Liquid composition, insulation resin layer, electrode for electrochemical element, electrode laminate and method for producing the same, electrochemical element, electrical apparatus, and mobile body

Abstract

To provide a liquid composition capable of forming a resin layer excellent in curl depression effect by volume shrinkage.SOLUTION: A liquid composition includes: a polymerizable compound expressed by a (meth)acrylic acid ester, or a di(meth)acrylic acid ester polymerizable compound having a specific structural unit; a non-crosslinkable resin composed of an acrylic acid ester; and a solvent. The solvent is a mixed solvent in which the polymerizable compound as a soluble good solvent and the polymerizable compound as an insoluble poor solvent. The solvent satisfies the following formula (1). A mix proportion X in the formula (1) is a content ratio based on a mass of the good solvent of the mixed solvent by percentage. A polymerizable compound soluble point is a minimum content ratio based on a mass of the good solvent of the mixed solvent in which the polymerizable compound is soluble by percentage.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid composition, an insulating resin layer, an electrode for an electrochemical element, an electrode laminate and a method for manufacturing the same, an electrochemical element, an electric device, and a moving body.

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 are also superior in terms of performance because they enable rapid charging. For this reason, it is expected that the demand will increase, such as for mounting on electric vehicles. In addition, the need for thin batteries for various wearable devices and medical patches is increasing, and the requirements for all-solid-state secondary batteries are diversifying.

[0003] As an all-solid-state secondary battery, for example, for the purpose of providing a solid battery that can suppress cracks generated during lamination pressing during manufacturing and short circuits due to tab contact, a positive electrode for a solid battery including a positive electrode current collector and a positive electrode active material layer containing a positive electrode active material formed on the positive electrode current collector has been reported, in which active material layer guides are arranged on two sides of the outer peripheral portion of the positive electrode active material layer (see, for example, Patent Document 1).

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a liquid composition capable of forming a resin layer excellent in curl suppression effect during film formation.

Means for Solving the Problems

[0005] The liquid composition of the present invention as a means for solving the problems is a liquid composition containing a polymerizable compound represented by General Formula (1) or General Formula (2), a non-crosslinked resin having a structural unit represented by General Formula (3), and a solvent,

Chemical Formula

Chemical formula

Chemical formula

Number

Advantages of the Invention

[0006] According to the present invention, it is possible to provide a liquid composition capable of forming a resin layer excellent in curl suppression effect during film formation.

Brief Description of the Drawings

[0007]

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

Embodiments for Carrying Out the Invention

[0008] Conventionally, when manufacturing an all-solid-state battery, for the purpose of improving the performance of the all-solid-state battery, that is, for the purpose of obtaining an all-solid-state battery having a high density, a laminate including a positive electrode, a solid electrolyte layer, and a negative electrode may be pressed at a very high pressure. At this time, there has been a concern that damage such as cracks may occur in the solid electrolyte layer.

[0009] In order to prevent damage in such all-solid-state batteries, a positive electrode for a solid battery provided with an active material layer guide has been proposed as in the invention described in Patent Document 1. Since the active material layer guide is provided to prevent short circuits, it is required to have insulation and to have a thickness comparable to that of the electrode mixture layer. In addition, since the active material layer guide is required to have a certain degree of viscoelasticity so as to withstand high-pressure pressing, it is preferably derived from a resin. When forming the active material layer guide by applying and curing a liquid composition in which a resin is dissolved, it is necessary to apply it with a liquid film thickness thicker than the desired thickness of the active material layer guide. At this time, since dripping at the edge end is a concern, it is common to use a photocurable liquid composition as the liquid composition when producing the active material layer guide.

[0010] The photocurable liquid composition often consists of a photoinitiator and an acrylic polyfunctional polymerizable compound. In the case of photocuring using such a photocurable liquid composition containing a polyfunctional polymerizable compound, in the process of the liquid composition changing from a liquid to a solid, a large number of polymerizable compounds polymerize into one molecule, so volume shrinkage occurs due to the gap between the van der Waals distance and the covalent bond distance. Also, when curing in a state where a diluting solvent is contained, since it polymerizes in a state greatly swollen by impregnation with the diluting solvent, volume shrinkage occurs in the solvent removal step. These volume shrinkages have raised concerns that peeling of the active material layer guide from the substrate, curling phenomena where the substrate warps up, and damage to the adjacent electrode mixture layer may occur as a result.

[0011] For the purpose of suppressing such volume shrinkage, adding a filler or an additive liquid to the liquid composition has been widely carried out (see, for example, Non-Patent Document 1). In particular, when using an additive liquid (generally called a solvent) having a boiling point of 300°C or lower, the additive liquid can be removed by heating and drying under normal pressure. However, currently, the difference in the volume shrinkage suppression effect accompanying changes in the solvent type has not been clearly presented.

[0012] Also, in the case of a material system specialized for all-solid-state secondary batteries, the liquid composition often contains a monomer and a nonpolar solvent with relatively weak intermolecular interactions, and such a liquid composition tends to have a lower viscosity. There is concern that a liquid film formed using a low-viscosity liquid composition flows easily on a substrate and is difficult to form a thick liquid film. For example, in the active material layer guide described in Patent Document 1, a film thickness equivalent to that of the active material layer (for example, 100 μm or more) is required for the purpose of suppressing short circuits, but it may be difficult to satisfy this requirement with a low-viscosity liquid composition.

[0013] It is generally known that adding a resin to a liquid composition increases its viscosity (see, for example, Non-Patent Document 2). However, for many resins, since the shape of the resin layer changes during volume contraction, there is concern that a resin layer with the desired shape cannot be obtained, or that the resin layer peels off from the substrate due to deformation of the resin layer caused by volume contraction.

[0014] The liquid composition of the present invention can sufficiently eliminate various concerns in the prior art. More specifically, it is possible to realize a liquid composition capable of forming a resin layer having an excellent curl suppression effect during film formation.

[0015] The details of the present invention are described below.

[0016] (Liquid Composition) As a first aspect of the liquid composition of the present invention, a liquid composition comprising a polymerizable compound represented by general formula (1) or general formula (2), a non-crosslinked resin having a structural unit represented by general formula (3), and a solvent, wherein the solvent is a mixed solvent comprising a good solvent in which the polymerizable compound is soluble and a poor solvent in which the polymerizable compound is insoluble, and the solvent satisfies formula (1).

[0017]

Chemical formula

[0018]

Chemical formula

[0019]

Chemical formula

[0020]

Number

[0021] As a second aspect of the liquid composition of the present invention, there is provided a liquid composition containing a polymerizable compound represented by general formula (1) or general formula (2), a non-crosslinked resin having a structural unit represented by general formula (3), and a solvent, wherein the polymerizable compound is a mixed compound containing a soluble polymerizable compound soluble in the solvent and an insoluble polymerizable compound insoluble in the solvent, and the polymerizable compound satisfies formula (2).

[0022]

Chemical formula

[0023]

Chemical formula

[0024]

Chem.

[0025]

Math.

[0026] In this specification, the "liquid composition of the first aspect" and the "liquid composition of the second aspect" may sometimes be simply referred to as the "liquid composition". In this specification, the "polymerizable compound represented by general formula (1) or general formula (2)" may sometimes be simply referred to as the "polymerizable compound". In this specification, the "non-crosslinked resin having a structural unit represented by general formula (3)" may sometimes be simply referred to as the "non-crosslinked resin".

[0027] <Polymerizable Compound> The polymerizable compound in the present invention is a compound having a plurality of monosubstituted ethylene, 1,1-disubstituted ethylene, 1,2-disubstituted ethylene, and / or diene compounds, which is represented by general formula (1) or general formula (2) and is capable of radical polymerization.

[0028]

Chem.

[0029] [Chemical formula] (In general formula (2), R3 and R4 represent a hydrogen atom or a methyl group.)

[0030] As n in general formula (1), from the viewpoint of curl suppression occurring during the curing of the liquid composition, 2 or 3 is preferable, and 2 is more preferable.

[0031] From the viewpoint of obtaining a more excellent curl suppression effect, the liquid composition of the present invention preferably contains a polymerizable compound in which R2 in general formula (1) is a polyester chain or a polymerizable compound represented by general formula (2), and more preferably contains a polymerizable compound in which R2 in general formula (1) is a polycaprolactone chain.

[0032] From the viewpoint of the polymerization rate, the polymerizable compound is preferably a compound having an acrylic group, that is, R1 in general formula (1) and R3 and R4 in general formula (2) are hydrogen atoms. Generally, since an acrylic group has high radical polymerizability, a cured product can be obtained in a short time by using a photopolymerization initiator or a thermal polymerization initiator in combination in the liquid composition. Although a cured product can be obtained without using a polymerization initiator in combination, when a polymerizable compound having an acrylic group is used as the polymerizable compound, that is, when R1 in general formula (1) and R3 and R4 in general formula (2) are hydrogen atoms, from the viewpoints of the polymerization rate and the equipment cost, it is preferable to use the polymerizable compound in combination with a thermal polymerization initiator or a photopolymerization initiator in the liquid composition, and it is more preferable to use the polymerizable compound in combination with a photopolymerization initiator.

[0033] Specific examples of the polymerizable compounds include bifunctional alkyl acrylates, neopentyl glycol hydroxypivalate 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 glycerol acrylates, trifunctional isocyanate acrylates, tetrafunctional pentaerythritol acrylates, tetrafunctional ditrimethylolpropane acrylates, tetrafunctional diglycerol 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 glycerol 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.

[0034] Examples of the bifunctional alkyl acrylate include, by trade name, 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.

[0035] 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.

[0036] Examples of the bifunctional 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.

[0037] Examples of the bifunctional 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.

[0038] Examples of the bifunctional 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.

[0039] 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.), and the like.

[0040] 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.), and the like.

[0041] Examples of bifunctional acrylic acid polymer ester acrylates include, for example, by trade name, Biscoat #230D (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

[0042] 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.), and the like.

[0043] 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.), and the like.

[0044] 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.), and the like.

[0045] Examples of trifunctional isocyanate acrylates include, for example, under the trade names NK Ester A-9300, A-9200YN (both manufactured by Shin-Nakamura Chemical Co., Ltd.), etc.

[0046] Examples of tetrafunctional pentaerythritol acrylates include, for example, under the trade names 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.

[0047] Examples of tetrafunctional ditrimethylolpropane acrylates include, for example, under the trade name NK Ester AD-TMP (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc.

[0048] Examples of tetrafunctional diglycerin tetraacrylates include, for example, under the trade name Light Acrylate DGE-4E (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0049] Examples of hexafunctional dipentaerythritol hexaacrylates include, for example, under the trade name Light Acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0050] 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 Co., Ltd.), 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.

[0051] As the polymerizable compound, at least one polymerizable compound represented by the general formula (1) or the general formula (2) 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 the general formula (2), or may contain two or more different polymerizable compounds represented by the general formula (1) or the general formula (2). In any case, in addition to the polymerizable compound represented by the general formula (1) or the general formula (2), a polymerizable compound that does not satisfy the general formula (1) or the general formula (2) 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) or the general formula (2). 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) or the general formula (2).

[0052] The photoinitiator is not particularly limited and can be appropriately selected according to the purpose. For example, alkylphenone-based photoinitiators, acylphosphine sulfite-based photoinitiators, oxime ester-based photoinitiators, etc. can be mentioned. 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 (above, manufactured by IGM Resins B.V.), etc. Specific examples of the acylphosphine sulfite-based photoinitiator include, by trade name, Omnirad TPO, Omnirad 819 (above, manufactured by IGM Resins B.V.), etc. Specific examples of the oxime ester-based photoinitiator include, by trade name, Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, manufactured by BASF Japan), etc.

[0053] The content of the photoinitiator 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.

[0054] <Non-crosslinked resin> The non-crosslinked resin in the present invention is a non-crosslinked polymer compound having a structural unit represented by the general formula (3). In other words, the non-crosslinked resin in the present invention is a non-crosslinked polymer compound containing an acrylic monomer having an acrylate group as a structural unit.

[0055] [Chemical formula] (In the general formula (3), R6 represents an alkyl group.)

[0056] Here, the "non-crosslinked polymer compound" means a polymer compound having no three-dimensional network structure formed by crosslinking, and does not include branched polymers, graft polymers, dendrimers, etc. that do not have a network structure.

[0057] Regarding q 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. 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.

[0058] Regarding R6 in the structural unit represented by the general formula (3), as long as it is an alkyl group, there is no particular limitation 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 R6 in the structural unit represented by the general formula (3) 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 even when there are processes such as compression in the process of manufacturing an electrochemical element, and can suppress peeling from the substrate.

[0059] As the non-crosslinked resin, it suffices that it contains at least one kind of structural unit represented by the general formula (3). That is, the non-crosslinked resin contained in the liquid composition may contain only the structural unit represented by the general formula (3), or may contain two or more different structural units represented by the general formula (3). In any case, in addition to the structural unit represented by the general formula (3), other structural units that do not satisfy the general formula (3) may be contained.

[0060] 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 general formula (3) and other structural units. 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.

[0061] The other structural units are not particularly limited and can be appropriately selected according to the purpose, but from the viewpoint of excellent curl suppression effect due to volume shrinkage, it is preferably a structural unit represented by the general formula (4).

[0062]

Chemical formula

[0063] Regarding r in the structural unit represented by the general formula (4), there is no particular limitation and it can be appropriately selected according to the purpose, but 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.

[0064] The copolymer of 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. There is no particular limitation on the method for obtaining the block copolymer, and it 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, and methods for stepwise producing block polymers using polycondensation or addition reactions for terminal diols and diamine polymers can be mentioned.

[0065] As the copolymer of 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, by trade name, Clarity LA4285, Clarity LA2270, Clarity LA2250, Clarity LA2140, Clarity LA2330, Clarity LA3320, Clarity LA3710, Clarity LK9243 (all manufactured by Kuraray Co., Ltd.), etc.

[0066] 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.

[0067] <Solvent> The solvent in the present invention is an organic solvent having a water content of 1 w% or less, and a low-polarity hydrophobic solvent with low reactivity with the solid electrolyte layer is preferred. The solvent is expected to act as a buffer for curing shrinkage because there is no variation in the intermolecular distance between solvents or between the resin and the solvent during polymerization.

[0068] Specific examples of the solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, anisole, and phenetole; hydrocarbon solvents such as hexane, heptane, nonane, octane, decane, methane, 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, isopentyl isovalerate, 2-ethylhexyl acetate, hexyl butyrate, ethyl benzoate, hexyl hexanoate, amyl n-octanoate, and hexyl acetate; and petroleum-based mixed solvents.

[0069] Examples of the petroleum-based mixed solvents include those sold under the trade names 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 Balchem Co., Ltd.).

[0070] The content of the solvent is not particularly limited and can be appropriately selected according to the purpose. From the perspective 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. From the perspective of film thickness control, it is preferably 70% by mass or less.

[0071] From the perspective of the diversity of the selection of the polymerizable compound, a plurality of solvents may be combined and used as the solvent in the present invention.

[0072] [First Aspect of the Liquid Composition] 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).

[0073]

Number

[0074] The "good solvent" in this specification refers to a solvent in which the polymerizable compound is soluble. The "poor solvent" in this specification refers to a solvent in which the polymerizable compound is insoluble. When the "mixed solvent" is described in this specification, it refers to a solvent containing a good solvent and a poor solvent. The "mixing ratio X" in this specification is the content ratio based on the mass of the good solvent in the mixed solvent, expressed as a percentage. The "polymerizable compound solubility point" in this specification is the minimum content ratio based on the mass of the good solvent in the mixed solvent in which the polymerizable compound is soluble, expressed as a percentage.

[0075] Here, the "soluble" in the first aspect will be explained. "Soluble" means that after mixing the solvent and the polymerizable compound and ultrasonically stirring for 15 minutes with an ultrasonic stirrer (USS-1), no cloudiness or phase separation occurs after standing at a predetermined temperature for 10 minutes. The predetermined temperature is not particularly limited as long as it is the environmental temperature during actual use, and for example, 25 °C can be mentioned. Note that the determination of soluble / insoluble is made according to the composition of the liquid composition. For example, the following patterns 1 to 3 can be mentioned.

[0076] [Pattern 1] In the case of a liquid composition containing one kind of polymerizable compound represented by the general formula (1) or the general formula (2) and two kinds of solvents (mixed solvent), the determination of soluble / insoluble is made based on the solvent ratio in the liquid composition containing 10 g of the mixed solvent and 1 g of the polymerizable compound represented by the general formula (1) or the general formula (2).

[0077] [Pattern 2] In the case of a liquid composition containing two polymerizable compounds (mixed compound) represented by the general formula (1) or the general formula (2) and two solvents (mixed solvent), the solubility / insolubility is determined based on the solvent ratio in the liquid composition containing 10 g of the mixed solvent and 1 g of the mixed compound.

[0078] [Pattern 3] In the case of a liquid composition containing two polymerizable compounds (mixed compound) represented by the general formula (1) or the general formula (2), a polymerizable compound that does not satisfy the general formula (1) or the general formula (2), and two solvents (mixed solvent), the solubility / insolubility is determined based on the monomer ratio in the liquid composition containing 10 g of the mixed solvent and 1 g of a mixture of the mixed compound and the polymerizable compound that does not satisfy the general formula (1) or the general formula (2).

[0079] Formula (1) can also be transformed into formula (1)'.

[0080]

Number

[0081] Since the liquid composition of the first form satisfies the formula (1) or the formula (1)', a resin layer having a high porosity can be formed based on the phase separation rate, 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 the formula (1)' approaches 0, curling due to volume shrinkage can be more effectively suppressed.

[0082] [Second aspect of the liquid composition] 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 the formula (2) from the viewpoint of the curling suppression effect due to volume shrinkage.

[0083]

Number

[0084] As used herein, the "soluble polymerizable compound" refers to a polymerizable compound that is soluble in a solvent. The "insoluble polymerizable compound" as used herein refers to a polymerizable compound that is insoluble in a solvent. When the term "mixed compound" is used herein, it refers to a polymerizable compound containing a soluble polymerizable compound and an insoluble polymerizable compound. The "mixing ratio Y" as used herein is a content ratio based on the mass of the insoluble polymerizable compound in the mixed compound, expressed as a percentage. The "solvent solubility point" as used herein is the minimum content ratio based on the mass of the insoluble polymerizable compound in a mixed compound that is soluble in a solvent, expressed as a percentage.

[0085] Here, the "soluble" in the second aspect will be described. "Soluble" means that when a polymerizable compound and a solvent are mixed and ultrasonically stirred with an ultrasonic stirrer (USS-1) for 15 minutes, and then left standing at a predetermined temperature for 10 minutes, 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 include 25°C. Note that the determination of soluble / insoluble is made according to the composition of the liquid composition. For example, the following patterns 4 to 6 can be mentioned.

[0086] [Pattern 4] In the case of a liquid composition containing one polymerizable compound represented by the general formula (1) or the general formula (2) and two solvents (mixed solvent), the determination of soluble / insoluble is made based on the monomer ratio in the liquid composition containing 10 g of the polymerizable compound represented by the general formula (1) or the general formula (2) and 1 g of the mixed solvent.

[0087] [Pattern 5] In the case of a liquid composition containing two polymerizable compounds (mixed compound) represented by the general formula (1) or the general formula (2) and two solvents (mixed solvent), the determination of soluble / insoluble is made based on the solvent ratio in the liquid composition containing 10 g of the mixed compound and 1 g of the mixed solvent.

[0088] [Pattern 6] In the case of a liquid composition containing two polymerizable compounds (mixed compound) represented by the general formula (1) or the general formula (2), a polymerizable compound that does not satisfy the general formula (1) or the general formula (2), and two solvents (mixed solvent), based on the monomer ratio in the liquid composition containing 10 g of a mixture of the mixed compound and the polymerizable compound that does not satisfy the general formula (1) or the general formula (2) and 1 g of the mixed solvent, a determination of soluble / insoluble is made.

[0089] Formula (2) can also be transformed into formula (2)'.

[0090]

Number

[0091] Since the second form of the liquid composition can form a resin layer having a high porosity based on the phase separation rate by satisfying the formula (2) or the formula (2)', the volume shrinkage during the curing of the liquid composition can be suppressed, and a high-quality resin layer can be formed. Also, as the "mixing ratio Y - solvent solubility point" in the formula (2)' approaches 0, curling due to volume shrinkage can be more suppressed.

[0092] <Manufacturing method of liquid composition> The manufacturing method of the liquid composition in the present invention is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably prepared through steps such as a step of mixing polymerizable compounds, a step of mixing polymerizable compounds with a solvent, a step of dissolving a polymerization initiator in a solvent, a step of dissolving a non-crosslinked resin in the liquid composition, and a step of stirring to obtain a uniform solution.

[0093] (Insulating resin layer) The insulating resin layer of the present invention is formed by curing a liquid composition and has a porous structure. Since the liquid composition is the same as that described in the item of (liquid composition), duplicate descriptions are omitted.

[0094] 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, when forming an insulating resin layer with an average thickness of 100 μm or more, it is more effective.

[0095] 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 both the resin phase and the pore phase are three-dimensional branched network continuous phases. These structures can be formed by polymerization-induced phase separation (see, for example, Japanese Patent Application Laid-Open No. 2003-1911628, International Publication No. 97-044363, Japanese Patent Application Laid-Open No. 2005-298757, Japanese Patent Application Laid-Open No. 2010-513589, Japanese Patent Application Laid-Open No. 2001-163907, and Japanese Patent Application Laid-Open No. 2001-138504, etc.).

[0096] [Polymerization-induced phase separation] Polymerization-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 in the process of polymerization of the polymerizable compound and the solvent are not compatible, representing a state in which phase separation occurs. There are other methods to obtain a porous structure by phase separation, but the porous structure having a co-continuous structure obtained by the polymerization-induced phase separation method has the merit of high resistance to chemicals and heat. Also, compared with other methods, it has merits such as a 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 etc. fill the pores and has a co-continuous structure by the resin skeleton. When this is dried, the solvent etc. are removed, and a porous resin having a co-continuous structure of a three-dimensional network structure remains.

[0097] Therefore, as a preferred form of the ink, it is preferable that the liquid composition is a mixture of a polymerizable compound (monomer) and a solvent, and that the resin after polymerization is insoluble in the solvent or does not form a gel or a sol.

[0098] As a method for confirming that the insulating resin layer has a co-continuous structure and the pores communicate with each other, for example, there is a method of observing an image of a cross-section of the insulating resin layer by a scanning electron microscope (SEM) or the like and confirming that the connection between the pores is continuous. [Example of image observation method using scanning electron microscope (SEM)] After subjecting the insulating resin layer to osmium staining, impregnating it with an epoxy resin under vacuum, cutting out the internal cross-sectional structure with a focused ion beam (FIB), and observing it using a scanning electron microscope (SEM).

[0099] The porosity of the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose, but 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 [Example of image observation method using scanning electron microscope (SEM)].

[0100] The air permeability of the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose, but 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 densitometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.) or the like. As an example, it may be determined that the pores communicate with each other when the air permeability is 1,000 seconds / 100 mL or less.

[0101] 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 determined, for example, from a cross-sectional photograph taken with a scanning electron microscope (SEM).

[0102] 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 less 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.

[0103] 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. Examples include a method of adjusting the content of the polymerizable compound in the liquid composition, a method of adjusting the content of the solvent in the liquid composition, and a method of adjusting the irradiation conditions of active energy rays.

[0104] The volume resistivity of the insulating resin layer is not particularly limited and can be appropriately selected according to the purpose. However, 1012 It is preferably at Ω·cm or more. Further, it is preferable to add a conductive filler or the like to form a resin layer having no conductive path.

[0105] (Electrode for Electrochemical Element) The electrode for an electrochemical element of the present invention has a substrate, an electrode composite layer disposed on the substrate, and an insulating resin layer disposed on the outer peripheral portion of the electrode composite layer. The insulating resin layer is formed by curing a liquid composition and has a porous structure. Since 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), duplicate descriptions are omitted. In this specification, the negative electrode and the positive electrode may be referred to as "electrodes", the electrode substrate for the negative electrode and the electrode substrate for the positive electrode may be referred to as "substrates", and the negative electrode composite layer and the positive electrode composite layer may be referred to as "electrode composite layers". Further, when the first electrode is a negative electrode, the second electrode refers to a positive electrode, and when the first electrode is a positive electrode, the second electrode refers to a negative electrode.

[0106] (Electrode Stack) The electrode for an electrochemical element of the present invention can be suitably applied to an electrode stack. 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. Since 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), duplicate descriptions are omitted.

[0107] Here, an embodiment of the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments at all. In each drawing, the same reference numerals are assigned to the same components, and redundant descriptions may be omitted. Also, the number, position, shape, etc. of the components are not limited to those of this embodiment, and may be set to the preferred number, position, shape, etc. for implementing the present invention.

[0108] 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 includes 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. However, the electrode composite layer 20 and the insulating resin layer 10 may be provided on both opposite sides of the first substrate 21.

[0109] 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 side 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 sides of the first substrate 21. Also, as shown in FIG. 2B, an adhesive layer 22 containing a metal that alloyizes with lithium may be provided between the substrate 21 and the electrode composite layer 20.

[0110] <Substrate> The substrate is not particularly limited as long as it has electronic conductivity and is stable against the applied potential, and can be appropriately selected according to the purpose. For example, aluminum foil, copper foil, stainless steel foil, titanium foil, etched foil obtained by etching them to form fine holes, carbon-coated foil with a surface layer coated with a carbon-containing resin layer, a perforated substrate used for a lithium-ion capacitor, and the like can be mentioned.

[0111] <Electrode composite layer> The electrode composite layer (hereinafter sometimes referred to as the "active material layer") is not particularly limited and can be appropriately selected according to the purpose. For example, it may contain an active material (negative electrode active material or positive electrode active material), and further, if necessary, it may contain a conductive aid, a binder, a dispersant, a solid electrolyte, and other components. 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, it is preferable that the electrode composite layer in the electrode for an electrochemical element or the electrode laminate contains an active material and a sulfide solid electrolyte.

[0112] 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 the solid electrolyte contained in the solid electrolyte layer, and more preferably a material having the same composition as the solid electrolyte layer. Since the electrode composite material layer having the opening 23 is easy to control in coating, it can be suitably manufactured by using an inkjet as the electrode composite material layer forming means.

[0113] <<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.

[0114] - Positive electrode active material - The positive electrode active material is not particularly limited as long as it is a material capable of reversibly occluding and releasing 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, and the like.

[0115] As the alkali metal-containing transition metal compound, a polyanion compound having XO 4 tetrahedra (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 lithium vanadium phosphate is more preferable from the viewpoints of lithium diffusion coefficient and output characteristics. When using a polyanion compound, it is preferably surface-coated and complexed with a conductive aid such as a carbon material in terms of electron conductivity.

[0116] It is preferable that at least a part of the surface of the alkali metal-containing transition metal compound is 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 depending on the purpose. For example, an oxide 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 lithium ion conductive oxides 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 MoO 4 and Li 2 WO 4 Among these, Li 4 Ti 5 O 12 , Li 2 ZrO 3 , or LiNbO 3 is preferred. The lithium ion conductive oxide may be a composite oxide. As the composite oxide, any combination of lithium ion conductive oxides may be used. For example, Li 4 SiO 4 -Li 3 BO 3 , and Li 4 SiO 4 -Li 3 PO4 Examples include the following.

[0117] - Negative electrode active material - 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 suitably used as the negative electrode active material.

[0118] <<Conductive aid>> The conductive aid is not particularly limited and 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 a conductive aid other than the carbon material, for example, metal particles such as aluminum and metal fibers can be used. The conductive aid may be pre-compounded with the active material.

[0119] 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, more preferably 8% by mass or less, based on the total amount of the liquid composition for the electrode mixture 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 mixture layer, it is suitable because the stability of the liquid composition for the electrode mixture layer is improved. When the content of the conductive assistant with respect to the active material is 8% by mass or less based on the total amount of the liquid composition for the electrode mixture layer, it is suitable because the stability of the liquid composition for the electrode mixture layer is further improved.

[0120] <<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, the binder preferably has a low tendency to increase the viscosity of the liquid composition for forming the electrode mixture layer.

[0121] As the binder, a high molecular compound can be used. Examples of the high molecular compound include 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 methacrylic acid (PMMA), polyethylene vinyl acetate (PEVA), and the like.

[0122] The content of the binder with respect to the active material 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 suitable because the active material can be firmly bound to the substrate.

[0123] <<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. For example, 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, polyalkylene polyamine-based, etc.; low-molecular-weight dispersants such as alkyl sulfonic acid-based, quaternary ammonium-based higher alcohol alkylene oxide-based, polyhydric alcohol ester-based, alkyl polyamine-based, etc.; inorganic dispersants such as polyphosphate-based dispersants, etc. can be mentioned.

[0124] <<Solid Electrolyte>> As the solid electrolyte, there is no particular limitation as long as it is a solid substance having electron insulation and showing ionic conductivity. However, from the viewpoint of having high ionic conductivity, sulfide solid electrolytes and oxide-based solid electrolytes are preferred.

[0125] 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. can be mentioned. 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 )) 3 )(0.1 ≦ x ≦ 0.4), LLT (Li having a perovskite-type crystal structure 0.33 La 0.55 TiO 3 ), amorphous LIPON (Li 2.9 PO 3.3 N 0.4 ), etc. can be mentioned. These solid electrolytes may be used alone or in combination of two or more.

[0126] 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 glass ceramics, etc. may be mentioned.

[0127] <Insulating resin layer> In the electrode for an electrochemical element and the electrode laminate of the present invention, the insulating resin layer is disposed on the outer peripheral portion of the electrode mixture layer provided on the substrate. Further, the insulating resin layer may be disposed on the substrate and on the outer peripheral portion of the substrate.

[0128] Here, an embodiment of the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments at all.

[0129] 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 mixture layer 20. In FIG. 4, the insulating resin layer 10 is provided adjacent to two long sides of the outer peripheral portion of the electrode mixture layer 20 and two corners of the long sides. In FIG. 5, the insulating resin layer 10 is provided continuously adjacent to all four sides of the outer peripheral portion of the electrode mixture layer 20. Note that the insulating resin layer may be provided adjacently intermittently.

[0130] As used herein, "disposed on the outer peripheral portion of the electrode mixture layer" means that an insulating resin layer may be disposed on at least two sides of the outer peripheral portion of the electrode mixture layer, or on three sides of the outer peripheral portion of the electrode mixture layer, or on all four sides of the outer peripheral portion of the electrode mixture layer. Further, the insulating resin layer may have a recess or a notch for protruding an electrode tab on any side.

[0131] As used herein, "disposed on the outer peripheral portion of the substrate" means that the insulating resin layer may be disposed so as to include the end portion of the substrate, or the insulating resin layer may be disposed so that the substrate is exposed as shown in FIGS. 3 to 5.

[0132] FIG. 6A is a schematic cross-sectional view (part 1) showing the positional relationship between the insulating resin layer and the electrode mixture layer in the 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 mixture layer in the 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 mixture layer in the 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 mixture layer in the electrode for an electrochemical element according to an embodiment of the present invention. The insulating resin layer 10 may be spaced apart from the electrode mixture layer 20 as shown in FIG. 6A, or may be in contact with the electrode mixture 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 mixture layer 20. When the insulating resin layer 10 is in contact with the electrode mixture layer 20, the opposing surfaces of the insulating resin layer 10 and the electrode mixture layer 20 may be in contact with each other in a partial region as shown in FIG. 6B, or the opposing surfaces of the insulating resin layer 10 and the electrode mixture layer 20 may be in full contact as shown in FIGS. 6C to 6D. Here, when the electrode mixture layer 20 is provided after the insulating resin layer 10 is formed, the electrode mixture 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 mixture layer 20 is formed, the insulating resin layer 10 overlaps the electrode mixture layer 20 side as shown in FIG. 6D.

[0133] FIG. 7 is a schematic top view showing the positional relationship between the insulating resin layer and the electrode mixture 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 mixture layer 20 are separated, the distance d between the insulating resin layer 10 and the electrode mixture layer 20 (the distance between the outer peripheral portion of the electrode mixture 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 mixture layer 20 are adjacent is set as d = 0, and the distance d between the electrode mixture layer and the insulating resin layer is the distance between the arrows shown in FIG. 7. As shown in FIGS. 6C to 6D, when the insulating resin layer overlaps the electrode mixture layer side and when the electrode mixture layer overlaps the insulating resin layer side, it is indicated by a negative value.

[0134] The distance d between the insulating resin layer 10 and the electrode mixture layer 20 (the distance between the outer peripheral portion of the electrode mixture 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 mixture layer 20 is 10 mm or less, the insulating resin layer and the electrode mixture layer are likely to come into contact with each other after the pressing process, so that the solid electrolyte layer can be uniformly formed on the insulating resin layer and the electrode mixture layer, which is suitable. Further, when the solid electrolyte layer is pressed, pressure can be uniformly applied to the solid electrolyte layer, which is suitable.

[0135] 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 mixture 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 mixture 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 mixture layer in the electrode for an electrochemical element according to an embodiment of the present invention. Regarding the electrode laminate of the present invention, there is no particular limitation on the relationship between the average thickness A of the electrode mixture layer and the average thickness B of the insulating resin layer, and it can be appropriately selected according to the purpose. For example, as shown in FIGS. 8A to 8C, A < B, A = B, or A > B may be possible. Among these, it is preferable that A = B or A < B.

[0136] The average thickness of the insulating resin layer is not particularly limited and can be appropriately selected according to various conditions such as the average thickness of the electrode mixture layer. However, it is preferably 1.0 μm or more and 150.0 μm or less, and more preferably 10.0 μm or more and 100.0 μm or less. When the average thickness of the insulating resin layer is 10.0 μm or more, it is possible to disperse the pressure load during pressing and prevent short-circuiting between the positive electrode and the negative electrode, which is preferable. When the average thickness of the insulating resin layer is 100.0 μm or less, it is possible to manufacture an electrochemical element with high density and excellent battery characteristics.

[0137] Regarding the electrode laminate of the present invention, the ratio (B / A) of the average thickness B of the insulating resin layer to the average thickness A of the electrode mixture layer is not particularly limited and can be appropriately selected according to the purpose. However, it is preferably 0.97 or more and 1.03 or less, and more preferably 0.98 or more and 1.02 or less.

[0138] There is no particular limitation on the method for measuring the average thickness A of the electrode mixture layer and the average thickness B of the insulating resin layer, and it can be appropriately selected according to the purpose. For example, it can be obtained by measuring the thicknesses at any three or more points and calculating the average value.

[0139] Since the insulating resin layer in the electrode laminate of the present invention has a porous structure, the thickness of the electrode mixture layer and the thickness of the insulating resin layer can be easily and highly accurately controlled by pressing. In addition, since the insulating resin layer can be formed by a coating and polymerization-induced phase separation method, its thickness can be easily controlled. If the insulating resin layer has a co-continuous structure, the pressure generated during pressing can be efficiently dispersed, suppressing the occurrence of defects such as breakage of the insulating resin layer and unevenness in height difference, and a high-quality insulating resin layer can be obtained.

[0140] The compression ratio of the insulating resin layer (after pressing at 500 MPa for 5 minutes) is not particularly limited and can be appropriately selected according to the purpose, but is preferably 1% or more and 50% or less, and more preferably 5% or more and 20% or less. When the compression ratio of the insulating resin layer is 50% or less, the strength of the insulating resin layer is improved, and the shape of the insulating resin layer can be sufficiently maintained when passing through the pressing process. When the compression ratio of the insulating resin layer is 1% or more, the pressure applied from the insulating resin layer to the solid electrolyte layer can be relaxed in the pressing process after the formation of the solid electrolyte layer.

[0141] <Solid electrolyte layer> As the solid electrolyte of the solid electrolyte layer, the materials described as the solid electrolyte of the electrode composite layer can be appropriately selected and used. 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 solid electrolyte layer is preferably a sulfide solid electrolyte layer containing a sulfide solid electrolyte.

[0142] The solid electrolyte layer may contain a binder. Examples of the binder include thermoplastic resins such as polyvinylidene fluoride (PVDF), acrylic resin, styrene-butadiene rubber, polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, etc., polyamide compounds, polyimide compounds, polyamideimide, ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), nitrile butadiene rubber (NBR), polymethyl methacrylate (PMMA), polybutyl methacrylate (PBMA), isoprene rubber, polyisobutene, polyethylene glycol (PEO), polyethylene vinyl acetate (PEVA), and the like.

[0143] (Method for manufacturing an electrode for an electrochemical element, and manufacturing apparatus for an electrode for an electrochemical element) The method for manufacturing an electrode for an electrochemical element according to the present invention may have an insulating resin layer forming step and an electrode composite layer forming step, and may have other steps as necessary. The manufacturing apparatus for an electrode for an electrochemical element according to the present invention may have a storage container, an insulating resin layer forming means, and an electrode composite layer forming means, and may have other means as necessary.

[0144] <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 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.

[0145] <Insulating resin layer forming step, and insulating resin layer forming means> The insulating resin layer forming step is a step of forming an insulating resin layer on a substrate. The insulating resin layer forming step preferably has a liquid composition applying step and a liquid composition curing step. The insulating resin layer forming means is a means for forming an insulating resin layer on a substrate. The insulating resin layer forming means preferably has a liquid composition applying means and a liquid composition curing means. The insulating resin layer forming step can be suitably carried out by the insulating resin layer forming means, the liquid composition applying step can be suitably carried out by the liquid composition applying means, and the liquid composition curing step can be suitably carried out by the liquid composition curing means.

[0146] <<Liquid composition applying step, and liquid composition applying means>> The liquid composition applying step is a step of applying a liquid composition onto a substrate. The liquid composition applying means is a means for applying the liquid composition contained in a storage container onto a substrate. There are no particular restrictions 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.

[0147] <<Liquid composition curing step, and liquid composition curing means>> The liquid composition curing step is a step of applying heat or light to the liquid composition to cure it. The liquid composition curing means is a means for applying heat or light to the liquid composition to cure it. 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.

[0148] In the liquid composition curing process and as the light in the liquid composition curing means, it is preferably an active energy ray. As the active energy ray, any ray can be used as long as it can impart the energy necessary for promoting the polymerization reaction of the polymerizable compound in the liquid composition, and it is not particularly limited. Examples include ultraviolet rays, electron beams, α-rays, β-rays, γ-rays, X-rays, and the like. Among these, ultraviolet rays are preferred. When using a particularly high-energy light source, the polymerization reaction can proceed without using a polymerization initiator.

[0149] There is no particular limitation on the irradiation intensity of the active energy ray, and it can be appropriately selected according to the purpose. However, it is preferably 1 W / cm 2 or less, more preferably 300 mW / cm 2 or less, and even more preferably 100 mW / cm 2 or less. Note that if the irradiation intensity of the active energy ray is too low, polymerization-induced phase separation will proceed excessively, resulting in easy occurrence of variations and coarsening of the porous structure. In addition, since the productivity decreases as the irradiation time becomes longer, it is preferably 10 mW / cm 2 or more, more preferably 30 mW / cm 2 or more.

[0150] <Electrode composite layer forming process and electrode composite layer forming means> The electrode composite layer forming process is a process of forming an electrode composite layer on a substrate. The electrode composite layer forming means is a means of forming an electrode composite layer on a substrate. There is no particular limitation on the electrode composite layer forming process and the electrode composite layer forming means, and they can be appropriately selected according to the purpose. For example, 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 can be mentioned. At this time, coating methods such as spraying, dispenser, die coater, and dip coating can be preferably used.

[0151] <Other processes, other means> As other steps in the method for manufacturing an electrode for an electrochemical element, there are no particular limitations as long as the effects of the present invention are not impaired, and they can be appropriately selected according to the purpose. For example, a solvent removal step and the like can be mentioned. As other means in the apparatus for manufacturing an electrode for an electrochemical element, there are no particular limitations as long as the effects of the present invention are not impaired, and they can be appropriately selected according to the purpose. For example, a solvent removal means and the like can be mentioned.

[0152] <<Solvent removal step, solvent removal means>> The solvent removal step is a step of removing the solvent from the insulating resin layer. The solvent removal means is a means for removing the solvent from the insulating resin layer. There are no particular limitations 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 them may be installed. There are no particular limitations 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 limited, but from the viewpoint of the energy used, 70°C to 150°C is preferable.

[0153] In the method for manufacturing an electrode for an electrochemical element, the order of the insulating resin layer formation step and the electrode mixture layer formation step is not particularly limited. That is, the electrode mixture layer formation step may be carried out before the insulating resin layer formation 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 formation step, the insulating resin layer formation step, and the solvent removal step. Similarly, the electrode composite layer forming step may be performed after the insulating resin layer forming step. After forming the insulating resin layer on the outer peripheral portion of the substrate, the electrode composite layer may be formed inside the insulating resin layer. In that case, the method for manufacturing the electrode for the electrochemical element is performed in the order of the insulating resin layer forming step, the electrode composite layer forming step, and the solvent removing step.

[0154] (Method for manufacturing an electrode laminate, and manufacturing apparatus for an electrode laminate) The method for manufacturing the electrode laminate of the present invention includes an insulating resin layer forming step, an electrode composite layer forming step, and a solid electrolyte layer forming step, and may include a pressing step and other steps as necessary. The manufacturing apparatus for the electrode laminate according to the present invention preferably includes a storage container, an insulating resin layer forming means, an electrode composite layer forming means, and a solid electrolyte layer forming means, and may include a pressing means and other means as necessary. Note that the storage container, the insulating resin layer forming step, the insulating resin layer forming means, the electrode composite layer forming step, the electrode composite layer forming means, other steps, and other means are the same as those described in the item of (Method for manufacturing an electrode for an electrochemical element, and manufacturing apparatus for an electrode for an electrochemical element), so duplicate descriptions are omitted.

[0155] <Pressing step, pressing means> The pressing step is a step of pressing the electrode composite layer and the insulating resin layer. The pressing means is a means for pressing the electrode composite layer and the insulating resin layer. The pressing step can be preferably performed by the pressing means.

[0156] There are no particular limitations on the pressing step and the pressing means, and a commercially available pressure molding apparatus can be used. The electrode composite layer and the insulating resin layer may be pressed in the substrate direction. Examples include uniaxial pressing, roll pressing, cold isostatic pressing (CIP), and hot pressing. Among these, cold isostatic pressing (CIP) that can apply isotropic pressure is preferable.

[0157] The timing for performing the pressing process is not particularly limited and can be appropriately selected according to the purpose. For example, after forming the electrode mixture layer and the insulating resin layer on the substrate, the electrode mixture layer and the insulating resin layer may be pressed, or after providing the solid electrolyte layer, pressing may be performed, or it may be performed at both timings. By performing the pressing process after forming the electrode mixture layer and the insulating resin layer on the substrate and before forming the solid electrolyte layer, the average thickness of the electrode mixture layer and the average thickness of the insulating resin layer can be made substantially equal, and even when a high pressure is applied when pressing the solid electrolyte layer provided on the electrode, the pressure load can be dispersed.

[0158] The pressing pressure is not particularly limited and can be appropriately selected according to the purpose, but it is preferably performed at a pressure that can crimp the substrate and the electrode mixture layer while densifying the electrode mixture layer. More specifically, it is preferably 1 MPa or more and 900 MPa or less, and more preferably 250 MPa or more and 700 MPa or less.

[0159] <Solid electrolyte layer forming process, and solid electrolyte layer forming means> The solid electrolyte layer forming process in the method for manufacturing the electrode laminate is a process of forming a solid electrolyte layer on the electrode mixture layer and the insulating resin layer. The solid electrolyte layer forming means in the manufacturing apparatus for the electrode laminate is means for forming a solid electrolyte layer on the electrode mixture layer and the insulating resin layer.

[0160] 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 on the electrode mixture layer and the insulating resin layer, and solidifying and drying it can be mentioned. The coating method is not particularly limited. For example, liquid ejection methods such as inkjet method, spray coating method, dispenser method, 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.

[0161] In the method for manufacturing an 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 removing 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, 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 the electrode laminate is carried out in the order of the insulating resin layer forming step, the solvent removing step, the electrode mixture layer forming step, the pressing step, and the solid electrolyte layer forming step.

[0162] [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 view showing an example of an apparatus (liquid ejection apparatus) for manufacturing an insulating resin layer for carrying out the method for manufacturing an electrode laminate according to an embodiment of the present invention. The apparatus 500 for manufacturing an insulating resin layer includes a conveyance unit 5, a printing unit 100, a polymerization unit 200, a heating unit 300, and a roller 7.

[0163] The conveyance 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 with an electrode composition layer provided thereon, or may be a substrate without an electrode composition layer. In the case of a substrate without an electrode composition layer, the electrode composition layer is provided after the insulating resin layer is formed.

[0164] -Printing section 100- The printing section 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.

[0165] The printing section 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.

[0166] 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 regions of ultraviolet rays and visible light. This is preferable because it prevents the liquid composition 6 from starting polymerization due to external light.

[0167] -Polymerization section 200- As shown in FIG. 9, in the case of photopolymerization, the polymerization section 200 includes 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.

[0168] 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 a precursor of 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 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.

[0169] 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 better 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 temperature control means capable of adjusting the temperature in order to realize stable polymerization progress conditions.

[0170] 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 include substrate heating (e.g., hot plate), IR heater, warm air heater, etc., and these may be used in combination. 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 film thickness to be formed.

[0171] 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.

[0172] -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 precursor 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.

[0173] In the heating section 300, a polymerization acceleration step of further promoting the curing (polymerization) reaction carried out in the polymerization section 200 by heating the insulating resin layer precursor with the heating device 3a, and an initiator removal step of heating and drying the photoinitiator remaining in the insulating resin layer precursor with the heating device 3a to remove it 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 precursor and the formed film thickness.

[0174] 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 method for manufacturing 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, by controlling the pump 310, the valves 311, 312, and 314, it is also possible to supply the liquid composition from the external tank 313 to the tank 307.

[0175] When using the manufacturing apparatus of an insulating resin layer, the liquid composition can be ejected at the target position of the object to which it is to be applied.

[0176] The manufacturing apparatus 500 of an insulating resin layer may be provided with a mechanism for capping the nozzle in order to prevent drying when the liquid composition 6 is not being ejected from the liquid ejection head.

[0177] 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 slender 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 on which the insulating resin layer 212 is to be formed is 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.

[0178] 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 heating heater, an infrared heater, a fan heater, etc. can be mentioned, and in the case of photo-polymerization, 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.

[0179] 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 tubes 308A and 308B, valves 311A, 311B, 312A, 312B, 314A, and 314B, and pumps 310A and 310B.

[0180] [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.

[0181] 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 covering the width of the recording area of a substrate of 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 the present 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.

[0182] The transfer drum 4000 faces a 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.

[0183] The absorption unit 4003 absorbs the liquid component from the liquid composition on the intermediate transfer body 4001 before transfer.

[0184] 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.

[0185] The cleaning unit 4005 cleans the intermediate transfer member 4001 after transfer, removing foreign substances such as ink and dust remaining on the intermediate transfer member 4001.

[0186] The outer peripheral surface of the pressure cylinder 621 is in pressure contact with the intermediate transfer member 4001. When the substrate passes through the transfer nip portion between the pressure 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 pressure cylinder 621 may be configured to include at least one grip mechanism for holding the tip portion of the substrate on its outer peripheral surface.

[0187] 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.

[0188] 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. At 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.

[0189] 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 to face the head 101 maintains the tensile state of the intermediate transfer belt 4006 when ink droplets are ejected from the head 101.

[0190] (Electrochemical element) The electrochemical element of the present invention preferably has an electrode laminate, and may further have an exterior as needed. Since the electrode laminate is the same as that described in the item of (electrode laminate), duplicate descriptions are omitted.

[0191] Here, an embodiment of the 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.

[0192] 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 41 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 side 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 sides of the first substrate 21, and this configuration may be a stacked battery in which these are stacked.

[0193] 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 composite layer) 20, a negative electrode (electrode composite layer) 40, a solid electrolyte layer 30, lead wires 50, lead wires 51, and an exterior 60. The positive electrode (electrode composite 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 60. Here, in the all-solid-state battery, the positive electrode (electrode composite layer) 20 and the negative electrode (electrode composite layer) 40 are stacked via the solid electrolyte layer 30, and the positive electrode (electrode composite layer) 20 is disposed on both sides of the negative electrode (electrode composite layer) 40. Note that the number of stacked layers of the positive electrode (electrode composite layer) 20 and the negative electrode (electrode composite layer) 40 is not particularly limited. Also, the number of positive electrodes (electrode composite layers) 20 and the number of negative electrodes (electrode composite layers) 40 may be the same or different.

[0194] The exterior is not particularly limited as long as it can seal the electrode laminate, and a known exterior can be appropriately selected according to the purpose.

[0195] The shape of the electrochemical element is not particularly limited and can be appropriately selected according to the purpose. For example, a laminate type, a cylinder type, a coin type, etc. can be mentioned.

[0196] In an electrochemical element in which a short circuit due to dendrite deposition can occur, usually, a configuration in which the negative electrode composite layer is larger than the positive electrode composite layer is common. At this time, when the positive electrode current collector and the negative electrode current collector are substantially the same size, on the positive electrode current collector, in the region where the negative electrode composite layer of the negative electrode faces, an excess portion where the positive electrode composite layer is not formed occurs. From the viewpoint of the characteristics of the electrochemical element, the insulating resin layer is preferably provided on the excess portion of the positive electrode, that is, the outer peripheral portion of the positive electrode composite layer. In addition, when the configuration is such that the negative electrode composite layer is smaller than the positive electrode composite layer when the electrochemical element is formed, the insulating resin layer is preferably provided on the excess portion of the negative electrode, that is, the outer peripheral portion of the negative electrode composite layer.

[0197] (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 composite 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 composite 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 composite layer forming step, the electrode composite 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 redundant descriptions are omitted.

[0198] <Element Formation Process and Element Formation Means> The element formation process is a process of manufacturing an electrochemical element using an electrode laminate. The element formation means is a means of manufacturing an electrochemical element using an electrode laminate. As a method of manufacturing an electrochemical element using an electrode laminate, there are no particular restrictions, and a known method of 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 one of installing, winding, or laminating a counter electrode and housing it in a container can be mentioned. Note that as the element formation process, it is not necessary to include all the processes of element formation, and it may include some of the element formation processes.

[0199] <Electrode Processing Process and Electrode Processing Means> The electrode processing process is a process of processing an electrode on which an insulating resin layer is formed, which is performed after the liquid composition application process in the insulating resin layer formation process. The electrode processing process may include at least one of a cutting process, a folding process, and a bonding process. The electrode processing means is a means of 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. The electrode processing means can, for example, cut an electrode on which an insulating resin layer is formed to produce a laminate of electrodes. The electrode processing means can, for example, wind or laminate a laminate of electrodes on which an insulating resin layer is formed. The electrode processing means has, for example, an electrode processing device, 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.

[0200] The applications of the electrochemical element are not particularly limited and can be appropriately selected according to the purpose. For example, mobile objects such as vehicles; electrical devices such as smartphones, notebook computers, pen input computers, mobile computers, e-book readers, 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 object include ordinary automobiles, large special automobiles, small special automobiles, trucks, large motorcycles, and ordinary motorcycles.

[0201] Here, an embodiment of the mobile object 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.

[0202] [Mobile object] FIG. 17 is a schematic view showing an example of a mobile object which is an electrochemical element according to an embodiment of the present invention. The mobile object 70 is, for example, an electric vehicle. The mobile object 70 includes a motor 71, an electrochemical element 72, and wheels 73.

[0203] 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 wheels 73, and as a result, the mobile object 70 can move. Since the mobile object 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, so that the mobile object can be moved safely and efficiently.

[0204] The mobile body 70 is not limited to an electric vehicle, and may be a PHEV, an HEV, or a locomotive or motorcycle capable of traveling by using a diesel engine and an electrochemical element in combination. Further, the mobile body 70 may be a transport robot used in a factory or the like that can travel using only an electrochemical element or using an engine and an electrochemical element in combination. Further, the mobile body 70 may be one in which only a part of the object moves without the entire object moving, for example, an assembly robot arranged on a manufacturing line in a factory, in which only an electrochemical element or an arm or the like can operate using an engine and an electrochemical element in combination.

Example

[0205] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0206] [Production of copolymer] <Resin production example 1> 1000 parts by mass of methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1000 parts by mass of toluene (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 25 °C for 8 hours under a nitrogen stream. After completion of stirring, 3 parts by mass of azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was heated and stirred at 100 °C for polymerization. At this time, the polymerization reaction was carried out until the weight average molecular weight reached 50,000 by gel permeation chromatography. After completion of the polymerization reaction, the polymer was purified by performing a series of operations of (1) reprecipitation using a large amount of methanol, (2) dissolving the precipitate using ethyl acetate, and (3) reprecipitation using methanol three times. The precipitate after reprecipitation was dried under reduced pressure at 80 °C to obtain polymethyl acrylate (Mw = 50,000).

[0207] <Resin production example 2> Polyethyl acrylate (Mw = 50,000) was obtained in the same manner as in Resin Production Example 1, except that ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of methyl acrylate and 4 parts by mass of azobisisobutyronitrile was added.

[0208] <Production Example 3 of Resin> Polyacrylic acid propyl (Mw = 50,000) was obtained in the same manner as in Production Example 1, except that acrylic acid - n - butyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of methyl acrylate, and 4 parts by mass of azobisisobutyronitrile was added.

[0209] <Production Example 4 of Resin> Polyacrylic acid - n - butyl (Mw = 18,000) was obtained in the same manner as in Production Example 1, except that acrylic acid - n - butyl was used instead of methyl acrylate, and 12 parts by mass of azobisisobutyronitrile was added.

[0210] <Production Example 5 of Resin> Polyacrylic acid - iso - butyl (Mw = 50,000) was obtained in the same manner as in Production Example 1, except that acrylic acid iso - butyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of methyl acrylate, and 4 parts by mass of azobisisobutyronitrile was added.

[0211] <Production Example 6 of Resin> A poly(acrylic acid - n - butyl - co - methyl methacrylate) random copolymer (Mw = 50,000) with a theoretical copolymerization ratio of acrylic acid - n - butyl to methyl methacrylate of 50:50 in terms of molar ratio was obtained in the same manner as in Production Example 1, except that 561 parts by mass of acrylic acid - n - butyl and 439 parts by mass of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of methyl acrylate.

[0212] <Production Example 7 of Resin> A poly(acrylic acid - n - butyl - co - methyl methacrylate) random copolymer (Mw = 50,000) with a theoretical copolymerization ratio of acrylic acid - n - butyl to methyl methacrylate of 60:40 in terms of molar ratio was obtained in the same manner as in Production Example 1, except that 657 parts by mass of acrylic acid - n - butyl and 343 parts by mass of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of methyl acrylate.

[0213] <Production Example 8 of Resin> A poly(butyl acrylate-co-methyl methacrylate) random copolymer (Mw = 50,000) with a theoretical copolymerization ratio of butyl acrylate to methyl methacrylate of 80:20 in terms of molar ratio was obtained in the same manner as in Production Example 1, except that 837 parts by mass of butyl acrylate and 163 parts by mass of methyl methacrylate were used instead of methyl acrylate.

[0214] <Production Example 9 of Resin> A poly(butyl acrylate-co-methyl methacrylate) random copolymer (Mw = 100,000) with a theoretical copolymerization ratio of butyl acrylate to methyl methacrylate of 80:20 in terms of molar ratio was obtained in the same manner as in Production Example 1, except that 837 parts by mass of butyl acrylate and 163 parts by mass of methyl methacrylate were used instead of methyl acrylate, and 2 parts by mass of azobisisobutyronitrile was added.

[0215] <Production Example 10 of Resin> A poly(butyl acrylate-r-methyl methacrylate) random copolymer (Mw = 180,000) with a theoretical copolymerization ratio of butyl acrylate to methyl methacrylate of 80:20 in terms of molar ratio was obtained in the same manner as in Production Example 1, except that 837 parts by mass of butyl acrylate and 163 parts by mass of methyl methacrylate were used instead of methyl acrylate, and 1 part by mass of azobisisobutyronitrile was added.

[0216] <Production Example 11 of Resin> 2.23 parts by mass of cuprous bromide (CuBr; manufactured by Fujifilm Wako Pure Chemical Corporation), 1.04 parts by mass of diethyl 2,5-dibromoadipate (DBADE; manufactured by Tokyo Chemical Industry Co., Ltd.), 85.14 parts by mass of n-butyl acrylate (BA; manufactured by Tokyo Chemical Industry Co., Ltd.), and 15.64 parts by mass of acetonitrile (ACN; manufactured by Tokyo Chemical Industry Co., Ltd.) were charged, and while nitrogen was passed through this, the temperature was raised to 80 °C. Next, a mixed solution of 0.35 parts by mass of N,N,N’,N’,N’’-pentamethyldiethylenetriamine (PMDETA; manufactured by Fujifilm Wako Pure Chemical Corporation) as an initiator and 2.00 parts of ACN was added, and a polymerization reaction was carried out until the weight-average molecular weight reached 25,000 by gel permeation chromatography. The reaction solution was filtered through activated alumina to remove the catalyst residue, and then the residual monomers and solvents were removed at 2.6 kPa and 80 °C for about 2 hours to obtain a polymer block of poly(butyl acrylate) (Mw = 25,200). 50 parts by mass of the obtained polymer block, 1.3 parts by mass of cuprous bromide, 50 parts by mass of methyl methacrylate, and 20 parts by mass of toluene as a polymerization solvent were mixed, and while nitrogen was passed through under stirring, the temperature was raised to 80 °C. Next, a mixed solution of 0.1 parts by mass of PMDETA as an initiator and 2.3 parts of toluene was added, and a polymerization reaction was carried out at 80 °C until the weight-average molecular weight reached 50,000. Catalyst removal was carried out in the same manner as in Resin Production Example 1. The obtained reaction solution was purified by performing a series of operations of (1) precipitation using a large amount of methanol, (2) dissolving the precipitate using ethyl acetate, and (3) reprecipitation using methanol three times. The precipitate after reprecipitation was filtered and dried to obtain a (butyl acrylate-b-methyl methacrylate) block copolymer (Mw = 50,000) with a theoretical copolymerization ratio of butyl acrylate to methyl methacrylate of 50:50 in terms of molar ratio.

[0217] <Resin Production Example 12> 2.23 parts by mass of cuprous bromide, 1.04 parts by mass of diethyl 2,5-dibromoadipate, 102.17 parts by mass of n-butyl acrylate, and 15.64 parts by mass of acetonitrile were charged, and while nitrogen was passed through this, the temperature was raised to 80 °C. Next, a mixed solution of 0.35 parts by mass of PMDETA and 2.00 parts by mass of ACN as an initiator was added, and a polymerization reaction was carried out until the weight-average molecular weight reached 30,000 by gel permeation chromatography. The reaction solution was filtered through activated alumina to remove the catalyst residue, and then the residual monomers and solvent were removed at 2.6 kPa and 80 °C for about 2 hours to obtain a polymer block of polybutyl acrylate (Mw = 29,800). 78 parts by mass of the obtained polymer block, 1.3 parts by mass of cuprous bromide, 35 parts by mass of methyl methacrylate, and 20 parts by mass of toluene as a polymerization solvent were mixed, and while nitrogen was passed through under stirring, the temperature was raised to 80 °C. Next, a mixed solution of 0.1 parts by mass of PMDETA and 2.3 parts by mass of toluene as an initiator was added, and a polymerization reaction was carried out at 80 °C until the weight-average molecular weight reached 50,000. Catalyst removal was carried out in the same manner as in Resin Production Example 1. The obtained reaction solution was purified by performing a series of operations of (1) precipitation using a large amount of methanol, (2) dissolving the precipitate using ethyl acetate, and (3) reprecipitation using methanol three times. The precipitate after reprecipitation was filtered and dried to obtain a (butyl acrylate-b-methyl methacrylate) block copolymer (Mw = 50,000) with a theoretical copolymerization ratio of butyl acrylate to methyl methacrylate of 60:40 in terms of molar ratio.

[0218] <Resin Production Example 13> 1.39 parts by mass of cuprous bromide, 0.65 parts by mass of diethyl 2,5-dibromoadipate, 136.22 parts by mass of n-butyl acrylate, and 15.64 parts by mass of acetonitrile were charged, and while passing nitrogen therethrough, the temperature was raised to 80 °C. Next, a mixed solution of 0.28 parts by mass of PMDETA and 2.00 parts by mass of ACN as an initiator was added, and a polymerization reaction was carried out by gel permeation chromatography until the weight average molecular weight reached 30,000. The reaction solution was filtered through activated alumina to remove the catalyst residue, and then the residual monomers and solvents were removed at 2.6 kPa and 80 °C for about 2 hours to obtain a polymer block of polybutyl acrylate (Mw = 29,800). 104 parts by mass of the obtained polymer block, 1.3 parts by mass of cuprous bromide, 35 parts by mass of methyl methacrylate, and 20 parts by mass of toluene as a polymerization solvent were mixed, and while passing nitrogen therethrough with stirring, the temperature was raised to 80 °C. Next, a mixed solution of 0.1 parts by mass of PMDETA and 2.3 parts by mass of toluene as an initiator was added, and a polymerization reaction was carried out at 80 °C until the weight average molecular weight reached 50,000. Catalyst removal was carried out in the same manner as in Resin Production Example 1. The obtained reaction solution was purified by performing a series of operations of (1) precipitation using a large amount of methanol, (2) dissolving the precipitate using ethyl acetate, and (3) reprecipitation using methanol three times. The precipitate after reprecipitation was filtered and dried to obtain a (butyl acrylate-b-methyl methacrylate) block copolymer (Mw = 50,000) with a theoretical copolymerization ratio of butyl acrylate to methyl methacrylate of 60:40 in terms of molar ratio.

[0219] <Resin Production Example 14> Into a three-necked flask with an internal volume of 200 ml that had been purged with nitrogen, 92 ml of toluene, 4.5 ml of a toluene solution of isobutylbis(2,6-di-tert-butyl-4-methylphenoxy)aluminum with a concentration of 0.7 mol / L, and 2.4 g of 1,2-dimethoxyethane as a polar additive were added. After stirring until the solution became uniform, 0.15 ml of a solution of sec-butyllithium (a cyclohexane solution with a concentration of 1.3 mol / L) as a polymerization initiator was added. Next, at 0 °C, 2.48 g of methyl methacrylate (MMA) was added as the first monomer and polymerized at 0 °C. A part (2 ml) of the solution was taken out as a sample from the polymerization system, 1 and measured by 1H-NMR. It was confirmed that the conversion rate of MMA was 99% or more. Then, it was poured into 20 ml of methanol, and the precipitated polymer (polymethyl methacrylate) (PMMA) was taken out and dried under reduced pressure. When dissolved in tetrahydrofuran (THF) and measured by gel permeation chromatography (GPC), it was found that the number average molecular weight of the polymer was 25,000. Next, after the polymerization of MMA, the solution was cooled to -30 °C, and 6.30 g of n-butyl acrylate (n-BA) was added as the second monomer over about 30 minutes. After the addition was completed, stirring was continued at -30 °C, and a part (2 ml) of the solution was taken out as a sample from the polymerization system, 1 and measured by 1H-NMR. It was confirmed that the conversion rate of n-BA was 99% or more. Also, when the obtained sample was analyzed by GPC in the same manner, the number average molecular weight of the obtained polymer was 106,300. After the polymerization of n-BA, 2.48 g of MMA was added as the third monomer to this solution at -30 °C and the solution was stirred. After the solution became uniform, stirring was continued at -30 °C for 1 hour, the temperature was raised to 0 °C, and polymerization was continued with further stirring. Then, a part (2 ml) of the solution was taken out from the polymerization system, 1 and measured by 1H-NMR. It was confirmed that the conversion rate of MMA was 90%. 10 ml of methanol was added to the polymerization system and reacted with stirring at room temperature for 1 hour to deactivate the active terminal of the polymer and stop the polymerization. The entire amount of the obtained solution was poured into 2 liters of methanol, the obtained precipitate was recovered, and the low-boiling substances were removed under reduced pressure to obtain the target resin.

[0220] <Resin Production Example 15> In <Resin Production Example 14>, the target resin was obtained by the same method as in <Resin Production Example 14>, except that the amounts of the first and third monomers (MMA) were each changed to 1.98 g and the amount of the second monomer (n-BA) was changed to 7.56 g.

[0221] <Resin Production Example 16> <In Resin Production Example 14, the target resin was obtained in the same manner as in Resin Production Example 14, except that the amounts of the first and third monomers (MMA) were each changed to 1.49 g and the amount of the second monomer (n-BA) was changed to 8.82 g.

[0222] <Resin Production Example 17> <In Resin Production Example 14, the target resin was obtained in the same manner as in Resin Production Example 14, except that the amounts of the first and third monomers (MMA) were each changed to 1.00 g and the amount of the second monomer (n-BA) was changed to 10.08 g.

[0223] <Resin Production Example 18> <In Resin Production Example 14, the target resin was obtained in the same manner as in Resin Production Example 14, except that the amounts of the first and third monomers (MMA) were each changed to 2.30 g and the amount of the second monomer (n-BA) was changed to 20.16 g.

[0224] <Resin Production Example 19> <In Resin Production Example 14, the target resin was obtained in the same manner as in Resin Production Example 14, except that the amounts of the first and third monomers (MMA) were each changed to 3.00 g and the amount of the second monomer (n-BA) was changed to 26.21 g.

[0225] <Resin Production Example 20> <In Resin Production Example 14, the target resin was obtained in the same manner as in Resin Production Example 14, except that the amounts of the first and third monomers (MMA) were each changed to 4.14 g and the amount of the second monomer (n-BA) was changed to 36.29 g.

[0226] The details of the materials and products in Resin Production Examples 1 to 20 are summarized in Table 1. Note that the Mw of polymethyl methacrylate described in Table 1 is the difference in the molecular weight of poly(n-butyl acrylate) from the Mw of the obtained block polymer, and is presumed to be the sum of the Mw of two polymethyl methacrylate chains formed at both ends of poly(n-butyl acrylate).

[0227] [Table 1]

[0228] (Examples 1 to 134 and Comparative Examples 1 to 8) [Formation of Insulating Resin Layer] [Preparation of Liquid Composition] As shown in Tables 2 to 5, a polymerizable compound and a solvent were mixed to prepare Mixture 1. Next, as shown in Tables 6 to 8, Liquid Composition 1 was prepared by mixing Mixture 1, the resin obtained in Resin Production Example 20, and a photopolymerization initiator (1-Benzoylcyclohexanol, manufactured by Tokyo Chemical Industry Co., Ltd.). Note that the addition amount of the photopolymerizable compound was 1% by mass based on the total amount of the polymerizable compound. The liquid compositions of Examples 2 to 134 and Comparative Examples 1 to 8 were adjusted in the same manner as in Example 1, except that the compositions described in Tables 2 to 8 were changed.

[0229] [Table 2]

[0230] [Table 3]

[0231] [Table 4]

[0232] [Table 5]

[0233]

Table 6

[0234]

Table 7

[0235]

Table 8

[0236] The details of each material described in Tables 2 to 8 are as follows. · PEG200DA (PEG200 diacrylate, manufactured by Daicel Ornex Co., Ltd.) · A-200 (polyethylene glycol #200 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) · A-400 (polyethylene glycol #400 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) · Biscoat #230D (1,6-hexanediol acrylic acid multimer ester, manufactured by Osaka Organic Chemical Industry Co., Ltd.) · KAYARAD HX220 (6-(propenoyloxy)hexanoic acid 3-[2,2-dimethyl-3-[[1-oxo-6-(propenoyloxy)hexyl]oxy]propoxy]-2,2-dimethyl-3-oxopropyl, manufactured by Nippon Kayaku Co., Ltd.) · KAYARAD HX620 (poly[oxy(1-oxo-1,6-hexanediyl)], a-hydroxy-w-[(1-oxo-2-propenyl)oxy]-, 3-hydroxy-2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropanoate (9CI) diester, manufactured by Nippon Kayaku Co., Ltd.) · 9G (polyethylene glycol #400 dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) · 14G (polyethylene glycol #600 dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) · CN2270NS (polyester acrylate, manufactured by Sartomer) · CN2273NS (polyester acrylate, manufactured by Sartomer) · CN2283NS (polyester acrylate, manufactured by Sartomer) · M6100 (polyester acrylate, manufactured by Toagosei Co., Ltd.) · M6500 (polyester acrylate, manufactured by Toagosei Co., Ltd.) · APG-200 (tripropylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) · APG-400 (tripropylene glycol #400 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) · MIRAMER M216 (phenol EO-modified acrylate, manufactured by Toyo Chemicals Co., Ltd.) · Light Acrylate HPP-A (hydroxypivalic acid neopentyl glycol acrylate adduct, manufactured by Kyoeisha Chemical Co., Ltd.) · M-310 (trimethylolpropane PO-modified triacrylate, manufactured by Toagosei Co., Ltd.) · M-321 (trimethylolpropane PO-modified triacrylate, manufactured by Toagosei Co., Ltd.) · ADTMP (ditrimethylolpropane tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) · A-NPG (neopentyl glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) · LOTRYL 35BA40 ((ethylene-acrylic acid-n-butyl) random copolymer, manufactured by Arkema)

[0237] <Formation of Insulating Resin Layer> After applying each liquid composition onto an aluminum foil (5 cm × 5 cm, thickness: 20 μm) using a bar coater, the coated area was cured by irradiating with ultraviolet light (light source: UV-LED (product name: FJ800, manufactured by Phoseon), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s). Next, using a hot plate, the cured product was heated at 120°C for 1 minute to remove the solvent, and then further dried at 120°C for 10 minutes to obtain each insulating resin layer with an average thickness of 100 μm.

[0238] [Evaluation Method of Curl Suppression Effect] When each insulating resin layer placed on a horizontal plane was viewed from the horizontal plane direction, the maximum distance (maximum warpage height) between the horizontal plane and the lower surface of the insulating resin layer was measured. Note that the lower surface of the insulating resin layer refers to the surface facing the water surface. Based on the measured value of the maximum warpage height, the curl suppression effect was evaluated. The number of measurement samples was 3, and the measured value adopted the average value of those samples. Note that those with a value of "△" or more have no problems in use. The results are shown in Tables 6 to 8. ―Evaluation Criteria for Curl Suppression Effect― ○: The maximum warpage height is 3 mm or less △: The maximum warpage height exceeds 3 mm and is less than 5 mm ×: The maximum warpage height is 5 mm or more

[0239] From the results of the examples, it is clear that the insulating resin layer formed by the liquid composition of the present invention is excellent in the curl suppression effect due to volume shrinkage.

[0240] In Comparative Examples 1 to 2, the non-crosslinked resin contained in the liquid composition does not have the structure represented by the general formula (3), and a porous structure is not formed in the insulating resin layer that is the cured product of the liquid composition. Therefore, the residual stress due to volume shrinkage cannot be dispersed, and curl occurs in the insulating resin layer. In Comparative Example 3, since the liquid composition 93 does not satisfy the relational expression of formula (1), separation occurred in the liquid composition after material mixing, and an insulating resin layer could not be formed. In Comparative Examples 4 to 6, since the liquid compositions 94 to 96 do not satisfy the relational expression of formula (2), separation occurs in the liquid composition after material mixing, and an insulating resin layer cannot be formed, or a porous structure is not formed in the insulating resin layer that is the cured product of the liquid composition. Therefore, the residual stress due to volume shrinkage cannot be dispersed, and curl occurs in the insulating resin layer. In Comparative Example 7, since the liquid composition 97 does not satisfy the relational expressions of Formula (1) and Formula (2), a porous structure is not formed in the insulating resin layer that is the cured product of the liquid composition. Therefore, the residual stress due to volume shrinkage cannot be dispersed, and curl occurred in the insulating resin layer. In Comparative Example 8, since the liquid composition 98 does not satisfy the relational expression of Formula (1), a porous structure is not formed in the insulating resin layer that is the cured product of the liquid composition. Therefore, the residual stress due to volume shrinkage cannot be dispersed, and curl occurred in the insulating resin layer.

[0241] (Example 135) [Fabrication of All-Solid-State Battery] [Fabrication of Active Material] As the positive electrode active material, a nickel-based positive electrode active material (NCM, manufactured by Toyoshima Seisakusho Co., Ltd.) was used. As the ion conductive oxide for surface coating of the NCM particles, LiNbO 3 was used. The LiNbO 3 coating layer was formed by hydrolyzing an alkoxide solution containing lithium and niobium on the surface of the NCM powder particles based on J. Mater. Chem. A. 2021, 9, 4117 - 4125. Specifically, it is as follows. First, metallic lithium (manufactured by Honjo Metal Co., Ltd.) was dissolved in absolute ethanol (manufactured by Kanto Chemical Co., Inc.) to prepare an ethanol solution of lithium ethoxide. To this solution, niobium pentaethoxide (Nb(OC 2 H 5 )) 5 (manufactured by High Purity Chemical Research Institute Co., Ltd.) was added to obtain an alkoxide solution containing lithium and niobium. Using a rolling fluidization apparatus, NCM1 powder was used as a fluidized bed, and the surface of the NCM powder particles was coated with the alkoxide by spraying the alkoxide solution to obtain a precursor powder. By heating this precursor powder at 350 °C in a dry air atmosphere, LNO / NCM in which a LiNbO 3 layer was formed on the surface of NCM1 was synthesized.

[0242] [Preparation of Liquid Composition for Solid Electrolyte Layer] As a sulfide solid electrolyte, based on the synthesis method described in J.Power Sources.2018,396,33-40, the argyrodite-type sulfide solid electrolyte Li 6 PS 5 Cl (LPSC) was synthesized. Specifically, 0.5 g of Li 2 S (99.9%, manufactured by Mitsuwa Chemical Co., Ltd.), 0.5 g of P 2 S 5 (99%, manufactured by Sigma-Aldrich), and 0.5 g of LiCl (99%, manufactured by Sigma-Aldrich) were pulverized for 40 hours using a planetary ball mill (PULVERISETTE, manufactured by Fritsch, Germany) to obtain a sulfide solid electrolyte. The pulverization was carried out in a zirconia pot (45 mL) using 15 zirconia balls (diameter: 10 mm) under the condition of 600 RPM. For the preparation of the liquid composition for the solid electrolyte layer, octane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the solvent. At this time, for the solvent octane, 10 g of molecular sieve 4A 1 / 16 (manufactured by Kanto Chemical Co., Inc.) was added per 100 ml, and then dehydration was carried out by standing for 12 hours. The one with a water content of 100 ppm or less was confirmed by a Karl Fischer moisture concentration meter and used. To 100 parts by mass of this solvent, 100 parts by mass of the synthesized sulfide solid electrolyte and 1 part by mass of a dispersant (Solspersetm (registered trademark) manufactured by Lubrizol) 21000) were added and mixed to obtain a liquid composition for the solid electrolyte layer.

[0243] <Fabrication of the positive electrode> As the positive electrode active material, 45.3% by mass of LNO / NMC, 2.2% by mass of acetylene black as the conductive material (manufactured by DENKA), 1.4% by mass of polybutyl methacrylate (PBMA, manufactured by Aldrich) as the binder, and 14.7% by mass of the sulfide solid electrolyte were dispersed in 36.4% by mass of anisole (manufactured by Tokyo Chemical Industry Co., Ltd.) to prepare a positive electrode coating. After applying this positive electrode coating on both sides of an aluminum foil substrate and drying, a positive electrode of 20 mm × 20 mm was obtained. The average thickness was 95 μm, and the battery capacity per unit area was 2.91 mAh / cm 2 was.

[0244] <Fabrication of the negative electrode> After attaching lithium metal (manufactured by Honjo Metal Co., Ltd.) with an average thickness of 50 μm onto a stainless steel foil, indium foil (manufactured by Nilaco Corporation) with a further thickness of 50 μm was attached thereon to obtain a negative electrode measuring 25 mm × 25 mm.

[0245] <Fabrication of the all-solid-state battery> Liquid composition 1 was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). The positive electrode was placed on the stage, and liquid composition 1 was applied such that the distance between the outer peripheral portion of the positive electrode and the insulating resin layer was set to 0.5 mm and the width of the insulating resin layer was 10 mm. Immediately thereafter, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (product name: FJ800, manufactured by Phoseon), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed for curing. Next, using a hot plate, the cured product was heated at 120 °C for 1 minute to remove the solvent, thereby obtaining a positive electrode-insulating resin layer. At this time, the average thickness of the insulating resin layer was 124 μm, and the curl of the insulating resin layer was 0 mm.

[0246] After sealing the positive electrode-insulating resin layer with an aluminum laminate, it was pressurized at 500 MPa for 5 minutes by cold isostatic pressing (CIP). After pressurization, the positive electrode-insulating resin layer was taken out from the aluminum laminate. The liquid composition for the solid electrolyte layer was applied onto the positive electrode by the bar coating method. After application, it was sealed again with an aluminum laminate and pressurized at 500 MPa for 5 minutes by CIP. While opposing the positive electrode-insulating resin layer and the negative electrode and attaching lead wires thereto, vacuum sealing was performed by lamination to fabricate all-solid-state battery 1. When measuring the battery voltage of the fabricated all-solid-state battery 1, it was 2.05 V. The capacity per unit area could be charged at a constant current up to 3.6 V at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material without any problems, and no short circuit was observed.

[0247] (Example 136) Liquid composition 5 was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). A positive electrode was placed on the stage, and the distance between the outer peripheral portion of the positive electrode and the insulating resin layer was set to 0.5 mm, and it was ejected and applied so that the resin frame was 10 mm. Immediately thereafter, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (product name: FJ800, manufactured by Phoseon), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed to cure it. Next, using a hot plate, the cured product was heated at 120 °C for 1 minute to remove the solvent, and a positive electrode-insulating resin layer was obtained. At this time, the average thickness of the insulating resin layer was 113 μm, and the curl of the insulating resin layer was 0 mm.

[0248] A all-solid-state battery 2 was produced in the same manner as in Example 135. When the battery voltage of the produced all-solid-state battery 2 was measured, it was 2.09 V. Thereafter, the capacity per unit area could be charged at a constant current up to 3.6 V at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material without any problems, and no short circuit was observed.

[0249] (Example 137) Liquid composition 11 was filled into an inkjet ejection device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). A positive electrode was placed on the stage, and the distance between the outer peripheral portion of the positive electrode and the insulating resin layer was set to 0.5 mm, and it was ejected and applied so that the resin frame was 10 mm. Immediately thereafter, under a nitrogen atmosphere, UV irradiation (light source: UV-LED (product name: FJ800, manufactured by Phoseon), wavelength: 365 nm, irradiation intensity: 30 mW / cm 2 , irradiation time: 20 s) was performed to cure it. Next, using a hot plate, the cured product was heated at 120 °C for 1 minute to remove the solvent, and a positive electrode-insulating resin layer was obtained. At this time, the average thickness of the insulating resin layer was 121 μm, and the curl of the insulating resin layer was 0 mm.

[0250] A all-solid-state battery 3 was fabricated in the same manner as in Example 135. When the battery voltage of the fabricated all-solid-state battery 3 was measured, it was 2.09 V. Thereafter, the capacity per unit area could be charged at a constant current up to 3.6 V at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material without any problems, and no short circuit was observed.

[0251] [Method for Measuring Capacity per Unit Area] The capacity per unit area of the electrode was measured using a charge-discharge measurement device TOSCAT3001 (manufactured by Toyo System Co., Ltd.).

[0252] First, the fabricated electrode was punched into a round shape with a diameter of 10 mm. Next, the electrode containing the solid electrolyte in the positive electrode was evaluated for capacity by the following method. Under an argon atmosphere, the positive electrode was punched into a capacity per unit area of a round electrode with a diameter of 10 mm. 80 g of a sulfide solid electrolyte was placed in a polyethylene terephthalate (PET) tube of a two-electrode cell (manufactured by Hokuen Co., Ltd.), and then a press pin was placed on it. Using a uniaxial press machine (P-6, manufactured by Riken Seiki Co., Ltd.), it was molded at a display pressure of 10 MPa for 1 minute. Next, the positive electrode punched into a diameter of 10 mm was placed so as to be in contact with the active material surface and the sulfide solid electrolyte surface in the PET tube, the press pin was set, and it was molded at a display pressure of 30 MPa for 1 minute using a uniaxial press machine. A stack of lithium (manufactured by Honjo Metal Co., Ltd.) with an average thickness of 50 μm and indium (manufactured by Nilaco Corporation) with an average thickness of 50 μm in that order on an SUS foil with an average thickness of 10 μm was arranged on the surface opposite to the positive electrode composite layer, and it was molded at a display pressure of 12 MPa for 3 seconds using a uniaxial press machine. With the press pin placed, the PET tube was placed in the two-electrode cell and sealed at a display pressure of 25 N·m with a digital torque wrench (KTC tool) to fabricate an electrochemical element. This electrochemical element was subjected to constant current charging up to 3.6 V at a current value of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material at room temperature (25°C), and then constant current discharging to 2.4 V to perform initial charge and discharge. Further, the same charge and discharge were performed twice, and the discharge capacity of the second time was measured as the capacity per unit area of the initial positive electrode.

[0253] Examples of aspects of the present invention include, for example, the following. <1> A liquid composition containing a polymerizable compound represented by the following general formula (1) or general formula (2), a non-crosslinked resin having a structural unit represented by the following general formula (3), and a solvent,

Chemical formula

Chemical formula

Chemical formula

Mathematical formula

Chemical formula

Chemical formula

Chemical formula

Mathematical formula

Chemical formula

[0254] The liquid composition according to any one of <1> to <8>, the insulating resin layer according to <9>, the electrode for an electrochemical element according to <10> to <13>, the electrode laminate according to <14> to <17>, the electrochemical element according to <18>, the electrical equipment according to <19>, the mobile body according to <20> to <21>, and the method for manufacturing an electrode laminate according to <22> to <23> can solve various conventional problems and achieve the object of the present invention.

Explanation of symbols

[0255] 10 Insulating resin layer 20 First electrode composite 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 composite 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 Overlap portion 2a Light irradiation device 2b Overlap inert gas circulation device 300 Heating section 3a Heating device 5 Conveyor section 6 Liquid composition 7 Roller

Prior art documents

Patent documents

[0256]

Patent Document 1

Patent Document 2

Non - patent documents

[0257]

Non - patent Document 1

Non - patent Document 2

Claims

1. A liquid composition comprising a polymerizable compound represented by the following general formula (1) or general formula (2), a non-crosslinked resin having a structural unit represented by the following general formula (3), and a solvent, 【Number】 (In the general formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrocarbon chain, an alkylene oxide chain, a polyester chain, or an acrylic polymer ester derivative, and n represents an integer of 2 or more and 6 or less.) 【Number】 (In the general formula (2), R3 and R4 represent a hydrogen atom or a methyl group.) 【Number】 (In the general formula (3), R6 represents an alkyl group.) The solvent is a mixed solvent containing a good solvent in which the polymerizable compound is soluble and a poor solvent in which the polymerizable compound is insoluble, The solvent is a liquid composition characterized by satisfying the following formula (1). 【Number 1】 (The mixing ratio X in the formula (1) represents the content ratio based on the mass of the good solvent in the mixed solvent as a percentage, and the polymerizable compound solubility point represents the minimum content ratio based on the mass of the good solvent in the mixed solvent in which the polymerizable compound is soluble as a percentage.)

2. A liquid composition comprising a polymerizable compound represented by the following general formula (1) or general formula (2), a non-crosslinked resin having a structural unit represented by the following general formula (3), and a solvent, 【Number】 (In the general formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrocarbon chain, an alkylene oxide chain, a polyester chain, or an acrylic polymer ester derivative, and n represents an integer of 2 or more and 6 or less.) 【Number】 (In the general formula (2), R3 and R4 represent a hydrogen atom or a methyl group.) 【Number】 (In the general formula (3), R6 represents an alkyl group.) The polymerizable compound is a mixed compound containing a soluble polymerizable compound soluble in the solvent and an insoluble polymerizable compound insoluble in the solvent, The polymerizable compound is a liquid composition characterized by satisfying the following formula (2). 【Number 2】 (The mixing ratio Y in the formula (2) represents the content ratio based on the mass of the insoluble polymerizable compound in the mixed compound as a percentage, and the solvent solubility point represents the minimum content ratio based on the mass of the insoluble polymerizable compound in the mixed compound soluble in the solvent as a percentage.)

3. The liquid composition according to claim 1 or 2, wherein the liquid composition contains a polymerizable compound in which R2 in the general formula (1) is a polyester chain or a polymerizable compound represented by the general formula (2).

4. The liquid composition according to claim 1 or 2, wherein R2 in the general formula (1) is a polymerizable compound having a polycaprolactone chain.

5. The liquid composition according to claim 1 or 2, wherein R6 in the general formula (3) is methyl, ethyl, iso-propyl, n-propyl, tert-butyl, iso-butyl, or n-butyl.

6. The liquid composition according to claim 1 or 2, wherein the non-crosslinked resin is a copolymer composed of two or more structural units.

7. The liquid composition according to claim 6, wherein the non-crosslinked resin further has a structural unit represented by the following general formula (4). 【Chemical Formula 7】 (In the general formula (4), R7 represents methyl, ethyl, iso-propyl, n-propyl, tert-butyl, iso-butyl, or n-butyl.)

8. The liquid composition according to claim 6, wherein the copolymer is a block copolymer.

9. An insulating resin layer obtained by curing the liquid composition according to claim 1 or 2, wherein the insulating resin layer has a porous structure.

10. A substrate, an electrode composite layer disposed on the substrate, and an insulating resin layer disposed on the outer peripheral portion of the electrode composite layer, and an electrode for an electrochemical element, wherein the insulating resin layer is a cured product of the liquid composition according to claim 1 or 2, and the insulating resin layer has a porous structure.

11. The electrode for an electrochemical element according to claim 10, wherein an adhesive layer containing a metal alloying with lithium is disposed between the substrate and the electrode composite layer.

12. The electrode for an electrochemical element according to claim 10, wherein the electrode composite layer has an opening.

13. The electrode for an electrochemical element according to claim 12, wherein the opening is filled with a sulfide solid electrolyte.

14. 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 and containing a solid electrolyte, and an electrode laminate, wherein the insulating resin layer is a cured product of the liquid composition according to claim 1 or 2, and the insulating resin layer has a porous structure.

15. The electrode laminate according to claim 14, wherein an adhesive layer containing a metal alloying with lithium is disposed between the substrate and the electrode composite layer.

16. The electrode composite layer has an opening, and the electrode laminate according to claim 14.

17. The electrode laminate according to claim 16, wherein the opening is filled with a sulfide solid electrolyte.

18. An electrochemical element comprising the electrode laminate according to claim 14.

19. An electric device comprising the electrochemical element according to claim 18.

20. A moving body comprising the electrochemical element according to claim 18.

21. The moving body according to claim 20, which is a vehicle.

22. An electrode composite layer forming step of forming an electrode composite layer on a substrate, An insulating resin layer forming step of forming an insulating resin layer on the outer peripheral portion of the electrode composite layer, A method for manufacturing an electrode laminate including a solid electrolyte layer forming step of forming a solid electrolyte layer on the insulating resin layer and the electrode composite layer, The insulating resin layer forming step includes a liquid composition applying step of applying the liquid composition according to claim 1 or 2 onto a substrate, and a liquid composition curing step of applying heat or light to the liquid composition to cure it. A method for manufacturing an electrode laminate, characterized by including.

23. The method for manufacturing an electrode laminate according to claim 22, wherein the liquid composition applying step is carried out by an inkjet method.

Images