may include 0.5 parts by weight or more and 1.5 parts by weight or less of the binder.

[0049] Based on 100 parts by weight of the solid electrolyte in the positive electrode active material layer (120), the positive electrode active material layer (120) may include 1 part by weight or more and 50 parts by weight or less of a conductive material. When the conductive material is included in the positive electrode active material layer (120) in an amount of less than 1 part by weight based on 100 parts by weight of the solid electrolyte in the positive electrode active material layer (120), the proportion of the conductive material may decrease, thereby lowering the electrical conductivity of the positive electrode active material layer (120). When the conductive material is included in the positive electrode active material layer (120) in an amount of more than 50 parts by weight based on 100 parts by weight of the solid electrolyte in the positive electrode active material layer (120), the proportion of the conductive material may be excessively high, so that a coating layer covering the surface of the solid electrolyte may not be properly formed.

[0050] The positive electrode active material layer (120) may further include additives such as fillers, coating agents, dispersants, and ion conductive aids in addition to the above-described positive electrode active material, solid electrolyte, conductive agent, and binder.

[0051] As an example, referring back to FIG. 1, the positive electrode active material layer (120) may include a base layer (121) provided on the positive electrode current collector (110) and a pattern layer (122) provided on the base layer (122). The pattern layer (122) may be adjacent to the first solid electrolyte layer (310) described below.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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, ketjen black, and graphene. In one embodiment, the cathode coating layer (220) may include a mixture of carbon black and silver (Ag).

[0056] 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.

[0057] 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).

[0058] 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).

[0059] A solid electrolyte layer (300) may be provided between the positive electrode layer (100) and the negative electrode layer (200). The solid electrolyte layer (300) may include a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics. The solid electrolyte in the solid electrolyte layer (300) may be the same as or different from any one of the materials included in the solid electrolyte in the positive electrode active material layer (120) described above.

[0060] The solid electrolyte layer (300) may include a first solid electrolyte layer (310) and a second solid electrolyte layer (320). The first solid electrolyte layer (310) may be adjacent to the positive electrode layer (100), and the second solid electrolyte layer (320) may be adjacent to the negative electrode layer (200).

[0061] The second solid electrolyte layer (320) can be in direct contact with the negative electrode coating layer (220). As a result, the second solid electrolyte layer (320) can suppress lithium dendrites formed between the negative electrode coating layer (220) and the negative electrode current collector (210). The second solid electrolyte layer (320) can effectively suppress negative electrode side reactions. As a result, the cell performance of the all-solid-state battery (10) according to the present invention can be improved.

[0062] The solid electrolyte in the solid electrolyte layer (300) may have a particle shape such as a sphere or ellipsoid.

[0063] The solid electrolyte in the solid electrolyte layer (300) may include a sulfide-based solid electrolyte. The solid electrolyte in the solid electrolyte layer (300) 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.

[0064] In one embodiment, the solid electrolyte in the solid electrolyte layer (300) is Li 7-a M a PS 6-c X c It may be an argyrodite-type compound containing, where X may be Cl, Br, or a combination thereof. M may be Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, or a combination thereof. Each of a and c may be a real number between 0 and 2.

[0065] 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 in the solid electrolyte layer (300) is, for example, 15 GPa to 35 GPa.

[0066] The solid electrolyte layer (300) may further include a binder. The binder included in the solid electrolyte layer (300) may be, for example, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, 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).

[0067] Referring back to FIG. 1, the first solid electrolyte layer (310) may have a first thickness (t1), and the second solid electrolyte layer (320) may have a second thickness (t2). The solid electrolyte layer (300) may have a third thickness (t3). The first thickness (t1) And the second thickness (t2) may have different thicknesses. The second thickness (t2) may be greater than the first thickness (t1).

[0068] The thinner the solid electrolyte layer (300), the higher the energy density, but on the other hand, it is difficult to suppress the formation of lithium dendrites in the negative electrode, which may cause a short circuit.

[0069] Solid electrolytes may create voids at the interface between the electrode and the electrolyte, which may act as interfacial resistance and lead to deterioration of battery performance.

[0070] Interfacial resistance can be reduced by simultaneously pressurizing the electrode and solid electrolyte layer. In one embodiment, since a sulfide-based solid electrolyte possesses both high ionic conductivity and mechanical softness, an all-solid-state battery with improved interfacial resistance can be manufactured through pressurization.

[0071] In one embodiment of the present invention, the positive electrode layer (120) and the negative electrode layer (220) may include a pressurizing process in the manufacturing process. In one embodiment of the present invention, the pressurizing process may be performed by applying different pressures to each of the positive electrode layer (120) and the negative electrode layer (220). In one embodiment of the present invention, the positive electrode layer (120) may be manufactured by applying a relatively high pressure compared to the negative electrode layer (220). For example, applying nano-scale particles to the positive and negative electrode active materials may increase the contact area with the solid electrolyte, thereby improving the interfacial resistance. In one embodiment, the positive electrode active material may include secondary particles in which at least two or more primary particles are aggregated in a polycrystal form for reasons such as improved adhesion to the electrode plate, capacity characteristics, and lifespan characteristics. In this case, the interfacial resistance between the positive electrode layer (120) and the first solid electrolyte layer (310) is observed to be greater than the interfacial resistance between the negative electrode layer (220) and the second solid electrolyte layer (320), so that the positive electrode laminate can be manufactured by applying a relatively high pressure compared to the negative electrode laminate. However, this is not limited thereto, and the positive electrode layer (120) and the negative electrode layer (220) can be manufactured through a pressurizing process that applies different pressures to each for various reasons.

[0072] One embodiment of the present invention can solve a process problem that may occur due to differences in interfacial resistance between the positive electrode layer (120) and the first solid electrolyte layer (310) and the negative electrode layer (220) and the second solid electrolyte layer (320) by dividing the solid electrolyte (300) into a first solid electrolyte layer (310) and a second solid electrolyte layer (320). For example, an all-solid-state battery manufactured according to the all-solid-state battery manufacturing method described below can provide an all-solid-state battery manufactured by applying different pressures to each of the positive electrode laminate and the negative electrode laminate.

[0073] One embodiment of the present invention divides a solid electrolyte layer (300) into a first solid electrolyte layer (310) and a second solid electrolyte layer (320) and adjusts the thickness of each layer differently, thereby increasing energy density while suppressing the formation of lithium dendrites within the negative electrode. This improves stability against short-circuit risk and impact and provides an all-solid-state battery (10) with high energy density.

[0074] The ratio of the second thickness t2 to the first thickness t1 (t2 / t1) may be 1 to 20. Specifically, the ratio of the second thickness t2 to the first thickness t1 (t2 / t1) may be 2 to 15, 4 to 11, or 4.5 to 5.5. When the ratio of the second thickness t2 to the first thickness t1 (t2 / t1) is within the above-mentioned numerical range, the formation of lithium dendrites in the negative electrode can be suppressed while increasing the energy density, thereby improving the stability against short-circuit risk and impact and providing an all-solid-state battery (10) with high energy density.

[0075] The first thickness (t1) may be 30 μm or less. Specifically, the first thickness (t1) may be 25 μm or less, 20 μm or less, 14 μm or less, or 10 μm or less. The first thickness (t1) may be 0.1 μm or more. Specifically, the first thickness (t1) may be 1 μm or more, 2 μm or more, 4 μm or more, or 5 μm or more. When the first thickness (t1) exceeds the above-mentioned numerical range, the energy density of the all-solid-state battery (10) may decrease. When the first thickness (t1) does not reach the above-mentioned numerical range, the first thickness (t1) may not reach the diameter of the active material powder in the positive electrode, making it difficult to form an interface.

[0076] The second thickness (t2) may be 30 μm or more. Specifically, it may be 35 μm or more, 40 μm or more, 45 μm or more, 50 μm or more, 55 μm or more, or 60 μm or more. The second thickness (t2) may be 120 μm or less. Specifically, the second thickness (t2) may be 90 μm or less, or 60 μm or less. When the second thickness (t2) is less than the above-mentioned numerical range, it may be difficult to suppress the formation of lithium dendrites in the negative electrode, which may cause a short circuit. When the second thickness (t2) exceeds the above-mentioned numerical range, the energy density of the all-solid-state battery (10) may decrease.

[0077] The third thickness (t3) may be 120 μm or less. Specifically, the third thickness (t3) may be 90 μm or less, or 60 μm or less. The third thickness (t3) may be 10 μm or more. Specifically, the third thickness (t3) may be 30 μm or more, or 50 μm or more. If the third thickness (t3) exceeds the above numerical range, the energy density of the all-solid-state battery (10) may decrease.

[0078] Referring to FIGS. 1 and 2, the area of ​​the anode layer (100) and the area of ​​the cathode layer (200) may be different from each other. Specifically, the area of ​​the cathode layer (200) may be larger than the area of ​​the anode layer (100). The anode layer (100) may be completely overlapped within the cathode layer (200).

[0079]

[0080] In one embodiment of the present invention, the first solid electrolyte layer (310) may have substantially the same area as the positive electrode layer (100). The second solid electrolyte layer (320) may have substantially the same area as the negative electrode layer (200).

[0081] Referring to FIGS. 1 and 2, the first solid electrolyte layer (310) may have a first width (W1) in the first direction (D1). The second solid electrolyte layer (320) may have a second width (W2) in the first direction (D1). The first width (W1) may be smaller than the second width (W2).

[0082] The difference between the second width (W2) and the first width (W1) may be 10 mm or less. Specifically, the difference between the second width (W2) and the first width (W1) may be 8 mm or less, 5 mm or less, or 3 mm or less. The difference between the second width (W2) and the first width (W1) may be 0.1 mm or more, 0.5 mm or more, or 1 mm or more. If the numerical range is exceeded, the size of the positive electrode layer (100) becomes relatively small, so the discharge capacity may be lowered, and the energy density of the all-solid-state battery (10) may be reduced. If the numerical range is not reached, it may be difficult to suppress the formation of lithium dendrites in the negative electrode, which may cause a short circuit.

[0083] The ratio (W2 / W1) of the second width (W2) to the first width (W1) may be 1 to 1.6. Specifically, the ratio (W2 / W1) of the second width (W2) to the first width (W1) may be 1 to 1.5, 1 to 1.4, 1 to 1.3, 1 to 1.2, or 1 to 1.1.

[0084] When the ratio (W2 / W1) of the second width (W2) to the first width (W1) exceeds the above numerical range, the energy density of the all-solid-state battery (10) is reduced.

[0085] Referring to FIGS. 1 and 2, the first solid electrolyte layer (310) may have a third width (W3) in the second direction (D2). The second solid electrolyte layer (320) may have a fourth width (W4) in the second direction (D2). The third width (W3) may be smaller than the fourth width (W4).

[0086] The difference between the third width (W3) and the fourth width (W4) may be 10 mm or less. Specifically, the difference between the third width (W3) and the fourth width (W4) may be 8 mm or less, 5 mm or less, or 3 mm or less. The difference between the fourth width (W4) and the third width (W3) may be 0.1 mm or more, 0.5 mm or more, or 1 mm or more. If the numerical range is exceeded, the size of the positive electrode layer (100) becomes relatively small, so the discharge capacity may be lowered and the energy density of the all-solid-state battery (10) may be reduced. If the numerical range is not reached, it may be difficult to suppress the formation of lithium dendrites in the negative electrode, which may cause a short circuit.

[0087] The ratio (W4 / W3) of the fourth width (W4) to the third width (W3) may be 1 to 1.6. Specifically, the ratio (W4 / W3) of the fourth width (W4) to the third width (W3) may be 1 to 1.5, 1 to 1.4, 1 to 1.3, 1 to 1.2, or 1 to 1.1.

[0088] When the ratio (W4 / W3) of the fourth width (W4) to the third width (W3) exceeds the above numerical range, the energy density of the all-solid-state battery (10) is reduced.

[0089] Figure 3 is a cross-sectional view illustrating an all-solid-state battery according to another embodiment of the present invention. In this embodiment, detailed descriptions of technical features that overlap with those previously described with reference to Figures 1 and 2 will be omitted, and differences will be described in detail.

[0090] Referring to FIG. 3, the negative electrode layer (200) of the all-solid-state battery (10) may further include a lithium metal layer (400) between the negative electrode current collector (210) and the negative electrode coating layer (220). The thickness of the lithium metal layer (400) may further increase when the all-solid-state battery (10) is charged. The negative electrode coating layer (220) serves as a protective layer for the lithium metal layer (400), and at the same time, may suppress the growth of lithium dendrites from the lithium metal layer (400).

[0091] The lithium metal layer (400) may be a metal thin film containing lithium or a lithium alloy. The lithium alloy may include, but is not limited to, a Li-Al alloy, a Li-Sn alloy, a Li-In alloy, a Li-Ag alloy, a Li-Au alloy, a Li-Zn alloy, a Li-Ge alloy, a Li-Si alloy, etc., and any lithium alloy may be used. The lithium metal layer (400) may contain one of these alloys or lithium. Alternatively, the lithium metal layer (400) may contain various types of alloys.

[0092] The lithium metal layer (400) may have a fifth width (W5) in the first direction (D1). The fifth width (W5) may be equal to or greater than the first width (W1). The fifth width (W5) may be equal to or less than the second width (W2). For example, the fifth width (W5) may be greater than the first width (W1) and less than the second width (W2).

[0093] Figure 4 is a cross-sectional view illustrating an all-solid-state battery according to another embodiment of the present invention. In this embodiment, detailed descriptions of technical features that overlap with those previously described with reference to Figures 1 to 3 will be omitted, and differences will be described in detail.

[0094] Referring to FIG. 4, the bi-cell all-solid-state battery (20) may include a first mono-cell (510) and a second mono-cell (520).

[0095] Each of the first and second monocells (510, 520) may include a positive electrode layer (100), a negative electrode layer (200), and a solid electrolyte layer (300) disposed between the positive electrode layer (100) and the negative electrode layer (200). The solid electrolyte layer (300) of each of the first and second monocells (510, 520) may include a first solid electrolyte layer (310) adjacent to the positive electrode layer (100) and having a first width (W1) and a first thickness (t1), and a second solid electrolyte layer (320) adjacent to the negative electrode layer (200) and having a second width (W2) and a second thickness (t2). The second monocell (520) may be disposed symmetrically with the first monocell (510). The anode layer (100) of the first monocell (510) and the anode layer (100) of the second monocell (520) may face each other.

[0096] Figure 5 is a cross-sectional view illustrating an all-solid-state battery according to another embodiment of the present invention. In this embodiment, detailed descriptions of technical features that overlap with those previously described with reference to Figures 1 to 4 will be omitted, and differences will be described in detail.

[0097] Referring to FIG. 5, the bi-cell all-solid-state battery (20) may further include an elastic member (ELP) disposed on one surface of the negative electrode layer (200). The elastic member (ELP) may be composed of members capable of absorbing volume changes (expansion) of the all-solid-state battery (20) due to charge and discharge and capable of elastic deformation, and more specifically, may be composed of a material having a lower elastic modulus than the positive electrode current collector and the negative electrode current collector. The material constituting the elastic member (ELP) may have a slope of a stress-displacement curve of 200 MPa or less at a displacement of 80% or less. Specifically, the material constituting the elastic member (ELP) may have a slope of a stress-displacement curve of 50 MPa or less at a displacement of 80% or less, and may have a slope of 10 MPa or less at a displacement of 50% or less.

[0098] The material of the above elastic member (ELP) may include, but is not limited to, epoxy resin, acrylic resin, polyimide resin, polyester resin, polypropylene resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polycarbonate resin, fluororesin such as PTFE, silicone rubber, etc. Each elastic member (ELP) may be composed of a single material, or may be composed of a combination of multiple materials. In addition, each elastic member (ELP) may include the same material, or may include different materials. In addition, the elastic member (ELP) may include an insulating material, and may insulate between each bi-cell all-solid-state battery (20). The insulating material may have a surface resistance of 1.0*10 17 Ω·cm 2It may be an ideal, and specifically, it may be a fluororesin such as PTFE or silicone rubber.

[0099] Since an elastic member (ELP) is arranged between each of the bi-cell all-solid-state batteries (20), the pressure generated when the all-solid-state batteries (20) are charged and expanded can be distributed, thereby reducing the unevenness of the pressure applied to each all-solid-state battery (20) by charging and discharging. In addition, this can suppress cracking or deformation of the electrolyte layer that may occur as charging and discharging are repeated, and can suppress deterioration of battery characteristics such as cycle characteristics.

[0100] Figure 6 is a cross-sectional view illustrating an all-solid-state battery according to another embodiment of the present invention. In this embodiment, detailed descriptions of technical features that overlap with those previously described with reference to Figures 1 to 5 will be omitted, and differences will be described in detail.

[0101] Referring to FIG. 6, the all-solid-state battery (20) may further include an inert member (INM) disposed on one side of the positive electrode layer (100) and the first solid electrolyte layer (310). By including the inert member (INM), cracking of the solid electrolyte layer (300) can be prevented during manufacturing of the all-solid-state battery (20) and / or during charging and discharging, and as a result, the cycle characteristics of the all-solid-state battery (20) can be improved.

[0102] The inert member (INM) may include at least one selected from a lithium ion insulator and a lithium ion conductor. The inert member (INM) may be an electronic insulator. That is, the inert member (INM) may not be an electronic conductor. The inert member (INM) may be an ionic insulator. That is, the inert member (INM) may not be an ionic conductor. The inert member (INM) includes, for example, an organic material, an inorganic material, or an organic-inorganic composite material. The organic material may be, for example, a polymer. The inorganic material may be, for example, a ceramic such as a metal oxide. The organic-inorganic composite material may be a composite of a polymer and a metal oxide.

[0103] The above inert member (INM) may be placed between the second solid electrolyte layer (320) of the first monocell (510) and the second solid electrolyte layer (320) of the second monocell (520). By including the inert member (INM), uniform pressurization is enabled during the manufacturing process of the all-solid-state battery (20), thereby preventing cracking of the solid electrolyte layer (300), and consequently improving the cycle characteristics of the all-solid-state battery (20).

[0104] The thickness of the inert member (INM) may be equal to or smaller than the sum of the thickness (t1) of the first solid electrolyte layer (310) of the first monocell (510) and the thickness of the anode layer (100), and the thickness (t1) of the first solid electrolyte layer (310) of the second monocell (520) and the thickness of the anode layer (100). The thickness of the inert member (INM) may be larger than the thickness of the anode layer (100). When the thickness of the inert member (INM) is smaller than the thickness of the anode layer (100), an appropriate pressure may not be applied to the side of the second solid electrolyte layer (320), and thus cracks may occur in the solid electrolyte layer (300). If the thickness of the above inert member (INM) is greater than the sum of the thickness (t1) of the first solid electrolyte layer (310) of the first monocell (510) and the thickness of the anode layer (100), and the thickness (t1) of the first solid electrolyte layer (310) of the second monocell (520) and the thickness of the anode layer (100), the anode layer (100) and the first solid electrolyte layer (310) may not be sufficiently pressurized.

[0105]

[0106] Fig. 7 is a cross-sectional view illustrating an anode (100) and a first solid electrolyte layer (310) on the anode according to an embodiment of the present invention. In this embodiment, detailed descriptions of technical features that overlap with those previously described with reference to Figs. 1 to 6 are omitted, and differences are described in detail.

[0107] Referring to FIG. 7, a positive electrode (100) according to one embodiment may include a positive electrode current collector (110); and a positive electrode active material layer (120) on the positive electrode current collector. A first solid electrolyte layer (310) may be provided on the positive electrode (100).

[0108] Referring back to FIG. 7, the patterned layer (122) may include a plurality of negative patterns (EGP) formed thereon. The negative patterns (EGP) may be adjacent to the first solid electrolyte layer (310). The solid electrolyte particles (SSP) of the first solid electrolyte layer (310) may fill the plurality of negative patterns (EGP). By having the first solid electrolyte layer (310) fill the negative patterns (EGP), the contact area between the positive active material layer (120) and the first solid electrolyte layer (310) may be increased. Through this, the interfacial resistance between the positive active material layer (120) and the first solid electrolyte layer (310) may be reduced, and as a result, battery capacity and rapid charge / discharge characteristics may be improved. A flat portion (FLP) may be formed between the negative patterns (EGP).

[0109] FIG. 8 is an enlarged view illustrating a positive electrode active material layer and a first solid electrolyte layer according to embodiments of the present invention. FIG. 9a is an enlarged view of a positive electrode active material layer for illustrating a patterned layer according to embodiments of the present invention. FIG. 10 is a plan view of a patterned layer for illustrating a patterned layer according to an embodiment of the present invention.

[0110] Referring to FIG. 8, the positive electrode active material layer (120) may include a base layer (121) provided on the positive electrode current collector (110) and a pattern layer (122) provided on the base layer (121). The pattern layer (122) may be adjacent to the first solid electrolyte layer (310). The pattern layer (122) may include a plurality of patterns (EGP).

[0111] The positive electrode active material layer (120) may include the positive electrode active material (CAM), conductive material (CDM), and binder (BND) described above with reference to FIG. 1. The positive electrode active material layer (120) may further include a solid electrolyte.

[0112] The cathode active material (CAM) may have a bimodal particle distribution. In other words, the cathode active material may include large particles (LAP) and small particles (SMP) having different particle sizes. In one embodiment, the average particle diameter (D50) of the large particles (LAP) may be 6 μm to 15 μm, specifically 8 μm to 14 μm. In one embodiment, the average particle diameter (D50) of the small particles (SMP) may be 1 μm to 5 μm, specifically 3 μm to 4 μm.

[0113] The first solid electrolyte layer (310) may include sulfide-based solid electrolyte particles (SSP) previously described with reference to FIG. 1. In one embodiment, the average particle diameter (D50) of the sulfide-based solid electrolyte particles (SSP) may be 1 μm to 4 μm, and more specifically, 2 μm to 3 μm.

[0114] Referring to FIG. 9A, the pattern layer (122) may have a fourth thickness (t4) in the third direction (D3). Each of the negative patterns (EGP) may have a maximum depth H in the third direction (D3). The fourth thickness (t4) may be substantially equal to the maximum depth (H) of the negative pattern (EGP) in the third direction.

[0115] In one embodiment, the maximum depth (H) of each of the negative patterns (EGP) may be smaller than the average particle diameter of the positive active material layer (LAP) and larger than the average particle diameter of the small particles (SMP). Specifically, the maximum depth (H) of the negative pattern (EGP) may be 3 μm to 12 μm, and specifically 4 μm to 10 μm. By having the above range, Li ion conduction by the positive active material layer (LAP) can be increased, and thereby ion conductivity at the interface between the positive active material layer (120) and the first solid electrolyte layer (310) can be significantly increased.

[0116] Referring to FIGS. 9A and 10, a plurality of negative patterns (EGP) may be arranged in an island shape. Each of the plurality of negative patterns (EGP) may have a first diameter (DI).

[0117] In one embodiment, the first diameter (DI) may be larger than the average particle diameter of the sulfide-based solid electrolyte. The first diameter (DI) may be smaller than the average particle diameter of the small particles (SMP). The first diameter may be smaller than twice the average particle diameter of the large particles (LAP).

[0118] In one embodiment, the first diameter (DI) may be 3.0 μm to 24 μm, and more specifically, 3.0 μm to 10 μm. When the first diameter is smaller than the above range, it is difficult for the solid electrolyte particles (SSP) to fill the negative patterns (EGP), and the effect of increasing the contact area with the positive active material (CAM) due to the negative patterns may be minimal. When the first diameter is larger than the above range, the effect of increasing the contact area between the solid electrolyte particles (SSP) and the positive active material (CAM) becomes minimal, while the number of negative patterns (EGP) that can be formed per unit area decreases, so that ionic conductivity may actually decrease.

[0119] Fig. 9a illustrates a case where the cross-sectional shape of the negative pattern (EGP) is a semicircle. However, the cross-sectional shape of the negative pattern (EGP) is not limited to that illustrated in Fig. 9a. Figs. 9b and 9c illustrate a case where the cross-sectional shape of the negative pattern (EGP) is a rectangle or a trapezoid, respectively. In this way, the cross-sectional shape of the negative pattern (EGP) may be a polygon or an ellipse.

[0120] Fig. 10 illustrates a case where the planar shape of the engraved pattern (EGP) is circular. However, the planar shape and arrangement of the engraved pattern (EGP) are not limited to those illustrated in Fig. 10. For example, the planar shape of the engraved pattern (EGP) may be elliptical or polygonal, and is not particularly limited.

[0121] FIG. 11 is a plan view illustrating a pattern layer (122) according to another embodiment. Referring to FIGS. 9 and 11, a plurality of negative patterns (EGP) may be arranged to be spaced apart in a first direction (D1). Each of the plurality of negative patterns (EGP) may extend in a second direction (D2). As described above with reference to FIG. 9A, each of the plurality of negative patterns (EGP) may have a first diameter (DI).

[0122]

[0123] FIG. 12 is a conceptual diagram illustrating a method for manufacturing a positive electrode for an all-solid-state battery, including a process of forming a pattern layer on top of a positive electrode active material layer according to one embodiment of the present invention.

[0124] Referring to FIG. 12, a positive electrode active material layer (120) may be provided on a positive electrode current collector (110). The positive electrode active material layer (120) may include large particle (LAP) and small particle (SMP), as previously described with reference to FIG. 8. The positive electrode active material layer (120) may further include a binder (BND), a conductive material (CDM), and a solid electrolyte, as appropriate.

[0125] Referring to FIG. 12, a pattern formation process can be performed on the positive electrode active material layer (120).

[0126] In one embodiment, the pattern forming process may be performed by a pressurizing machine in which a plurality of relief patterns are formed. More specifically, the pattern forming process may be performed by a roll pressing method. A relief pattern may be formed on the upper roll. A pattern may not be formed on the lower roll. A plurality of intaglio patterns (EGP) may be formed on the positive electrode active material layer (120) by the upper roll. That is, through the pattern forming process, the positive electrode active material layer may be formed with a pattern layer (122) including a plurality of intaglio patterns (EGP), and a base layer (121) having no pattern may be formed thereunder.

[0127] In the pattern forming process, a first pressure may be applied to the anode layer (120). The first pressure may be substantially equal to or greater than the second pressure described below. The first pressure may be greater than the third pressure. In one embodiment, the first pressure may be 1.5 ton / cm to 5.5 ton / cm, more specifically, 2 ton / cm to 4 ton / cm, or 2.5 ton / cm to 3.5 ton / cm. In one example, the first pressure may be 3.5 ton / cm.

[0128] The above pressurization process can be carried out at a relatively high temperature. Specifically, the pressurization process can be carried out at 60 to 180°C, 80 to 150°C, or 100 to 130°C.

[0129] FIGS. 13a to 13d and FIG. 14 are conceptual diagrams for explaining a method for manufacturing an all-solid-state battery according to one embodiment of the present invention.

[0130] Referring to FIGS. 13a to 13d and FIG. 14, an all-solid-state battery (10) according to one embodiment of the present invention can be manufactured by stacking a positive electrode layer (100) and a first solid electrolyte layer (310), then applying a second pressure to form a positive electrode laminate, stacking a negative electrode layer (200) and the second solid electrolyte layer (320), then applying a third pressure to form a negative electrode laminate, and then combining the positive electrode laminate and the negative electrode laminate so that the first solid electrolyte layer (310) and the second solid electrolyte layer (320) are in contact with each other.

[0131] The present invention manufactures the positive electrode laminate and the negative electrode laminate by applying separate pressurization methods, so that the second pressure and the third pressure can be controlled differently. Through this, a relatively low pressure can be applied to a laminate among the positive electrode laminate and the negative electrode laminate that has weak mechanical strength or is structurally unbalanced and thus may be damaged when pressurized at high pressure. The second pressure may be greater than the third pressure. The second pressure may be less than the first pressure described with reference to FIG. 12.

[0132] The formation of the above-described positive and negative electrode laminates may include a pressing process using a roll press. However, this method is not necessarily limited to this method, and any pressing process applicable in the relevant technical field may be applied. For example, pressing processes such as a hydraulic plate press and a warm isostatic press may be applied.

[0133] When roll press is applied during the formation process of the above-mentioned positive electrode laminate, the second pressure may be 1 ton / cm to 5 ton / cm, and more specifically, 1.5 ton / cm to 4.0 ton / cm or 2 ton / cm to 3.5 ton / cm. For example, the second pressure may be 3.5 ton / cm.

[0134] When roll press is applied during the formation of the above-described negative electrode laminate, the third pressure may be 0.5 ton / cm to 4.5 ton / cm, and more specifically, 1.0 ton / cm to 3.5 ton / cm or 1.5 ton / cm to 3.0 ton / cm. For example, the third pressure may be 3.0 ton / cm.

[0135] The above pressurization process can be carried out at a relatively high temperature. Specifically, the pressurization process can be carried out at 60 to 180°C, 80 to 150°C, or 100 to 130°C.

[0136] The formation of the above positive electrode laminate and negative electrode laminate may include a preheating process prior to the pressurizing process. Specifically, the positive electrode laminate and negative electrode laminate may be preheated to ±10°C or ±5°C of the temperature at which the pressurizing process is performed. The preheating process can prevent damage to the positive electrode laminate and negative electrode laminate due to rapid temperature changes during the high-temperature pressurizing process.

[0137] Referring again to FIGS. 13a to 13d, in a method for manufacturing an all-solid-state battery according to another embodiment of the present invention, forming a positive electrode laminate includes laminating a first functional layer (FNL1) on a first solid electrolyte layer before applying the second pressure, forming a negative electrode laminate includes laminating a second functional layer (FNL2) on the second solid electrolyte layer before applying the third pressure, and may further include removing the first functional layer (FNL1) and the second functional layer (FNL2) before combining the positive electrode laminate and the negative electrode laminate. The first functional layer (FNL1) and the second functional layer (FNL2) can prevent damage to the solid electrolyte by preventing the solid electrolyte layer from being directly exposed during a high-temperature pressurization process.

[0138] The first functional layer (FNL1) and the second functional layer (FNL2) may include a plate or foil containing 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. The first functional layer (FNL1) and the second functional layer (FNL2) may include polyethylene terephthalate (PET), polycarbonate (PC), polyimide (PI), or a mixture thereof.

[0139] Referring to FIG. 14, an all-solid-state battery (10) according to one embodiment of the present invention can be manufactured by combining the positive electrode laminate and the negative electrode laminate so that the first solid electrolyte layer (310) and the second solid electrolyte layer (320) are in contact with each other, and applying a fourth pressure.

[0140] The formation of the above-described positive and negative electrode laminates may include a pressurizing process using a hydraulic plate press. However, this method is not necessarily limited to this method, and any pressurizing process applicable in the relevant technical field may be applied. For example, pressurizing processes such as roll press and warm isostatic press may be applied.

[0141] When roll press is applied during the formation process of the above-mentioned all-solid-state battery (10), the fourth pressure may be 0.1 ton / cm or more. Specifically, the fourth pressure may be 0.5 ton / cm or more, and may be 1.0 ton / cm or more. The fourth pressure may be 2.0 ton / cm or less. Specifically, the linear pressure of the fourth pressure may be 1.5 ton / cm or less.

[0142] Figure 15 is a conceptual diagram illustrating a method for manufacturing an all-solid-state battery according to another embodiment of the invention. In this embodiment, detailed descriptions of technical features that overlap with those previously described with reference to Figures 12 to 14 will be omitted, and differences will be described in detail.

[0143] An all-solid-state battery according to another embodiment of the present invention may include first and second monocells (510, 520). The second monocell (520) may be arranged symmetrically vertically with the first monocell (510) and joined by pressurization.

[0144]

[0145] Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are merely examples of the present invention, and the present invention is not limited to the following examples.

[0146]

[0147] Example 1

[0148] (Cathode layer manufacturing)

[0149] A 10 μm thick Ni foil was prepared as a negative electrode current collector. In addition, carbon black (CB) with a primary particle size of approximately 30 nm and silver (Ag) particles with an average particle size (D50) of approximately 60 nm were prepared as negative electrode active materials. 4 g of a mixed powder of carbon black (CB) and silver (Ag) particles in a weight ratio of 3:1 was placed in a container, and 4 g of an NMP solution containing 7 wt% PVDF binder (Kureha #9300) was added thereto to prepare a mixed solution. Subsequently, a slurry was prepared by stirring the mixed solution while adding NMP little by little. The prepared slurry was applied to a Ni sheet using a bar coater and dried in air at 80 °C for 10 minutes. The laminate thus obtained was vacuum dried at 40 °C for 10 hours. The dried laminate was cold rolled at a pressure of 1.5 ton / cm to flatten the surface of the first negative electrode active material layer of the laminate. The negative electrode layer was manufactured through the above process. The thickness of the first negative electrode active material layer included in the negative electrode layer was approximately 7 μm. The areas of the first negative electrode active material layer and the negative electrode current collector were the same.

[0150]

[0151] (Anode layer manufacturing)

[0152] LiNi coated with Li2O-ZrO2 (LZO) as a cathode active material 0.8 Co 0.15 Mn 0.05 O2(NCM) was prepared. The LZO-coated cathode active material was prepared according to the method disclosed in Korean Patent Publication No. 10-2016-0064942. According to the method, large particles with an average particle diameter (D50) of 14 μm and small particles with an average particle diameter (D50) of 4 μm were prepared in a 4:1 (wt.%) ratio and then mixed to prepare a bimodal cathode active material.

[0153] Argyrodite-type crystal Li6PS5Cl (D50 = 0.5 μm, crystalline) was prepared as a solid electrolyte. Polytetrafluoroethylene (PTFE) binder was prepared as a binder. Carbon nanofibers (CNF) were prepared as a conductive agent. These materials were mixed with xylene solvent in a weight ratio of positive electrode active material : solid electrolyte : conductive agent : binder = 84 : 11.5 : 3 : 1.5, and the slurry was molded into a sheet shape, and then vacuum dried at 40 ° C. for 8 hours to produce a positive electrode sheet. The manufactured positive electrode sheets were each placed on the cross-section of a positive electrode current collector made of aluminum foil coated on one side with carbon. Thereafter, heated roll pressing was performed using a roll press machine having an island-shaped relief pattern as shown in FIGS. 9a and 10 formed on the upper roll. The heated roll pressing was performed at 120 ° C. and a pressure of 3 ton / cm. Through this, a positive electrode layer having negative patterns with a diameter of 5 μm and a depth of 10 μm was manufactured (see Figs. 8 and 10). That is, the thickness (t4) of the pattern layer was 10 μm. The total thickness of the positive electrode layer was approximately 120 μm. The thickness of the positive electrode active material layer was approximately 107 μm, and the thickness of the carbon-coated (1 mm thick) aluminum foil was approximately 13 μm. The areas of the positive electrode active material layer and the positive electrode current collector were the same.

[0154]

[0155] (Manufacturing of solid electrolyte layer, dry)

[0156] A mixture was prepared by adding 1 part by weight of a polytetrafluoroethylene (PTFE) first binder and 1 part by weight of a polyvinylidene fluoride (PVDF) second binder to 98 parts by weight of the solid electrolyte, Li6PS5Cl, which is an argyrodite-type crystal (D50 = 3 ㎛, crystalline), in a grind mixer and mixing them. The prepared mixture was added to a mortar heated to 80°C and stirred to prepare a dough. The prepared dough was passed through a roller and formed into a sheet to prepare a solid electrolyte membrane of a certain thickness. A solid electrolyte layer was manufactured by the above process. The solid electrolyte layers were prepared as a first solid electrolyte layer having substantially the same area as the positive electrode layer, and a second solid electrolyte layer having substantially the same area as the negative electrode layer, respectively. The elastic modulus of the sulfide-based solid electrolyte was about 15 GPa to 30 GPa.

[0157]

[0158] (Manufacturing of all-solid-state batteries)

[0159] The positive electrode layer and the first solid electrolyte layer were laminated and pressed using a roll press method. A positive electrode laminate was manufactured by applying a linear pressure of 3.5 ton / cm at 120°C. The negative electrode layer and the second solid electrolyte layer were laminated and pressed using a roll press method. A negative electrode laminate was manufactured by applying a linear pressure of 3.0 ton / cm at 140°C. The positive electrode laminate and the negative electrode laminate were combined to manufacture an all-solid-state battery.

[0160] Referring to Fig. 1, the second width (W2) of the second solid electrolyte layer was manufactured to be 4 mm larger than the first width (W1) of the first solid electrolyte layer. The thickness (t1) of the first solid electrolyte layer was 60 μm, and the thickness (t2) of the second solid electrolyte layer was manufactured to be 5 μm.

[0161]

[0162] Example 2

[0163] An all-solid-state battery was manufactured in the same manner as Example 1, except that, when manufacturing the positive electrode layer, the positive pattern of the upper roll was changed so that negative patterns with a diameter of 5 μm and a depth of 5 μm were formed on the pattern layer. In other words, Example 2 manufactured an all-solid-state battery so that the thickness of the pattern layer was 5 μm.

[0164]

[0165] Example 3

[0166] An all-solid-state battery was manufactured in the same manner as Example 1, except that the thickness (t1) of the first solid electrolyte layer was 30 μm, and the thickness (t2) of the second solid electrolyte layer was 30 μm.

[0167]

[0168] Example 4

[0169] An all-solid-state battery was manufactured in the same manner as Example 3, except that, when manufacturing the positive electrode layer, the positive pattern of the upper roll was changed so that negative patterns with a diameter of 5 μm and a depth of 5 μm were formed on the pattern layer. In other words, Example 4 manufactured an all-solid-state battery so that the thickness of the pattern layer was 5 μm.

[0170]

[0171] Example 5

[0172] An all-solid-state battery was manufactured in the same manner as Example 1, except that the thickness (t1) of the first solid electrolyte layer was 5 μm and the thickness (t2) of the second solid electrolyte layer was 55 μm.

[0173]

[0174] Example 6

[0175] An all-solid-state battery was manufactured in the same manner as Example 5, except that, when manufacturing the positive electrode layer, the positive pattern of the upper roll was changed so that negative patterns with a diameter of 5 μm and a depth of 5 μm were formed on the pattern layer. In other words, Example 6 manufactured an all-solid-state battery so that the thickness of the pattern layer was 5 μm.

[0176]

[0177] Example 7

[0178] An all-solid-state battery was manufactured in the same manner as Example 5, except that, when manufacturing the positive electrode layer, the positive pattern of the upper roll was changed so that negative patterns with a diameter of 5 μm and a depth of 4.2 μm were formed on the pattern layer. In other words, Example 7 manufactured an all-solid-state battery so that the thickness of the pattern layer was 4.2 μm.

[0179]

[0180] Example 8

[0181] An all-solid-state battery was manufactured in the same manner as Example 5, except that, when manufacturing the positive electrode layer, the positive pattern of the upper roll was changed so that negative patterns with a diameter of 5 μm and a depth of 12 μm were formed on the pattern layer. In other words, Example 8 manufactured an all-solid-state battery so that the thickness of the pattern layer was 12 μm.

[0182]

[0183] Comparative Example 1

[0184] i) The first solid electrolyte layer was manufactured to have a first width (W1) and a second width (W2) of the second solid electrolyte layer that were manufactured to be substantially the same, ii) the first solid electrolyte layer had a thickness (t1) of 60 ㎛ and did not include the second solid electrolyte layer, and iii) the positive electrode layer was manufactured by pressing with an upper roll without a pattern, thereby not forming a pattern layer on the positive electrode layer, and an all-solid-state battery was manufactured in the same manner as in Example 1, except that the positive electrode layer was manufactured without a pattern layer.

[0185]

[0186] Comparative Example 2

[0187] An all-solid-state battery was manufactured in the same manner as Example 1, except that i) the first width (W1) of the first solid electrolyte layer and the second width (W2) of the second solid electrolyte layer were manufactured to be substantially the same, ii) the thickness (t2) of the second solid electrolyte layer was 60 ㎛ and the first solid electrolyte layer was not included, and iii) no pattern layer was formed on the positive electrode layer by pressing with an upper roll without a pattern during the manufacture of the positive electrode layer.

[0188]

[0189] Comparative Example 3

[0190] An all-solid-state battery was manufactured in the same manner as Example 5, except that a patterned layer was not formed on the positive electrode layer by pressing with an upper roll without a pattern during the manufacture of the positive electrode layer.

[0191]

[0192] Comparative Example 4

[0193] An all-solid-state battery was manufactured in the same manner as Example 1, except that, when manufacturing the positive electrode layer, the positive pattern of the upper roll was changed so that negative patterns with a diameter of 5 μm and a depth of 1 μm were formed on the pattern layer. In other words, in Comparative Example 4, an all-solid-state battery was manufactured so that the thickness of the pattern layer was 1 μm.

[0194]

[0195] Comparative Example 5

[0196] An all-solid-state battery was manufactured in the same manner as Example 3, except that, when manufacturing the positive electrode layer, the positive pattern of the upper roll was changed so that negative patterns with a diameter of 5 μm and a depth of 1 μm were formed on the pattern layer. In other words, in Comparative Example 5, an all-solid-state battery was manufactured so that the thickness of the pattern layer was 1 μm.

[0197]

[0198] Comparative Example 6

[0199] An all-solid-state battery was manufactured in the same manner as Example 5, except that, when manufacturing the positive electrode layer, the positive pattern of the upper roll was changed so that negative patterns with a diameter of 5 μm and a depth of 1 μm were formed on the pattern layer. In other words, in Comparative Example 6, an all-solid-state battery was manufactured so that the thickness of the pattern layer was 1 μm.

[0200]

[0201]

[0202] Comparative Example 7

[0203] An all-solid-state battery was manufactured in the same manner as Example 5, except that, when manufacturing the positive electrode layer, the positive pattern of the upper roll was changed so that negative patterns with a diameter of 5 μm and a depth of 15 μm were formed on the pattern layer. In other words, in Comparative Example 7, an all-solid-state battery was manufactured so that the thickness of the pattern layer was 15 μm.

[0204]

[0205] Evaluation Example 1: Impact Safety

[0206] The impact stability level of the all-solid-state batteries manufactured by the Examples and Comparative Examples was confirmed by a sine wave vibration test (Sine test: f=55Hz; force=25gf; duration=1hr, 3-axis). Specifically, 10 samples were manufactured for each Example and Comparative Example, and then a sine wave vibration test was performed. The results of the impact stability test were classified into ○○ (excellent, 0 to 1 broken cell), ○ (good, 2 to 3 broken cells), △ (fair, 4 to 6 broken cells), and X (poor, 7 to 10 broken cells) based on the number of broken cells among the 10 samples. The classification results are shown in Table 1 below.

[0207]

[0208] Evaluation Example 2: Energy Density

[0209] The energy density (Wh / L) of the all-solid-state batteries manufactured by the examples and comparative examples was measured by the standard calculation method (based on an 80Ah stack cell, capacity*standard voltage / volume). The results of the energy density evaluation experiment are shown in Table 1 below: if the energy density is 900 Wh / L or more, ○○ (excellent); if it is 800 Wh / L to 900 Wh / L, ○ (good); if it is 600 Wh / L to 800 Wh / L, △ (fair); and if it is 600 Wh / L or less, X (poor).

[0210]

[0211] Evaluation Example 3: Internal resistance of an all-solid-state battery

[0212] After measuring the direct current internal resistance (DC-IR) of the all-solid-state batteries manufactured by the examples and comparative examples, the area of ​​the cathode layer (cm) 2 ) is calculated by multiplying the internal resistance of the solid-state battery (cell resistance, (Ωcm) 2 ) are shown in Table 1.

[0213]

[0214] Evaluation Example 4: Initial Capacity

[0215] The all-solid-state batteries manufactured by the Examples and Comparative Examples were evaluated by the following charge-discharge tests. The charge-discharge tests were performed by placing the all-solid-state batteries in a thermostatic chamber at 45°C. The first cycle was charged at a constant current of 0.1C until the battery voltage reached 4.25 V, and then charged at a constant voltage of 4.25 V with a 0.05C cut-off condition when the battery voltage reached 4.25 V. Subsequently, the battery was discharged at a constant current of 0.1C until the battery voltage reached 2.5 V. The discharge capacity of the first cycle was taken as the initial capacity. The results are shown in Table 1 below. The initial capacities were measured under the standard method (first discharge amount) conditions and are shown in Table 1 below.

[0216]

[0217] Evaluation Example 5: Evaluation of life characteristics at the time of short-circuit occurrence

[0218] The all-solid-state batteries manufactured by the Examples and Comparative Examples were evaluated by the following charge-discharge tests. The charge-discharge tests were performed by placing the all-solid-state batteries in a thermostatic chamber at 45°C. In the first cycle, the batteries were charged at a constant current of 0.33C until the battery voltage reached 4.25 V, and when the voltage reached 4.25 V, constant voltage charging was performed at 4.25 V with a 0.1C cut-off condition. Subsequently, the batteries were discharged at a constant current of 0.33C until the voltage reached 2.5 V. From the second cycle onwards, charging and discharging were performed up to 350 cycles under the same conditions as the first cycle. As the number of cycles at which a short circuit occurred increases, this means that the life characteristics improve. The results of the charge-discharge tests are shown in Table 1 below. The occurrence of a short circuit was confirmed using the standard method (charge amount during life = discharge amount * 10%), and the number of times the life progressed until that point was recorded and shown in Table 1 below.

[0219] W2-W1(mm)t1(㎛)t2(㎛)t4(㎛)Impact stabilityEnergy densityCell resistance(Ω·cm) 2 )Initial capacity (mAh / g) Short circuit occurrence time (times) Example 1 460 510 X △ 36.6188 < 50 Example 2 460 55 X △ 55.2173 < 50 Example 3 430 3010 △ △ 35.6189 > 200 Example 4 430 305 △ △ 50.2177 > 200 Example 5 455 510 ○ △ 30.6192 > 300 Example 6 455 5 ○ △ 52 .2176>300Example 745554.2○△60.5170>200Example 8455513○△30.3193>300Comparative Example 10600-X△110.0131<1Comparative Example 20060-○△105.0135<1Comparative Example 34555-○△90.5146<100Comparative Example 446051X△80.0154<50Comparative Example 5430301△△82.0153<100Comparative Example 645551○X82.0153<100Comparative Example 7455515○X120123<50">n" means that no short circuit occurs even after n cycle tests." <n"은, n회 사이클 시험 동안 단락이 발생함을 의미함.t1=제1 고체 전해질층의 두께, t2=제2 고체 전해질층의 두께, t4= 패턴층의 두께(음각 패턴의 깊이).W1=제1 고체 전해질층의 제1 방향으로의 제1 폭(W1).W2=제2 고체 전해질층의 제1 방향으로의 제2 폭(W2).

[0220] Referring to Table 1, all of the all-solid-state batteries of Examples 1 to 7, in which a negative pattern was formed on the positive electrode active material layer, had low internal resistance (61Ω·cm). 2 Hereinafter), it can be confirmed that the initial capacity is excellent. Furthermore, it can be confirmed that the all-solid-state batteries of Examples 5 to 7, in which the thickness (t2) of the second solid electrolyte layer adjacent to the negative electrode layer is thicker than the thickness (t1) of the first solid electrolyte layer adjacent to the positive electrode layer, also have excellent impact stability and lifespan characteristics (short-circuit occurrence time).

[0221] On the other hand, it can be confirmed that the all-solid-state batteries of Comparative Examples 1 to 3, in which no pattern was formed on the positive electrode active material layer, all had an increase in internal resistance and a decrease in initial capacity. In addition, it can be confirmed that the all-solid-state battery of Comparative Example 7, in which the depth of the engraved pattern was greater than the average particle diameter of the positive electrode active material particles, had a very large internal resistance and a small initial capacity. In addition, the all-solid-state batteries of Comparative Examples 4 to 6, in which the depth of the engraved pattern was less than the average particle diameter of the positive electrode active material particles, had an internal resistance of 80 Ω·cm. 2 You can see that it is rising rapidly.

[0222] In addition, it can be confirmed that the all-solid-state batteries of Comparative Examples 1 and 2, in which the solid electrolyte layer was formed as a single layer without dividing, suffered a short circuit in only one cycle.

Claims

1. A positive electrode current collector; and a positive electrode active material layer provided on the positive electrode current collector, The positive electrode active material of the positive electrode active material layer includes large and small particles having different average particle sizes, The above positive electrode active material layer includes a plurality of negative patterns provided on the upper portion thereof, A positive electrode for an all-solid-state battery, wherein the maximum depth in the third direction of each of the plurality of negative patterns is smaller than the average particle diameter of the opposing particles and larger than the average particle diameter of the small particles.

2. In paragraph 1, The average particle size of the above particles is 6 ㎛ to 15 ㎛, An all-solid-state battery positive electrode having an average particle size of 1 ㎛ to 5 ㎛.

3. In paragraph 1, A positive electrode for an all-solid-state battery, wherein each of the plurality of negative patterns has a maximum depth of 3 μm to 12 μm in the third direction.

4. In paragraph 1, A positive electrode for an all-solid-state battery, wherein each of the plurality of negative patterns has a diameter of 3 ㎛ to 24 ㎛.

5. A positive electrode layer, wherein the positive electrode layer includes a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector; cathode layer; and Including a solid electrolyte layer provided between the positive electrode layer and the negative electrode layer, The positive electrode active material of the positive electrode active material layer includes large and small particles having different average particle diameters, The above positive electrode active material layer includes a plurality of negative patterns provided on the upper portion thereof, The solid electrolyte particles of the solid electrolyte layer fill each of the plurality of negative patterns, An all-solid-state battery, wherein the maximum depth in the third direction of each of the plurality of negative patterns is smaller than the average particle diameter of the opposing particles and larger than the average particle diameter of the small particles.

6. In paragraph 5, The average particle size of the above particles is 6 ㎛ to 15 ㎛, An all-solid-state battery, wherein the average particle size of the above particles is 1 ㎛ to 5 ㎛.

7. In paragraph 5, A solid-state battery in which each of the plurality of negative patterns has a maximum depth of 3 μm to 12 μm in the third direction.

8. In paragraph 5, An all-solid-state battery, wherein each of the plurality of negative patterns has a diameter of 3 μm to 24 μm.

9. In paragraph 5, The above solid electrolyte layer comprises sulfide-based solid electrolyte particles, An all-solid-state battery, wherein the average particle diameter of the above sulfide-based solid electrolyte particles is 1 ㎛ to 4 ㎛.

10. In paragraph 1, The above solid electrolyte layer: A first solid electrolyte layer adjacent to the positive electrode layer and having a first width and a first thickness, and a second solid electrolyte layer adjacent to the negative electrode layer and having a second width and a second thickness, An all-solid-state battery, wherein the second width is greater than the first width, and the second thickness is greater than the first thickness.

11. In paragraph 10, An all-solid-state battery, wherein the first thickness is 30 μm or less.

12. In paragraph 10, An all-solid-state battery, wherein the second thickness is 30 ㎛ or more.

13. In paragraph 10, An all-solid-state battery, wherein the sum of the first thickness and the second thickness is 120 μm or less.

14. In paragraph 10, An all-solid-state battery in which the first thickness t1 and the second thickness t2 satisfy the following equation 1: [Formula 1] 1 ≤ t2 / t1≤ 20.

15. In paragraph 10, An all-solid-state battery, wherein the difference between the second width and the first width is 10 mm or less.

16. Forming a positive electrode active material layer on a positive electrode current collector, wherein the positive electrode active material of the positive electrode active material layer includes large and small particles having different average particle sizes; Pressurizing the positive electrode active material layer with a first pressure using a pressurizer having a plurality of positive patterns formed thereon, thereby forming a positive electrode layer having a plurality of negative patterns formed thereon; Laminating the above-mentioned positive electrode layer and the first solid electrolyte layer and then applying a second pressure to form a positive electrode laminate; Laminating a cathode layer and a second solid electrolyte layer and then applying a third pressure to form a cathode laminate; and Including combining the positive electrode laminate and the negative electrode laminate so that the first solid electrolyte layer and the second solid electrolyte layer are in contact with each other, A method for manufacturing an all-solid-state battery, wherein the maximum depth in the third direction of each of the plurality of negative patterns is smaller than the average particle diameter of the opposing particles and larger than the average particle diameter of the small particles.

17. In paragraph 16, A method for manufacturing an all-solid-state battery, wherein each of the plurality of negative patterns has a maximum depth of 3 ㎛ to 12 ㎛.

18. A method for manufacturing an all-solid-state battery, wherein the width of the first solid electrolyte layer is smaller than the width of the second solid electrolyte layer in the 16th paragraph.

19. In paragraph 16, The above first pressure is greater than the above second pressure, A method for manufacturing an all-solid-state battery, wherein the second pressure is greater than the third pressure.

20. In paragraph 16, Forming the above-mentioned positive electrode laminate comprises laminating a first functional layer on the first solid electrolyte layer before applying the second pressure, Forming the above cathode laminate includes laminating a second functional layer on the second solid electrolyte layer before applying the third pressure, A method for manufacturing an all-solid-state battery, further comprising removing the first functional layer and the second functional layer before combining the positive electrode laminate and the negative electrode laminate.

Images