Electrode and method for manufacturing all-solid battery

Abstract

An object of the present application is to provide an electrode capable of reducing the resistance of an all-solid battery and a manufacturing method of an all-solid battery. An electrode is an electrode for an all-solid battery having a current collector and an electrode layer, characterized in that a contact surface of the current collector and the electrode layer is joined by an adhesive layer, the adhesive layer is composed of a plurality of adhesive lines arranged in a stripe shape on the contact surface, a ratio (B / A) of a coating width B (mm) of the adhesive lines to an electrical conductivity A (mS) of the electrode layer is 75.00 or less, a distance C (mm) between adjacent adhesive lines is greater than 0.2 mm and 7 mm or less, and a ratio (B / C) of the coating width B of the adhesive lines to the distance C between adjacent adhesive lines is 2.00 or less.

Description

Technical Field

[0001] This disclosure relates to electrodes and methods for manufacturing all-solid-state batteries. Background Technology

[0002] All-solid-state batteries have attracted attention for using solid electrolytes instead of electrolytes containing organic solvents as the electrolyte between the positive and negative electrodes.

[0003] Patent Document 1 discloses an all-solid-state battery having a joining means for joining a current collector and battery cells stacked adjacent to the current collector.

[0004] Prior art literature

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2017-204377 Summary of the Invention

[0007] There is a need to reduce the resistance of all-solid-state batteries. In Patent Document 1, a hot melt is used as a bonding method, and the hot melt is arranged in an L-shape at the corner of the battery cell. The hot melt arrangement area in the battery cell is small, resulting in a higher resistance of the all-solid-state battery.

[0008] This disclosure was made in view of the above-mentioned circumstances, and its main purpose is to provide an electrode capable of reducing the resistance of an all-solid-state battery and a method for manufacturing an all-solid-state battery.

[0009] The electrode disclosed herein is an all-solid-state battery electrode having a current collector and an electrode layer, characterized in that...

[0010] The contact surface between the current collector and the electrode layer is bonded by an adhesive layer.

[0011] The adhesive layer is composed of a plurality of adhesive lines arranged in a striped pattern on the contact surface.

[0012] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the electrode layer is 75.00 or less.

[0013] The distance C (mm) between adjacent adhesive lines is greater than 0.2 mm and less than 7 mm.

[0014] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 2.00 or less.

[0015] The method for manufacturing an all-solid-state battery disclosed herein comprises a first electrode layer, a solid electrolyte layer, and a second electrode layer sequentially disposed therein, a first current collector and the first electrode layer being bonded together by a bonding agent layer, and the second electrode layer and the second current collector being bonded together by a bonding agent layer. The method is characterized by having:

[0016] The process of preparing the first layer stack, wherein the first layer stack is a stack in which the first electrode layer, the solid electrolyte layer, and the second electrode layer are sequentially arranged;

[0017] A process of forming a bonding agent layer consisting of a plurality of bonding agent lines arranged in a stripe pattern by applying bonding agent in a stripe pattern to the surface of the first electrode layer in contact with the first current collector or the surface of the first current collector in contact with the first electrode layer, and the surface of the second electrode layer in contact with the second current collector or the surface of the second current collector in contact with the second electrode layer; and

[0018] A current collector bonding process in which the first electrode layer and the first current collector are bonded using the bonding agent layer, and the second electrode layer and the second current collector are bonded using the bonding agent layer.

[0019] The first electrode, which includes the first electrode layer and the first current collector, and the second electrode, which includes the second electrode layer and the second current collector, are the electrodes described above.

[0020] The method for manufacturing an all-solid-state battery disclosed herein is characterized by having a first electrode layer, a solid electrolyte layer, and a second electrode layer sequentially disposed on both sides of a first current collector, wherein the second electrode layer and the second current collector are bonded together by a bonding agent layer.

[0021] The process of preparing the second stacked body, wherein the second stacked body is a stacked body in which the first electrode layer, the solid electrolyte layer and the second electrode layer are sequentially disposed on both sides of the first current collector;

[0022] A process of forming a bonding agent layer consisting of multiple bonding agent lines arranged in a striped pattern by applying bonding agent in a striped pattern to the surface of the second electrode layer in contact with the second current collector or the surface of the second current collector in contact with the second electrode layer; and

[0023] The current collector bonding process, which uses the adhesive layer to bond the second electrode layer and the second current collector,

[0024] The second electrode, which includes the second electrode layer and the second current collector, is the electrode described above.

[0025] This disclosure provides an electrode that can reduce the resistance of an all-solid-state battery and a method for manufacturing an all-solid-state battery. Attached Figure Description

[0026] Figure 1 This is a cross-sectional schematic diagram showing an example of the electrode of this disclosure.

[0027] Explanation of reference numerals in the attached figures

[0028] 11 Current collector

[0029] 12 Electrode Layers

[0030] 13 Bonding lines

[0031] B. Coating width of the bonding agent line

[0032] C. Distance between adjacent bonding lines Detailed Implementation

[0033] 1. Electrode

[0034] The electrode disclosed herein is an all-solid-state battery electrode having a current collector and an electrode layer, characterized in that...

[0035] The contact surface between the current collector and the electrode layer is bonded by an adhesive layer.

[0036] The adhesive layer is composed of a plurality of adhesive lines arranged in a striped pattern on the contact surface.

[0037] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the electrode layer is 75.00 or less.

[0038] The distance C (mm) between adjacent adhesive lines is greater than 0.2 mm and less than 7 mm.

[0039] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 2.00 or less.

[0040] Figure 1 This is a cross-sectional schematic diagram showing an example of the electrode of this disclosure.

[0041] like Figure 1 As shown, the electrode of this disclosure has a current collector 11 and an electrode layer 12. The contact surfaces of the current collector 11 and the electrode layer 12 are bonded by an adhesive layer consisting of a plurality of adhesive lines 13 arranged in a stripe pattern. B is the coating width of the adhesive line 13, and C is the distance between adjacent adhesive lines 13.

[0042] [electrode]

[0043] The electrode disclosed herein has a current collector and an electrode layer.

[0044] The contact surfaces of the current collector and the electrode layer are bonded together through an adhesive layer. That is, an adhesive layer is disposed between the current collector and the electrode layer, and the current collector and the electrode layer are bonded together through the adhesive layer. The contact surface between the current collector and the electrode layer can be the surface of the current collector that contacts the electrode layer, or the surface of the electrode layer that contacts the current collector. The surface of the current collector that contacts the electrode layer is bonded to the surface of the electrode layer that contacts the current collector through the adhesive layer. The surface of the electrode layer that contacts the current collector is bonded to the surface of the current collector that contacts the electrode layer through the adhesive layer.

[0045] [Bond Layer]

[0046] The bonding agent layer consists of multiple bonding agent lines arranged in a stripe pattern on the contact surface between the current collector and the electrode layer. That is, only a portion of the contact surface between the current collector and the electrode layer needs to be bonded by the bonding agent layer, or not the entire contact surface needs to be bonded.

[0047] The term "striped" refers to a striped pattern. Any striped pattern can be parallel; it can be vertical or horizontal stripes.

[0048] The number of adhesive threads can be three or more, with no particular upper limit.

[0049] The length of the adhesive line can be, for example, 1 to 10 mm.

[0050] In the electrode of this disclosure, the ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the electrode layer is 75.00 or less.

[0051] The distance C (mm) between adjacent adhesive lines should be greater than 0.2mm and less than 7mm. Additionally, the spacing between multiple adhesive lines should be greater than 0.2mm and less than 7mm.

[0052] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines should be less than 2.00.

[0053] The adhesive used in the adhesive layer is not particularly limited as long as it has bonding function in a solid state. Examples of adhesives include viscous resins and hot melt adhesives. Examples of viscous resins include acrylic resins, rubber resins, siloxane resins, and urethane resins. Examples of hot melt adhesives are resins with a melting point below 140°C, such as ethylene-vinyl acetate resins.

[0054] [Electrode layer]

[0055] The electrode layer contains electrode active materials and may include solid electrolytes, conductive materials, adhesives, etc., as needed.

[0056] The electrode layer can be either a positive or negative electrode layer. Two electrode layers with different types of active materials can be prepared, allowing one to be used as the positive electrode layer and the other as the negative electrode layer.

[0057] As the electrode active material, any material that can be used as an active material in an all-solid-state battery can be adopted, and the same active material as the active materials exemplified as the positive and negative active materials described later can be adopted.

[0058] As a solid electrolyte, the same solid electrolyte as that illustrated in the solid electrolyte layer described later can be exemplified.

[0059] As conductive materials and adhesives, the same conductive materials and adhesives as those exemplified in the positive electrode layer described later can be used.

[0060] The thickness of the electrode layer is not particularly limited; for example, it can be 10–100 μm or 10–20 μm.

[0061] The conductivity A (mS) of the electrode layer can be, for example, 0.008 to 0.03 mS.

[0062] [Current Collector]

[0063] As a current collector, the same current collector as those exemplified as positive and negative current collectors described later can be used.

[0064] [All-solid-state battery]

[0065] The electrodes disclosed herein are electrodes for use in all-solid-state batteries.

[0066] The all-solid-state battery disclosed herein can have a positive electrode, a solid electrolyte layer, and a negative electrode. It is sufficient that at least one of the positive and negative electrodes is an electrode of this disclosure. Two electrodes with different types of active materials can be prepared, one of which can be used as the positive electrode and the other as the negative electrode.

[0067] [positive electrode]

[0068] The positive electrode consists of a positive electrode layer and a positive current collector.

[0069] [Positive electrode layer]

[0070] The positive electrode layer contains positive electrode active material, and can also contain any component such as solid electrolyte, conductive material, and binder.

[0071] There are no particular restrictions on the type of positive electrode active material; any material suitable for use as an active material in all-solid-state batteries can be used. Examples of positive electrode active materials include metallic lithium (Li), lithium alloys, LiCoO2, and LiNi. 0.8 Co 0.15 Al 0.05 O2, LiNi x Co 1-x O2 (0 < x < 1), LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2, LiMnO2, dissimilar element-substituted Li-Mn spinels, lithium titanate, lithium metal phosphate, LiCoN, Li2SiO3 and Li4SiO4, transition metal oxides, TiS2, Si, SiO2, Si alloys, and lithium storage intermetallic compounds, etc. Dissimilar element-substituted Li-Mn spinels include, for example, LiMn... 1.5 Ni 0.5 O4, LiMn 1.5 Al 0.5 O4, LiMn 1.5 Mg 0.5 O4, LiMn 1.5 Co 0.5 O4, LiMn 1.5 Fe 0.5 O4 and LiMn 1.5 Zn 0.5 O4, etc. Lithium titanate, for example, is Li4Ti5O. 12 Examples of lithium metal phosphates include LiFePO4, LiMnPO4, LiCoPO4, and LiNiPO4. Transition metal oxides include V2O5 and MoO3. Storage-grade intermetallic compounds of lithium include Mg2Sn, Mg2Ge, Mg2Sb, and Cu3Sb.

[0072] Examples of lithium alloys include Li-Au, Li-Mg, Li-Sn, Li-Si, Li-Al, Li-B, Li-C, Li-Ca, Li-Ga, Li-Ge, Li-As, Li-Se, Li-Ru, Li-Rh, Li-Pd, Li-Ag, Li-Cd, Li-In, Li-Sb, Li-Ir, Li-Pt, Li-Hg, Li-Pb, Li-Bi, Li-Zn, Li-Tl, Li-Te, and Li-At. Examples of Si alloys include alloys of Si with metals such as Li; additionally, alloys of Si with at least one metal selected from Sn, Ge, and Al can also be used.

[0073] The shape of the positive electrode active material is not particularly limited, but it can be in particle form. When the positive electrode active material is in particle form, it can be either primary particles or secondary particles.

[0074] A coating containing Li-ion-conducting oxides can be formed on the surface of the positive electrode active material. This is because it can inhibit the reaction between the positive electrode active material and the solid electrolyte.

[0075] Examples of Li-ion-conducting oxides include LiNbO3 and Li4Ti5O. 12 Including Li3PO4, etc. The coating thickness is, for example, 0.1 nm or more, and can be 1 nm or more. On the other hand, the coating thickness is, for example, 100 nm or less, and can be 20 nm or less. The coating can, for example, cover more than 70% of the surface of the positive electrode active material, and can cover more than 90% of the surface of the positive electrode active material.

[0076] As a solid electrolyte, the same solid electrolyte as that exemplified in the solid electrolyte layer can be shown.

[0077] The content of solid electrolyte in the positive electrode layer is not particularly limited. When the total mass of the positive electrode layer is set to 100% by mass, it can be in the range of, for example, 1% to 80% by mass.

[0078] As a conductive material, known conductive materials can be used, such as carbon materials and metal particles. As carbon materials, at least one selected from acetylene black, furnace black, VGCF, carbon nanotubes, and carbon nanofibers can be used. From the viewpoint of electronic conductivity, at least one selected from VGCF, carbon nanotubes, and carbon nanofibers can be used. As metal particles, particles such as Ni, Cu, Fe, and SUS (stainless steel) can be used.

[0079] The amount of conductive material in the positive electrode layer is not particularly limited.

[0080] Examples of adhesives (binders) include acrylonitrile butadiene rubber (ABR), butadiene rubber (BR), polyvinylidene fluoride (PVdF), and styrene butadiene rubber (SBR). The amount of adhesive in the positive electrode layer is not particularly limited.

[0081] The thickness of the positive electrode layer is not particularly limited; for example, it can be 10–100 μm or 10–20 μm.

[0082] The positive electrode layer can be formed using previously known methods.

[0083] For example, a slurry for the positive electrode layer is prepared by adding the positive electrode active material and other components as needed into a solvent and stirring. The slurry for the positive electrode layer is then coated onto one side of a support and dried to obtain the positive electrode layer.

[0084] Solvents such as butyl acetate, butyl butyrate, mesitylene, tetrahydronaphthalene, heptane, and N-methyl-2-pyrrolidone (NMP) are examples.

[0085] There are no particular limitations on the method of coating the positive electrode layer with paste on one side of the support. Examples include doctor blade coating, metal mask printing, electrostatic coating, dip coating, spray coating, roll coating, gravure coating, and screen printing.

[0086] As a support, a self-supporting support can be appropriately selected and is not particularly limited, such as metal foils such as Cu and Al.

[0087] Alternatively, another method for forming the positive electrode layer is to press-form a powder containing a positive electrode active material and other components as needed to form the positive electrode layer. When pressing the powder of the positive electrode mixture, a pressing pressure of 1 MPa or more and 2000 MPa or less is typically applied.

[0088] There are no particular restrictions on the method of applying pressure; for example, methods such as using a plate press machine or a roll press machine to apply pressure can be listed.

[0089] [Positive current collector]

[0090] As the positive electrode current collector, a known metal suitable for use as a current collector in an all-solid-state battery can be used. Examples of such metals include metallic materials containing one or more elements selected from Cu, Ni, Al, V, Au, Pt, Mg, Fe, Ti, Co, Cr, Zn, Ge, and In. Examples of positive electrode current collectors include SUS, aluminum, nickel, iron, titanium, and carbon.

[0091] The shape of the positive current collector is not particularly limited and can be various forms such as foil or mesh. The thickness of the positive current collector varies depending on the shape, but for example, it can be in the range of 1μm to 50μm, or in the range of 5μm to 20μm.

[0092] [negative electrode]

[0093] The negative electrode consists of a negative electrode layer and a negative electrode current collector.

[0094] [Negative electrode layer]

[0095] The negative electrode layer contains at least a negative electrode active material, and may contain solid electrolyte, conductive material, and binder as needed.

[0096] Examples of anode active materials include graphite, mesophase carbon microspheres (MCMB), highly oriented pyrolytic graphite (HOPG), hard carbon, soft carbon, elemental lithium, lithium alloys, elemental Si, Si alloys, and Li4Ti5O. 12 Etc. As lithium alloys and Si alloys, the same materials as those exemplified in the positive electrode active material can be used.

[0097] The shape of the negative electrode active material is not particularly limited; examples include particulate and plate-like forms. When the negative electrode active material is in particulate form, it can be either primary or secondary particles.

[0098] The conductive materials and adhesives used in the negative electrode layer can be the same as those used in the positive electrode layer. The solid electrolyte used in the negative electrode layer can be the same as those used in the solid electrolyte layer.

[0099] The thickness of the negative electrode layer is not particularly limited; for example, it can be 10–100 μm or 10–20 μm.

[0100] The content of the negative electrode active material in the negative electrode layer is not particularly limited, for example, it can be 20% to 90% by mass.

[0101] [Negative current collector]

[0102] The material of the negative current collector can be a material that is not alloyed with Li, such as SUS, copper, and nickel. The form of the negative current collector can be, for example, foil or plate. The top view shape of the negative current collector is not particularly limited; for example, circular, elliptical, rectangular, and arbitrary polygonal shapes can be used. Furthermore, the thickness of the negative current collector varies depending on the shape, but can be, for example, in the range of 1 μm to 50 μm, or in the range of 5 μm to 20 μm.

[0103] [Solid electrolyte layer]

[0104] The solid electrolyte layer contains at least a solid electrolyte.

[0105] As the solid electrolyte contained in the solid electrolyte layer, known solid electrolytes suitable for all-solid-state batteries can be appropriately used, including inorganic solid electrolytes such as sulfide-based solid electrolytes, oxide-based solid electrolytes, hydride-based solid electrolytes, halide-based solid electrolytes, and nitride-based solid electrolytes. Sulfide-based solid electrolytes may contain sulfur (S) as the main anionic element. Oxide-based solid electrolytes may contain oxygen (O) as the main anionic element. Hydride-based solid electrolytes may contain hydrogen (H) as the main anionic element. Halide-based solid electrolytes may contain halogen (X) as the main anionic element. Nitride-based solid electrolytes may contain nitrogen (N) as the main anionic element.

[0106] Sulfide-based solid electrolytes can be sulfide glasses, crystallized sulfide glasses (glass ceramics), or crystalline materials obtained through solid-state reaction treatment of raw material compositions.

[0107] The crystalline state of sulfide-based solid electrolytes can be confirmed, for example, by powder X-ray diffraction using CuKα rays.

[0108] Chalcogenide glasses can be obtained by amorphous treatment of a raw material composition (e.g., a mixture of Li2S and P2S5). Examples of amorphous treatments include mechanical milling.

[0109] Glass ceramics, for example, can be obtained by heat treatment of sulfide glass.

[0110] The heat treatment temperature can be any temperature higher than the crystallization temperature (Tc) observed by thermal analysis of the sulfide glass, typically above 195°C. On the other hand, there is no particular upper limit to the heat treatment temperature.

[0111] The crystallization temperature (Tc) of sulfide glass can be determined by differential thermal analysis (DTA).

[0112] The heat treatment time is not particularly limited as long as it is the time required to achieve the desired crystallinity of the glass-ceramic, for example, it can be in the range of 1 minute to 24 hours, of which the range of 1 minute to 10 hours can be cited as an example.

[0113] The method of heat treatment is not particularly limited; for example, the method of using a firing furnace can be cited.

[0114] Examples of oxide-based solid electrolytes include solid electrolytes containing Li, Y (where Y is at least one of Nb, B, Al, Si, P, Ti, Zr, Mo, W, and S), and O. A specific example of an oxide-based solid electrolyte is Li7La3Zr2O. 12 Li 7-x La3(Zr 2-x Nb x )O 12 (0≤x≤2), Li5La3Nb2O 12 Garnet-type solid electrolytes, etc.; perovskite-type solid electrolytes such as (Li,La)TiO3, (Li,La)NbO3, (Li,Sr)(Ta,Zr)O3, etc.; NASICON-type solid electrolytes such as Li(Al,Ti)(PO4)3, Li(Al,Ga)(PO4)3, etc.; Li-PO solid electrolytes such as Li3PO4, LIPON (a compound obtained by replacing part of the O in Li3PO4 with N), etc.; Li-BO solid electrolytes such as Li3BO3, a compound obtained by replacing part of the O in Li3BO3 with C, etc.

[0115] Hydride-based solid electrolytes include those containing Li and hydrogen-containing complex anions.

[0116] Examples of complex anions include (BH4). - (NH2) - (AlH4) - and (AlH6) 3- wait.

[0117] As a halide-based solid electrolyte, Li can be cited as an example. 6-3z Y z X6 (where X is at least one of Cl and Br, and z satisfies 0 < z < 2), etc.

[0118] Examples of nitride-based solid electrolytes include Li3N.

[0119] From an operational point of view, solid electrolytes can also be in particle form.

[0120] The average particle size of solid electrolytes is not particularly limited; for example, it can be 10 nm or more, or 100 nm or more. On the other hand, the average particle size of solid electrolytes can be 25 μm or less, or 10 μm or less.

[0121] In this disclosure, unless otherwise specified, the average particle size is the median particle size (D) of the volume reference determined by laser diffraction-scattering particle size distribution measurement.50 The value of ). Furthermore, in this disclosure, the so-called median particle size (D) 50 The volume average diameter (VOD) refers to the diameter when the cumulative volume of particles arranged sequentially from the smallest particles is half (50%) of the total volume.

[0122] Regarding solid electrolytes, one type of solid electrolyte can be used alone, or two or more solid electrolytes can be used. Furthermore, when using two or more solid electrolytes, they can be mixed, or a multilayer structure can be created by forming two or more individual layers of solid electrolyte.

[0123] The proportion of solid electrolyte in the solid electrolyte layer is not particularly limited, for example, it can be 50% or more by mass, it can be in the range of 60% or more and less than 100% by mass, it can be in the range of 70% or more and less than 100% by mass, or it can be 100% by mass.

[0124] From the viewpoint of enabling plasticity, the solid electrolyte layer may contain a binder. Examples of such binders include materials used as binders in the positive electrode layer. However, to facilitate high output, from the viewpoint of preventing excessive aggregation of the solid electrolyte and forming a solid electrolyte layer with uniformly dispersed solid electrolyte, the binder content in the solid electrolyte layer can be set to 5% by mass or less.

[0125] The thickness of the solid electrolyte layer is not particularly limited, but is usually above 0.1 μm and below 1 mm.

[0126] Methods for forming a solid electrolyte layer include coating a solid electrolyte layer containing a solid electrolyte onto a support with a slurry and then drying it, and pressing a powder containing a solid electrolyte material into shape. The support may be the same as the support exemplified in the positive electrode layer. When pressing a powder containing a solid electrolyte material into shape, a pressing pressure of 1 MPa or more and 2000 MPa or less is typically applied.

[0127] There are no particular limitations on the pressurization method; examples of pressurization methods exemplified in the formation of the positive electrode layer can be cited.

[0128] All-solid-state batteries may have an outer casing for housing the stacked structure and constraint components as needed. The stacked structure shall sequentially include a positive current collector, a positive electrode layer, a solid electrolyte layer, a negative electrode layer, and a negative current collector.

[0129] There are no particular limitations on the material of the outer casing, as long as it is stable in the electrolyte. Examples include polypropylene, polyethylene, and acrylic resins.

[0130] The constraint member only needs to be able to apply constraint pressure in the stacking direction to the laminate, and any known constraint member that can be used as a constraint member for an all-solid-state battery can be used. Examples include a constraint member having a plate-like portion having two surfaces that hold the laminate, a rod-like portion connecting two plate-like portions, and an adjustment portion connected to the rod-like portion and used to adjust the constraint pressure via a threaded structure, etc. The desired constraint pressure can be applied to the laminate through the adjustment portion.

[0131] The constraint pressure is not particularly limited; for example, it can be above 0.1 MPa, above 1 MPa, or above 5 MPa. This is because increasing the constraint pressure facilitates good contact between layers. On the other hand, the constraint pressure can be below 100 MPa, below 50 MPa, or below 20 MPa. This is because when the constraint pressure is too high, high rigidity is required for the constraint member, allowing for the possibility of larger constraint members.

[0132] All-solid-state batteries can be batteries with only one of the above-mentioned stacked bodies, or they can be batteries formed by stacking multiple stacked bodies.

[0133] As an all-solid-state battery, it can be a primary battery or a secondary battery, especially a secondary battery. Secondary batteries can be repeatedly charged and discharged. Secondary batteries are useful, for example, as batteries for vehicles. Furthermore, all-solid-state batteries can also be all-solid-state lithium secondary batteries or all-solid-state lithium-ion secondary batteries.

[0134] Examples of shapes for all-solid-state batteries include coin-shaped, laminated, cylindrical, and square-shaped.

[0135] The applications of all-solid-state batteries are not particularly limited, and examples include power sources for hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), battery electric vehicles (BEVs), gasoline vehicles, and diesel vehicles. In particular, they can be used as power sources for driving hybrid electric vehicles, plug-in hybrid electric vehicles, or electric vehicles. Furthermore, the all-solid-state batteries of this disclosure can also be used as power sources for mobile bodies other than vehicles (such as railway trains, ships, and aircraft), and as power sources for electrical products such as information processing devices.

[0136] 2. Manufacturing method of all-solid-state batteries

[0137] 2-1. Manufacturing Method 1

[0138] The first method for manufacturing an all-solid-state battery disclosed herein comprises a method for manufacturing an all-solid-state battery wherein a first electrode layer, a solid electrolyte layer, and a second electrode layer are sequentially disposed, a first current collector and the first electrode layer are bonded together by a bonding agent layer, and the second electrode layer and the second current collector are bonded together by a bonding agent layer, characterized in that it has:

[0139] The process of preparing the first layer stack, wherein the first layer stack is a stack in which the first electrode layer, the solid electrolyte layer, and the second electrode layer are sequentially arranged;

[0140] A process of forming a bonding agent layer consisting of a plurality of bonding agent lines arranged in a stripe pattern by applying bonding agent in a stripe pattern to the surface of the first electrode layer in contact with the first current collector or the surface of the first current collector in contact with the first electrode layer, and the surface of the second electrode layer in contact with the second current collector or the surface of the second current collector in contact with the second electrode layer; and

[0141] A current collector bonding process in which the first electrode layer and the first current collector are bonded using the bonding agent layer, and the second electrode layer and the second current collector are bonded using the bonding agent layer.

[0142] The first electrode, which includes the first electrode layer and the first current collector, and the second electrode, which includes the second electrode layer and the second current collector, are the electrodes described above.

[0143] The all-solid-state battery obtained by the first manufacturing method is provided with a first electrode layer, a solid electrolyte layer, and a second electrode layer in sequence. The first current collector and the first electrode layer are bonded together by a bonding agent layer, and the second electrode layer and the second current collector are bonded together by a bonding agent layer.

[0144] In the all-solid-state battery obtained using the first manufacturing method, both the first electrode, comprising a first electrode layer and a first current collector, and the second electrode, comprising a second electrode layer and a second current collector, are electrodes of this disclosure. One of the first electrode and the second electrode is a positive electrode, and the other is a negative electrode. The first electrode layer is a positive electrode layer when the first electrode is a positive electrode, and a negative electrode layer when the first electrode is a negative electrode. The second electrode layer is a positive electrode layer when the second electrode is a positive electrode, and a negative electrode layer when the second electrode is a negative electrode. The first current collector is a positive current collector when the first electrode is a positive electrode, and a negative current collector when the first electrode is a negative electrode. The second current collector is a positive current collector when the second electrode is a positive electrode, and a negative current collector when the second electrode is a negative electrode.

[0145] The first manufacturing method includes (1) a first laminate preparation step, (2) a bonding agent layer formation step, and (3) a current collector bonding step. The order of the (1) first laminate preparation step and (2) bonding agent layer formation step is not particularly limited.

[0146] (1) Preparation process of the first layer of the stack

[0147] The first layer preparation process is the process of preparing the first layer, which is a stack in which the first electrode layer, the solid electrolyte layer, and the second electrode layer are arranged in sequence.

[0148] The first electrode layer can be prepared, for example, by the following method: First, a paste for the first electrode layer is applied to a support and dried to form the first electrode layer. A paste for the second electrode layer is applied to another support and dried to form the second electrode layer. A solid electrolyte layer is then prepared. The first electrode layer is placed on one side of the solid electrolyte layer, and the support is removed from the first electrode layer. The second electrode layer is placed on the other side of the solid electrolyte layer, and the support is removed from the second electrode layer. This yields the first electrode layer.

[0149] (2) Bonding layer formation process

[0150] The bonding agent layer forming process is as follows: a bonding agent layer consisting of a plurality of bonding agent lines arranged in a stripe pattern is formed by applying bonding agent in a stripe pattern to the surface of the first electrode layer in contact with the first current collector or the surface of the first current collector in contact with the first electrode layer, and the surface of the second electrode layer in contact with the second current collector or the surface of the second current collector in contact with the second electrode layer.

[0151] The bonding agent used in the bonding agent layer may be the same material as the bonding agent described in section 1. Electrode above.

[0152] (3) Current collector bonding process

[0153] The current collector bonding process is a process of bonding the first electrode layer and the first current collector using the bonding agent layer, and bonding the second electrode layer and the second current collector using the bonding agent layer.

[0154] The bonding method is not particularly limited, and examples include applying pressing pressure to a laminate containing a first electrode layer, a first current collector, a second electrode layer, and a second current collector, and performing hot pressing. The heating temperature during hot pressing can be, for example, 140°C or higher. The pressing pressure can be, for example, 1 MPa or higher.

[0155] 2-2. Second manufacturing method

[0156] The second method for manufacturing an all-solid-state battery disclosed herein is characterized by having a first electrode layer, a solid electrolyte layer, and a second electrode layer sequentially disposed on both sides of a first current collector, wherein the second electrode layer and the second current collector are bonded together by a bonding agent layer.

[0157] The process of preparing the second stacked body, wherein the second stacked body is a stacked body in which the first electrode layer, the solid electrolyte layer and the second electrode layer are sequentially disposed on both sides of the first current collector;

[0158] A process of forming a bonding agent layer consisting of multiple bonding agent lines arranged in a striped pattern by applying bonding agent in a striped pattern to the surface of the second electrode layer in contact with the second current collector or the surface of the second current collector in contact with the second electrode layer; and

[0159] The current collector bonding process, which uses the adhesive layer to bond the second electrode layer and the second current collector,

[0160] The second electrode, which includes the second electrode layer and the second current collector, is the electrode described above.

[0161] The all-solid-state battery obtained by the second manufacturing method has a first electrode layer, a solid electrolyte layer, and a second electrode layer sequentially disposed on both sides of the first current collector. The second electrode layer and the second current collector are bonded together by a bonding agent layer.

[0162] In the all-solid-state battery obtained using the second manufacturing method, the second electrode, comprising a second electrode layer and a second current collector, is the electrode of this disclosure. One of the first electrode and the second electrode is a positive electrode, and the other is a negative electrode. The first electrode layer is a positive electrode layer when the first electrode is a positive electrode, and a negative electrode layer when the first electrode is a negative electrode. The second electrode layer is a positive electrode layer when the second electrode is a positive electrode, and a negative electrode layer when the second electrode is a negative electrode. The first current collector is a positive current collector when the first electrode is a positive electrode, and a negative current collector when the first electrode is a negative electrode. The second current collector is a positive current collector when the second electrode is a positive electrode, and a negative current collector when the second electrode is a negative electrode.

[0163] The second manufacturing method includes (A) a second-layer stack preparation step, (B) a bonding agent layer formation step, and (C) a current collector bonding step. The order of the (A) second-layer stack preparation step and (B) bonding agent layer formation step is not particularly limited.

[0164] (A) Preparation process for the second layer of the stack

[0165] The second-layer stack preparation process is the process of preparing a second-layer stack in which the first electrode layer, the solid electrolyte layer, and the second electrode layer are sequentially arranged on both sides of the first current collector.

[0166] The second-layer stack can be prepared, for example, by the following method: First, a paste for the first electrode layer is applied to both sides of the first current collector and dried to form the first electrode layer. A solid electrolyte layer is then disposed on each of the two first electrode layers. A paste for the second electrode layer is applied to each of the two supports and dried to form the second electrode layer. The second electrode layer is then disposed on the opposite side of each of the two solid electrolyte layers to the first electrode layer, and the supports are removed from the second electrode layers. This yields the second-layer stack.

[0167] (B) Adhesive layer formation process

[0168] The bonding agent layer forming process is a process of forming a bonding agent layer consisting of a plurality of bonding agent lines arranged in a stripe pattern by applying bonding agent in a stripe pattern to the surface of the second electrode layer that contacts the second current collector or the surface of the second current collector that contacts the second electrode layer.

[0169] The bonding agent used in the bonding agent layer may be the same material as the bonding agent described in electrode 1 above.

[0170] (C) Current collector bonding process

[0171] The current collector bonding process is a process of bonding the second electrode layer and the second current collector using the bonding agent layer.

[0172] The joining method may be the same as that exemplified in the first manufacturing method.

[0173] [Example]

[0174] (Example 1)

[0175] [Fabrication of the positive electrode layer]

[0176] Using a rolling flow coating apparatus (manufactured by Powerco), the positive electrode active material particles (in Li) are coated under atmospheric conditions. 1.15 Ni 1 / 3 Co 1 / 3 Mn 1 / 3 Particles with O2 as the main phase are coated with lithium niobate and sintered in an atmospheric atmosphere to obtain positive electrode active material particles with a lithium niobate coating.

[0177] PVdF, the above-mentioned positive electrode active material particles, sulfide-based solid electrolyte (Li2S-P2S5 glass ceramic), and VGCF (manufactured by Showa Denko Corporation) are added to a polypropylene container. The resulting positive electrode layer slurry is stirred for 30 seconds using an ultrasonic dispersion device (UH-50 manufactured by ESMOT Corporation).

[0178] Next, the container was vibrated for 3 minutes using a shaker (TTM-1 manufactured by Shibata Scientific Corporation), and the positive electrode layer slurry was further stirred for 30 seconds using an ultrasonic dispersion device. After vibrating the container for 3 minutes, the positive electrode layer slurry was applied to the aluminum foil using an applicator and a doctor blade method. The positive electrode layer slurry was then allowed to dry naturally and dried on a heating plate at 100°C for 30 minutes, thereby obtaining a positive electrode mixture on the aluminum foil (substrate). The laminate of the aluminum foil (substrate) and the positive electrode mixture was densified at 4 t / cm to obtain a positive electrode layer on the aluminum foil (substrate). Furthermore, the coating amount of the positive electrode layer slurry was adjusted so that the thickness of the positive electrode layer obtained when the positive electrode mixture was densified at 4 t / cm was 15 μm.

[0179] [Making the negative electrode]

[0180] PVdF and negative electrode active material particles (Li4Ti5O) were added to the polypropylene container. 12 Using LTO particles and the same sulfide-based solid electrolyte (Li2S-P2S5 glass-ceramic) as described above, the resulting negative electrode layer slurry was stirred for 30 minutes using an ultrasonic dispersion device. The negative electrode layer slurry was then coated onto a copper foil using a doctor blade method. Afterward, the negative electrode layer slurry was allowed to dry naturally, and then dried on a heating plate at 100°C for 30 minutes, thus obtaining a negative electrode with a negative electrode layer on the copper foil (negative electrode current collector). Subsequently, the negative electrode layer slurry was also coated onto the back side of the copper foil (negative electrode current collector) and dried, thereby forming a negative electrode layer on the back side of the copper foil (negative electrode current collector).

[0181] [Fabrication of the solid electrolyte layer]

[0182] Heptane, BR, and a sulfide-based solid electrolyte (Li2S-P2S5 glass-ceramic) were added to a polypropylene container. The resulting solid electrolyte layer slurry was stirred using an ultrasonic dispersion device for 30 seconds. Next, the container was vibrated for 30 minutes using a shaker (Shibata Scientific TTM-1), and the solid electrolyte layer slurry was further stirred using an ultrasonic dispersion device for 30 seconds. After vibrating the container for 3 minutes, the solid electrolyte layer slurry was applied to aluminum foil using a coating tool and a doctor blade method. The solid electrolyte layer slurry was then allowed to dry naturally and dried on a heated plate at 100°C for 30 minutes, thereby forming a solid electrolyte layer on the aluminum foil substrate.

[0183] Fabrication of carbon-coated aluminum foil (positive current collector)

[0184] Furnace black as a conductive material and PVdF as a binder were weighed in a ratio of 25 vol%:75 vol%. NMP was then added to prepare a carbon coating composition. Next, the carbon coating composition was coated onto one side of an aluminum foil to a film thickness of 2 μm, and the carbon coating composition was dried at 100°C for 1 hour to produce a carbon-coated aluminum foil. The carbon-coated aluminum foil was cut to a foil size of 69.0 mm × 73.0 mm (carbon coating size 69.0 mm × 71.0 mm).

[0185] (B) Adhesive layer formation process

[0186] Subsequently, a hot melt adhesive (Hybon ZH234-1, manufactured by Hitachi Chemical) is applied to one side of the carbon-coated aluminum foil in a striped pattern with an adhesive line width B of 0.8 mm and a spacing between adhesive lines (distance C between adjacent adhesive lines) of 0.4 mm, thereby forming an adhesive layer.

[0187] (A) Preparation process for the second layer of the stack

[0188] [Creating the second layer of the stack]

[0189] Solid electrolyte layers are bonded to both sides of the negative electrode with direct contact between each negative electrode layer and each solid electrolyte layer, and pressed at 1.6 t / cm. Then, aluminum foil, serving as the substrate, is peeled off from each solid electrolyte layer. Next, positive electrode layers are bonded to each solid electrolyte layer with direct contact between the positive electrode layer and the solid electrolyte layer, and pressed at 1.6 t / cm. Then, aluminum foil, serving as the substrate, is peeled off from each positive electrode layer, and the resulting second laminate is pressed at 5 t / cm. Finally, the positive electrode layer is laser-trimmed to a size of 70.0 mm × 70.0 mm, and the negative electrode is cut to a size of 72.0 mm × 72.0 mm.

[0190] Then, the terminals are soldered to the second layer of the stack.

[0191] (C) Current collector bonding process

[0192] By bonding each positive electrode layer and each carbon-coated aluminum foil (positive electrode current collector) via an adhesive layer, the carbon-coated aluminum foil (positive electrode current collector) is arranged on both sides of the second laminate in a region located 2.0 mm from the negative electrode end. A pressure of 1 MPa is applied to this region, and it is heated to 140°C, thereby bonding each positive electrode layer and each carbon-coated aluminum foil (positive electrode current collector). The resulting electrode body is then vacuum-sealed into a laminated outer casing to obtain an all-solid-state battery.

[0193] Subsequently, the all-solid-state battery was constrained at 5 MPa and kept at 80°C for 80 hours.

[0194] [Methods for evaluating electrical conductivity]

[0195] The method for determining the conductivity (mS / cm) of the positive electrode mixture is as follows.

[0196] Two laminates of aluminum foil (substrate) and positive electrode agent obtained in the [positive electrode layer fabrication] process were prepared. The two laminates were bonded together with the positive electrode agent in contact with each other to obtain a bond. The bond was pressed at 4 t / cm and then punched to a size with a diameter of 11.28 mm. The resistance between the two aluminum foils of the obtained sample was measured. The conductivity (mS / cm) of the positive electrode agent was calculated from the sample thickness / sample cross-sectional area / sample resistance. The conductivity (mS / cm) of the positive electrode agent was 8 mS / cm. The results are shown in Table 1.

[0197] Furthermore, the conductivity A(mS) of the positive electrode layer is calculated using the following formula. The conductivity A(mS) of the positive electrode layer is 0.012 mS. The results are shown in Table 1.

[0198] The conductivity A (mS) of the positive electrode layer = the conductivity of the positive electrode mixture (mS / cm) * the thickness of the positive electrode layer (cm)

[0199] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the positive electrode layer is 66.67.

[0200] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 2.00.

[0201] (Comparative Example 1)

[0202] (B) In the bonding agent layer formation process, bonding agent is applied in an L-shape along the edges near the four vertices of the carbon-coated aluminum foil on one side. Otherwise, an all-solid-state battery is obtained using the same method as in Example 1.

[0203] (Examples 2-5, Comparative Examples 2-3)

[0204] (B) In the bonding agent layer formation process, the bonding agent line spacing C was changed to 0.2 mm in Comparative Example 2, 0.8 mm in Example 2, 3 mm in Example 3, 5 mm in Example 4, 7 mm in Example 5, and 9 mm in Comparative Example 3. Otherwise, an all-solid-state battery was obtained using the same method as in Example 1.

[0205] The ratio (B / A) of the coating width B (mm) of the binder line to the conductivity A (mS) of the positive electrode layer in Examples 2-5 and Comparative Examples 2-3 was 66.67.

[0206] Regarding the ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines, Comparative Example 2 has a ratio of 4.00, Example 2 has a ratio of 1.00, Example 3 has a ratio of 0.27, Example 4 has a ratio of 0.16, Example 5 has a ratio of 0.11, and Comparative Example 3 has a ratio of 0.09.

[0207] (Comparative Example 4)

[0208] (B) In the bonding agent layer formation process, the coating width B of the bonding agent line was changed to 1.2 mm and the distance C between the bonding agent lines was changed to 3 mm. Otherwise, the all-solid-state battery was obtained by the same method as in Example 1.

[0209] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the positive electrode layer is 100.00.

[0210] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 0.40.

[0211] (Comparative Example 5)

[0212] (B) In the binder layer formation process, the coating width B of the binder lines was changed to 1.6 mm, the distance C between the binder lines was changed to 3 mm, the conductivity of the positive electrode compound was changed to 12 mS / cm, and the conductivity A (mS) of the positive electrode layer was changed to 0.018 mS. Otherwise, an all-solid-state battery was obtained using the same method as in Example 1. The conductivity (mS / cm) of the positive electrode compound was changed by adjusting the VGCF content in the positive electrode compound.

[0213] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the positive electrode layer is 88.89.

[0214] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 0.53.

[0215] (Example 6)

[0216] (B) In the binder layer formation process, the coating width B of the binder lines was changed to 1.2 mm, the distance C between the binder lines was changed to 3 mm, the conductivity of the positive electrode compound was changed to 12 mS / cm, and the conductivity A (mS) of the positive electrode layer was changed to 0.018 mS. Otherwise, an all-solid-state battery was obtained using the same method as in Example 1. The conductivity (mS / cm) of the positive electrode compound was changed by adjusting the VGCF content in the positive electrode compound.

[0217] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the positive electrode layer is 66.67.

[0218] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 0.40.

[0219] (Example 7)

[0220] (B) In the binder layer formation process, the coating width B of the binder lines was changed to 1.6 mm, the distance C between the binder lines was changed to 3 mm, the conductivity of the positive electrode compound was changed to 20 mS / cm, and the conductivity A (mS) of the positive electrode layer was changed to 0.030 mS. Otherwise, an all-solid-state battery was obtained using the same method as in Example 1. The conductivity (mS / cm) of the positive electrode compound was changed by adjusting the VGCF content in the positive electrode compound.

[0221] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the positive electrode layer is 53.33.

[0222] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 0.53.

[0223] (Example 8)

[0224] (B) In the binder layer formation process, the coating width B of the binder lines was changed to 1.2 mm, the distance C between the binder lines was changed to 3 mm, the thickness of the positive electrode layer was changed to 20 μm, and the conductivity A (mS) of the positive electrode layer was changed to 0.016 mS. Otherwise, an all-solid-state battery was obtained using the same method as in Example 1. The thickness of the positive electrode layer was changed by adjusting the amount of positive electrode layer slurry coated onto the substrate.

[0225] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the positive electrode layer is 75.00.

[0226] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 0.40.

[0227] (Comparative Example 6)

[0228] (B) In the binder layer formation process, the distance C between binder lines was changed to 3 mm, the thickness of the positive electrode layer was changed to 10 μm, and the conductivity A (mS) of the positive electrode layer was changed to 0.008 mS. Otherwise, an all-solid-state battery was obtained using the same method as in Example 1. The thickness of the positive electrode layer was changed by adjusting the amount of positive electrode layer slurry applied to the substrate.

[0229] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the positive electrode layer is 100.00.

[0230] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 0.27.

[0231] (Example 9)

[0232] (B) In the binder layer formation process, the coating width B of the binder lines was changed to 0.6 mm, the distance C between the binder lines was changed to 3 mm, the thickness of the positive electrode layer was changed to 10 μm, and the conductivity A (mS) of the positive electrode layer was changed to 0.008 mS. Otherwise, an all-solid-state battery was obtained using the same method as in Example 1. The thickness of the positive electrode layer was changed by adjusting the amount of positive electrode layer slurry coated onto the substrate.

[0233] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the positive electrode layer is 75.00.

[0234] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 0.20.

[0235] (Example 10)

[0236] (B) In the binder layer formation process, the binder line spacing C was changed to 3 mm, the thickness of the positive electrode layer was changed to 10 μm, the conductivity of the positive electrode compound was changed to 12 mS / cm, and the conductivity A (mS) of the positive electrode layer was changed to 0.012 mS. Otherwise, an all-solid-state battery was obtained using the same method as in Example 1. The thickness of the positive electrode layer was changed by adjusting the amount of positive electrode layer slurry applied to the substrate. The conductivity (mS / cm) of the positive electrode compound was changed by adjusting the VGCF content in the positive electrode compound.

[0237] The ratio (B / A) of the coating width B (mm) of the adhesive line to the conductivity A (mS) of the positive electrode layer is 66.67.

[0238] The ratio (B / C) of the coating width B of the adhesive line to the distance C between adjacent adhesive lines is 0.27.

[0239] [Resistance Evaluation Methods]

[0240] For each all-solid-state battery, constant current constant voltage (CCCV) charging was performed at the upper limit voltage of 2.95V and a rate of 1C (cut current 0.01C), followed by CCCV discharging at the lower limit voltage of 1.50V and a rate of 1C (cut current 0.01C).

[0241] The voltage of each solid-state battery was set to 2.36V, and it was charged at a constant current (CC) rate of 2C for 10 seconds. The resistance of each solid-state battery was calculated based on the voltage change. The results are shown in Tables 1 and 2.

[0242] Table 1

[0243]

[0244] Table 2

[0245]

[0246] [Evaluation Results]

[0247] As shown in Tables 1-2, the resistance of the all-solid-state batteries in Examples 1-10 is lower than that of the all-solid-state batteries in Comparative Examples 1-6.

[0248] In Comparative Example 1 of the prior art, since the adhesive is not applied to the entire contact surface between the current collector and the electrode layer, the force for bonding the current collector and the electrode layer, other than the sealing pressure, is insufficient, resulting in a higher resistance in the all-solid-state battery.

[0249] On the other hand, in Examples 1 to 10, the current collector and electrode layer can be fully bonded together by the bonding agent, resulting in lower resistance of the all-solid-state battery.

[0250] It is believed that when the ratio (B / A) of the coating width B (mm) of the binder line to the conductivity A (mS) of the positive electrode layer exceeds 75.00, the conductivity A (mS) of the positive electrode layer is insufficient, the effective reaction portion decreases, and the resistance of the all-solid-state batteries in Comparative Examples 4 to 6 increases.

[0251] It is believed that when the distance C (mm) between adjacent bonding lines is greater than 7 mm, the force of bonding the current collector and electrode layer by bonding agent is insufficient, and the resistance of the all-solid cell in Comparative Example 3 becomes higher.

[0252] It is believed that when the ratio (B / C) of the coating width B of the binder line to the distance C between adjacent binder lines is greater than 2, the contact area between the current collector and the electrode layer is insufficient, and the resistance of the all-solid-state battery in Comparative Example 2 becomes higher.

Claims

1. An electrode, comprising a current collector and an electrode layer, for use in an all-solid-state battery, characterized in that, The contact surface between the current collector and the electrode layer is bonded by an adhesive layer. The adhesive layer is composed of a plurality of adhesive lines arranged in a longitudinal or transverse stripe pattern on the contact surface. The ratio of the coating width B of the adhesive line to the conductivity A of the electrode layer, i.e., B / A, is 53.33 or more and 75.00 or less, where the unit of the coating width B is mm and the unit of the conductivity A is mS. The distance C between adjacent adhesive lines is 0.4 mm or more and 7 mm or less. The ratio of the coating width B of the adhesive line to the distance C between adjacent adhesive lines, i.e., B / C, is 0.16 or more and 2.00 or less. The adhesive layer is composed of an adhesive, which is at least one of a viscous resin and a resin with a melting point below 140°C.

2. A method for manufacturing an all-solid-state battery, wherein the all-solid-state battery is sequentially disposed with a first electrode layer, a solid electrolyte layer, and a second electrode layer, a first current collector and the first electrode layer are bonded by a bonding agent layer, and the second electrode layer and the second current collector are bonded by a bonding agent layer, the manufacturing method being characterized by having: The process of preparing the first layer stack, wherein the first layer stack is a stack in which the first electrode layer, the solid electrolyte layer, and the second electrode layer are sequentially arranged; A process of forming a bonding agent layer consisting of a plurality of bonding agent lines arranged in a longitudinal or transverse stripe pattern by applying a bonding agent in a longitudinal or transverse stripe pattern to the surface of the first electrode layer in contact with the first current collector or the surface of the first current collector in contact with the first electrode layer, and the surface of the second electrode layer in contact with the second current collector or the surface of the second current collector in contact with the second electrode layer; and A current collector bonding process in which the first electrode layer and the first current collector are bonded using the bonding agent layer, and the second electrode layer and the second current collector are bonded using the bonding agent layer. The ratio of the coating width B of the adhesive line to the conductivity A of the electrode layer, i.e., B / A, is 53.33 or more and 75.00 or less. The coating width B is in mm, and the conductivity A is in mS. The distance C between adjacent adhesive lines is 0.4 mm or more and 7 mm or less. The ratio of the coating width B of the adhesive line to the distance C between adjacent adhesive lines, i.e., B / C, is 0.16 or more and 2.00 or less. The adhesive layer is composed of an adhesive, which is at least one of a viscous resin and a resin with a melting point below 140°C.

3. A method for manufacturing an all-solid-state battery, wherein a first electrode layer, a solid electrolyte layer, and a second electrode layer are sequentially disposed on both sides of a first current collector, the second electrode layer and the second current collector being bonded by a bonding agent layer, the manufacturing method being characterized by having: The process of preparing the second stacked body, wherein the second stacked body is a stacked body in which the first electrode layer, the solid electrolyte layer and the second electrode layer are sequentially disposed on both sides of the first current collector; A process of forming a bonding agent layer consisting of multiple bonding agent lines arranged in a longitudinal or transverse stripe pattern by applying a bonding agent in a longitudinal or transverse stripe pattern to the surface of the second electrode layer in contact with the second current collector or the surface of the second current collector in contact with the second electrode layer; and The current collector bonding process, which uses the adhesive layer to bond the second electrode layer and the second current collector, The ratio of the coating width B of the adhesive line to the conductivity A of the electrode layer, i.e., B / A, is 53.33 or more and 75.00 or less. The coating width B is in mm, and the conductivity A is in mS. The distance C between adjacent adhesive lines is 0.4 mm or more and 7 mm or less. The ratio of the coating width B of the adhesive line to the distance C between adjacent adhesive lines, i.e., B / C, is 0.16 or more and 2.00 or less. The adhesive layer is composed of an adhesive, which is at least one of a viscous resin and a resin with a melting point below 140°C.

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