All-solid-state battery, manufacturing method therefor, and equipment for manufacturing same

Abstract

The present invention relates to an all-solid-state battery, a method for manufacturing same, and equipment for manufacturing same. More specifically, the present invention provides a method comprising: forming a first composite sheet including a first carrier film and a first composite layer; forming a first datum hole in the first carrier film in a self-aligned manner with the first composite layer; forming a second composite sheet including a second carrier film and a second composite layer; forming a second datum hole in the second carrier film in a self-aligned manner with the second composite layer; aligning the first datum hole and the second datum hole with each other; and laminating the first composite layer of the first composite sheet and the second composite layer of the second composite sheet together.

Description

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

[0001] The present invention relates to an all-solid-state battery, a method for manufacturing the same, and equipment for manufacturing the same.

[0002]

[0003] 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.

[0004] Recently, all-solid-state batteries, which replace the electrolyte with a solid electrolyte, have been proposed. 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 significantly improve safety compared to lithium-ion batteries that use electrolytes.

[0005]

[0006] The problem to be solved by the present invention is to provide a method for manufacturing an all-solid-state battery with improved process efficiency.

[0007] Another problem to be solved by the present invention is to provide a manufacturing facility for an all-solid-state battery that can improve process efficiency.

[0008]

[0009] According to the concept of the present invention, a method for manufacturing an all-solid-state battery may include forming a first composite sheet including a first carrier film and a first composite layer; forming a first datum hole in the first carrier film in self-alignment with the first composite layer; forming a second composite sheet including a second carrier film and a second composite layer; forming a second datum hole in the second carrier film in self-alignment with the second composite layer; aligning the first datum hole and the second datum hole with each other; and laminating the first composite layer of the first composite sheet with the second composite layer of the second composite sheet.

[0010] According to another concept of the present invention, a manufacturing facility for an all-solid-state battery may include a first guide roll for guiding a first composite sheet including a first carrier film and a first composite layer; a second guide roll for guiding a second composite sheet including a second carrier film and a second composite layer; a guide pin configured to align a first datum hole of the first carrier film and a second datum hole of the second carrier film with each other; and a laminating roll configured to laminate the first composite layer and the second composite layer.

[0011] According to another concept of the present invention, an all-solid-state battery may include a positive electrode layer; a negative electrode layer; and a solid electrolyte layer between the positive electrode layer and the negative electrode layer. The negative electrode layer includes a negative electrode current collector and a negative electrode coating layer on the negative electrode current collector, and the negative electrode current collector includes a tab portion protruding from one side thereof, and the tab portion may include a datum hole.

[0012]

[0013] The method for manufacturing an all-solid-state battery according to the present invention can effectively laminate two materials by using a self-aligned datum hole and a physical guide pin.

[0014] The manufacturing equipment for an all-solid-state battery according to the present invention can be simplified because the sensor unit for measuring the alignment of two materials and the unit for correcting the alignment can be omitted. The reliability of the equipment can be improved.

[0015]

[0016] FIG. 1 is a plan view of an all-solid-state battery according to embodiments of the present invention.

[0017] Figure 2 is a cross-sectional view taken along line A-A' of Figure 1.

[0018] FIGS. 3 and 4 are plan views illustrating a method of forming a composite sheet according to embodiments of the present invention.

[0019] FIGS. 5, 6 and 7 are cross-sectional views taken along line B-B' of FIGS. 3 and 4, illustrating a method for forming a composite sheet according to embodiments of the present invention.

[0020] Figure 8 is a schematic diagram of equipment for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0021] Figures 9, 10 and 11 are cross-sectional views illustrating a process for manufacturing an all-solid-state battery using the equipment of Figure 8.

[0022] Figure 12 is a plan view of an all-solid-state battery according to one embodiment of the present invention.

[0023] Fig. 13 is a cross-sectional view taken along line A-A' of Fig. 12.

[0024] Figure 14 is a cross-sectional view schematically illustrating a method for manufacturing an all-solid-state battery according to one embodiment of the present invention.

[0025]

[0026] 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.

[0027] 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.

[0028] 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.

[0029] The terminology used herein is for the purpose of describing embodiments and is not intended to limit the present invention. In this specification, the singular also includes the plural unless specifically stated otherwise. As used herein, the words "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components.

[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 plan view of an all-solid-state battery according to embodiments of the present invention. Fig. 2 is a cross-sectional view taken along line A-A' of Fig. 1.

[0033] Referring to FIGS. 1 and 2, the all-solid-state battery (10) according to the present invention 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] A positive electrode layer (100) according to one embodiment of the present invention may include a positive electrode current collector (110) and a positive electrode active material layer (120) disposed on the positive electrode current collector (110). The positive electrode active material layer (120) may include a positive electrode active material, a solid electrolyte, a conductive material, and a binder.

[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 positive electrode active material of the positive electrode active material layer (120) may include a material that can reversibly absorb and desorb lithium ions. The positive electrode active material may include a plurality of particles. The positive electrode active material may include, for example, 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, lithium iron phosphate, nickel sulfide, copper sulfide, lithium sulfide, iron oxide, or vanadium oxide, but is not necessarily limited thereto. The positive electrode active materials may be each alone or may be a mixture of two or more types.

[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-cMn b B c D α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2), Li a Nor 1-b-c Mn b B c O 2-α F α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Nor b E c G d O2(0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1), Li a Nor b Co c Mn d GeO2(0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0.001≤e≤0.1), Li a NiG b O2(0.9≤a≤1, 0.001≤b≤0.1), Li a CoG b O2(0.90≤a≤1, 0.001≤b≤0.1), Li a MnG b O2(0.90≤a≤1, 0.001≤b≤0.1), Li a Mn2GbO4(0.90≤a≤1, 0.001≤b≤0.1), QO2, QS2, LiQS2, V2O5, LiV2O5, LiIO2, LiNiVO4, Li 3-f J2(PO4)3(0≤f≤2), Li 3-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 positive electrode active material may have a particle shape such as a sphere or an ellipsoid, for example. The particle size and content of the positive electrode active material are not particularly limited.

[0043] The solid electrolyte of the positive electrode active material layer (120) may have a particle shape. The solid electrolyte may be dispersed between the positive electrode active materials. The solid electrolyte may include a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics. Examples of the sulfide-based solid electrolyte include Li2S-P2S5, Li2S-P2S5-LiX (X is a halogen element), Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (m, n are positive numbers, capital letter “Z” represents Ge, Zn or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are positive numbers, capital letter “M” is one of P, Si, Ge, B, Al, Ga In), Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may include at least one selected from (0≤x≤2).

[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-xPS 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 average particle diameter than the first and second solid electrolytes in the solid electrolyte layer (300) described later. For example, the average particle diameter of the solid electrolyte 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 average particle diameter of the solid electrolyte in the solid electrolyte layer (300). Meanwhile, the average particle diameter 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, 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. If 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, the proportion of the conductive material may decrease, thereby lowering the electrical conductivity of the positive electrode active material layer (120). If 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, the proportion of the conductive material may be excessively high, so that a covering 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] 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.

[0052] 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.

[0053] 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.

[0054] 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).

[0055] 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.

[0056] 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 cell.

[0057] 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).

[0058] 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.

[0059] 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).

[0060] Referring to FIG. 2, the first solid electrolyte layer (310) may include a first solid electrolyte. The first solid electrolyte may have a particle shape such as a sphere or an ellipsoid. The first solid electrolyte may include a sulfide-based solid electrolyte. The first solid electrolyte may be amorphous, crystalline, or a mixture thereof. In addition, the solid electrolyte may include, for example, at least sulfur (S), phosphorus (P), and lithium (Li) as constituent elements among the above-described sulfide-based solid electrolyte materials. For example, the solid electrolyte may be a material including Li2S-P2S5. When using a sulfide-based solid electrolyte material including Li2S-P2S5 to form the solid electrolyte, the mixing molar ratio of Li2S and P2S5 is, for example, in the range of Li2S:P2S5=50:50 to 90:10.

[0061] In one embodiment, the first solid electrolyte is Li 7-a M a PS6-c X c It may be an argyrodite-type compound containing . Here, 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.

[0062] The density of the argyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. When the argyrodite-type solid electrolyte has a density of 1.5 g / cc or more, the internal resistance of the all-solid-state battery is reduced, and the defect of the solid electrolyte membrane being penetrated and short-circuited due to the formation of lithium dendrites can be prevented. The elastic modulus of the first solid electrolyte is, for example, 15 GPa to 35 GPa.

[0063] The first solid electrolyte layer (310) 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 first solid electrolyte layer (310) 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).

[0064] The second solid electrolyte layer (320) may include a second solid electrolyte. The second solid electrolyte may have a particle shape such as a sphere or ellipsoid.

[0065] The second solid electrolyte may include a sulfide-based solid electrolyte. The description of the second solid electrolyte may be the same as or similar to that described above for the first solid electrolyte. In one embodiment, the second solid electrolyte may have substantially the same composition as the first solid electrolyte. In another embodiment, the second solid electrolyte may have a similar composition to the first solid electrolyte.

[0066] The second solid electrolyte can be in direct contact with the negative electrode coating layer (220). As a result, the second solid electrolyte can suppress lithium dendrites formed between the negative electrode coating layer (220) and the negative electrode current collector (210). The second solid electrolyte 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.

[0067] The first solid electrolyte layer (310) may have a first thickness (TK1), and the second solid electrolyte layer (320) may have a second thickness (TK2). The first thickness (TK1) and the second thickness (TK2) may be the same or different. In one embodiment, the first thickness (TK1) may be greater than the second thickness (TK2). For example, the first thickness (TK1) may be 1.1 to 5 times the second thickness (TK2).

[0068] Referring back to FIGS. 1 and 2, the positive electrode layer (100) and the first solid electrolyte layer (310) may form a positive electrode composite layer (CSH). The negative electrode layer (200) and the second solid electrolyte layer (320) may form a negative electrode composite layer (ASH). The positive electrode composite layer (CSH) may be laminated on the negative electrode composite layer (ASH).

[0069] The area of ​​the cathode composite layer (ASH) and the area of ​​the cathode composite layer (CSH) may be different. Specifically, the area of ​​the cathode composite layer (ASH) may be larger than that of the cathode composite layer (CSH). The cathode composite layer (CSH) may be completely overlapped within the cathode composite layer (ASH).

[0070] 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).

[0071] Specifically, the positive electrode composite layer (CSH) may have a first width (WI1) in a first direction (D1). The negative electrode composite layer (ASH) may have a second width (WI2) in the first direction (D1). The first width (WI1) may be smaller than the second width (WI2). The positive electrode composite layer (CSH) may have a third width (WI3) in the second direction (D2). The negative electrode composite layer (ASH) may have a fourth width (WI4) in the second direction (D2). The third width (WI3) may be smaller than the fourth width (WI4).

[0072] The all-solid-state battery (10) according to the present embodiment can be manufactured by forming a negative electrode composite layer (ASH) on a first carrier film, forming a positive electrode composite layer (CSH) on a second carrier film, and then laminating the negative electrode composite layer (ASH) and the positive electrode composite layer (CSH).

[0073]

[0074] FIGS. 3 and 4 are plan views illustrating a method for forming a composite sheet according to embodiments of the present invention. FIGS. 5, 6, and 7 are cross-sectional views taken along line B-B' of FIGS. 3 and 4, illustrating a method for forming a composite sheet according to embodiments of the present invention.

[0075] Referring to FIGS. 3 and 5, the first composite sheet (CPS1) can be unwound from a reel and provided in the form of a web. The first composite sheet (CPS1) can travel along the first direction (D1).

[0076] The first composite sheet (CPS1) may include a first carrier film (CAF1) and a negative electrode composite layer (ASH) on the first carrier film (CAF1). For example, the negative electrode composite layer (ASH) may include a negative electrode current collector (210), a negative electrode coating layer (220), and a second solid electrolyte layer (320) sequentially laminated as described above with reference to FIG. 2.

[0077] In one embodiment of the present invention, forming the negative electrode composite layer (ASH) may include coating a negative electrode coating layer (220) on a negative electrode current collector (210), and coating a second solid electrolyte layer (320) on the negative electrode coating layer (220). By providing the manufactured negative electrode composite layer (ASH) on a first carrier film (CAF1), a first composite sheet (CPS1) may be prepared.

[0078] Referring to FIGS. 4 and 6, a negative electrode composite layer (ASH) can be blanked (or patterned) using a punching die (PMD). By selectively punching the negative electrode composite layer (ASH) on the first carrier film (CAF1), the shape of the negative electrode composite layer (ASH) described above with reference to FIG. 1 can be formed. A plurality of negative electrode composite layers (ASH) formed using the punching die (PMD) can be arranged along the first direction (D1) at a constant pitch on the first carrier film (CAF1).

[0079] Referring to FIGS. 6 and 7, when a punching die (PMD) is punched on a first composite sheet (CPS1), a negative electrode composite layer (ASH) can be patterned to fit the mold of the punching die (PMD). The punching die (PMD) according to embodiments of the present invention can include at least one protrusion (PRP). The protrusion (PRP) can be configured to penetrate the first carrier film (CAF1). When the negative electrode composite layer (ASH) is patterned, at least one first datum hole (DTH1) can be formed in the first carrier film (CAF1) by the protrusion (PRP). In other words, the punching die (PMD) can punch the negative electrode composite layer (ASH) and simultaneously punch the first carrier film (CAF1).

[0080] A first datum hole (DTH1) may be formed together with a patterned cathode composite layer (ASH). The first datum hole (DTH1) and the patterned cathode composite layer (ASH) may be self-aligned with each other by a single punching die (PMD). In one embodiment, the first datum hole (DTH1) may be spaced apart from the patterned cathode composite layer (ASH) in a second direction (D2). The patterned cathode composite layer (ASH) may be formed at the center of the first carrier film (CAF1). The first datum hole (DTH1) may be formed at the periphery of the first carrier film (CAF1).

[0081] The cathode composite layer (CSH) can also be formed in substantially the same manner as the cathode composite layer (ASH) described above. The cathode composite layer (CSH) can be provided on a second carrier film (CAF2) having at least one second datum hole (DTH2) formed therein. The second composite sheet (CPS2), which will be described later, can be prepared in substantially the same manner as the first composite sheet (CPS1).

[0082]

[0083] FIG. 8 is a schematic diagram of equipment for manufacturing an all-solid-state battery according to embodiments of the present invention. FIGS. 9, 10, and 11 are cross-sectional views illustrating a process for manufacturing an all-solid-state battery using the equipment of FIG. 8.

[0084] Referring to FIGS. 8 and 9, a first composite sheet (CPS1) and a second composite sheet (CPS2) may be provided between a pair of guide rolls (GDR1, GDR2). The pair of guide rolls (GDR1, GDR2) may include a first guide roll (GDR1) and a second guide roll (GDR2). The first composite sheet (CPS1) may be provided on the first guide roll (GDR1). The second composite sheet (CPS2) may be provided on the second guide roll (GDR2). The first guide roll (GDR1) and the second guide roll (GDR2) may be interlocked with each other. As a result, the negative composite layer (ASH) of the first composite sheet (CPS1) and the positive composite layer (CSH) of the second composite sheet (CPS2) may be interlocked with each other and come into contact with each other.

[0085] The negative composite layer (ASH) of the first composite sheet (CPS1) and the positive composite layer (CSH) of the second composite sheet (CPS2) can be precisely aligned. According to embodiments of the present invention, the negative composite layer (ASH) of the first composite sheet (CPS1) and the positive composite layer (CSH) of the second composite sheet (CPS2) can be aligned using the first datum hole (DTH1) and the second datum hole (DTH2).

[0086] The first datum hole (DTH1) of the first carrier film (CAF1) and the second datum hole (DTH2) of the second carrier film (CAF2) can be vertically aligned with each other. The first datum hole (DTH1) and the second datum hole (DTH2) can be aligned with each other by physical means. For example, a guide pin (GDP) for aligning the first composite sheet (CPS1) and the second composite sheet (CPS2) can be provided. The guide pin (GDP) can be configured to move up and down along the third direction (D3). The guide pin (GDP) can be configured to sequentially penetrate the first datum hole (DTH1) and the second datum hole (DTH2). By having the guide pin (GDP) penetrate the first datum hole (DTH1) and the second datum hole (DTH2), the cathode composite layer (ASH) adjacent to the first datum hole (DTH1) and the anode composite layer (CSH) adjacent to the second datum hole (DTH2) can be aligned with each other.

[0087] The guide pin (GDP) can be raised and penetrate the first datum hole (DTH1) and the second datum hole (DTH2) to align the cathode composite layer (ASH) and the anode composite layer (CSH). Afterwards, the guide pin (GDP) can be lowered again. The guide pin (GDP) can repeat the above-described process, thereby achieving a continuous process.

[0088] According to a comparative example of the present invention, the alignment of the cathode composite layer (ASH) and the anode composite layer (CSH) can be performed using a sensor or machine vision. However, this can easily lead to process defects due to signal distortion caused by the resolution of the sensor, measurement position, and / or external noise. In addition, since the unit for measuring alignment and the unit for correcting alignment exist separately, there is a problem of errors between them. Furthermore, the alignment method according to the comparative example has the problem of complex equipment and increased production costs.

[0089] In contrast, according to the embodiments of the present invention described above, the cathode composite layer (ASH) and the anode composite layer (CSH) can be easily aligned with simple equipment using self-aligned datum holes and physical guide pins. In particular, unlike the comparative example, there is no need for separate units for measuring alignment and for correcting alignment, thereby improving process reliability.

[0090] Referring to FIGS. 8 and 10, a laminating process may be performed on the negative electrode composite layer (ASH) of the aligned first composite sheet (CPS1) and the positive electrode composite layer (CSH) of the second composite sheet (CPS2). The laminating process may be performed using a pair of laminating rolls (LMR1, LMR2). That is, the laminating process may include a roll press process. The line pressure of the laminating process may be 1 ton / cm to 5 ton / cm, 1 ton / cm to 4 ton / cm, 1 ton / cm to 3 ton / cm, or 1 ton / cm to 2.5 ton / cm.

[0091] The above laminating process can be performed at room temperature or at a higher temperature than room temperature. For example, the above laminating process can be performed at 25°C to 150°C. Through the above laminating process, the negative electrode composite layer (ASH) and the positive electrode composite layer (CSH) can be compressed and attached to each other. Specifically, the second solid electrolyte layer (320) of the negative electrode composite layer (ASH) and the first solid electrolyte layer (310) of the positive electrode composite layer (CSH) can be attached to each other (see FIG. 2).

[0092] Referring to FIGS. 8 and 11, after the laminating process, the first carrier film (CAF1) and the second carrier film (CAF2) can be detached from the negative electrode composite layer (ASH) and the positive electrode composite layer (CSH), respectively. The remaining negative electrode composite layer (ASH) and positive electrode composite layer (CSH) can form the all-solid-state battery (10) described above with reference to FIGS. 1 and 2.

[0093] The detached first carrier film (CAF1) can be recovered and re-wound into a reel. The recovered first carrier film (CAF1) can also be reused. The detached second carrier film (CAF2) can be recovered and re-wound into a reel. The recovered second carrier film (CAF2) can also be reused.

[0094] An additional pressing process may be performed on the laminate of the negative electrode composite layer (ASH) and the positive electrode composite layer (CSH) (i.e., the all-solid-state battery (10)). The pressing process is not limited to a specific method, and any pressing process applicable in the relevant technical field may be applied. For example, at least one pressing process among roll pressing, hydraulic plate pressing, and warm isostatic pressing may be applied.

[0095] The pressurization process may be performed at a temperature of 25°C to 150°C. The pressurization process may be performed at a pressure of 400 MPa to 550 MPa. The pressurization time may vary depending on the temperature and pressure, and may be, for example, less than 30 minutes.

[0096]

[0097] Fig. 12 is a plan view of an all-solid-state battery according to one embodiment of the present invention. Fig. 13 is a cross-sectional view taken along line A-A' of Fig. 12. In the embodiments described below, detailed descriptions of technical features that overlap with those previously described with reference to Figs. 1 to 11 will be omitted, and differences will be described in detail.

[0098] Referring to FIGS. 12 and 13, the negative electrode collector (210) may include a tab portion (TBP). For example, the tab portion (TBP) may protrude from one side of the negative electrode collector (210) in the second direction (D2). The tab portion (TBP) may include at least one first datum hole (DTH1). The first datum hole (DTH1) may be formed through the punching process described above with reference to FIGS. 5 to 7. The first datum hole (DTH1) may remain on a non-coated portion of the negative electrode collector (210), for example, on the tab portion (TBP), as shown in FIG. 12.

[0099] The all-solid-state battery (10) according to the present invention may further include a gasket (GSK). The gasket (GSK) may be provided to surround the cathode composite layer (CSH). The gasket (GSK) may fill the step on the side surface of the all-solid-state battery (10) caused by the difference in area between the anode composite layer (ASH) and the cathode composite layer (CSH). The gasket (GSK) may surround the four side surfaces of the cathode composite layer (CSH). For example, the thickness of the gasket (GSK) may be substantially the same as the thickness of the cathode composite layer (CSH).

[0100] The upper surface of the second solid electrolyte layer (320) may include a first region in contact with the first solid electrolyte layer (310) and a second region in contact with the gasket (GSK). The second region may be a peripheral region of the upper surface of the second solid electrolyte layer (320). The second region may surround the first region.

[0101] Fig. 14 is a cross-sectional view schematically illustrating a method for manufacturing an all-solid-state battery according to one embodiment of the present invention. Referring to Fig. 14, a gasket (GSK) can be bonded to an all-solid-state battery (10) using the equipment of Fig. 8 described above.

[0102] Specifically, an all-solid-state battery (10) that has been pressurized can be provided on a first carrier film (CAF1). The first carrier film (CAF1) and the all-solid-state battery (10) can form a first composite sheet (CPS1). At least one first datum hole (DTH1) that is formed in a self-aligned manner with the all-solid-state battery (10) can be formed on the first carrier film (CAF1).

[0103] A gasket (GSK) may be provided on a second carrier film (CAF2). The second carrier film (CAF2) and the gasket (GSK) may form a second composite sheet (CPS2). At least one second datum hole (DTH2) formed in a self-aligned manner with the all-solid-state battery (10) may be formed on the second carrier film (CAF2).

[0104] The guide pin (GDP) can be raised to align the all-solid-state battery (10) and the gasket (GSK) by penetrating the first datum hole (DTH1) and the second datum hole (DTH2). Thereafter, the guide pin (GDP) can be lowered again. The gasket (GSK) can be inserted to surround the positive electrode composite layer (CSH). The gasket (GSK) can directly cover the exposed surface of the negative electrode composite layer (ASH).

[0105] Afterwards, a laminating process can be performed as described above with reference to FIG. 10. After the laminating process, the first carrier film (CAF1) and the second carrier film (CAF2) can be detached as shown in FIG. 11.

[0106]

[0107] While embodiments of the present invention have been described with reference to the attached drawings, the present invention may be implemented in other specific forms without altering the technical spirit or essential features thereof. Therefore, it should be understood that the embodiments described above are exemplary in all respects and are not limiting.

Claims

1. Forming a first composite sheet including a first carrier film and a first composite layer; Forming a first datum hole in the first carrier film in a self-aligning manner with the first composite layer; Forming a second composite sheet comprising a second carrier film and a second composite layer; Forming a second datum hole in the second carrier film in a self-aligning manner with the second composite layer; Aligning the first datum hole and the second datum hole with each other; and A method for manufacturing an all-solid-state battery, comprising laminating the first composite layer of the first composite sheet and the second composite layer of the second composite sheet to each other.

2. In paragraph 1, A method for manufacturing an all-solid-state battery, wherein forming the first datum hole includes blanking the first composite layer and punching the first carrier film at the same time.

3. In paragraph 1, A method for manufacturing an all-solid-state battery, wherein forming the second datum hole includes punching the second carrier film while simultaneously punching the second composite layer.

4. In paragraph 1, A method for manufacturing an all-solid-state battery, comprising laminating the first composite layer and the second composite layer with each other and then detaching the first carrier film and the second carrier film.

5. In paragraph 1, The above first composite layer includes a cathode layer, A method for manufacturing an all-solid-state battery, wherein the second composite layer includes a positive electrode layer.

6. In paragraph 5, The first composite layer further includes a first solid electrolyte layer on the cathode layer, The second composite layer further includes a second solid electrolyte layer on the anode layer, A method for manufacturing an all-solid-state battery, wherein the first solid electrolyte layer and the second solid electrolyte layer are directly attached to each other by the laminating.

7. In paragraph 5, A method for manufacturing an all-solid-state battery, wherein the area of ​​the cathode layer is larger than the area of ​​the anode layer.

8. In paragraph 1, Further comprising performing a pressurizing process on the laminate of the first composite layer and the second composite layer, A method for manufacturing an all-solid-state battery, wherein the pressurizing process includes at least one of roll press, plate press, and warm isostatic press.

9. In paragraph 1, The above first composite layer includes a laminate in which a cathode layer and an anode layer are laminated, A method for manufacturing an all-solid-state battery, wherein the second composite layer includes a gasket.

10. In paragraph 9, A method for manufacturing an all-solid-state battery, wherein the gasket is inserted to surround the positive electrode layer by the laminating.

11. A first guide roll for guiding a first composite sheet including a first carrier film and a first composite layer; A second guide roll for guiding a second composite sheet including a second carrier film and a second composite layer; A guide pin configured to align the first datum hole of the first carrier film and the second datum hole of the second carrier film with each other; and An all-solid-state battery manufacturing facility comprising a laminating roll configured to laminate the first composite layer and the second composite layer.

12. In paragraph 11, Further comprising a first punching mold for punching the first composite sheet, An all-solid-state battery manufacturing facility, wherein the first punching mold is configured to form the first datum hole in the first carrier film in a self-aligned manner with the first composite layer.

13. In paragraph 11, Further comprising a second punching mold for punching the second composite sheet, An all-solid-state battery manufacturing facility, wherein the second punching mold is configured to form the second datum hole in the second carrier film in a self-aligned manner with the second composite layer.

14. In paragraph 11, An all-solid-state battery manufacturing facility, wherein the guide pin is configured to sequentially penetrate the first datum hole and the second datum hole.

15. In paragraph 1, The above first composite layer includes a cathode layer, An all-solid-state battery manufacturing facility, wherein the second composite layer includes a cathode layer.

16. In paragraph 15, The first composite layer further includes a first solid electrolyte layer on the cathode layer, The second composite layer further includes a second solid electrolyte layer on the anode layer, An all-solid-state battery manufacturing facility in which the first solid electrolyte layer and the second solid electrolyte layer are directly attached to each other by the laminating.

17. In paragraph 15, A manufacturing facility for an all-solid-state battery, wherein the area of ​​the cathode layer is larger than the area of ​​the anode layer.

18. In paragraph 11, The above first composite layer includes a laminate in which a cathode layer and an anode layer are laminated, An all-solid-state battery manufacturing facility, wherein the second composite layer includes a gasket.

19. In paragraph 18, An all-solid-state battery manufacturing facility, wherein the gasket is inserted to surround the positive electrode layer by the laminating process.

20. Bipolar layer; cathode layer; and Including a solid electrolyte layer between the positive electrode layer and the negative electrode layer, The above negative electrode layer includes a negative electrode current collector and a negative electrode coating layer on the negative electrode current collector, The above negative electrode collector includes a tab portion protruding from one side thereof, An all-solid-state battery, wherein the tab portion includes a datum hole.

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