Electrode manufacturing method, composite electrode, electrochemical element, and electrode manufacturing apparatus

Abstract

To provide a method for manufacturing an electrode that can prevent curling (warping) of an electrode even when an insulating resin layer is used as a positive electrode guide when manufacturing the electrode.SOLUTION: A method for manufacturing an electrode includes an insulating resin layer forming step including applying an insulating resin layer forming liquid composition containing a first solvent and a polymerizable compound onto a substrate and forming an insulating resin layer, an electrode mixture layer forming step of applying an electrode mixture layer forming liquid composition containing an active material and a second solvent onto the substrate to form an electrode mixture layer, and a removal step of simultaneously removing the first solvent and the second solvent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for manufacturing an electrode, a composite electrode, an electrochemical element, and an apparatus for manufacturing an electrode.

Background Art

[0002] All-solid-state secondary batteries are superior in terms of safety because they are more resistant to temperature changes and have a lower risk of ignition compared to conventional lithium-ion secondary batteries, and they are also superior in terms of performance because they enable rapid charging. For this reason, it is expected that the demand for all-solid-state secondary batteries will increase, such as for use in electric vehicles. In addition, the need for thin-film batteries for various wearable devices and medical patches is increasing, and the requirements for all-solid-state secondary batteries are diversifying.

[0003] In an all-solid-state battery composed of a positive electrode, a negative electrode, and a solid electrolyte layer, in order to improve the performance of the all-solid-state battery, a laminate including a positive electrode, a solid electrolyte layer, and a negative electrode may be pressed at a very high pressure. However, during this pressing, damage such as cracks occurs in the solid electrolyte, and as a result, there has been a problem that a short circuit occurs between the positive electrode and the negative electrode when the all-solid-state battery is in use.

[0004] There is known a method for manufacturing a thin-film electrode in which an electrode composite layer is formed on an electrode substrate, and a resin layer adhered to at least one of the peripheral portion of the electrode composite layer and the surface of the electrode composite layer is provided in a direction along the plane of the electrode substrate (see, for example, Patent Document 1).

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a method for manufacturing an electrode that can prevent curling (warping) of the electrode even when an insulating resin layer is used as a guide during the manufacture of the electrode.

Means for Solving the Problems

[0006] The method for manufacturing an electrode of the present invention as a means for solving the problems includes: an insulating resin layer forming step including applying a liquid composition for forming an insulating resin layer having a first solvent and a polymerizable compound onto a substrate and forming an insulating resin layer; an electrode mixture layer forming step of applying a liquid composition for forming an electrode mixture layer containing an active material and a second solvent onto the substrate to form an electrode mixture layer; and a removing step of simultaneously removing the first solvent and the second solvent.

Advantages of the Invention

[0007] According to the present invention, even when an insulating resin layer is used as a guide in manufacturing an electrode, it is possible to provide a method for manufacturing an electrode that can prevent curling (warping) of the electrode.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2A

Figure 2B

Figure 2C

Figure 3

Figure 4

Figure 5

Figure 6A

Figure 6B

Figure 6C

Figure 6D

Figure 7

Figure 8A

Figure 8B

Figure 8C

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15

Figure 16

Figure 17

Figure 18

Figure 19

DETAILED DESCRIPTION OF THE INVENTION

[0009] The method for manufacturing an electrode of the present invention is an invention based on the inventors' finding of the following problems in the prior art. That is, in a method for manufacturing an all-solid-state battery using a conventional positive electrode for a solid battery, in order to prevent short-circuiting between the positive electrode and the negative electrode in the all-solid-state battery, a positive electrode guide is arranged on the outer peripheral portion of the surface of the positive electrode electrode composite layer facing the solid electrolyte layer, and lamination and pressing are performed. However, since a very high pressure is applied during the production of the all-solid-state battery, cracks in the positive electrode guide and pressure load on the electrode occur, and there is still a problem that damage is caused to the electrode and the solid electrolyte layer due to the pressure load. Note that since the positive electrode guide requires a certain degree of viscoelasticity to withstand pressing, it is preferably made of resin. Considering productivity and the diversity of the shapes of the electrode composite material layer, it is considered preferable to form a coating film by using a coater to apply a liquid composition. However, Patent Document 1 does not disclose that an insulating resin layer is manufactured from a liquid composition. In addition, a method has been reported in which an insulating resin layer parallel to the outside of the positive electrode composite material layer and the electrode composite material layer is simultaneously coated to improve productivity. However, Patent Document 1 does not describe forming an insulating resin layer with a film thickness required as an electrode composite material layer guide.

[0010] In recent years, the inkjet method has attracted attention as an industrial coater because it can handle micro to precise pattern coating, minimize material loss, and enable precise pattern coating from CAD data etc. without a plate-making (mask). Furthermore, inkjet printing has high film thickness uniformity, enables highly accurate landing and divided coating, and can perform wiring drawing such as irregular coating, fine wiring, and microchips. Therefore, it is expected to form a resin electrode composite material layer guide using a photocurable liquid composition.

[0011] Generally, photocurable liquid compositions often consist of a photoinitiator and an acrylic polyfunctional monomer. In the case of photocuring using such a polyfunctional monomer, there is a problem that when a large number of monomers polymerize into one molecule, volume shrinkage (hereinafter referred to as "curing shrinkage") occurs due to the gap from the van der Waals distance to the covalent bond distance, and phenomena such as curling and peeling from the substrate often occur. When forming an insulating resin layer by applying and curing a liquid composition as an electrode composite layer guide, the electrode composite layer is thicker than the electrode substrate (current collector foil) serving as the base material from the perspective of the energy density of the battery, and inevitably the thickness of the insulating resin layer also becomes thicker. Therefore, the influence of the curing shrinkage of the insulating resin layer is large, and the curling of the electrode substrate appears particularly significantly. As a result, handling in the pressing process and the laminating process becomes difficult, which causes problems such as cracks in the guide in the pressing process and peeling between the active material and the insulating resin layer during lamination, leading to defects and short circuits, and ultimately resulting in poor yield and reduced productivity.

[0012] The details of the present invention are described below.

[0013] (Method for manufacturing an electrode and apparatus for manufacturing an electrode) The method for manufacturing an electrode according to the present invention includes an insulating resin layer forming step, an electrode composite layer forming step, and a removing step, and may have other steps as necessary. The apparatus for manufacturing an electrode according to the present invention includes an insulating resin layer forming means, an electrode composite layer forming means, and a removing means, and may have other means as necessary.

[0014] FIG. 18 is a schematic diagram showing a method for manufacturing an electrode according to an embodiment of the present invention. The method for manufacturing an electrode according to an embodiment of the present invention includes an insulating resin layer forming step S1, an electrode composite layer forming step S2, and a removing step S3. FIG. 19 is a schematic diagram showing a method for manufacturing an electrode according to another embodiment of the present invention. The method for manufacturing an electrode according to another embodiment of the present invention includes an insulating resin layer forming step S1, an electrode composite layer forming step S2, a removing step S3, a pressing step S4, and a solid electrolyte layer forming step S5. Hereinafter, each step and each means will be described in detail.

[0015] <Insulating resin layer forming step and insulating resin layer forming means> The insulating resin layer forming step includes applying a liquid composition for forming an insulating resin layer containing a first solvent and a polymerizable compound onto a substrate, and forming an insulating resin layer. The insulating resin layer forming step preferably includes a liquid composition applying step and a liquid composition curing step. The insulating resin layer forming means includes means for applying a liquid composition for forming an insulating resin layer containing a first solvent and a polymerizable compound onto a substrate, and means for forming an insulating resin layer. The insulating resin layer forming means preferably includes a liquid composition applying means and a liquid composition curing means. The insulating resin layer forming step can be preferably carried out by the insulating resin layer forming means. The liquid composition applying step can be preferably carried out by the liquid composition applying means. The liquid composition curing step can be preferably carried out by the liquid composition curing means.

[0016] <<Liquid composition applying step, and liquid composition applying means>> The liquid composition applying step is a step of applying a liquid composition for forming an insulating resin layer containing a first solvent and a polymerizable compound onto a substrate. The liquid composition applying means is means for applying the liquid composition contained in a storage container onto a substrate. There are no particular limitations on the liquid composition applying step and the liquid composition applying means, and they can be appropriately selected according to the purpose. For example, any printing device corresponding to various printing methods such as spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method, etc. can be used. Among these, from the viewpoint of being able to form an insulating resin layer with high precision, the inkjet printing method (system) is preferable.

[0017] <Storage container> The storage container includes a liquid composition for forming an insulating resin layer and a container, and is a storage container in which the liquid composition for forming an insulating resin layer is stored in the container. Examples of the container include a glass bottle, a plastic container, a plastic bottle, a stainless steel bottle, a one-gallon can, a drum can, and the like.

[0018] -Liquid composition for forming an insulating resin layer- The liquid composition for forming an insulating resin layer includes a first solvent and a polymerizable compound, and further includes other components as necessary.

[0019] --First solvent-- Examples of the first solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, anisole, and phenetole; hydrocarbon solvents such as hexane, heptane, nonane, octane, decane, menthane, cyclohexane, cyclooctane, and p-menthane; ester solvents such as ethyl butyrate, ethyl valerate, ethyl hexanoate, ethyl heptanoate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, ethyl undecanoate, ethyl laurate, methyl butyrate, methyl valerate, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, methyl laurate, ethyl isovalerate, isoamyl acetate, isobutyl isobutyrate, methyl 3-methoxyisobutyrate, butyl isobutyrate, isobutyl isovalerate, butyl 2-methylbutyrate, butyl isovalerate, heptyl acetate, isoamyl isovalerate, 2-ethylhexyl acetate, hexyl butyrate, ethyl benzoate, hexyl hexanoate, amyl n-octanoate, and hexyl acetate; and petroleum-based mixed solvents.

[0020] Examples of the petroleum-based mixed solvents include, by trade name, ISOPAR E, ISOPAR G, ISOPAR H, ISOPAR H BHT, ISOPAR L, ISOPAR M, EXXSOL D40, EXXSOL D80, EXXSOL D110, EXXSOL D130, EXXSOL DSP80 / 100, and EXXSOL DSP145 / 60 (all manufactured by Ando Balakemi Co., Ltd.).

[0021] The content of the solvent is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of the curl suppression effect, it is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more based on the total amount of the liquid composition. Further, from the viewpoint of film thickness control, it is preferably 70% by mass or less.

[0022] From the viewpoint of the diversity of the selection of the polymerizable compound, a plurality of solvents may be used in combination as the solvent in the present invention.

[0023] As a first aspect of the liquid composition of the present invention, the solvent in the liquid composition is a mixed solvent containing a good solvent and a poor solvent from the viewpoint of the curl suppression effect due to volume shrinkage, and satisfies the formula (1).

[0024]

Number

[0025] As used herein, the "good solvent" refers to a solvent in which the polymerizable compound is soluble. As used herein, the "poor solvent" refers to a solvent in which the polymerizable compound is insoluble. When the term "mixed solvent" is used herein, it refers to a solvent containing a good solvent and a poor solvent. As used herein, the "mixing ratio X" refers to the content ratio based on the mass of the good solvent in the mixed solvent, expressed as a percentage. As used herein, the "polymerizable compound solubility point" refers to the minimum content ratio based on the mass of the good solvent in a mixed solvent in which the polymerizable compound is soluble, expressed as a percentage.

[0026] Here, the "soluble" in the first aspect will be described. "Soluble" means that after mixing the solvent and the polymerizable compound and ultrasonically stirring for 15 minutes with an ultrasonic stirrer (USS-1), and then standing for 10 minutes at a predetermined temperature, no cloudiness or phase separation occurs. The predetermined temperature is not particularly limited as long as it is the environmental temperature during actual use, and examples thereof include 25°C. Note that the solubility / insolubility is determined according to the composition of the liquid composition. For example, the following patterns 1 to 5 can be mentioned.

[0027] [Pattern 1] In the case of a liquid composition containing two polymerizable compounds (mixed compound) represented by the general formula (1) and one solvent, the solubility / insolubility is determined using a mixture of 10 g of the solvent and 1 g of the mixed compound (monomer ratio (mass ratio) in the liquid composition).

[0028] [Pattern 2] In the case of a liquid composition containing one polymerizable compound represented by the general formula (1), one polymerizable compound not satisfying the general formula (1), and one solvent, the solubility / insolubility is determined using a mixture of 10 g of the solvent and 1 g of a mixture of the polymerizable compound represented by the general formula (1) and the polymerizable compound not satisfying the general formula (1) (monomer ratio (mass ratio) in the liquid composition).

[0029] [Pattern 3] In the case of a liquid composition containing one polymerizable compound represented by the general formula (1) and two solvents (mixed solvent), the solubility / insolubility is determined using a mixture of 10 g of the mixed solvent (monomer ratio (mass ratio) in the liquid composition) and 1 g of the polymerizable compound represented by the general formula (1).

[0030] [Pattern 4] In the case of a liquid composition containing two polymerizable compounds (mixed compound) represented by the general formula (1) and two solvents (mixed solvent), the solubility / insolubility is determined using a mixture of 10 g of the mixed solvent (monomer ratio (mass ratio) in the liquid composition) and 1 g of the mixed compound (monomer ratio (mass ratio) in the liquid composition).

[0031] [Pattern 5] In the case of a liquid composition containing two polymerizable compounds (mixed compound) represented by the general formula (1), a polymerizable compound that does not satisfy the general formula (1), and two solvents (mixed solvent), the solubility / insolubility is determined using a mixture of 10 g of the mixed solvent (monomer ratio (mass ratio) in the liquid composition) and 1 g of a mixture of the mixed compound and the polymerizable compound that does not satisfy the general formula (1) (monomer ratio (mass ratio) in the liquid composition).

[0032] Formula (1) can also be transformed into formula (1)'.

[0033]

Number

[0034] Since the liquid composition of the first form satisfies formula (1) or formula (1)', a resin layer having a high porosity based on the phase separation rate can be formed, so that the volume shrinkage during the curing of the liquid composition can be suppressed, and a high-quality resin layer can be formed. In addition, as the "mixing ratio X - polymerizable compound solubility point" in formula (1)' approaches 0, curling due to volume shrinkage can be more effectively suppressed.

[0035] As a second aspect of the liquid composition of the present invention, the polymerizable compound in the liquid composition is a mixed compound containing a soluble polymerizable compound and an insoluble polymerizable compound, and preferably satisfies formula (2) from the viewpoint of the curling suppression effect due to volume shrinkage.

[0036]

Number

[0037] --Polymerizable compound-- The polymerizable compound in the present invention is a compound having a plurality of monosubstituted ethylenes, 1,1-disubstituted ethylenes, 1,2-disubstituted ethylenes, and / or diene compounds, which is represented by the general formula (1) and capable of radical polymerization. Moreover, as the polymerizable compound, it is preferable that each polymerizable compound is a crosslinkable resin formed by a crosslinking reaction. The crosslinking reaction is not particularly limited and can be appropriately selected according to the purpose, but it is preferably carried out by photocuring.

[0038]

Chemical formula

[0039] As n in general formula (1), from the viewpoint of curl suppression occurring during curing of the liquid composition, 2 or 3 is preferable, and 2 is more preferable.

[0040] As R2 in general formula (1), from the viewpoint of obtaining a more excellent curl suppression effect, a polyester chain is preferable, and a polycaprolactone chain is more preferable.

[0041] As the polymerizable compound, from the viewpoint of polymerization rate, it is preferable that the compound has an acrylic group, that is, R1 in general formula (1) is a hydrogen atom. Generally, since an acrylic group has high radical polymerizability, a cured product can be obtained in a short time by using a photoinitiator or a thermal initiator in combination in the liquid composition. A cured product can also be obtained without using a polymerization initiator in combination. However, when a polymerizable compound having an acrylic group is used as the polymerizable compound, that is, when R1 in general formula (1) is a hydrogen atom, from the viewpoints of polymerization rate and equipment cost, it is preferable to use the polymerizable compound in combination with a thermal initiator or a photoinitiator in the liquid composition, and it is more preferable to use the polymerizable compound in combination with a photoinitiator.

[0042] Specific examples of the polymerizable compounds include bifunctional alkyl acrylates, hydroxypivalic acid neopentyl glycol acrylate adducts, bifunctional polyethylene glycol acrylates, bifunctional polypropylene glycol acrylates, bifunctional polytetramethylene glycol acrylates, bifunctional cyclic acrylates, bifunctional alkoxylated aromatic acrylates, bifunctional acrylic acid multimer ester acrylates, bifunctional caprolactam-modified acrylates, trifunctional trimethylolpropane acrylates, trifunctional alkoxylated glycerin acrylates, trifunctional isocyanate acrylates, tetrafunctional pentaerythritol acrylates, tetrafunctional ditrimethylolpropane acrylates, tetrafunctional diglycerin tetraacrylates, hexafunctional dipentaerythritol hexaacrylates, polyester acrylates, and the like. Among these, from the viewpoint of volume shrinkage, bifunctional alkyl acrylates, bifunctional polyethylene glycol acrylates, bifunctional alkoxylated aromatic acrylates, bifunctional acrylic acid multimer ester acrylates, trifunctional trimethylolpropane acrylates, trifunctional alkoxylated glycerin acrylates, and trifunctional isocyanate acrylates are preferred, and bifunctional alkyl acrylates, bifunctional polyethylene glycol acrylates, bifunctional alkoxylated aromatic acrylates, and bifunctional acrylic acid multimer ester acrylates are more preferred. Among bifunctional alkyl acrylates, bifunctional polyethylene glycol acrylates, bifunctional alkoxylated aromatic acrylates, and bifunctional acrylic acid multimer ester acrylates, bifunctional polyethylene glycol acrylates, bifunctional acrylic acid multimer ester acrylates, and bifunctional polyester acrylates are more preferred.

[0043] Examples of the bifunctional alkyl acrylate include, for example, those with the trade names NK Ester A-HD-N, A-NON-N, A-DOD-N, A-NPG (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate NP-A, MPD-A, 1,6HX-A, 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD NPGDA (manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0044] Examples of the neopentyl glycol acrylate adduct of hydroxypivalic acid include, for example, under the trade names, Light Acrylate HPP-A (manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat #195, Biscoat #230, Biscoat #260 (manufactured by Osaka Organic Chemical Industry Co., Ltd. above), Miramer M210, Miramer M216 (manufactured by Miwow above), KAYARAD FM-400 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0045] Examples of the difunctional polyethylene glycol acrylate include, for example, under the trade names, NK Ester A-200, NK Ester A-400, NK Ester A-600, NK Ester A-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd. above), Light Acrylate 3EG-A, Light Acrylate 4EG-A, Light Acrylate 9EG-A, Light Acrylate 14EG-A (manufactured by Kyoeisha Chemical Co., Ltd. above), Brenmer ADE-200, Brenmer ADE-300, Brenmer ADE-400A (manufactured by NOF Corporation above), Miramer M202 (manufactured by Miwow), and the like.

[0046] Examples of the difunctional polypropylene glycol acrylate include, for example, under the trade names, NK Ester APG-200, NK Ester APG-400, NK Ester APG-700 (manufactured by Shin-Nakamura Chemical Co., Ltd. above), Biscoat #310HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Brenmer ADP-400 (manufactured by NOF Corporation), Miramer M210, Miramer M216, Miramer M220 (manufactured by Miwow above), and the like.

[0047] Examples of the difunctional polytetramethylene glycol acrylate include, for example, under the trade names, NK Ester A-PTMG65 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate PTMGA-250 (manufactured by Kyoeisha Chemical Co., Ltd.), Brenmer ADT-250 (manufactured by NOF Corporation), and the like.

[0048] Examples of bifunctional cyclic acrylates include, for example, by trade name, NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD R-604, KAYARAD R-684 (both manufactured by Nippon Kayaku Co., Ltd.), etc.

[0049] Examples of bifunctional alkoxylated aromatic acrylates include, for example, by trade name, NK Ester ABE-300, A-BPE-4, A-BPE-10, A-BPE-20 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate BP-4EAL, BA-134, BP-10EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat #540 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD R-551, KAYARAD R-712 (both manufactured by Nippon Kayaku Co., Ltd.), etc.

[0050] Examples of bifunctional acrylic acid polymer esters include, for example, by trade name, Biscoat #230D (manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc.

[0051] Examples of bifunctional caprolactam-modified acrylates include, for example, by trade name, KAYARAD HX-220, KAYARAD HX-620 (both manufactured by Nippon Kayaku Co., Ltd.), etc.

[0052] Examples of trifunctional trimethylolpropane acrylates include, for example, by trade name, NK Ester A-TMPT, A-TMPT-9EO, AT-20E (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate TMP-3EO-A, Light Acrylate TMP-6EO-3A (both manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat #295 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc.

[0053] Examples of trifunctional alkoxylated glycerin acrylates include, for example, by trade name, NK Ester A-GLY-3E, A-GLY-9E, A-GLY-20E (all manufactured by Shin-Nakamura Chemical Co., Ltd.), etc.

[0054] Examples of trifunctional isocyanate acrylate include, for example, by trade name, NK Ester A-9300, A-9200YN (both manufactured by Shin-Nakamura Chemical Co., Ltd.), etc.

[0055] Examples of tetrafunctional pentaerythritol acrylate include, for example, by trade name, NK Ester A-TMMT, ATM-35E (both manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate PE-3A, Light Acrylate PE-4A (both manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0056] Examples of tetrafunctional ditrimethylolpropane acrylate include, for example, by trade name, NK Ester AD-TMP (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc.

[0057] Examples of tetrafunctional diglycerin tetraacrylate include, for example, by trade name, Light Acrylate DGE-4E (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0058] Examples of hexafunctional dipentaerythritol hexaacrylate include, for example, by trade name, Light Acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0059] Examples of the polyester acrylate include, by trade name, Aronix M-6100, Aronix M-6200, Aronix M-6250, Aronix M-6500, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050 (manufactured by Toagosei Co., Ltd.), Ebecryl 81, Ebecryl 88, Ebecryl 80, Ebecryl 657, Ebecryl 1657, Ebecryl 800, Ebecryl 805, Ebecryl 808, Ebecryl 810, Ebecryl 1810, Ebecryl 450, Ebecryl 1830, Ebecryl 1870, Ebecryl 2870, Ebecryl 830, Ebecryl 835, Ebecryl 870, Ebecryl 84, IRR 302 (manufactured by Daicel Allnex), RCC13-429 (manufactured by San Nopco Ltd.), Dia Beam UK-4003, Dia Beam UK-4203 (manufactured by Mitsubishi Chemical Corporation), CN2203, CN2270, CN2271, CN2273, CN2274 (manufactured by Arkema), KAYARAD HX-220, KAYARAD HX-620 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0060] As the polymerizable compound, at least one polymerizable compound represented by the general formula (1) may be included. That is, the polymerizable compound contained in the liquid composition may contain only the polymerizable compound represented by the general formula (1), or may contain two or more different polymerizable compounds represented by the general formula (1). In any case, in addition to the polymerizable compound represented by the general formula (1), a polymerizable compound that does not satisfy the general formula (1) may be included. Here, from the viewpoint of being able to suppress the deterioration of the sulfide solid electrolyte, it is preferable that the liquid composition of the present invention does not contain a polymerizable compound that does not satisfy the general formula (1). Further, from the viewpoint that the range in which the physical properties (for example, elastic modulus) of the insulating resin layer can be controlled can be expanded, it is preferable that the liquid composition of the present invention contains two or more different polymerizable compounds represented by the general formula (1). As the polymerizable compound, it is sufficient that at least one polymerizable compound satisfying the conditions described in the general formula (2) is included. That is, the polymerizable compound contained in the liquid composition may be only a polymerizable compound satisfying the conditions described in one general formula (2), or may have two or more different polymerizable compounds satisfying the conditions described in the general formula (2). Also, in any case, in addition to the polymerizable compound satisfying the conditions described in the general formula (2), it may have a polymerizable compound that does not satisfy the conditions described in the general formula (2). Note that, in terms of being able to suppress the deterioration of the sulfide solid electrolyte, it is preferable that the liquid composition does not have a polymerizable compound that does not satisfy the conditions described in the general formula (2). Furthermore, in terms of being able to expand the range in which the physical properties of the insulating resin layer, such as the elastic modulus, can be controlled, it is preferable that the liquid composition has two or more different polymerizable compounds satisfying the conditions described in the general formula (2).

[0061] The photoinitiator is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include alkylphenone-based photoinitiators, acylphosphine sulfite-based photoinitiators, and oxime ester-based photoinitiators. Specific examples of the alkylphenone-based photoinitiator include, by trade name, Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V., etc.). Specific examples of the acylphosphine sulfite-based polymerization initiator include, by trade name, Omnirad TPO, Omnirad 819 (both manufactured by IGM Resins B.V.), and the like. Specific examples of the oxime ester-based polymerization initiator include, by trade name, Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (all manufactured by BASF Japan), and the like.

[0062] The content of the polymerization initiator is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of obtaining a sufficient curing rate, when the total amount of the polymerizable compound is 100.0% by mass, it is preferably 0.05% by mass or more and 10.0% by mass or less, and more preferably 0.1% by mass or more and 5.0% by mass or less.

[0063] <Non-crosslinked resin> The non-crosslinked resin in the present invention is a non-crosslinked high molecular compound having a structural unit represented by the general formula (2). In other words, the non-crosslinked resin in the present invention is a non-crosslinked high molecular compound containing an acrylic monomer having an acrylate group as a structural unit.

[0064]

Chemical formula

[0065] Here, the "non-crosslinked high molecular compound" means a high molecular compound that does not have a three-dimensional network structure formed by crosslinking, and does not include branched high molecular compounds, graft polymers, dendrimers, etc. that do not have a network structure.

[0066] Regarding m in the structural unit represented by the general formula (2), there is no particular limitation and it can be appropriately selected according to the purpose. However, from the viewpoint of controlling the viscosity of the liquid composition, it is preferably 100 or more and 100,000 or less, and more preferably 1,000 or more and 100,000 or less.

[0067] As R3 in the structural unit represented by the general formula (2), there is no particular limitation as long as it is an alkyl group, and it can be appropriately selected according to the purpose. However, from the viewpoint of increasing the glass transition point, it is preferably methyl, ethyl, iso-propyl, n-propyl, tert-butyl, iso-butyl, or n-butyl. When R3 in the structural unit represented by the general formula (2) has these structures, the glass transition point does not become lower than room temperature, so that a solid resin layer can be obtained. Since the solid resin layer has sufficient strength, it can maintain its shape and suppress peeling from the substrate even when there are processes such as compression in the process of manufacturing the electrochemical element.

[0068] As the non-crosslinked resin, at least one kind of structural unit represented by the general formula (2) may be included. That is, the non-crosslinked resin contained in the liquid composition may contain only the structural unit represented by the general formula (2), or may contain two or more different structural units represented by the general formula (2). In any case, in addition to the structural unit represented by the general formula (2), other structural units that do not satisfy the general formula (2) may be included.

[0069] From the viewpoint of increasing the glass transition temperature, the non-crosslinked resin in the present invention is preferably a copolymer composed of two or more kinds of structural units. In other words, the non-crosslinked resin in the present invention is preferably a copolymer containing the structural unit represented by the first general formula (2) and other structural units different from the structural unit represented by the first general formula (2). When the non-crosslinked resin is a copolymer composed of two or more kinds of structural units, the glass transition point does not become lower than room temperature, so that a solid resin layer can be obtained. Since the solid resin layer has sufficient strength, it can maintain its shape and suppress peeling from the substrate even when there are processes such as compression in the process of manufacturing the electrochemical element.

[0070] Other structural units are not particularly limited and can be appropriately selected according to the purpose. For example, while satisfying the structural unit represented by the general formula (2), there are structures different from the structural unit represented by the first general formula (2), or structures that do not satisfy the structural unit represented by the general formula (2). From the viewpoint of controlling the glass transition point, it is preferably a structure that does not satisfy the structural unit represented by the general formula (2). From the viewpoint of excellent curl suppression effect due to volume shrinkage, it is preferably a structural unit represented by the general formula (3).

[0071]

Chemical formula

[0072] Regarding p in the structural unit represented by the general formula (3), there is no particular limitation and it can be appropriately selected according to the purpose. From the viewpoint of controlling the viscosity of the liquid composition, it is preferably 100 or more and 100,000 or less, more preferably 1,000 or more and 100,000 or less.

[0073] The copolymer related to the non-crosslinked resin in the present invention is preferably a block copolymer from the viewpoint of the curl suppression effect due to volume shrinkage. The method for obtaining a block copolymer is not particularly limited and can be appropriately selected according to the purpose. For example, anionic polymerization methods (including coordination anionic polymerization), cationic polymerization methods, radical polymerization methods (including atom transfer radical polymerization and reversible addition fragmentation chain transfer polymerization), ring-opening metathesis polymerization methods, methods for stepwise producing block polymers using polycondensation or addition reactions for terminal diols and diamine polymers, etc. can be mentioned.

[0074] As the copolymer related to the non-crosslinked resin in the present invention, those synthesized as appropriate may be used, or commercially available products may be used. Examples of commercially available copolymers include, for example, under the trade names, Clarity LA4285, Clarity LA2270, Clarity LA2250, Clarity LA2140, Clarity LA2330, Clarity LA3320, Clarity LA3710, Clarity LK9243 (manufactured by Kuraray Co., Ltd., etc.).

[0075] The number-average molecular weight (Mw) of the non-crosslinked resin of the present invention is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of thickening property, it is preferably 5,000 or more.

[0076] <<Liquid Composition Curing Step, and Liquid Composition Curing Means>> The liquid composition curing step is a step of curing the liquid composition by applying heat or light thereto. The liquid composition curing means is means for curing the liquid composition by applying heat or light thereto. By applying heat or light to the liquid composition, the polymerizable compound in the liquid composition polymerizes and polymerization-induced phase separation occurs, and an insulating resin layer having a porous structure is obtained.

[0077] The light in the liquid composition curing step and the liquid composition curing means is preferably an active energy ray. The active energy ray may be any ray that can impart the energy necessary for promoting the polymerization reaction of the polymerizable compound in the liquid composition, and is not particularly limited. Examples thereof include, for example, ultraviolet rays, electron beams, α-rays, β-rays, γ-rays, X-rays, etc. Among these, ultraviolet rays are preferable. When a particularly high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator.

[0078] The irradiation intensity of the active energy ray is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 1 W / cm 2 or less, and preferably 300 mW / cm 2It is more preferable that it is as follows, 100 mW / cm 2 It is even more preferable that it is as follows. In addition, if the irradiation intensity of the active energy ray is too low, polymerization-induced phase separation proceeds excessively, and variations and coarsening of the porous structure are likely to occur. Also, since productivity decreases as the irradiation time becomes longer, it is preferably 10 mW / cm 2 or more, and more preferably 30 mW / cm 2 or more.

[0079] (Insulating resin layer) The insulating resin layer of the present invention is formed by curing a liquid composition for forming an insulating resin layer and has a porous structure.

[0080] When the insulating resin layer has a porous structure, residual stress due to volume shrinkage is less likely to occur, so curl can be suppressed. In particular, it is more effective when forming an insulating resin layer having an average thickness of 100 μm or more.

[0081] As the porous structure, a co-continuous structure having a resin as a skeleton is preferable. Here, the "co-continuous structure" means a structure in which two or more substances or phases each have a continuous structure and do not form an interface. In the present embodiment, it means a structure in which a resin phase and a pore phase are both three-dimensional branched network continuous phases. These structures can be formed by polymerization-induced phase separation (see, for example, JP-A-2003-1911628, WO97 / 044363, JP-A-2005-298757, JP-T-2010-513589, JP-A-2001-163907, and JP-A-2001-138504).

[0082] [Polymerization-induced phase separation] Coincidence-induced phase separation means that before the start of polymerization, the polymerizable compound and the solvent are compatible, and after the start of polymerization, the polymer (resin) generated during the polymerization process of the polymerizable compound and the solvent are incompatible, resulting in a phase-separated state. There are other methods to obtain a porous structure by phase separation, but the porous structure with a co-continuous structure obtained by the polymerization-induced phase separation method has the advantage of high resistance to chemicals and heat. Also, compared with other methods, it has the advantages of short process time and easy surface modification. Next, the formation process of a porous structure using the polymerization-induced phase separation method with a liquid composition containing a polymerizable compound will be described. The polymerizable compound undergoes a polymerization reaction by light irradiation or the like to form a resin. During this process, the solubility of the growing resin in the solvent decreases, and phase separation occurs between the resin and the solvent. Finally, the resin forms a porous structure in which the solvent and the like fill the pores and has a co-continuous structure by the resin skeleton. When this is dried, the solvent and the like are removed, leaving a porous resin having a co-continuous structure of a three-dimensional network structure.

[0083] Therefore, as a preferred form of the ink, the liquid composition preferably contains a polymerizable compound (monomer) and a solvent mixed together, and the resin after polymerization is insoluble in the solvent or does not form a gel or sol.

[0084] As a method for confirming that the insulating resin layer has a co-continuous structure and the pores are connected, for example, a method of observing an image of a cross-section of the insulating resin layer with a scanning electron microscope (SEM) or the like to confirm that the connection between the pores is continuous can be mentioned. [An example of the image observation method by scanning electron microscope (SEM)] After osmium staining is performed on the insulating resin layer, it is impregnated with epoxy resin under vacuum, the internal cross-sectional structure is cut out with a focused ion beam (FIB), and observed using a scanning electron microscope (SEM).

[0085] The porosity of the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 30% or more, more preferably 50% or more. Also, it is preferably 90% or less, more preferably 85% or less. When the porosity of the insulating resin layer is 30% or more, it is possible to relieve the pressure applied from the insulating resin layer to the solid electrolyte layer in the pressing step after the formation of the solid electrolyte layer, which is preferable. When the porosity of the insulating resin layer is 90% or less, the strength of the insulating resin layer is improved, and when passing through the pressing step, the shape of the insulating resin layer can be sufficiently maintained, which is preferable. As a method for measuring the porosity of the insulating resin layer, it can be measured by the same method as described in the item of [an example of the image observation method using a scanning electron microscope (SEM)].

[0086] The air permeability of the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 1,000 seconds / 100 mL or less, more preferably 500 seconds / 100 mL or less, and even more preferably 300 seconds / 100 mL or less. The air permeability is measured in accordance with JIS P8117 and can be measured using, for example, a Gurley densometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.). As an example, it may be determined that the pores communicate when the air permeability is 1,000 seconds / 100 mL or less.

[0087] The cross-sectional shape of the pores in the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. Examples include a substantially circular shape, a substantially elliptical shape, and a substantially polygonal shape. Here, the size of the pores refers to the length of the longest part in the cross-sectional shape of the insulating resin layer. The size of the pores in the insulating resin layer can be obtained, for example, from a cross-sectional photograph taken with a scanning electron microscope (SEM).

[0088] The size of the pores in the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. However, the ratio of the size of the pores to the median diameter of the solid electrolyte contained in the liquid composition (liquid composition for solid electrolyte layer) for forming the solid electrolyte layer provided on the insulating resin layer is preferably smaller than 1, and more preferably 0.8 or less. When the size of the pores in the insulating resin layer is larger than the median diameter of the solid electrolyte, the solid electrolyte is likely to be contained in the pores of the insulating resin layer. By making the size of the pores in the insulating resin layer smaller than the median diameter of the solid electrolyte, a configuration can be achieved in which the solid electrolyte is less likely to be contained in the insulating resin layer, which is advantageous in terms of pressure dispersion during pressing and pressure relaxation from the insulating resin layer to the solid electrolyte layer.

[0089] The method for controlling the size and porosity of the pores in the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. For example, methods such as adjusting the content of the polymerizable compound in the liquid composition, adjusting the content of the solvent in the liquid composition, and adjusting the irradiation conditions of the active energy ray can be mentioned.

[0090] The volume resistivity of the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 10 12 Ω·cm or more.

[0091] <Electrode composite layer forming step, and electrode composite layer forming means> The electrode composite layer forming step is a step of forming an electrode composite layer by applying a liquid composition for forming an electrode composite layer containing an active material and a second solvent on a substrate. The electrode composite layer forming means is means for forming an electrode composite layer by applying a liquid composition for forming an electrode composite layer containing an active material and a second solvent on a substrate. The electrode composite layer formation process and the means for forming the electrode composite layer are not particularly limited and can be appropriately selected according to the purpose. For example, there is a method of applying a dispersion liquid obtained by dispersing a powdery active material, a binder, a conductive material, etc. in a liquid onto a substrate, fixing it, and drying it. At this time, coating methods such as spraying, dispenser, die coater, dip coating, etc. can be preferably used.

[0092] -Liquid Composition for Electrode Composite Layer Formation- The liquid composition for electrode composite layer formation contains an active material and a second solvent, and may further contain a conductive auxiliary agent, a binder as a resin, a dispersant, a solid electrolyte, and other components as necessary. When the solid electrolyte layer is a sulfide solid electrolyte layer, the cured product (insulating resin layer) of the liquid composition of the present invention can suppress the deterioration of the ionic conductivity of the sulfide solid electrolyte layer. Therefore, the electrode composite layer in the electrode for an electrochemical device or the electrode laminate preferably contains an active material and a sulfide solid electrolyte.

[0093] --Active Material-- As the active material, a positive electrode active material or a negative electrode active material can be used. Note that the positive electrode active material or the negative electrode active material may be used alone or in combination of two or more.

[0094] The positive electrode active material is not particularly limited as long as it is a material that can reversibly occlude and release alkali metal ions, but an alkali metal-containing transition metal compound can be used. Examples of the alkali metal-containing transition metal compound include lithium-containing transition metal compounds such as composite oxides containing one or more elements selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium and lithium. Examples of the lithium-containing transition metal compound include lithium cobaltate, lithium nickelate, lithium manganate, etc.

[0095] The alkali metal-containing transition metal compound has XO in its crystal structure 4A polyanion-based compound having a tetrahedron (X = P, S, As, Mo, W, Si, etc.) can be used. Among these, from the viewpoint of cycle characteristics, lithium-containing transition metal phosphate compounds such as lithium iron phosphate and lithium vanadium phosphate are preferable, and from the viewpoints of lithium diffusion coefficient and output characteristics, lithium vanadium phosphate is more preferable. When using a polyanion-based compound, in terms of electronic conductivity, it is preferably surface-coated and complexed with a conductive aid such as a carbon material.

[0096] The alkali metal-containing transition metal compound preferably has at least a part of its surface coated with an ion-conductive oxide. As the ion-conductive oxide, a lithium ion-conductive oxide is preferable. The lithium ion-conductive oxide is not particularly limited and can be appropriately selected according to the purpose. For example, oxides represented by the general formula LixAOy (A is B, C, Al, Si, P, S, Ti, Zr, Nb, Mo, Ta, Sc, V, Y, Ca, Sr, Ba, Hf, Ta, Cr or W, and x and y are positive numbers) can be mentioned. Specific examples of the lithium ion-conductive oxide include Li 3 BO 3 、LiBO 2 、Li 2 CO 3 、LiAlO 2 、Li 4 SiO 4 、Li 2 SiO 3 、Li 3 PO 4 、Li 2 SO 4 、Li 2 TiO 3 、Li 4 Ti 5 O 12 、Li 2 Ti 2 O 5 、Li 2 ZrO 3 、LiNbO 3 、LiTaO 3 、Li 2 MoO4 and Li 2 WO 4 and the like. Among these, Li 4 Ti 5 O 12 、Li 2 ZrO 3 、or LiNbO 3 is preferred. In addition, the lithium ion conductive oxide may be a composite oxide. As the composite oxide, any combination of lithium ion conductive oxides can be adopted. For example, Li 4 SiO 4 -Li 3 BO 3 、and Li 4 SiO 4 -Li 3 PO 4 and the like can be mentioned.

[0097] The negative electrode active material is not particularly limited as long as it can reversibly occlude and release alkali metal ions, and can be appropriately selected according to the purpose. For example, a carbon material containing graphite having a graphite-type crystal structure can be used. Examples of the carbon material include natural graphite, spherical or fibrous artificial graphite, non-graphitizable carbon (hard carbon), graphitizable carbon (soft carbon), and the like. Examples of materials other than the carbon material include lithium titanate, titanium oxide, and the like. From the viewpoint of increasing the energy density of the lithium ion battery, high-capacity materials such as silicon, tin, silicon alloy, tin alloy, silicon oxide, silicon nitride, and tin oxide can also be preferably used as the negative electrode active material.

[0098] --Second solvent-- As the second solvent (dispersion medium), there is no particular limitation as long as it can disperse the active material, and it can be appropriately selected according to the purpose. For example, aqueous dispersion media such as water, ethylene glycol, or propylene glycol; N-methyl-2-pyrrolidone, 2-pyrrolidone, cyclohexanone, ethyl lactate, butyl acetate, mesitylene, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dibutyl ether, diethyl ether, di-tert-butyl ether, 2-n-butoxymethanol, 2-dimethyl ethanol, N,N-dimethylacetamide, anisole, diethoxyethane, normal hexane, heptane, octane, nonane, decane, p-menthane and other organic dispersion media; and the like. These may be used alone or in combination of two or more.

[0099] There is no particular limitation on the boiling point of the second solvent, and it can be appropriately selected according to the purpose. However, from the viewpoint of storage stability, it is preferably 70°C or higher. When the boiling point is 70°C or higher, for example, when stored at room temperature, the occurrence of precipitation due to the concentration effect caused by the volatilization of the solvent can be suppressed, and the storage stability is excellent. Also, from the viewpoint of battery characteristics, the boiling point of the second solvent is preferably 210°C or lower. Further, in order to suppress a large difference from the first solvent in the removal rate in the removal step described later, the difference in boiling point between the second solvent and the first solvent is preferably less than 40°C, and more preferably within 20°C. If the boiling point difference becomes large, the solvent tends to be biased toward the low-boiling solvent with a high removal rate, resulting in a bias of the constituent components and affecting the characteristics of the obtained structure. The smaller the boiling point difference, the more the bias can be suppressed. Also, there is no particular limitation on the difference between the boiling point of the first solvent and the boiling point of the second solvent, and it can be appropriately selected according to the purpose. However, it is preferably 40°C or lower. When the difference is 40°C or lower, the boiling point of the first solvent and the second solvent can be removed simultaneously. Simultaneous removal in the present invention means putting two liquid films into a drying device and removing a plurality of solvents simultaneously in one drying step. It means drying a liquid film containing two or more solvents and evaporating and removing a plurality of solvents in parallel without selectively removing only a specific solvent. When the boiling point of the first solvent is 40 °C or more lower than the boiling point of the second solvent, the first solvent is likely to be selectively removed first in the solvent removal step, and curling is likely to occur in the insulating resin layer as the solvent is removed from the resin. Also, it is presumed that problems occur in the battery characteristics due to the deviation of the constituent components because the second solvent contained in the positive electrode diffuses toward the porous structure of the resin insulating layer near the interface between the insulating resin layer and the positive electrode. On the other hand, when the boiling point of the first solvent is 40 °C or more higher than the boiling point of the second solvent, the second solvent is likely to be selectively removed in the solvent removal step, and the first solvent contained in the insulating resin layer diffuses to the positive electrode side near the interface between the insulating resin layer and the positive electrode, resulting in a deviation of the constituent components such as the active material, binder, dispersant, and solid electrolyte, so it is presumed that problems occur in the battery characteristics.

[0100] As the second solvent, a solvent that does not change the volume of the insulating resin layer by 10% or more is preferable. Specific examples of such solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, decyl acetate, isopropyl acetate, isobutyl acetate, isoamyl acetate (isopentyl acetate), methyl propionate, ethyl propionate, propyl propionate, butyl propionate, pentyl propionate, hexyl propionate, heptyl propionate, octyl propionate, nonyl propionate, decyl propionate, isopropyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, pentyl butyrate, hexyl butyrate, heptyl butyrate, octyl butyrate, nonyl butyrate, decyl butyrate, isopropyl butyrate, isobutyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, pentyl valerate, hexyl valerate, heptyl valerate, octyl valerate, nonyl valerate, decyl valerate, isopropyl valerate, isobutyl valerate, isoamyl valerate (isopentyl valerate), methyl hexanoate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, pentyl hexanoate, hexyl hexanoate, heptyl hexanoate, octyl hexanoate, nonyl hexanoate, isopropyl hexanoate, isobutyl hexanoate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, butyl heptanoate, pentyl heptanoate, hexyl heptanoate, heptyl heptanoate, octyl heptanoate, isopropyl heptanoate, isobutyl heptanoate, methyl octanoate, ethyl octanoate, propyl octanoate, butyl octanoate, pentyl octanoate, hexyl octanoate, heptyl octanoate, isopropyl octanoate, isobutyl octanoate, methyl nonanoate, ethyl nonanoate, propyl nonanoate, butyl nonanoate, pentyl nonanoate, hexyl nonanoate, isopropyl nonanoate, isobutyl nonanoate, methyl decanoate, ethyl decanoate, propyl decanoate, butyl decanoate, pentyl decanoate, isopropyl decanoate, isobutyl decanoate, methyl undecanoate, ethyl undecanoate, propyl undecanoate, butyl undecanoate, isopropyl undecanoate, isobutyl undecanoate, methyl dodecanoate,Ethyl dodecanoate, propyl dodecanoate, isopropyl dodecanoate, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate, butyl isobutyrate, pentyl isobutyrate, hexyl isobutyrate, heptyl isobutyrate, octyl isobutyrate, nonanyl isobutyrate, decanyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, methyl isovalerate, ethyl isovalerate, propyl isovalerate, butyl isovalerate, pentyl isovalerate, hexyl isovalerate, heptyl isovalerate, octyl isovalerate, nonanyl isovalerate, decanyl isovalerate, isopropyl isovalerate, isobutyl isovalerate, isoamyl isovalerate, methyl isohexanoate, ethyl isohexanoate, propyl isohexanoate, butyl isohexanoate, pentyl isohexanoate, hexyl isohexanoate, heptyl isohexanoate, octyl isohexanoate, nonanyl isohexanoate, isopropyl isohexanoate, isobutyl isohexanoate, t-butyl acetate, 2-ethylhexyl acetate, ethyl pivalate, t-butyl propionate, methyl 2-ethylbutyrate, ethyl 2-ethylbutyrate, ethyl t-butylacetate, ethyl DL-2-methylbutyrate, etc. are mentioned.

[0101] The resin of the insulating resin layer changes in volume, for example, by swelling with the second solvent. That the second solvent does not change the volume of the insulating resin layer by 10% or more can be determined by heating and drying the swollen resin at 120 °C for 1 hour, calculating the weight of the swollen solvent per unit volume from the weights before and after drying, and calculating the solvent volume using the solvent specific gravity.

[0102] The content of the second solvent is not particularly limited and can be appropriately selected according to the purpose. However, with respect to the total amount of the liquid composition for forming the electrode composite layer, 10% by mass or more is preferable. By setting the content to 10% by mass or more, the generation of spots occurring during film formation can be suppressed, and a liquid layer of the liquid composition for forming the electrode composite layer with high uniformity can be formed. Also, as the content of the second solvent, with respect to the total amount of the liquid composition for forming the electrode composite layer, 80% by mass or more is preferable. By setting the content to 80% by mass or less, a liquid composition with a viscosity that easily forms a liquid layer with high uniformity can be obtained.

[0103] --Binder-- The binder is not particularly limited as long as it can bind negative electrode materials to each other, positive electrode materials to each other, negative electrode materials to the negative electrode substrate, and positive electrode materials to the positive electrode substrate, and can be appropriately selected according to the purpose. When the liquid composition for forming the electrode mixture layer is used for inkjet ejection, from the viewpoint of suppressing nozzle clogging of the liquid ejection head, it is preferable that the binder is one that does not easily increase the viscosity of the liquid composition for forming the electrode mixture layer.

[0104] A polymer compound can be used as the binder. The polymer compound is not particularly limited and can be appropriately selected according to the purpose. For example, thermoplastic resins such as polyvinylidene fluoride (PVDF), acrylic resin, polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, polyamide compounds, polyimide compounds, polyamideimide, ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), nitrile butadiene rubber (NBR), isoprene rubber, polyisobutene, polyethylene glycol (PEO), polymethyl methacrylate (PMMA), polyethylene vinyl acetate (PEVA), etc. can be mentioned.

[0105] The content of the binder is not particularly limited and can be appropriately set according to the purpose. However, it is preferably 1% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less, based on the total amount of the liquid composition for the electrode mixture layer. When the content of the binder with respect to the active material is 1% by mass or more based on the total amount of the liquid composition for the electrode mixture layer, it is preferable because the active material can be firmly bound to the substrate. As the resin, it is preferably insoluble in the first solvent at 1% or less. By preventing the resin from dissolving in the first solvent, the binding property of the electrode film can be prevented from decreasing. Examples of such resins include polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), nitrile butadiene rubber (NBR), isoprene rubber, and acrylic resin.

[0106] --Conductive aid-- There are no particular restrictions on the conductive aid, and it can be appropriately selected according to the purpose. For example, carbon black produced by the furnace method, acetylene method, gasification method, etc., and carbon materials such as carbon nanofibers, carbon nanotubes, graphene, and graphite particles can be used. As conductive aids other than carbon materials, for example, metal particles such as aluminum and metal fibers can be used. Note that the conductive aid may be pre-compounded with the active material.

[0107] The content of the conductive aid with respect to the active material is not particularly limited and can be appropriately set according to the purpose. However, it is preferably 10% by mass or less, and more preferably 8% by mass or less, based on the total amount of the liquid composition for the electrode composite layer. When the content of the conductive aid with respect to the active material is 10% by mass or less based on the total amount of the liquid composition for the electrode composite layer, it is suitable because the stability of the liquid composition for the electrode composite layer is improved. When the content of the conductive aid with respect to the active material is 8% by mass or less based on the total amount of the liquid composition for the electrode composite layer, it is more suitable because the stability of the liquid composition for the electrode composite layer is further improved.

[0108] --Dispersant-- As the dispersant, there is no particular limitation as long as it can improve the dispersibility of the active material in the liquid composition for the electrode composite layer. Examples include polymer dispersants such as polyethylene oxide-based, polypropylene oxide-based, polycarboxylic acid-based, naphthalenesulfonic acid formalin condensation-based, polyethylene glycol-based, polycarboxylic acid partial alkyl ester-based, polyether-based, and polyalkylene polyamine-based; low-molecular-weight dispersants such as alkylsulfonic acid-based, quaternary ammonium-based, higher alcohol alkylene oxide-based, polyhydric alcohol ester-based, and alkyl polyamine-based; and inorganic dispersants such as polyphosphate-based dispersants.

[0109] --Solid electrolyte-- As the solid electrolyte, there is no particular limitation as long as it is a solid substance having electron insulation and exhibiting ionic conductivity. From the viewpoint of having high ionic conductivity, sulfide solid electrolytes and oxide-based solid electrolytes are preferred.

[0110] Examples of the sulfide solid electrolyte include, for example, Li 10 GeP 2 S 12 , and Li having an argyrodite-type crystal structure 6 PS 5 X (X = F, Cl, Br, I), etc. Examples of the oxide-based solid electrolyte include, for example, LLZ (Li having a garnet-type crystal structure 7 La 3 Zr 2 O 12 ), LATP (Li1+xAlxTi having a NASICON-type crystal structure 20 x(PO 4 )) (0.1 ≦ x ≦ 0.4), LLT (Li having a perovskite-type crystal structure 3 La 0.33 TiO 0.55 ), and amorphous LIPON (Li having a NASICON-type crystal structure 3 PO 2.9 N 3.3 ), etc. 0.4 These solid electrolytes may be used alone or in combination of two or more. These solid electrolytes may be used alone or in combination of two or more.

[0111] As electrolyte materials to be dissolved or dispersed in a liquid to form these solid electrolyte layers, for example, materials that are precursors of solid electrolytes such as Li 2 S and P 2 S 5 , LiCl, Li 2 S-P 2 S 5 -based glass, Li 7 P 3 S 11 -based glass ceramics, etc. may be mentioned.

[0112] <<Solvent removal step, solvent removal means>> The solvent removal step is a step of simultaneously removing the first solvent and the second solvent. As the solvent removal step, it is preferable to perform the removal step after performing a crosslinking reaction of a polymerizable compound to form an insulating resin layer. The solvent removal means is a means for simultaneously removing the first solvent and the second solvent. By simultaneously removing the first solvent and the second solvent, even when an insulating resin layer formed by polymerizing a polymerizable compound is used as a guide in manufacturing an electrode, curling (warping) of the electrode can be prevented.

[0113] Here, the factors causing curling of the electrode in the manufacture of the electrode are mainly two: shrinkage during polymerization and shrinkage due to removal of the solvent by drying. When making a guide with a resin by polymerization, shrinkage due to polymerization becomes a problem. At this time, shrinkage due to polymerization can be prevented by making the resin have a porous structure, but it is presumed that the self-weight load on the resin increases due to removal of the solvent from the porous structure of the electrode and the insulating layer, resulting in curling. In addition, when the resin is a crosslinkable resin, the problem becomes prominent. Therefore, in the present invention, since the resin has a porous structure to prevent shrinkage due to polymerization while simultaneously removing the first solvent and the second solvent, shrinkage due to solvent removal can also be prevented. Thus, even when an insulating resin layer formed by polymerizing a polymerizable compound is used as a guide in manufacturing an electrode, curling (warping) of the electrode can be prevented. When the resin is a crosslinkable resin, curling (warping) of the electrode can be more effectively prevented.

[0114] There are no particular restrictions on the solvent removal step and the solvent removal means, and they can be appropriately selected according to the purpose. For example, a method of removing the solvent from the insulating resin layer by heating can be mentioned. At this time, heating under reduced pressure promotes the removal of the solvent and can reduce the amount of residual solvent in the insulating resin layer, which is preferable. When heating, it may be heated by a stage or by a heating mechanism other than the stage. The heating mechanism may be installed on either the upper or lower side of the substrate, or a plurality of heating mechanisms may be installed. There are no particular restrictions on the heating mechanism, and examples include a resistance heating heater, an infrared heater, a fan heater, etc. The heating temperature at this time is not particularly restricted, but from the viewpoint of the energy used, 70°C to 150°C is preferable.

[0115] <Other processes, other means> As other processes in the method for manufacturing an electrode for an electrochemical element, there are no particular restrictions as long as the effects of the present invention are not impaired, and they can be appropriately selected according to the purpose. As other means in the manufacturing apparatus for an electrode for an electrochemical element, there are no particular restrictions as long as the effects of the present invention are not impaired, and they can be appropriately selected according to the purpose.

[0116] In the method for manufacturing an electrode for an electrochemical element, the order of the insulating resin layer forming step and the electrode mixture layer forming step is not particularly limited. That is, the electrode mixture layer forming step may be carried out before the insulating resin layer forming step, and after forming the electrode mixture layer, an insulating resin layer may be formed on the outer peripheral portion of the electrode mixture layer. In that case, the method for manufacturing an electrode for an electrochemical element is carried out in the order of the electrode mixture layer forming step, the insulating resin layer forming step, and the solvent removing step. Similarly, the electrode mixture layer forming step may be carried out after the insulating resin layer forming step, and after forming the insulating resin layer on the outer peripheral portion on the substrate, the electrode mixture layer may be formed inside the insulating resin layer. In that case, the method for manufacturing an electrode for an electrochemical element is carried out in the order of the insulating resin layer forming step, the electrode mixture layer forming step, and the solvent removing step. Note that the insulating resin layer forming step and the electrode mixture layer forming step may be carried out simultaneously.

[0117] (Method for manufacturing an electrode laminate, and apparatus for manufacturing an electrode laminate) The method for manufacturing an electrode laminate of the present invention has an insulating resin layer forming step, an electrode mixture layer forming step, and a solid electrolyte layer forming step, and may have a pressing step and other steps as necessary. The apparatus for manufacturing an electrode laminate according to the present invention preferably has a housing container, an insulating resin layer forming means, an electrode mixture layer forming means, and a solid electrolyte layer forming means, and may have a pressing means and other means as necessary. Note that the housing container, the insulating resin layer forming step, the insulating resin layer forming means, the electrode mixture layer forming step, the electrode mixture layer forming means, other steps, and other means are the same as those described in the section (Method for manufacturing an electrode for an electrochemical element, and apparatus for manufacturing an electrode for an electrochemical element), and thus redundant descriptions are omitted.

[0118] <Pressing step, pressing means> The pressing step is a step of pressing the electrode mixture layer and the insulating resin layer. The pressing means is a means for pressing the electrode mixture layer and the insulating resin layer. The pressing step can be preferably carried out by the pressing means.

[0119] There are no particular restrictions on the pressing process and pressing means, and it can be carried out using a commercially available pressure molding device. The electrode composite material layer and the insulating resin layer may be pressed in the substrate direction. For example, uniaxial pressing, roll pressing, cold isostatic pressing (CIP), hot pressing, etc. can be mentioned. Among these, cold isostatic pressing (CIP) that can apply isotropic pressure is preferable.

[0120] There are no particular restrictions on the timing of performing the pressing process, and it can be appropriately selected according to the purpose. For example, after forming the electrode composite material layer and the insulating resin layer on the substrate, the electrode composite material layer and the insulating resin layer may be pressed, or it may be pressed after providing the solid electrolyte layer, or it may be performed at both timings. By performing the pressing process after forming the electrode composite material layer and the insulating resin layer on the substrate and before forming the solid electrolyte layer, the average thickness of the electrode composite material layer and the average thickness of the insulating resin layer can be made substantially equal. Even when a high pressure is applied when pressing the solid electrolyte layer provided on the electrode, the pressure load can be dispersed.

[0121] There are no particular restrictions on the pressing pressure, and it can be appropriately selected according to the purpose. However, it is preferably carried out at a pressure that can crimp the substrate and the electrode composite material layer while densifying the electrode composite material layer. More specifically, 1 MPa or more and 900 MPa or less are preferable, and 250 MPa or more and 700 MPa or less are more preferable.

[0122] <Solid electrolyte layer forming process, and solid electrolyte layer forming means> The solid electrolyte layer forming process in the method for manufacturing an electrode laminate is a process of forming a solid electrolyte layer on the electrode composite material layer and the insulating resin layer. The solid electrolyte layer forming means in the manufacturing apparatus for an electrode laminate is a means for forming a solid electrolyte layer on the electrode composite material layer and the insulating resin layer.

[0123] The method for forming the solid electrolyte layer is not particularly limited and can be appropriately selected according to the purpose. For example, a method of applying a liquid composition containing a solid electrolyte and, if necessary, a binder onto the electrode mixture layer and the insulating resin layer, followed by solidifying and drying it, can be mentioned. The coating method is not particularly limited. For example, liquid ejection methods such as the inkjet method, spray coating method, dispenser method, etc., and spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, etc. can be mentioned.

[0124] In the method for manufacturing the electrode laminate, the order of the insulating resin layer forming step and the electrode mixture layer forming step is not particularly limited. That is, the electrode mixture layer forming step may be carried out before the insulating resin layer forming step, and after forming the electrode mixture layer, an insulating resin layer may be formed on the outer peripheral portion of the electrode mixture layer. In that case, the method for manufacturing the electrode laminate is carried out in the order of the electrode mixture layer forming step, the insulating resin layer forming step, the solvent removal step, the pressing step, and the solid electrolyte layer forming step. Similarly, the electrode mixture layer forming step may be carried out after the insulating resin layer forming step. After forming the insulating resin layer on the outer peripheral portion on the substrate, the electrode mixture layer may be formed inside the insulating resin layer. In that case, the method for manufacturing the electrode laminate is carried out in the order of the insulating resin layer forming step, the solvent removal step, the electrode mixture layer forming step, the pressing step, and the solid electrolyte layer forming step.

[0125] [Embodiment of forming an insulating resin layer or an electrode laminate by directly applying a liquid composition to a substrate] FIG. 9 is a schematic diagram showing an example of a manufacturing apparatus (liquid ejection apparatus) for an insulating resin layer for carrying out the method for manufacturing an electrode laminate according to an embodiment of the present invention. The manufacturing apparatus 500 for the insulating resin layer includes a conveyance unit 5, a printing unit 100, a polymerization unit 200, a heating unit 300, and a roller 7.

[0126] The conveying unit 5 conveys the printing substrate at a preset speed in the order of the printing unit 100, the polymerization unit 200, and the heating unit 300. The printing substrate may be a substrate provided with an electrode paste layer on the substrate, or a substrate without an electrode paste layer. When it is a substrate without an electrode paste layer, the electrode paste layer is provided after the insulating resin layer is formed.

[0127] -Printing Unit 100- The printing unit 100 includes a printing device 1a which is an example of a liquid composition applying means for performing a liquid composition applying step of applying a liquid composition onto a printing substrate, a storage container 1b for storing the liquid composition 6, and a supply tube 1c for supplying the liquid composition stored in the storage container 1b to the printing device 1a.

[0128] The printing unit 100 discharges the liquid composition 6 from the printing device 1a onto the printing substrate to form the liquid composition into a thin film. Note that the storage container 1b may be configured to be integrated with the manufacturing device of the insulating resin layer, or may be configured to be removable from the manufacturing device of the insulating resin layer. Further, it may be a container used for adding to a storage container integrated with the manufacturing device of the insulating resin layer or a storage container removable from the manufacturing device of the insulating resin layer.

[0129] The storage container 1b and the supply tube 1c are not particularly limited as long as they can stably store and supply the liquid composition 6, and can be appropriately selected according to the purpose. The materials constituting the storage container 1b and the supply tube 1c preferably have light-shielding properties in the relatively short wavelength region of ultraviolet rays and visible light. This is preferable because it prevents the liquid composition 6 from starting polymerization due to external light.

[0130] -Polymerization Unit 200- As shown in FIG. 9, in the case of photopolymerization, the polymerization unit 200 has a light irradiation device 2a which is an example of a liquid composition curing means for performing a liquid composition curing step, and a polymerization inert gas circulation device 2b for circulating a polymerization inert gas.

[0131] The light irradiation device 2a irradiates light on the thin-film liquid composition formed by the printing unit 100 in the presence of a polymerization-inert gas, and causes photopolymerization to obtain an insulating resin layer. The light irradiation device 2a is not particularly limited as long as it can initiate and proceed with the polymerization of the compound in the liquid composition, and can be appropriately selected according to the absorption wavelength of the photoinitiator contained in the liquid composition. Examples thereof include ultraviolet light sources such as high-pressure mercury lamps, metal halide lamps, hot cathode tubes, cold cathode tubes, and LEDs. However, since the shorter the wavelength of the irradiated light, the more likely it is to reach deep parts, it is preferable to select a light source according to the thickness of the insulating resin layer to be formed.

[0132] The polymerization-inert gas circulation device 2b plays a role of preventing the polymerization reaction of the polymerizable compound present near the surface of the liquid composition from being inhibited by reducing the concentration of oxygen having polymerization activity contained in the atmosphere. Here, examples of the polymerization-inert gas include nitrogen, carbon dioxide, argon, and the like. The O 2 concentration is preferably less than 20% (an environment with a lower oxygen concentration than the atmosphere) in consideration of obtaining a more effective inhibition reduction effect, more preferably 0% or more and 15% or less, and even more preferably 0% or more and 5% or less. In addition, the polymerization-inert gas circulation device 2b preferably has a temperature control means capable of adjusting the temperature in order to realize stable polymerization progress conditions.

[0133] In the case of thermal polymerization, the polymerization unit 200 may be a heating device. The heating device is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include substrate heating (for example, a hot plate), an IR heater, a hot air heater, etc., and these may be used in combination. In addition, regarding the heating temperature, time, or light irradiation conditions, they can be appropriately selected according to the polymerizable compound contained in the liquid composition and the formed film thickness.

[0134] The overlapping portion 200 is not particularly limited and can be appropriately selected according to the purpose such as the polymerization initiator used and the polymerization mode. For example, in the case of photopolymerization, a light irradiation device that irradiates ultraviolet light with a wavelength of 365 nm for 3 seconds, and in the case of thermal polymerization, a heating device that heats at 150 °C under vacuum drying for 12 hours can be mentioned.

[0135] -Heating section 300- The heating section 300 includes a heating device 3a which is an example of a solvent removal means for performing a solvent removal step. As shown in FIG. 9, the heating device 3a heats the insulating resin layer formed by the polymerization section 200 to dry and remove the remaining solvent. At this time, the solvent removal may be carried out under reduced pressure.

[0136] In the heating section 300, a polymerization acceleration step of further promoting the curing (polymerization) reaction performed in the polymerization section 200 by heating the insulating resin layer with the heating device 3a, and an initiator removal step of heating and drying and removing the photoinitiator remaining in the insulating resin layer with the heating device 3a are also performed. Note that these polymerization acceleration step and initiator removal step do not have to be simultaneous with the solvent removal step, and may be carried out before or after the solvent removal step. After the solvent removal step, the heating section 300 performs a polymerization completion step of heating the insulating resin layer under reduced pressure. Regarding the heating temperature and time, they can be appropriately selected according to the boiling point of the solvent contained in the insulating resin layer and the formed film thickness.

[0137] FIG. 10 is a schematic diagram showing another example in a manufacturing apparatus (liquid ejection apparatus) of an insulating resin layer for carrying out a manufacturing method of an electrode laminate according to an embodiment of the present invention. The liquid ejection apparatus 300' enables the liquid composition to circulate through the liquid ejection head 306, the liquid ejection head tank 307, and the tube 308 by controlling the pump 310, the valve 311, and the valve 312. The liquid ejection device 300’ is provided with an external tank 313. When the liquid composition in the liquid ejection head tank 307 decreases, it is also possible to supply the liquid composition from the external tank 313 to the tank 307 by controlling the pump 310 and the valves 311, 312, and 314.

[0138] When using the manufacturing apparatus of an insulating resin layer, the liquid composition can be ejected to the targeted position of the object to be applied.

[0139] When the liquid composition 6 is not being ejected from the liquid ejection head, the manufacturing apparatus 500 of the insulating resin layer may be provided with a mechanism for capping the nozzle in order to prevent drying.

[0140] FIG. 11 is a schematic diagram (part 1) for explaining a method of manufacturing an electrode for an electrochemical element according to an embodiment of the present invention. The method of manufacturing the electrode 210 for an electrochemical element, on which an insulating resin layer is provided on a substrate, includes a step of sequentially ejecting a liquid composition 12A onto the substrate 211 using the liquid ejection device 300’. First, a long and narrow substrate 211 is prepared. Then, the substrate 211 is wound around a cylindrical core and set on the feed roller 304 and the take-up roller 305 so that the side where the insulating resin layer 212 is to be formed is on the upper side in FIG. 11. Here, the feed roller 304 and the take-up roller 305 rotate counterclockwise and convey the substrate 211 in the direction from right to left in FIG. 11. Then, in the same manner as in FIG. 10, droplets of the liquid composition 12A are ejected from the liquid ejection head 306 installed above the substrate 211 between the feed roller 304 and the take-up roller 305 onto the sequentially conveyed substrate 211. Note that a plurality of liquid ejection heads 306 may be installed in a direction substantially parallel or substantially perpendicular to the conveyance direction of the substrate 211. Next, the substrate 211 onto which the droplets of the liquid composition 12A have been ejected is conveyed to the polymerization section 309 by the feed roller 304 and the take-up roller 305. As a result, the liquid composition 12A is polymerized to form the insulating resin layer 212, and an electrode 210 for an electrochemical element provided with the insulating resin layer on the substrate is obtained. Thereafter, the electrode 210 for an electrochemical element is cut into a desired size by punching or the like.

[0141] The polymerization section 309 may be installed on either the upper or lower side of the substrate 211, or a plurality of polymerization sections may be installed. The polymerization section 309 is not particularly limited as long as it does not directly contact the liquid composition 12A and can be appropriately selected according to the purpose. For example, in the case of thermal polymerization, a resistance heater, an infrared heater, a fan heater, etc. can be mentioned, and in the case of photopolymerization, an ultraviolet irradiation device, etc. can be mentioned. Note that a plurality of polymerization sections 309 may be installed. The conditions for heating or light irradiation are not particularly limited and can be appropriately selected according to the purpose.

[0142] FIG. 12 is a schematic diagram showing still another example in a manufacturing apparatus (liquid ejection apparatus) for an insulating resin layer for carrying out a method for manufacturing an electrode laminate according to an embodiment of the present invention. The liquid ejection apparatuses 300A' and 300B' may be used in combination. That is, the tank may supply the liquid composition from the external tanks 313A and 313B connected to the tanks 307A and 307B, and the liquid ejection head may have a plurality of heads 306A and 306B. Accordingly, it may also have the tubes 308A and 308B, the valves 311A, 311B, 312A, 312B, and 314A, and the pumps 310A and 310B.

[0143] [Embodiment of forming an insulating resin layer or an electrode laminate by indirectly applying a liquid composition to a substrate] FIG. 13 is a configuration diagram (part 1) showing an example of a printing unit that employs an inkjet method and a transfer method as liquid composition applying means in a manufacturing apparatus for an insulating resin layer according to an embodiment of the present invention. In the printing unit of FIG. 13, a drum-shaped intermediate transfer body is used. The printing unit 400' is an inkjet printer that forms an insulating resin layer on a substrate by transferring a liquid composition or an insulating resin layer to the substrate via an intermediate transfer body 4001. The printing unit 400' includes an inkjet unit 420, a transfer drum 4000, a pretreatment unit 4002, an absorption unit 4003, a heating unit 4004, and a cleaning unit 4005.

[0144] The inkjet unit 420 includes a head module 422 that holds a plurality of heads 101. The head 101 discharges a liquid composition onto the intermediate transfer body 4001 supported by the transfer drum 4000 to form a liquid composition film on the intermediate transfer body 4001. Each head 101 is a line head, and nozzles are arranged in a range that covers the width of the recording area of the substrate with the maximum size that can be used. The head 101 has a nozzle surface on which nozzles are formed on its lower surface, and the nozzle surface faces the surface of the intermediate transfer body 4001 with a minute gap therebetween. In the case of this embodiment, since the intermediate transfer body 4001 is configured to circulate and move on a circular orbit, the plurality of heads 101 are arranged radially.

[0145] The transfer drum 4000 faces the pressure cylinder 621 to form a transfer nip portion. The pretreatment unit 4002 applies a reaction liquid for increasing the viscosity of the liquid composition, for example, onto the intermediate transfer body 4001 before the discharge of the liquid composition by the head 101.

[0146] The absorption unit 4003 absorbs the liquid component from the liquid composition on the intermediate transfer body 4001 before transfer.

[0147] The heating unit 4004 heats the liquid composition on the intermediate transfer member 4001 before transfer. By heating the liquid composition, the liquid composition is thermally polymerized to form an insulating resin layer. Also, the solvent is removed, improving the transferability to the substrate.

[0148] The cleaning unit 4005 cleans the intermediate transfer member 4001 after transfer to remove foreign substances such as ink and dust remaining on the intermediate transfer member 4001.

[0149] The outer peripheral surface of the impression cylinder 621 is in pressure contact with the intermediate transfer member 4001. When the substrate passes through the transfer nip portion between the impression cylinder 621 and the intermediate transfer member 4001, the insulating resin layer on the intermediate transfer member 4001 is transferred to the substrate. Note that the impression cylinder 621 may be configured to include at least one grip mechanism for holding the leading end portion of the substrate on its outer peripheral surface.

[0150] FIG. 14 is a configuration diagram (part 2) showing an example of a printing unit that employs an inkjet method and a transfer method as liquid composition applying means in an apparatus for manufacturing an insulating resin layer according to an embodiment of the present invention. An endless belt-shaped intermediate transfer member is used in the printing unit of FIG. 14. The printing unit 400″ is an inkjet printer that forms an insulating resin layer by transferring a liquid composition or an insulating resin layer onto a substrate via the intermediate transfer belt 4006. The printing unit 400″ includes an inkjet unit 420, a transfer roller 622, an intermediate transfer belt 4006, a heating unit 4007, a cleaning roller 4008, a driving roller 4009a, a counter roller 4009b, a shape maintaining roller 4009c, a shape maintaining roller 4009d, a shape maintaining roller 4009e, and a shape maintaining roller 4009f.

[0151] The printing unit 400″ ejects droplets of the liquid composition onto the outer peripheral surface of the intermediate transfer belt 4006 from a plurality of heads 101 provided in the inkjet unit 420. The liquid composition on the intermediate transfer belt 4006 is heated by the heating unit 4007 and thermally polymerized to form an insulating resin layer. In the transfer nip portion where the intermediate transfer belt 4006 faces the transfer roller 622, the insulating resin layer on the intermediate transfer belt 4006 is transferred to the substrate. The surface of the intermediate transfer belt 4006 after transfer is cleaned by the cleaning roller 4008.

[0152] The intermediate transfer belt 4006 is spanned over a driving roller 4009a, a counter roller 4009b, a plurality of shape - maintaining rollers 4009c, a shape - maintaining roller 4009d, a shape - maintaining roller 4009e, a shape - maintaining roller 4009f, and a plurality of support rollers 4009g and moves in the direction of the arrow in FIG. 14. The support roller 4009g provided opposite to the head 101 maintains the tensile state of the intermediate transfer belt 4006 when ink droplets are ejected from the head 101.

[0153] (Electrochemical element) The electrochemical element of the present invention preferably has an electrode (hereinafter, may be referred to as a “composite electrode”) or an electrode laminate, and further may have an exterior as required. As the electrode, it has an insulating resin layer containing an insulating resin, an electrode mixture layer containing an active material and a resin, and the electrode mixture layer penetrates into the insulating resin layer in the vertical direction of the interface between the insulating resin layer and the electrode mixture layer. As the electrode, it can be manufactured by the manufacturing method of the electrode of the present invention. Note that since the electrode laminate is the same as that described in the item of (electrode laminate), the overlapping description is omitted.

[0154] (Electrode for electrochemical element) The electrode for an electrochemical element of the present invention has a substrate, an electrode mixture layer disposed on the substrate, and an insulating resin layer disposed on the outer peripheral portion of the electrode mixture layer. The insulating resin layer is formed by curing a liquid composition and has a porous structure. The liquid composition is the same as that described in the item (Liquid Composition), and the insulating resin layer is the same as that described in the item (Insulating Resin Layer). Therefore, overlapping descriptions are omitted. In this specification, the negative electrode and the positive electrode are collectively referred to as the "electrode", the electrode substrate for the negative electrode and the electrode substrate for the positive electrode are collectively referred to as the "substrate", and the negative electrode composite layer and the positive electrode composite layer may be collectively referred to as the "electrode composite layer". When the first electrode is the negative electrode, the second electrode refers to the positive electrode, and when the first electrode is the positive electrode, the second electrode refers to the negative electrode.

[0155] (Electrode laminate) The electrode for an electrochemical element of the present invention can be suitably applied to an electrode laminate. The electrode for an electrochemical element of the present invention has a substrate, an electrode composite layer disposed on the substrate, an insulating resin layer disposed on the outer peripheral portion of the electrode composite layer, and a solid electrolyte layer disposed on the electrode composite layer and the insulating resin layer. The insulating resin layer is formed by curing a liquid composition and has a porous structure. The liquid composition is the same as that described in the item (Liquid Composition), and the insulating resin layer is the same as that described in the item (Insulating Resin Layer). Therefore, overlapping descriptions are omitted.

[0156] FIG. 1 is a schematic cross-sectional view showing an electrode for an electrochemical element according to an embodiment of the present invention. The electrode 25 for an electrochemical element has a first substrate 21, a first electrode composite layer 20 disposed on the first substrate 21, and an insulating resin layer 10 disposed on the outer peripheral portion of the first electrode composite layer 20. In FIG. 1, a configuration in which the electrode composite layer 20 and the insulating resin layer 10 are provided on one side of the first substrate 21 is illustrated, but the electrode composite layer 20 and the insulating resin layer 10 may be provided on both opposite sides of the first substrate 21.

[0157] FIG. 2A is a schematic cross-sectional view showing an electrode laminate according to an embodiment of the present invention. FIG. 2B is a schematic cross-sectional view showing an electrode laminate according to another embodiment of the present invention. FIG. 2C is a schematic cross-sectional view showing an electrode laminate according to still another embodiment of the present invention. The electrode laminate 35 includes a first substrate 21, a first electrode composite layer 20 disposed on the first substrate 21, an insulating resin layer 10 disposed on the outer peripheral portion of the first electrode composite layer 20, and a solid electrolyte layer 30 disposed on the first electrode composite layer 20 and the insulating resin layer 10. In FIGS. 2A to 2C, a configuration in which the electrode composite layer 20, the insulating resin layer 10, and the solid electrolyte layer 30 are provided on one surface of the first substrate 21 is illustrated. However, the electrode composite layer 20, the insulating resin layer 10, and the solid electrolyte layer 30 may be provided on both opposite surfaces of the first substrate 21. Further, as shown in FIG. 2B, an adhesive layer 22 containing a metal that alloyizes with lithium may be provided between the substrate and the electrode composite layer.

[0158] The electrode composite layer may have an opening 23 as shown in FIG. 2C. The number of the openings 23 is preferably one or more, and more preferably a plurality. The opening 23 may penetrate the electrode composite layer from the surface of the electrode composite layer to the surface of the substrate, or may not penetrate to the surface of the substrate. The opening 23 may be a cavity or may be filled with a material 24. When the opening 23 is filled with the material 24, the material 24 may be a single species or a mixture of two or more species. However, in any case, the material (compound or composition) of the material 24 is different from the material constituting the electrode composite layer. From the viewpoint of improving ionic conductivity, the material 24 is preferably a material having a solid electrolyte contained in the solid electrolyte layer, and more preferably a material having the same composition as the solid electrolyte layer. The electrode composite layer having the opening 23 can be suitably manufactured by using an inkjet as an electrode composite layer forming means because coating control is easy.

[0159] FIG. 3 is a schematic top view showing an electrode for an electrochemical element according to an embodiment of the present invention. FIG. 4 is a schematic top view showing an electrode for an electrochemical element according to another embodiment of the present invention. FIG. 5 is a schematic top view showing an electrode for an electrochemical element according to still another embodiment of the present invention. In FIG. 3, the insulating resin layer 10 is provided so as to be adjacent to two sides of the outer peripheral portion of the electrode composite layer 20. In FIG. 4, the insulating resin layer 10 is provided adjacent to two long sides and two corners of the long sides of the outer peripheral portion of the electrode composite layer 20. In FIG. 5, the insulating resin layer 10 is provided continuously adjacent to all four sides of the outer peripheral portion of the electrode composite layer 20. Note that the insulating resin layer may be provided intermittently adjacent.

[0160] As used herein, "arranged on the outer peripheral portion of the electrode composite layer" means that the insulating resin layer may be arranged on at least two sides of the outer peripheral portion of the electrode composite layer, or on three sides of the outer peripheral portion of the electrode composite layer, or on all four sides of the outer peripheral portion of the electrode composite layer. Further, the insulating resin layer may have a recess or a notch for protruding the electrode tab on any side.

[0161] As used herein, "arranged on the outer peripheral portion of the substrate" means that the insulating resin layer may be arranged so as to include the end portion of the substrate, or the insulating resin layer may be arranged so that the substrate is exposed as shown in FIGS. 3 to 5.

[0162] FIG. 6A is a schematic cross-sectional view (part 1) showing the positional relationship between the insulating resin layer and the electrode composite layer in an electrode for an electrochemical element according to an embodiment of the present invention. FIG. 6B is a schematic cross-sectional view (part 2) showing the positional relationship between the insulating resin layer and the electrode composite layer in an electrode for an electrochemical element according to an embodiment of the present invention. FIG. 6C is a schematic cross-sectional view (part 3) showing the positional relationship between the insulating resin layer and the electrode composite layer in an electrode for an electrochemical element according to an embodiment of the present invention. FIG. 6D is a schematic cross-sectional view (part 4) showing the positional relationship between the insulating resin layer and the electrode composite layer in an electrode for an electrochemical element according to an embodiment of the present invention. The insulating resin layer 10 may be separated from the electrode composite layer 20 as shown in FIG. 6A, or may be in contact with the electrode composite layer 20 as shown in FIGS. 6B to 6D. Among these, it is preferable that the insulating resin layer 10 is in contact with the electrode composite layer 20. When the insulating resin layer 10 is in contact with the electrode composite layer 20, the facing surfaces of the insulating resin layer 10 and the electrode composite layer 20 may be in contact with each other in a partial region as shown in FIG. 6B, or the facing surfaces of the insulating resin layer 10 and the electrode composite layer 20 may be in full contact as shown in FIGS. 6C to 6D. Here, when the electrode composite layer 20 is provided after the insulating resin layer 10 is formed, the electrode composite layer 20 overlaps the insulating resin layer 10 side as shown in FIG. 6C. Similarly, when the insulating resin layer 10 is provided after the electrode composite layer 20 is formed, the insulating resin layer 10 overlaps the electrode composite layer 20 side as shown in FIG. 6D.

[0163] FIG. 7 is a schematic top view showing the positional relationship between the insulating resin layer and the electrode composite layer in the electrode for an electrochemical element according to an embodiment of the present invention. Here, when the insulating resin layer 10 and the electrode composite layer 20 are separated, the distance d between the insulating resin layer 10 and the electrode composite layer 20 (the distance between the outer peripheral portion of the electrode composite layer 20 and the insulating resin layer) is defined as shown in FIG. 7. That is, the state where the insulating resin layer 10 and the electrode composite layer 20 are adjacent is set as d = 0, and the distance d between the electrode composite layer and the insulating resin layer is the distance between the arrows shown in FIG. 7. In addition, as shown in FIGS. 6C to D, when the insulating resin layer overlaps the electrode composite layer side and when the electrode composite layer overlaps the insulating resin layer side, it is indicated by a negative value.

[0164] The distance d between the insulating resin layer 10 and the electrode composite layer 20 (the distance between the outer peripheral portion of the electrode composite layer 20 and the insulating resin layer) is not particularly limited and can be appropriately selected according to the purpose, but it is preferably 10 mm or less, more preferably 5 mm or less, and even more preferably 1 mm or less. When the distance d between the insulating resin layer 10 and the electrode composite layer 20 is 10 mm or less, the insulating resin layer and the electrode composite layer are likely to come into contact with each other after the pressing process. Therefore, it is preferable because the solid electrolyte layer can be uniformly formed on the insulating resin layer and the electrode composite layer. Further, when the solid electrolyte layer is pressed, it is preferable because pressure can be uniformly applied to the solid electrolyte layer.

[0165] FIG. 8A is a schematic cross-sectional view (part 1) showing the relationship between the average thicknesses of the insulating resin layer and the electrode composite layer in the electrode for an electrochemical element according to an embodiment of the present invention. FIG. 8B is a schematic cross-sectional view (part 2) showing the relationship between the average thicknesses of the insulating resin layer and the electrode composite layer in the electrode for an electrochemical element according to an embodiment of the present invention. FIG. 8C is a schematic cross-sectional view (part 3) showing the relationship between the average thicknesses of the insulating resin layer and the electrode composite layer in the electrode for an electrochemical element according to an embodiment of the present invention.

[0166] FIG. 15 is a schematic cross-sectional view showing an electrochemical element according to an embodiment of the present invention. The electrochemical element 45 includes a first substrate 21, a first electrode composite layer 20 disposed on the first substrate 21, an insulating resin layer 10 disposed on the outer peripheral portion of the first electrode composite layer 20, a solid electrolyte layer 30 disposed on the first electrode composite layer 20 and the insulating resin layer 10, a second electrode composite layer 40 disposed on the solid electrolyte layer 30, and a second substrate 31 disposed on the second electrode composite layer. The electrochemical element 45 is a single cell layer, and these can be stacked to form a stacked battery. In FIG. 15, a configuration in which the electrode composite layer 20, the insulating resin layer 10, and the solid electrolyte layer 30 are provided on one surface of the first substrate 21 is illustrated. However, the electrode composite layer 20, the insulating resin layer 10, and the solid electrolyte layer 30 may be provided on both opposing surfaces of the first substrate 21, and this configuration may be a stacked battery in which these are stacked.

[0167] FIG. 16 is a schematic cross-sectional view showing an example of an all-solid-state battery which is an electrochemical element according to an embodiment of the present invention. The all-solid-state battery shown in Fig. 16 includes a positive electrode (electrode mixture layer) 20, a negative electrode (electrode mixture layer) 40, a solid electrolyte layer 30, lead wires 50, lead wire 51, and an exterior package 60. The positive electrode (electrode mixture layer) 20 includes a positive electrode substrate 21 and an insulating resin layer 10 disposed on the positive electrode substrate 21. A lead wire 50 is connected to the positive electrode substrate 21, and a lead wire 51 is connected to the negative electrode substrate 41. The lead wires 50 and 51 are drawn out to the outside of the exterior package 60. Here, in the all-solid-state battery, the positive electrode (electrode mixture layer) 20 and the negative electrode (electrode mixture layer) 40 are laminated via the solid electrolyte layer 30, and the positive electrode (electrode mixture layer) 20 is disposed on both sides of the negative electrode (electrode mixture layer) 40. Note that the number of laminations of the positive electrode (electrode mixture layer) 20 and the negative electrode (electrode mixture layer) 40 is not particularly limited. Also, the number of the positive electrode (electrode mixture layer) 20 and the number of the negative electrode (electrode mixture layer) 40 may be the same or different.

[0168] The exterior package is not particularly limited as long as it can seal the electrode laminate, and a known exterior package can be appropriately selected according to the purpose.

[0169] The shape of the electrochemical element is not particularly limited and can be appropriately selected according to the purpose. Examples include a laminate type, a cylinder type, and a coin type.

[0170] In an electrochemical element in which a short circuit due to dendrite deposition can occur, generally, a configuration in which the negative electrode mixture layer is larger than the positive electrode mixture layer is common. At this time, if the positive electrode current collector and the negative electrode current collector are substantially the same size, an excess portion where the positive electrode mixture layer is not formed occurs in the region where the negative electrode mixture layer of the negative electrode faces on the positive electrode current collector. From the viewpoint of the characteristics of the electroelement, the insulating resin layer is preferably provided at the excess portion of the positive electrode, that is, the outer peripheral portion of the positive electrode mixture layer. Note that if a configuration is adopted in which the negative electrode mixture layer is smaller than the positive electrode mixture layer when the electrochemical element is formed, the insulating resin layer is preferably provided at the excess portion of the negative electrode, that is, the outer peripheral portion of the negative electrode mixture layer.

[0171] (Method for manufacturing an electrochemical element and manufacturing apparatus for an electrochemical element) The method for manufacturing an electrochemical element according to the present invention preferably includes an insulating resin layer forming step, an electrode mixture layer forming step, a pressing step, a solid electrolyte layer forming step, an element forming step, and an electrode processing step, and may have other steps as necessary. The manufacturing apparatus for an electrochemical element according to the present invention preferably includes an insulating resin layer forming means, an electrode mixture layer forming means, a pressing means, a solid electrolyte layer forming means, an element forming means, and an electrode processing means, and may have other means as necessary. Note that the insulating resin layer forming step, the insulating resin layer forming means, the electrode mixture layer forming step, the electrode mixture layer forming means, the pressing step, the pressing means, the solid electrolyte layer forming step, the solid electrolyte layer forming means, other steps, and other means are the same as those described in the items of (Method for manufacturing an electrode for an electrochemical element and manufacturing apparatus for an electrode for an electrochemical element) and (Method for manufacturing an electrode laminate and manufacturing apparatus for an electrode laminate), so duplicate descriptions are omitted.

[0172] <Element forming step and element forming means> The element forming step is a step of manufacturing an electrochemical element using an electrode laminate. The element forming means is a means for manufacturing an electrochemical element using an electrode laminate. As a method for manufacturing an electrochemical element using an electrode laminate, there is no particular limitation, and a known method for manufacturing an electrochemical element can be appropriately selected according to the purpose. For example, a method of making a power storage element by performing at least any one of installing, winding, or laminating a counter electrode and housing it in a container can be mentioned. Note that the element forming step does not necessarily need to include all the steps of element formation, and may include some of the steps of element formation.

[0173] <Electrode processing step and electrode processing means> The electrode processing step is a step of processing an electrode on which an insulating resin layer is formed, which is performed after the liquid composition applying step in the insulating resin layer forming step. The electrode processing step may include at least one of a cutting step, a folding step, and a bonding step. The electrode processing means is a means for processing an electrode on which an insulating resin layer is formed. The electrode processing means may include at least one of a cutting means, a folding means, and a bonding means. For example, the electrode processing means can cut an electrode on which an insulating resin layer is formed to produce a laminate of electrodes. For example, the electrode processing means can wind or laminate a laminate of electrodes on which an insulating resin layer is formed. For example, the electrode processing means has an electrode processing apparatus, and performs cutting, zigzag folding, lamination, and winding of a laminate of electrodes on which an insulating resin layer is formed according to the target battery form.

[0174] The use of the electrochemical element is not particularly limited and can be appropriately selected according to the purpose. For example, mobile bodies such as vehicles; electrical devices such as smartphones, notebook computers, pen input computers, mobile computers, e-book players, mobile phones, mobile faxes, mobile copiers, mobile printers, headphone stereos, video movies, liquid crystal TVs, handy cleaners, portable CDs, mini discs, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, lighting fixtures, toys, game devices, watches, strobes, cameras, etc. Among these, vehicles and electrical devices are preferred. Examples of the mobile body include ordinary automobiles, large special automobiles, small special automobiles, trucks, large motorcycles, and ordinary motorcycles.

[0175] Here, an embodiment of a mobile body which is an electrochemical element according to the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments at all.

[0176] [Mobile body] FIG. 17 is a schematic diagram showing an example of a mobile body which is an electrochemical element according to an embodiment of the present invention. The mobile body 70 is, for example, an electric vehicle. The mobile body 70 includes a motor 71, an electrochemical element 72, and wheels 73.

[0177] The electrochemical element 72 is an electrochemical element according to the present invention. The electrochemical element 72 drives the motor 71 by supplying power to the motor 71. The driven motor 71 can drive the wheel 73, and as a result, the moving body 70 can move. Since the moving body 70 includes the electrochemical element 72, it can prevent a short circuit between the positive electrode and the negative electrode, and can be driven by the power from the electrochemical element having excellent battery characteristics, and can move the moving body safely and efficiently.

[0178] The moving body 70 is not limited to an electric vehicle, and may be a PHEV, an HEV, or a locomotive or a motorcycle capable of traveling by using a diesel engine and an electrochemical element in combination. Further, the moving body 70 may be a transport robot used in a factory or the like that can travel using only the electrochemical element or using an engine and an electrochemical element in combination. Further, the moving body 70 is not a thing in which the whole object moves, but only a part moves, for example, an assembly robot arranged on a manufacturing line in a factory, which can operate an arm or the like using only the electrochemical element or using an engine and an electrochemical element in combination.

Examples

[0179] Hereinafter, the present invention will be specifically described by giving examples and comparative examples, but the present invention is not limited to these examples at all. In the following examples and comparative examples, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0180] <Synthesis of Solid Electrolyte 1> As the solid electrolyte 1, an argyrodite-type sulfide solid electrolyte Li6PS5Cl (LPSC) was synthesized according to the known literature 1 "J. Power Sources. 2018, 396, 33 - 40". The solid electrolyte paint was prepared as follows. Octane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the solvent. As the dehydrated solvent, one confirmed to have a water content of 100 ppm or less by a Karl Fischer moisture concentration meter was used. To 100 parts by mass of this solvent, 100 parts by mass of the above synthesized solid electrolyte and 1 part by mass of a dispersant (Solspersem™ 21000, manufactured by Lubrizol) were added and mixed to obtain a solid electrolyte coating material.

[0181] <Surface coating of ion-conductive oxide on active material> A nickel-based positive electrode active material (lithium nickel cobalt manganese oxide, hereinafter sometimes referred to as "NCM1"; average primary particle size 3.5 μm, manufactured by Toshima Manufacturing Co., Ltd.) was used as the positive electrode active material. LiNbO 3 LiNbO 3 The layer was formed by hydrolyzing an alkoxide solution containing lithium and niobium on the surface of the NCM1 powder particles, with reference to the publicly known document 2 "J. Mater. Chem. A. 2021, 9, 4117-4125". First, metallic lithium (manufactured by Honjo Metals Co., Ltd.) was dissolved in absolute ethanol (manufactured by Kanto Chemical Co., Ltd.) to prepare an ethanol solution of lithium ethoxide. Furthermore, niobium pentaethoxide (Nb(OC 2 H 5 ) 5 ) (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was added to obtain an alkoxide solution containing lithium and niobium. The NCM1 powder was made into a fluidized bed using a rolling fluidizer (MP-01, manufactured by Powrex Corporation), and the alkoxide solution was sprayed onto the fluidized bed to obtain a precursor powder in which the surfaces of the NCM1 powder particles were coated with alkoxide. This powder was heated at 350°C in a dry air atmosphere to form LiNbO on the surface of the NCM1. 3 Layered LNO / NCM1 was synthesized.

[0182] <Method of making negative electrode> <Negative electrode 1> A lithium metal (manufactured by Honjo Metals Co., Ltd.) with an average thickness of 50 μm was attached onto a stainless steel foil substrate (50 mm × 50 mm, average thickness: 20 μm) as an electrode substrate, and then an indium foil (manufactured by Nilaco Corporation) with a thickness of 50 μm was attached to obtain a negative electrode 1 with a size of 22 mm × 22 mm.

[0183] <Negative electrode 2> As the negative electrode active material, 45.5% by mass of graphite (Gr, manufactured by Sigma-Aldrich), 1.4% by mass of acetylene black (Denka Black, manufactured by Denka Co., Ltd.) as the conductive material, 1.8% by mass of acrylonitrile-butadiene rubber (NBR, manufactured by Sigma-Aldrich) as the binder, and 14.8% by mass of solid electrolyte 1 were dispersed in 36.5% by mass of anisole to prepare negative electrode paint 2. After applying negative electrode paint 2 to both sides of a stainless steel foil substrate (50 mm × 50 mm, average thickness: 20 μm), it was dried to obtain a 25 mm × 25 mm negative electrode 2. The average thickness of negative electrode 2 was 61 μm, and the battery capacity per unit area was 3.38 mAh / cm 2 It was.

[0184] <Negative electrode 3> As the negative electrode active material, 45.5% by mass of silicon (Si, manufactured by Sigma-Aldrich), 1.4% by mass of acetylene black (Denka Black, manufactured by Denka Co., Ltd.) as the conductive material, 1.8% by mass of acrylonitrile-butadiene rubber (NBR, manufactured by Sigma-Aldrich) as the binder, and 14.8% by mass of solid electrolyte 1 were dispersed in 36.5% by mass of anisole to prepare negative electrode paint 3. After applying negative electrode paint 3 to both sides of the stainless steel foil substrate, it was dried to obtain a 25 mm × 25 mm negative electrode 3. The average thickness of negative electrode 3 was 21 μm, and the battery capacity per unit area was 3.61 mAh / cm 2 It was.

[0185] <Preparation of the first liquid composition for forming the insulating resin layer> The first liquid composition for forming the insulating resin layer was prepared by mixing the materials in the following proportions. <First liquid composition 1> As the first solvent, 22.5% by mass of p-menthane (manufactured by Tokyo Chemical Industry Co., Ltd.), 27.5% by mass of ethyl octanoate (manufactured by Tokyo Chemical Industry Co., Ltd.), 50.0% by mass of polyethylene glycol (200) diacrylate (manufactured by Daicel Ornex Co., Ltd.) as a polymerizable compound, and 0.5% by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization initiator were mixed to obtain the first liquid composition 1 for forming an insulating resin layer.

[0186] <First Liquid Composition 2> As the first solvent, 31.0% by mass of n-decane (manufactured by Tokyo Chemical Industry Co., Ltd.), 29.0% by mass of 2-ethylhexyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 50.0% by mass of CN2283NS (manufactured by Arkema) as a polymerizable compound, and 0.5% by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization initiator were mixed to obtain the first liquid composition 2.

[0187] <First Liquid Composition 3> As the first solvent, 31.0% by mass of n-dodecane (manufactured by Tokyo Chemical Industry Co., Ltd.), 29.0% by mass of 2-ethylhexyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 50.0% by mass of CN2283NS (manufactured by Arkema) as a polymerizable compound, and 0.5% by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization initiator were mixed to obtain the first liquid composition 3.

[0188] <Preparation of the Second Liquid Composition for Forming the Positive Electrode Composite Material Layer> <Second Liquid Composition 1> As the positive electrode active material, 45.3% by mass of LNO / NMC1, 2.2% by mass of acetylene black (Denka Black, manufactured by Denka Co., Ltd.) as a conductive material, 1.4% by mass of polybutyl methacrylate (PBMA, manufactured by Aldrich) as a binder, and 14.7% by mass of solid electrolyte 1 were dispersed in 36.4% by mass of anisole (manufactured by Tokyo Chemical Industry Co., Ltd.) as the second solvent to prepare the second liquid composition 1 for forming the positive electrode composite material layer.

[0189] <Second Liquid Composition 2> As the positive electrode active material, 45.3% by mass of LNO / NMC1, 2.2% by mass of acetylene black (Denka Black, manufactured by Denka Co., Ltd.) as the conductive material, 1.4% by mass of polybutyl methacrylate (PBMA, manufactured by Aldrich) as the binder, and 14.7% by mass of solid electrolyte 1 were dispersed in 36.4% by mass of methyl hexanoate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the second solvent to prepare the second liquid composition 2 for forming the positive electrode composite layer.

[0190] <Second Liquid Composition 3> As the positive electrode active material, 45.3% by mass of LNO / NMC1, 2.2% by mass of acetylene black (Denka Black, manufactured by Denka Co., Ltd.) as the conductive material, 1.4% by mass of polybutyl methacrylate (PBMA, manufactured by Aldrich) as the binder, and 14.7% by mass of solid electrolyte 1 were dispersed in 36.4% by mass of butyl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the second solvent to prepare the second liquid composition 3 for forming the positive electrode composite layer.

[0191] <Second Liquid Composition 4> As the positive electrode active material, 45.3% by mass of LNO / NMC1, 2.2% by mass of acetylene black (Denka Black, manufactured by Denka Co., Ltd.) as the conductive material, 1.4% by mass of polybutyl methacrylate (PBMA, manufactured by Aldrich) as the binder, and 14.7% by mass of solid electrolyte 1 were dispersed in 36.4% by mass of butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the second solvent to prepare the second liquid composition 4 for forming the positive electrode composite layer.

[0192] (Example 1) <Fabrication of Positive Electrode> The first liquid composition 1 for forming the insulating resin layer was filled into an inkjet discharge device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industries Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) was placed on the stage, and it was discharged and applied so as to have an outer shape of 40 mm × 40 mm, a width of 10 mm of the insulating resin layer, and an opening of 20 mm × 20 mm where the current collector was exposed inside. Subsequently, immediately, under a nitrogen atmosphere, the coated area was irradiated with UV light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) and cured. Subsequently, the second liquid composition 1 was discharged and applied using an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of an opening of 20 mm × 20 mm. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to simultaneously remove the first solvent and the second solvent, and an electrode 1 having a positive electrode composite layer - insulating resin layer was obtained on the electrode substrate. Regarding the obtained electrode 1, the size of the surface of the positive electrode layer was 21 mm × 21 mm, and the amount of warpage of the substrate was 0 mm. When the average thicknesses of the insulating resin layer and the positive electrode layer were measured using a laser microscope (Keyence, VKX-3000), both were 97 μm, and the positive electrode contacted and covered up to the uppermost part of the end of the insulating resin layer, forming a continuous positive electrode composite layer - insulating resin layer.

[0193] Regarding Example 1, based on the following evaluation criteria, "warpage", "press resistance", and "battery performance" were evaluated respectively. The results are shown in Table 1.

[0194] [Warpage] With the electrode substrate of the obtained electrode placed on a horizontal plane, the maximum value (mm) of the height of the upward warpage at the end of the electrode substrate was measured as "warpage" and evaluated based on the following evaluation criteria. - Evaluation criteria - ◎: Warpage is 0 mm or more and less than 1 mm, and there is no warpage, which is extremely good 〇: Warpage is 1 mm or more and less than 5 mm, and there is little warpage, which is good ×: Warpage is 5 mm or more, and there is a large warpage, which causes problems in use

[0195] [Press resistance] After sealing the obtained electrode with an aluminum laminate, it was pressurized at 500 MPa for 5 minutes by cold isostatic pressing (CIP). After pressurization, the electrode was taken out from the aluminum laminate, and the presence or absence of cracks in the electrode film formation region was evaluated based on the following criteria by visual observation. - Evaluation Criteria - 〇: Good without cracks ×: Cracks occurred and there are problems in use

[0196] [Battery Performance] <Fabrication of Battery> After sealing Electrode 1 of Example 1 with an aluminum laminate, it was pressurized at 500 MPa for 5 minutes by cold isostatic pressing (CIP). After pressurization, Electrode 1 was taken out from the aluminum laminate. No cracks occurred in the electrode. A solid electrolyte layer was coated and formed on the positive electrode by the bar coating method to obtain an electrode laminate. After coating, it was sealed again with an aluminum laminate and pressurized at 500 MPa for 5 minutes by CIP. Electrode 1 and Negative Electrode 1 were opposed to form a single cell layer, and after attaching lead wires to each, they were vacuum-sealed by lamination to fabricate All-Solid-State Battery 1 of Example 1.

[0197] When measuring the battery voltage of the fabricated All-Solid-State Battery 1 according to the following procedure, it was 2.08 V. The capacity per unit area was 141 mAh / g at the initial discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed. - Evaluation Criteria - ◎: Initial discharge capacity is 140 mAh / g or more 〇: Initial discharge capacity is 130 mAh / g or more and less than 140 mAh / g △: Initial discharge capacity is 120 mAh / g or more and less than 130 mAh / g ×: Initial discharge capacity is less than 120 mAh / g

[0198] (Example 2) <Fabrication of Positive Electrode> The first liquid composition 1 and the second liquid composition 1 for forming a resin layer were respectively filled into inkjet ejection devices equipped with different GEN5 heads (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm), which is a current collector, was placed on the stage, and the positive electrode paint was ejected and applied to a 20 mm × 20 mm area. Subsequently, the first liquid composition 1 was ejected and applied in a shape that has an outer shape of 40 mm × 40 mm, an insulating resin layer width of 10 mm, and an electrode composite layer of 20 mm × 20 mm inside and surrounds the outer periphery. Immediately thereafter, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed on the coated area to cure it. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to simultaneously remove the first solvent and the second solvent, thereby obtaining electrode 2. Regarding the obtained electrode 2, the size of the surface of the positive electrode layer was 20 mm × 20 mm, and the warpage amount of the substrate was 0 mm. When the average thicknesses of the insulating resin layer and the positive electrode layer were measured using a laser microscope (Keyence, VKX-3000), both were 98 μm. The positive electrode contacted and covered up to the uppermost part of the end of the insulating resin layer, forming a continuous positive electrode composite layer-insulating resin layer. Also, no cracks occurred in the electrode after pressing.

[0199] <Fabrication of Battery> In Example 2, all-solid-state battery 2 of Example 2 was fabricated in the same manner as in Example 1, except that electrode 2 was used instead of electrode 1. When the battery voltage of the fabricated all-solid-state battery 2 was measured, it was 2.07 V. The capacity per unit area was 138 mAh / g at the first discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0200] Regarding Example 2, based on the same evaluation criteria as in Example 1, "warpage", "press resistance", and "battery performance" were respectively evaluated. The results are shown in Table 1.

[0201] (Example 3) <Fabrication of the positive electrode> The first liquid composition 1 and the second liquid composition 1 for forming the resin layer were respectively filled into an inkjet ejection device equipped with a separate GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) as a current collector was placed on the stage, and the first liquid composition 1 was shaped with an outer shape of 40 mm × 40 mm, a width of the insulating resin layer of 10 mm, and an opening of 20 mm × 20 mm where the current collector was exposed inside. The positive electrode paint was ejected onto the 20 mm × 20 mm area, and the first liquid composition 1 and the second liquid composition 1 for forming the resin layer were simultaneously applied. Thereafter, immediately, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed to cure it. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to simultaneously remove the first solvent and the second solvent, and an electrode 3 having a positive electrode composite layer - insulating resin layer was obtained on the electrode substrate. Regarding the obtained electrode 3, the size of the surface of the positive electrode layer was 20.5 mm × 20.5 mm, and the warp amount of the substrate was 1 mm. When the average thickness of the insulating resin layer was measured using a laser microscope (Keyence, VKX-3000), it was 97 μm. At this time, the positive electrode contacted and covered up to a height of 97 μm at the end of the insulating resin layer, forming a continuous positive electrode composite layer - insulating resin layer. The average thickness of the positive electrode composite layer was 98 μm. Also, no cracks occurred in the electrode after pressing.

[0202] <Fabrication of the battery> In Example 1, except that electrode 3 was used instead of electrode 1, the all-solid-state battery 3 of Example 3 was fabricated in the same manner as in Example 1. When measuring the battery voltage of the fabricated all-solid-state battery 3, it was 2.08 V. The capacity per unit area was 138 mAh / g at the first discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0203] Regarding Example 3, based on the same evaluation criteria as in Example 1, "warpage", "press resistance", and "battery performance" were evaluated respectively. The results are shown in Table 1.

[0204] (Example 4) <Fabrication of Positive Electrode> The first liquid composition 2 for forming the resin layer was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) as a current collector was placed on the stage, and the first liquid composition 1 was ejected and applied in a shape having an outer shape of 40 mm × 40 mm, an insulating resin layer width of 10 mm, and an opening of 20 mm × 20 mm where the current collector was exposed inside. Then, immediately, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed on the coated area to cure it. Next, the second liquid composition 1 was ejected and applied using an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of the 20 mm × 20 mm opening. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to simultaneously remove the first solvent and the second solvent, and an electrode 4 having a positive electrode composite layer - insulating resin layer was obtained on the electrode substrate. Regarding the obtained electrode 4, the size of the surface of the positive electrode layer was 21 mm × 21 mm, and the amount of warpage of the base material was 3 mm. The average thicknesses of the insulating resin layer and the positive electrode layer were both 97 μm when measured using a laser microscope (Keyence Corporation, VKX-3000). The positive electrode contacted and covered up to the uppermost part of the end of the insulating resin layer, forming a continuous positive electrode composite layer - insulating resin layer. Also, no cracks occurred in the electrode after pressing.

[0205] <Fabrication of Battery> In Example 1, the all-solid-state battery 4 of Example 4 was fabricated in the same manner as in Example 1, except that electrode 4 was used instead of electrode 1. When measuring the battery voltage of the fabricated all-solid-state battery 4, it was 2.01 V. The capacity per unit area was 135 mAh / g in the initial discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0206] Regarding Example 4, "warpage", "press resistance", and "battery performance" were evaluated based on the same evaluation criteria as in Example 1. The results are shown in Table 1.

[0207] (Example 5) <Fabrication of Positive Electrode> The first liquid composition 1 for forming a resin layer was filled into an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) as a current collector was placed on the stage, and the first liquid composition 1 was discharged and applied in a shape surrounding the outer periphery with an outer shape of 40 mm × 40 mm, a width of 10 mm for the insulating resin layer, and an electrode composite layer of 20 mm × 20 mm inside. Thereafter, immediately, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed to cure it. Subsequently, the second liquid composition 1 was applied using a die coating apparatus so as to fill the inside of an opening of 20 mm × 20 mm. Next, using a hot plate, the substrate was heated at 120°C for 10 minutes to simultaneously remove the first solvent and the second solvent, thereby obtaining the electrode 5. Regarding the obtained electrode 5, the size of the surface of the positive electrode layer was 20 mm × 20 mm, and the amount of warpage of the substrate was 0 mm. The average thicknesses of the insulating resin layer and the positive electrode layer were both 98 μm when measured using a laser microscope (Keyence Corporation, VKX-3000). Although the positive electrode was in contact with the end of the insulating resin layer, it did not cover to the uppermost part, and the positive electrode composite layer - insulating resin layer was not a continuous structure. Also, no cracks occurred in the electrode after pressing.

[0208] <Fabrication of Battery> In Example 5, the all-solid-state battery 5 of Example 5 was fabricated in the same manner as in Example 1, except that the electrode 5 was used instead of the electrode 1. When the battery voltage of the fabricated all-solid-state battery 5 was measured, it was 2.01 V. The capacity per unit area was 129 mAh / g at the initial discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0209] Regarding Example 5, "warpage", "press resistance", and "battery performance" were evaluated based on the same evaluation criteria as in Example 1. The results are shown in Table 1.

[0210] (Example 6) <Fabrication of Positive Electrode> The first liquid composition 2 for forming the insulating resin layer was filled into an inkjet discharge apparatus equipped with an inkjet head (MH5421F, manufactured by Ricoh Industries Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) was placed on the stage, and it was discharged and applied so as to have an opening of 20 mm × 20 mm with an outer shape of 40 mm × 40 mm and a width of the insulating resin layer of 10 mm and the current collector exposed inside. Subsequently, immediately under a nitrogen atmosphere, UV irradiation was performed on the coating area (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s), and it was cured. Subsequently, the second liquid composition 2 was discharged and applied using an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of an opening of 20 mm × 20 mm. Next, using a hot plate, the substrate was heated at 120°C for 10 minutes to remove the first solvent and the second solvent, and an electrode 6 having a positive electrode composite layer - insulating resin layer was obtained on the electrode substrate. Regarding the obtained electrode 1, the size of the surface of the positive electrode layer was 21 mm × 21 mm, and the amount of warpage of the substrate was 3 mm. When the average thicknesses of the insulating resin layer and the positive electrode layer were measured using a laser microscope (Keyence, VKX-3000), the insulating resin layer was 120 μm, the positive electrode layer was 98 μm, and the insulating resin layer contacted and covered up to the top of the positive electrode layer, forming a continuous positive electrode composite layer - insulating resin layer. Also, no cracks occurred in the electrode after pressing.

[0211] <Fabrication of Battery> In Example 1, an all-solid-state battery 6 of Example 6 was fabricated in the same manner as in Example 1, except that electrode 6 was used instead of electrode 1. When the battery voltage of the fabricated all-solid-state battery 5 was measured, it was 2.02 V. The capacity per unit area was 131 mAh / g at the initial discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0212] Regarding Example 6, "warpage", "press resistance", and "battery performance" were evaluated respectively based on the same evaluation criteria as in Example 1. The results are shown in Table 1.

[0213] (Example 7) <Fabrication of Positive Electrode> The first liquid composition 2 for forming an insulating resin layer was filled into an inkjet ejection device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industries Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) was placed on the stage, and it was ejected and applied so as to have an opening of 20 mm × 20 mm with an outer shape of 40 mm × 40 mm and a width of the insulating resin layer of 10 mm where the current collector was exposed inside. Immediately thereafter, in a nitrogen atmosphere, UV irradiation was performed on the coated area (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) to cure it. Subsequently, the second liquid composition 2 was ejected and applied using an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of the 20 mm × 20 mm opening. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to remove the first solvent and the second solvent, and an electrode 7 having a positive electrode composite layer - insulating resin layer was obtained on the electrode substrate. Regarding the obtained electrode 1, the size of the surface of the positive electrode layer was 21 mm × 21 mm, and the warpage amount of the substrate was 3 mm. When the average thicknesses of the insulating resin layer and the positive electrode layer were measured using a laser microscope (Keyence, VKX-3000), the insulating resin layer was 70 μm, the positive electrode layer was 98 μm, and the positive electrode layer contacted and covered up to the top of the insulating resin layer, forming a continuous positive electrode composite layer - insulating resin layer. Also, no cracks occurred in the electrode after pressing.

[0214] <Fabrication of Battery> In Example 1, an all-solid-state battery 7 of Example 7 was fabricated in the same manner as in Example 1, except that electrode 6 was used instead of electrode 1. When the battery voltage of the fabricated all-solid-state battery 5 was measured, it was 2.03 V. The capacity per unit area was 130 mAh / g at the first discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0215] For Example 7, “warpage”, “press resistance”, and “battery performance” were evaluated based on the same evaluation criteria as in Example 1. The results are shown in Table 1.

[0216] (Example 8) <Fabrication of the positive electrode> The first liquid composition 2 and the second liquid composition 2 for forming the resin layer were respectively filled into inkjet ejection devices equipped with different GEN5 heads (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm), which is a current collector, was placed on the stage, and the positive electrode paint was ejected and applied in a 20 mm × 20 mm area. Subsequently, the first liquid composition 1 was ejected and applied in a shape that has an outer shape of 40 mm × 40 mm, an insulating resin layer width of 10 mm, and an electrode composite layer of 20 mm × 20 mm inside and surrounds the outer periphery. Thereafter, immediately, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed on the coated area for curing. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to remove the first solvent and the second solvent, and electrode 8 was obtained. Regarding the obtained electrode 2, the size of the surface of the positive electrode layer was 20 mm × 20 mm, and the warpage amount of the substrate was 3 mm. When the average thicknesses of the insulating resin layer and the positive electrode layer were measured using a laser microscope (Keyence, VKX-3000), the insulating resin layer was 120 μm, the positive electrode layer was 98 μm, and the insulating resin layer contacted and covered up to the top of the positive electrode layer, forming a continuous positive electrode composite layer-insulating resin layer. Also, no cracks occurred in the electrode after pressing.

[0217] <Fabrication of the battery> In Example 1, all-solid-state battery 8 of Example 8 was fabricated in the same manner as in Example 1, except that electrode 6 was used instead of electrode 1. When measuring the battery voltage of the fabricated all-solid-state battery 8, it was 2.02 V. The capacity per unit area was 130 mAh / g at the initial discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0218] Regarding Example 8, based on the same evaluation criteria as in Example 1, "warpage", "press resistance", and "battery performance" were evaluated respectively. The results are shown in Table 1.

[0219] (Example 9) <Fabrication of positive electrode> The first liquid composition 2 and the second liquid composition 2 for forming the resin layer were respectively filled into inkjet ejection devices equipped with different GEN5 heads (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) as a current collector was placed on the stage, and the positive electrode paint was ejected and applied in a 20 mm × 20 mm area. Subsequently, the first liquid composition 1 was ejected and applied in a shape with an outer shape of 40 mm × 40 mm, an insulating resin layer width of 10 mm, and an internal electrode composite layer of 20 mm × 20 mm, surrounding the outer periphery. Immediately thereafter, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed to cure it. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to remove the first solvent and the second solvent, and the electrode 9 was obtained. Regarding the obtained electrode 2, the size of the surface of the positive electrode layer was 20 mm × 20 mm, and the warpage amount of the substrate was 3 mm. When measuring the average thickness of the insulating resin layer and the positive electrode layer using a laser microscope (Keyence, VKX-3000), the insulating resin layer was 70 μm, the positive electrode layer was 98 μm, and the positive electrode layer was in contact with and covered up to the top of the insulating resin layer, forming a continuous positive electrode composite layer-insulating resin layer. Also, no cracks occurred in the electrode after pressing.

[0220] <Fabrication of battery> In Example 1, all-solid-state battery 9 of Example 9 was fabricated in the same manner as in Example 1, except that electrode 9 was used instead of electrode 1. When the battery voltage of the fabricated all-solid-state battery 9 was measured, it was 2.01 V. The capacity per unit area was 131 mAh / g in the initial discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0221] For Example 9, "warpage", "press resistance", and "battery performance" were evaluated based on the same evaluation criteria as in Example 1. The results are shown in Table 1.

[0222] (Example 10) (Fabrication of positive electrode) The first liquid composition 2 for forming an insulating resin layer was filled into an inkjet discharge device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industries Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) was placed on the stage, and it was discharged and applied so as to have an opening of 20 mm × 20 mm with an outer shape of 30 mm × 30 mm and a width of the insulating resin layer of 5 mm and the current collector exposed inside. Thereafter, immediately, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed on the coated area to cure it. Subsequently, the second liquid composition 2 was discharged and applied using an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of the 20 mm × 20 mm opening. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to remove the first solvent and the second solvent, and an electrode 10 having a positive electrode composite layer - insulating resin layer was obtained on the electrode substrate. Regarding the obtained electrode 1, the size of the surface of the positive electrode layer was 21 mm × 21 mm, and the amount of warp of the base material was 3 mm. When the average thicknesses of the insulating resin layer and the positive electrode layer were measured using a laser microscope (Keyence Corporation, VKX-3000), both were 97 μm. The positive electrode contacted and covered up to the uppermost part of the end of the insulating resin layer, forming a continuous positive electrode composite layer-insulating resin layer. Also, no cracks occurred in the electrode after pressing. <Fabrication of Battery> In Example 10, an all-solid-state battery 10 of Example 10 was fabricated in the same manner as in Example 1, except that electrode 10 was used instead of electrode 1. When the battery voltage of the fabricated all-solid-state battery 10 was measured, it was 2.03 V. The capacity per unit area was 132 mAh / g in the initial discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed. Regarding Example 10, "warp", "press resistance", and "battery performance" were evaluated based on the same evaluation criteria as in Example 1. The results are shown in Table 1.

[0223] (Example 11) <Fabrication of Positive Electrode> The first liquid composition 2 for forming the insulating resin layer was filled into an inkjet discharge device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industries Co., Ltd.). An aluminum foil substrate (60 mm × 60 mm, average thickness: 15 μm) was placed on the stage, and it was discharged and applied so as to have an opening of 20 mm × 20 mm with an outer shape of 50 mm × 50 mm and a width of 15 mm of the insulating resin layer where the current collector was exposed inside. Thereafter, immediately, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed to cure it. Subsequently, the second liquid composition 2 was discharged and applied using an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of the 20 mm × 20 mm opening. Next, using a hot plate, the substrate was heated at 120°C for 10 minutes to remove the first solvent and the second solvent, and an electrode 11 having a positive electrode composite layer - insulating resin layer was obtained on the electrode substrate. Regarding the obtained electrode 11, the size of the surface of the positive electrode layer was 21 mm × 21 mm, and the warp amount of the substrate was 3 mm. When the average thicknesses of the insulating resin layer and the positive electrode layer were measured using a laser microscope (Keyence Corporation, VKX - 3000), both were 97 μm. The positive electrode contacted and covered up to the uppermost part of the end of the insulating resin layer, forming a continuous positive electrode composite layer - insulating resin layer. Also, no cracks occurred in the electrode after pressing.

[0224] <Fabrication of Battery> In Example 11, an all - solid - state battery 11 was fabricated in the same manner as in Example 1, except that electrode 11 was used instead of electrode 1. When the battery voltage of the fabricated all - solid - state battery 11 was measured, it was 2.01 V. The capacity per unit area was 131 mAh / g in the first discharge capacity. Constant - current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short - circuit was observed. For Example 11, "warp", "press resistance", and "battery performance" were evaluated respectively based on the same evaluation criteria as in Example 1. The results are shown in Table 1.

[0225] (Example 12) <Fabrication of Positive Electrode> The first liquid composition 3 for forming the insulating resin layer was filled into an inkjet discharge device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industries Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) was placed on the stage, and it was discharged and coated so as to have an outer shape of 40 mm × 40 mm, a width of the insulating resin layer of 10 mm, and an opening of 20 mm × 20 mm where the current collector was exposed inside. Thereafter, immediately, under a nitrogen atmosphere, UV irradiation (light source: UV - LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2, irradiation time: 20 s), and it was cured. Subsequently, the second liquid composition 2 was discharged and applied using an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of an opening of 20 mm × 20 mm. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to remove the first solvent and the second solvent, and an electrode 12 having a positive electrode composite layer - insulating resin layer was obtained on the electrode substrate. Regarding the obtained electrode 12, the size of the surface of the positive electrode layer was 21 mm × 21 mm, and the warpage amount of the substrate was 0 mm. When the average thicknesses of the insulating resin layer and the positive electrode layer were measured using a laser microscope (Keyence, VKX - 3000), both were 98 μm. The positive electrode contacted and covered up to the uppermost part of the end of the insulating resin layer, forming a continuous positive electrode composite layer - insulating resin layer. Also, no cracks occurred in the electrode after pressing.

[0226] <Fabrication of battery> In Example 12, an all - solid - state battery 12 of Example 12 was fabricated in the same manner as in Example 1, except that electrode 12 was used instead of electrode 1. When the battery voltage of the fabricated all - solid - state battery 12 was measured, it was 2.02 V. The capacity per unit area was 133 mAh / g at the first discharge capacity. Constant - current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short - circuit was observed.

[0227] Regarding Example 12, based on the same evaluation criteria as in Example 1, "warpage", "press resistance", and "battery performance" were evaluated respectively. The results are shown in Table 1.

[0228] (Example 13) <Fabrication of positive electrode> The first liquid composition 2 for forming an insulating resin layer was filled into an inkjet ejection device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industries Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) was placed on the stage, and it was ejected and applied so as to have an opening of 20 mm × 20 mm with an outer shape of 40 mm × 40 mm and a width of the insulating resin layer of 10 mm where the current collector was exposed inside. Immediately thereafter, in a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed on the coated area to cure it. Subsequently, the second liquid composition 3 was ejected and applied using an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of the 20 mm × 20 mm opening. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to remove the first solvent and the second solvent, and an electrode 13 having a positive electrode composite layer - insulating resin layer was obtained on the electrode substrate. Regarding the obtained electrode 13, the size of the surface of the positive electrode layer was 21 mm × 21 mm, and the warpage amount of the substrate was 3 mm. When the average thicknesses of the insulating resin layer and the positive electrode layer were measured using a laser microscope (Keyence, VKX-3000), both were 98 μm. The positive electrode contacted and covered up to the uppermost part of the end of the insulating resin layer, forming a continuous positive electrode composite layer - insulating resin layer. Also, no cracks occurred in the electrode after pressing.

[0229] <Fabrication of Battery> In Example 13, an all-solid-state battery 13 was fabricated in the same manner as in Example 1, except that electrode 13 was used instead of electrode 1. When the battery voltage of the fabricated all-solid-state battery 13 was measured, it was 2.07 V. The capacity per unit area was 140 mAh / g at the first discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0230] For Example 13, “warpage”, “press resistance”, and “battery performance” were evaluated based on the same evaluation criteria as in Example 1. The results are shown in Table 1.

[0231] (Example 14) <Fabrication of the positive electrode> The first liquid composition 2 for forming the insulating resin layer was filled into an inkjet discharge device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industries Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) was placed on the stage, and it was discharged and applied so as to have an opening of 20 mm × 20 mm with an outer shape of 40 mm × 40 mm and a width of the insulating resin layer of 10 mm where the current collector was exposed inside. Then, immediately, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed on the coated area to cure it. Subsequently, the second liquid composition 4 was discharged and applied using an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of the 20 mm × 20 mm opening. Next, using a hot plate, the substrate was heated at 120 °C for 10 minutes to remove the first solvent and the second solvent, and an electrode 14 having a positive electrode composite layer - insulating resin layer was obtained on the electrode substrate. Regarding the obtained electrode 14, the size of the surface of the positive electrode layer was 21 mm × 21 mm, and the warpage amount of the substrate was 3 mm. The average thicknesses of the insulating resin layer and the positive electrode layer were measured using a laser microscope (Keyence, VKX-3000), and both were 98 μm. The positive electrode contacted and covered up to the uppermost part of the end of the insulating resin layer, forming a continuous positive electrode composite layer - insulating resin layer. Also, no cracks occurred in the electrode after pressing.

[0232] <Fabrication of the battery> A all-solid-state battery 14 of Example 14 was fabricated in the same manner as in Example 1, except that electrode 14 was used instead of electrode 1 in Example 1. When measuring the battery voltage of the fabricated all-solid-state battery 14, it was 2.02 V. The capacity per unit area was 132 mAh / g at the initial discharge capacity. Constant current charging up to 3.6 V was possible without problems at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0233] For Example 14, based on the same evaluation criteria as in Example 1, "warpage", "press resistance", and "battery performance" were evaluated respectively. The results are shown in Table 1.

[0234] (Comparative Example 1) The first liquid composition 2 for forming the resin layer was filled into an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) as a current collector was placed on the stage, and the first liquid composition 1 was discharged and applied in a shape having an outer shape of 40 mm × 40 mm, an insulating resin layer width of 10 mm, and an opening of 20 mm × 20 mm where the current collector was exposed inside. Immediately thereafter, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed on the coated area to cure it. Next, using a hot plate, the solvent was removed by heating the substrate at 120 °C for 1 minute. The amount of warpage of the substrate was 5 mm. The warpage of the substrate was large, and in the next step, it was not possible to discharge and apply the second liquid composition 1 to fill the inside of the 20 mm × 20 mm opening using an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). When the average thickness of the insulating resin layer was measured using a laser microscope (Keyence, VKX-3000), it was 97 μm.

[0235] For Comparative Example 1, based on the same evaluation criteria as in Example 1, "warpage" was evaluated. The results are shown in Table 1. Since it was not possible to form the positive electrode layer by applying the second liquid composition 1, "press resistance" and "battery performance" were not evaluated.

[0236] (Comparative Example 2) The second liquid composition 1 was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) as a current collector was placed on the stage, and the positive electrode paint was ejected and applied to a 20 mm × 20 mm area. Next, using a hot plate, the substrate was heated at 120°C for 1 minute to remove the solvent. The warpage amount of the substrate was 5 mm. Since the warpage of the substrate was large, in the next step, the first liquid composition 2 for forming a resin layer was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). It was not possible to eject and apply the first liquid composition 1 in a shape having an outer shape of 40 mm × 40 mm, an insulating resin layer width of 10 mm, and an electrode composite layer of 20 mm × 20 mm inside and surrounding the outer periphery. When the average thickness of the positive electrode composite layer was measured using a laser microscope (Keyence, VKX-3000), it was 97 μm.

[0237] Regarding Comparative Example 2, "warpage" was evaluated based on the same evaluation criteria as in Example 1. The results are shown in Table 1. Note that since it was not possible to form a positive electrode layer by applying the second liquid composition 1, "press resistance" and "battery performance" were not evaluated.

[0238]

Table 1

[0239] Examples of aspects of the present invention include, for example, the following. <1> An insulating resin layer forming step including applying a liquid composition for forming an insulating resin layer containing a first solvent and a polymerizable compound on a substrate and forming an insulating resin layer. An electrode composite layer forming step of forming an electrode composite layer by applying a liquid composition for forming an electrode composite layer having an active material and a second solvent on the substrate. A method for manufacturing an electrode, comprising: a removing step of simultaneously removing the first solvent and the second solvent. <2> The method for manufacturing an electrode according to <1>, wherein the step of forming the insulating resin layer includes polymerizing the applied liquid composition for forming the insulating resin layer. <3> The method for manufacturing an electrode according to <2>, wherein the insulating resin layer contains a crosslinkable resin. <4> The method for manufacturing an electrode according to <3>, wherein the crosslinkable resin is formed by a crosslinking reaction of a polymerizable compound. <5> The method for manufacturing an electrode according to <4>, wherein polymerization is performed by irradiating light on the liquid composition for forming the insulating resin layer. <6> The method for manufacturing an electrode according to <4>, wherein the removing step is performed after the crosslinking reaction. <7> The method for manufacturing an electrode according to any one of <1> to <6>, wherein the difference between the boiling point of the first solvent and the boiling point of the second solvent is 40 °C or less. <8> The method for manufacturing an electrode according to any one of <1> to <7>, wherein the insulating resin layer and the electrode composite layer are in contact on the same plane. <9> The electrode composite layer contains a resin, The method for manufacturing an electrode according to any one of <1> to <8>, wherein the solubility of the resin in the first solvent is 1% or less. <10> The method for manufacturing an electrode according to any one of <1> to <9>, wherein the second solvent does not change the volume of the insulating resin layer by 10% or more. <11> The method for manufacturing an electrode according to any one of <1> to <10>, wherein in the application, the liquid composition for forming the electrode composite layer is applied by an inkjet method. <12> An insulating resin layer containing a polymerizable compound, An electrode composite layer containing an active material and a resin, A composite electrode, wherein the electrode composite layer penetrates into the insulating resin layer in a direction perpendicular to the interface between the insulating resin layer and the electrode composite layer. <13> The composite electrode according to <12>, wherein the electrode composite layer is on top at the interface between the insulating resin layer and the electrode composite layer. An electrochemical element characterized by having the composite electrode described in <14>, <12> or <13>. Insulating resin layer forming means including applying a liquid composition for forming an insulating resin layer containing a first solvent and a polymerizable compound onto a substrate and forming an insulating resin layer. Electrode mixture layer forming means for forming an electrode mixture layer by applying a liquid composition for forming an electrode mixture layer having an active material and a second solvent onto the substrate. A manufacturing apparatus for an electrode, comprising removing means for simultaneously removing the first solvent and the second solvent.

[0240] The method for manufacturing an electrode according to any one of <1> to <11>, the composite electrode according to <12> to <13>, the electrochemical element according to <14>, and the manufacturing apparatus for an electrode according to <15> can solve various conventional problems and achieve the object of the present invention.

Explanation of symbols

[0241] 10 Insulating resin layer 20 First electrode mixture layer 21 First substrate 22 Adhesive layer 23 Opening 24 Material 25 Electrode for electrochemical element 30 Solid electrolyte layer 31 Second substrate 35 Electrode laminate 40 Second electrode mixture layer 41 Second electrode 45 Electrochemical element 500 Manufacturing apparatus for insulating resin layer 100 Printing section 1a Printing apparatus 1b Storage container 1c Supply tube 200 Polymerization section 2a Light irradiation apparatus 2b Polymerization inert gas circulation apparatus 300 Heating section 3a Heating apparatus 5 Conveying section 6 Liquid composition 7 Roller

Prior art documents

Patent documents

[0242]

Patent Document 1

Claims

1. an insulating resin layer forming step including applying an insulating resin layer forming liquid composition containing a first solvent and a polymerizable compound onto a substrate and forming an insulating resin layer; an electrode mixture layer forming step of applying an electrode mixture layer forming liquid composition containing an active material and a second solvent onto the substrate to form an electrode mixture layer; and a removing step of simultaneously removing the first solvent and the second solvent.

2. The method for producing an electrode according to claim 1 , wherein the insulating resin layer forming step includes polymerizing the applied insulating resin layer forming liquid composition.

3. The method for producing an electrode according to claim 2 , wherein the insulating resin layer contains a cross-linkable resin.

4. The method for producing an electrode according to claim 3 , wherein the crosslinkable resin is formed by a crosslinking reaction of a polymerizable compound.

5. The method for producing an electrode according to claim 4 , wherein the liquid composition for forming an insulating resin layer is polymerized by irradiating the liquid composition with light.

6. The method for producing an electrode according to claim 4 , wherein the removing step is carried out after the crosslinking reaction.

7. 7. The method for producing an electrode according to claim 1, wherein the difference between the boiling points of the first solvent and the second solvent is 40° C. or less.

8. The method for manufacturing an electrode according to claim 1 , wherein the insulating resin layer and the electrode mixture layer are in contact with each other on the same plane.

9. The electrode mixture layer contains a resin, The method for manufacturing an electrode according to claim 1 , wherein the resin has a solubility of 1% or less in the first solvent.

10. The method for manufacturing an electrode according to claim 1 , wherein the second solvent does not change the volume of the insulating resin layer by 10% or more.

11. The method for manufacturing an electrode according to claim 1 , wherein the electrode mixture layer forming liquid composition is applied by an ink jet method.

12. an insulating resin layer containing a polymerizable compound; an electrode mixture layer including an active material and a resin; A composite electrode, characterized in that the electrode mixture layer permeates into the insulating resin layer in a direction perpendicular to an interface between the insulating resin layer and the electrode mixture layer.

13. The composite electrode according to claim 12 , wherein at the interface between the insulating resin layer and the electrode mixture layer, the electrode mixture layer is on top.

14. An electrochemical element comprising the composite electrode according to claim 12 or 13.

15. An insulating resin layer forming means including applying an insulating resin layer forming liquid composition containing a first solvent and a polymerizable compound onto a substrate and forming an insulating resin layer; an electrode mixture layer forming means for applying an electrode mixture layer forming liquid composition containing an active material and a second solvent onto the substrate to form an electrode mixture layer; and a removal means for simultaneously removing the first solvent and the second solvent.

Images