Electrode for electrochemical elements, manufacturing method thereof, electrode laminate for electrochemical elements, electrochemical element, and all-solid electrochemical element

Abstract

To provide a method of manufacturing an electrode for electrochemical elements which suppresses the spread of leakage of a liquid composition on a substrate.SOLUTION: Disclosed is a method of manufacturing an electrode for electrochemical elements comprising a substrate, an electrode mixture layer provided on the substrate, and a structure layer provided in at least a part of an edge of the electrode mixture layer. The manufacturing method includes a structure layer formation step. The structure layer formation step includes: a first liquid composition application step of applying a first liquid composition containing a first polymerizable compound and a first solvent onto the substrate; a polymerized substance layer formation step of the first liquid composition of forming a polymerized substance layer of the first liquid composition by polymerizing the first liquid composition which is applied in the first liquid composition application step; and a second liquid composition application step of applying a second liquid composition containing a second polymerizable compound and a second solvent onto the polymerized substance layer of the first liquid composition. In the method of manufacturing the electrode for electrochemical elements, the polymerized substance layer of the first liquid composition has a porous structure.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] The present invention relates to an electrode for an electrochemical device and a method for producing the same, an electrode laminate for an electrochemical device, an electrochemical device, and an all-solid-state electrochemical device. [Background technology]

[0002] All-solid-state secondary batteries are more resistant to temperature changes than conventional lithium-ion secondary batteries, have a lower risk of fire, and are expected to have high performance, such as the ability to charge quickly, leading to increased demand for them in electric vehicles, etc. Furthermore, there is a growing need for thin batteries to be installed in various wearable devices and medical patches, and the requirements for all-solid-state secondary batteries are diversifying.

[0003] In all-solid-state batteries that are composed of a positive electrode, a negative electrode, and a solid electrolyte layer, the laminate including the positive electrode, the solid electrolyte layer, and the negative electrode may be pressed under very high pressure to achieve high density in order to improve the performance of the all-solid-state battery. Damage such as cracks in the solid electrolyte that occurs during this pressing can lead to short circuits between the positive electrode and the negative electrode, so techniques have been proposed to prevent such damage.

[0004] For example, as a technique for partially coating an electrode for an electrochemical element with a resin, a technique for forming an insulating layer made of an insulating resin film has been proposed in order to provide corrosion resistance and adhesiveness around the electrode tabs that make up a lithium ion battery (see, for example, Patent Document 1). Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a method for producing an electrode for an electrochemical device that can suppress the wetting and spreading of a liquid composition on a substrate. [Means for solving the problem]

[0006] As a means for solving the above problems, the method for producing an electrode for an electrochemical element of the present invention comprises the steps of: A method for manufacturing an electrode for an electrochemical element, the electrode having a substrate, an electrode mixture layer provided on the substrate, and a structure layer provided on at least a part of a peripheral portion of the electrode mixture layer, the method comprising: The method for manufacturing an electrode for an electrochemical device includes a structural layer forming step, The structural layer forming step includes: a first liquid composition application step of applying a first liquid composition containing a first polymerizable compound and a first solvent onto a substrate; a first liquid composition polymer layer forming step of polymerizing the first liquid composition applied in the first liquid composition application step to form a polymer layer of the first liquid composition; a second liquid composition application step of applying a second liquid composition containing a second polymerizable compound and a second solvent onto the polymerized layer of the first liquid composition, The polymerized layer of the first liquid composition has a porous structure. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a method for producing an electrode for an electrochemical device that can suppress the wetting and spreading of a liquid composition on a substrate. [Brief explanation of the drawings]

[0008] [Figure 1A] FIG. 1A is a schematic cross-sectional view showing an electrode for an electrochemical device obtained by a method for producing an electrode for an electrochemical device according to one embodiment of the present invention. [Figure 1B] FIG. 1B is a schematic cross-sectional view showing an electrode for an electrochemical device obtained by a method for producing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 2A] FIG. 2A is a schematic cross-sectional view showing an electrode for an electrochemical device according to one embodiment of the present invention. [Figure 2B] FIG. 2B is a schematic cross-sectional view showing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 2C]FIG. 2C is a schematic cross-sectional view showing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 3A] FIG. 3A is a schematic top view showing an electrode for an electrochemical device according to one embodiment of the present invention. [Figure 3B] FIG. 3B is a schematic top view showing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 3C] FIG. 3C is a schematic top view showing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 3D] FIG. 3D is a schematic top view showing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 3E] FIG. 3E is a schematic top view showing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 3F] FIG. 3F is a schematic top view showing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 3G] FIG. 3G is a schematic top view showing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 3H] FIG. 3H is a schematic top view showing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 3I] FIG. 3I is a schematic top view showing an electrode for an electrochemical device according to another embodiment of the present invention. [Figure 4] FIG. 4 is a schematic diagram showing a method for producing an electrode for an electrochemical device according to one embodiment of the present invention. [Figure 5] FIG. 5 is a schematic diagram showing a manufacturing apparatus (liquid ejection apparatus) for an electrochemical element member according to one embodiment of the present invention. [Figure 6] FIG. 6 is a schematic diagram showing a manufacturing apparatus (liquid ejection apparatus) for an electrode for an electrochemical element according to another embodiment of the present invention. [Figure 7] FIG. 7 is a schematic diagram showing a modified example of the manufacturing apparatus for an electrochemical element member according to one embodiment of the present invention. [Figure 8]FIG. 8 is a structural diagram (part 1) showing an example of a printing unit employing an inkjet system and a transfer system as a liquid composition applying means in an apparatus for manufacturing an electrochemical element member according to one embodiment of the present invention. [Figure 9] FIG. 9 is a structural diagram (part 2) showing an example of a printing unit employing an inkjet system and a transfer system as a means for applying a first liquid composition and a means for applying a polymerized layer of a second liquid composition in an apparatus for manufacturing an electrode for an electrochemical element according to one embodiment of the present invention. [Figure 10] FIG. 10 is a schematic cross-sectional view showing an electrode laminate for an electrochemical device according to one embodiment of the present invention. [Figure 11] FIG. 11 is a schematic cross-sectional view showing an all-solid-state electrochemical device according to one embodiment of the present invention. [Figure 12] FIG. 12 is a schematic cross-sectional view showing an example of an all-solid-state electrochemical device according to one embodiment of the present invention. [Figure 13] FIG. 13 is a schematic diagram showing an example of a moving body that is an electrochemical device according to one embodiment of the present invention. [Figure 14] FIG. 14 is an explanatory diagram for explaining a method for evaluating wetting and spreading. [Figure 15] FIG. 15 is an explanatory diagram for explaining the flatness evaluation method. DETAILED DESCRIPTION OF THE INVENTION

[0009] In conventional electrode manufacturing methods including Patent Document 1, an insulating layer (insulating resin coating) is produced by applying an insulating layer-forming liquid composition to a substrate (e.g., an electrode substrate). Generally, the surface condition of a substrate varies depending not only on the type of metal but also on various manufacturing conditions such as the manufacturing process and lot. This means that it is not possible to adequately control the wetting and spreading of the insulating layer-forming liquid composition, making it difficult to form a uniform film.

[0010] The method for producing an electrode for an electrochemical device of the present invention can fully resolve various concerns in the prior art. The electrode for an electrochemical device obtained by the method for producing an electrode for an electrochemical device of the present invention has a laminate structure of at least two layers including a polymer layer of a first liquid composition and a polymer layer of a second liquid composition. The polymer layer of the first liquid composition serves as a surface modifier for the substrate and can suppress the wetting and spreading of the second liquid composition that is subsequently applied. In other words, a method for producing an electrode for an electrochemical device can be realized that can suppress the wetting and spreading of the liquid composition on the substrate.

[0011] The present invention will be described in detail below.

[0012] (Method for manufacturing electrodes for electrochemical elements and apparatus for manufacturing electrodes for electrochemical elements) The method for producing an electrode for an electrochemical device of the present invention includes a structure layer forming step, and may include other steps as necessary. The manufacturing apparatus for an electrode for an electrochemical device according to the present invention includes a structure layer forming step, and may include other means as necessary. The method for producing an electrode for an electrochemical device can be suitably carried out by an apparatus for producing an electrode for an electrochemical device.

[0013] In this specification, the "first liquid composition" and the "second liquid composition" may be referred to as the "liquid composition."

[0014] <Structural Layer Forming Step and Structural Layer Forming Means> The structure layer forming step is a step of forming a structure layer, and includes a first liquid composition applying step, a polymerized material layer forming step of the first liquid composition, and a second liquid composition applying step, and may also include a polymerized material layer forming step of the second liquid composition and a drying step of the polymerized material layer of the liquid composition, as necessary. The structure layer forming means is a means for forming a structure layer, and includes a means for applying a first liquid composition, a means for forming a layer of a polymer of the first liquid composition, and a means for applying a second liquid composition, and may, if necessary, include a means for forming a layer of a polymer of the second liquid composition and a means for drying the layer of a polymer of the liquid composition. The structural layer forming step can be suitably carried out by a structural layer forming means.

[0015] In this specification, the "polymerized layer of the first liquid composition" and the "polymerized layer of the second liquid composition" may be referred to as the "polymerized layer of the liquid composition."

[0016] <<First liquid composition application step and first liquid composition application means>> The first liquid composition applying step is a step of applying a first liquid composition containing a first polymerizable compound and a first solvent onto a substrate. The first liquid composition applying means is a means for applying a first liquid composition containing a first polymerizable compound and a first solvent onto a substrate. The first liquid composition application step can be suitably carried out by a first liquid composition application means.

[0017] The means (step) for applying the first liquid composition is not particularly limited and can be appropriately selected depending on the purpose, and examples include spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, inkjet printing, etc. Among these, the inkjet method (system) is preferred from the viewpoint of being able to apply the first liquid composition to desired locations with high precision.

[0018] <<<Base>>> The substrate is not particularly limited as long as it has electron conductivity and is stable to an applied potential, and can be appropriately selected depending on the purpose. Examples include aluminum foil, copper foil, stainless steel foil, titanium foil, conductive polymers, etched foils obtained by etching these to form fine holes, carbon-coated foils whose surface is coated with a carbon-containing resin layer, and perforated substrates used in lithium ion capacitors.

[0019] The average thickness of the substrate is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 μm or more and 50 μm or less from the viewpoint of suppressing a decrease in battery capacity and ensuring strength.

[0020] The substrate may be a substrate on which an electrode mixture layer containing an active material is previously provided. When a substrate having an electrode mixture layer containing an active material previously provided thereon is used as the substrate, the first liquid composition application step preferably applies the first liquid composition onto the substrate and to the peripheral edge of the electrode mixture layer.

[0021] <<<First Liquid Composition>>> The first liquid composition contains a first polymerizable compound and a first solvent, and may contain a polymerization initiator and other components as necessary.

[0022] The first liquid composition forms a polymerized layer of the first liquid composition having a porous structure. In other words, a polymerized layer of the first liquid composition having a porous structure (sometimes referred to as a "porous structure," "resin structure," or "porous resin") with a resin skeleton is formed by polymerization and curing of the first polymerizable compound in the first liquid composition. Here, "forming a polymerized layer of the first liquid composition having a porous structure" includes not only the case where a porous structure is formed in the first liquid composition, but also the case where a precursor of the porous structure (e.g., the skeleton of a porous resin) is formed in the first liquid composition, and then a polymerized layer of the first liquid composition having a porous structure is formed by subsequent treatment (e.g., heat treatment, etc.).

[0023] <<<<<First polymerizable compound>>>> The first polymerizable compound means a compound that can form a polymer by the action of heat, light, electromagnetic waves, or the like. As the first polymerizable compound, a compound having a polymerizable functional group with a double bond is preferred, and a compound having multiple acrylic functional groups is more preferred, because it has a high polymerization rate, suppresses the generation of by-products that adversely affect the properties of the electrochemical element, and suppresses the generation of functional groups that may cause undesired reactions when the electrochemical element is formed.

[0024] From the viewpoint of suppressing curling that may occur during curing of the first liquid composition, the first polymerizable compound is preferably a compound represented by general formula (1) or general formula (2) and having a plurality of radically polymerizable monosubstituted ethylenes, 1,1-disubstituted ethylenes, 1,2-disubstituted ethylenes, and / or diene compounds.

[0025] [ka] (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.)

[0026] [ka] (In the general formula (2), R3 and R4 represent a hydrogen atom or a methyl group.)

[0027] In general formula (1), n ​​is preferably 2 or 3, and more preferably 2, from the viewpoint of suppressing curling that may occur when the first liquid composition is cured.

[0028] From the viewpoint of obtaining a more excellent curl suppression effect, the first liquid composition preferably contains a first polymerizable compound in which R2 in general formula (1) is a polyester chain or a first polymerizable compound represented by general formula (2), and more preferably contains a first polymerizable compound in which R2 in general formula (1) is a polycaprolactone chain.

[0029] From the viewpoint of polymerization rate, the first 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 preferably hydrogen atoms. Generally, acrylic groups have high radical polymerizability, and therefore, by using a photopolymerization initiator or a thermal polymerization initiator in the first liquid composition, a cured product can be obtained in a short time. Although a cured product can be obtained without using a polymerization initiator, when a first polymerizable compound having an acrylic group is used as the first polymerizable compound, i.e., when R1 in general formula (1) and R3 and R4 in general formula (2) are hydrogen atoms, from the viewpoint of polymerization rate and equipment cost, it is preferable to use the first polymerizable compound in combination with a thermal polymerization initiator or a photopolymerization initiator in the first liquid composition, and it is more preferable to use the first polymerizable compound in combination with a photopolymerization initiator.

[0030] Specific examples of the first polymerizable compound include bifunctional alkyl acrylates, hydroxypivalic acid neopentyl glycol acrylic acid adducts, bifunctional polyethylene glycol acrylates, bifunctional polypropylene glycol acrylates, bifunctional polytetramethylene glycol acrylates, bifunctional cyclic acrylates, bifunctional alkoxylated aromatic acrylates, bifunctional acrylic acid polymer ester acrylates, bifunctional caprolactam-modified acrylates, trifunctional trimethylolpropane acrylates, trifunctional alkoxylated glycerin acrylates, trifunctional isocyanate acrylates, tetrafunctional pentaerythritol acrylates, tetrafunctional ditrimethylolpropane acrylates, tetrafunctional diglycerin tetraacrylates, hexafunctional dipentaerythritol hexaacrylates, and polyester acrylates. Among these, from the viewpoint of suppressing volumetric shrinkage, bifunctional alkyl acrylates, bifunctional polyethylene glycol acrylates, bifunctional alkoxylated aromatic acrylates, bifunctional acrylic acid polymer ester acrylates, trifunctional trimethylolpropane acrylates, trifunctional alkoxylated glycerin acrylates, and trifunctional isocyanate acrylates are preferred, and bifunctional alkyl acrylates, bifunctional polyethylene glycol acrylates, bifunctional alkoxylated aromatic acrylates, and bifunctional acrylic acid polymer ester acrylates are more preferred. Furthermore, among the difunctional alkyl acrylates, difunctional polyethylene glycol acrylates, difunctional alkoxylated aromatic acrylates, and difunctional acrylic acid polymer ester acrylates, difunctional polyethylene glycol acrylates, difunctional acrylic acid polymer ester acrylates, and difunctional polyester acrylates are more preferred.

[0031] Examples of bifunctional alkyl acrylates include, by trade name, NK Ester A-HD-N, A-NON-N, A-DOD-N, A-NPG (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate NP-A, MPD-A, 1,6HX-A, 1,9ND-A (all manufactured by Kyoeisha Chemical Co., Ltd.), and KAYARAD NPGDA (manufactured by Nippon Kayaku Co., Ltd.).

[0032] Examples of hydroxypivalic acid neopentyl glycol acrylic acid adducts include, by trade name, Light Acrylate HPP-A (manufactured by Kyoeisha Chemical Co., Ltd.), Viscoat #195, Viscoat #230, Viscoat #260 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Miramer M210, Miramer M216 (all manufactured by Miwow), and KAYARAD FM-400 (manufactured by Nippon Kayaku Co., Ltd.).

[0033] Examples of bifunctional polyethylene glycol acrylates include trade names such as NK Ester A-200, NK Ester A-400, NK Ester A-600, and NK Ester A-1000 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate 3EG-A, Light Acrylate 4EG-A, Light Acrylate 9EG-A, and Light Acrylate 14EG-A (all manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer ADE-200, Blenmer ADE-300, and Blenmer ADE-400A (all manufactured by NOF Corporation), and Miramer M202 (manufactured by Miwow).

[0034] Examples of bifunctional polypropylene glycol acrylates include trade names such as NK Ester APG-200, NK Ester APG-400, and NK Ester APG-700 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Viscoat #310HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Blenmer ADP-400 (manufactured by NOF Corporation), Miramer M210, Miramer M216, and Miramer M220 (all manufactured by Miwow).

[0035] Examples of bifunctional polytetramethylene glycol acrylates include trade names such as NK Ester A-PTMG65 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate PTMGA-250 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar ADT-250 (manufactured by NOF Corporation).

[0036] Examples of bifunctional cyclic acrylates include, 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, and KAYARAD R-684 (all manufactured by Nippon Kayaku Co., Ltd.).

[0037] Examples of bifunctional alkoxylated aromatic acrylates include, 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.), Viscoat #540 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD R-551, KAYARAD R-712 (all manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0038] An example of the bifunctional acrylic acid polymer ester acrylate is Viscoat #230D (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

[0039] Examples of bifunctional caprolactam-modified acrylates include trade names such as KAYARAD HX-220 and KAYARAD HX-620 (both manufactured by Nippon Kayaku Co., Ltd.).

[0040] Examples of trifunctional trimethylolpropane acrylates include, 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 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Viscoat #295 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

[0041] Examples of trifunctional alkoxylated glycerin acrylates include trade names such as NK Ester A-GLY-3E, A-GLY-9E, and A-GLY-20E (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0042] Examples of trifunctional isocyanate acrylates include NK Ester A-9300 and A-9200YN (both manufactured by Shin-Nakamura Chemical Co., Ltd.) under their trade names.

[0043] Examples of tetrafunctional pentaerythritol acrylates include trade names such as NK Ester A-TMMT and ATM-35E (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate PE-3A, and Light Acrylate PE-4A (all manufactured by Kyoeisha Chemical Co., Ltd.).

[0044] An example of a tetrafunctional ditrimethylolpropane acrylate is NK Ester AD-TMP (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0045] An example of a tetrafunctional diglycerin tetraacrylate is Light Acrylate DGE-4E (manufactured by Kyoeisha Chemical Co., Ltd.).

[0046] An example of the hexafunctional dipentaerythritol hexaacrylate is Light Acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.).

[0047] Examples of polyester acrylates include trade names such as 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, and Aronix M-9050 (all 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, and Ebecryl 1830, Ebecryl 1870, Ebecryl 2870, Ebecryl 830, Ebecryl 835, Ebecryl 870, Ebecryl 84, IRR 302 (all manufactured by Daicel-Allnex Co., Ltd.), RCC13-429 (manufactured by San Nopco Ltd.), Diabeam UK-4003, Diabeam UK-4203 (all manufactured by Mitsubishi Chemical Corporation), CN2203, CN2270, CN2271, CN2273, CN2274 (all manufactured by Arkema), KAYARAD HX-220, KAYARAD HX-620 (all manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0048] The content of the first polymerizable compound is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of ensuring strength while suppressing cure shrinkage due to polymerization, it is preferably 20% by mass or more and 70% by mass or less relative to the total amount of the first liquid composition.

[0049] The first polymerizable compound preferably contains at least one first polymerizable compound represented by general formula (1) or general formula (2). That is, the polymerizable compound contained in the first liquid composition may contain only the first polymerizable compound represented by general formula (1) or general formula (2), or may contain two or more different first polymerizable compounds represented by general formula (1) or general formula (2). In either case, in addition to the first polymerizable compound represented by general formula (1) or general formula (2), a polymerizable compound not satisfying general formula (1) or general formula (2) may also be contained. Here, from the viewpoint of being able to suppress deterioration of a solid electrolyte layer containing a sulfide solid electrolyte, it is preferable that the first liquid composition does not contain a polymerizable compound that does not satisfy general formula (1) or general formula (2). Furthermore, from the viewpoint of being able to expand the range in which the physical properties (e.g., elastic modulus) of the polymerized layer of the first liquid composition can be controlled, it is preferable that the first liquid composition contains two or more different polymerizable compounds represented by general formula (1) or general formula (2).

[0050] <<<<First Solvent>>>> The first solvent is preferably an organic solvent having a water content of 1 wt % or less. When the first liquid composition is used in producing an all-solid-state electrochemical device, the first solvent is preferably a low-polarity hydrophobic solvent that has low reactivity with the solid electrolyte layer. The first solvent is expected to act as a buffer against cure shrinkage because there is no change in the intermolecular distance between the solvents or between the resin and the solvent during polymerization.

[0051] The first solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the first solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, anisole, and phenetole; hydrocarbon solvents such as hexane, heptane, nonane, octane, decane, menthane, cyclohexane, cyclooctane, and p-menthane; ethyl butyrate, ethyl valerate, ethyl hexanoate, ethyl heptanoate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, ethyl undecanoate, ethyl laurate, methyl butyrate, methyl valerate, and methyl hexanoate. Examples of suitable solvents include ester-based solvents such as methyl ether, methyl heptanoate, methyl octanoate, methyl nonanoate, methyl decanoate, methyl undecanoate, methyl laurate, ethyl isovalerate, isoamyl acetate, isobutyl isobutyrate, methyl 3-methoxyisobutyrate, butyl isobutyrate, isobutyl isovalerate, butyl 2-methylbutyrate, butyl isovalerate, heptyl acetate, isoamyl isovalerate, 2-ethylhexyl acetate, hexyl butyrate, ethyl benzoate, hexyl hexanoate, amyl n-octanoate, and hexyl acetate, as well as petroleum-based mixed solvents.

[0052] Examples of petroleum-based mixed solvents include trade names such as 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 Bara Chemie Co., Ltd.).

[0053] The first solvent preferably contains a porogen. The porogen is a liquid that is compatible with the first polymerizable compound and becomes incompatible with the polymer (resin) (causing phase separation) during the polymerization of the first polymerizable compound in the first liquid composition. When the porogen is contained in the first liquid composition, a porous structure is formed when the first polymerizable compound is polymerized. Furthermore, the porogen is preferably capable of dissolving a compound (polymerization initiator) that generates radicals or acids when exposed to light or heat. The porogens may be used alone or in combination of two or more. In this embodiment, the liquid is not polymerizable.

[0054] The boiling point of a single porogen or a combination of two or more porogens is preferably 50°C or higher and 250°C or lower, more preferably 70°C or higher and 200°C or lower, and even more preferably 120°C or higher and 190°C or lower, at normal pressure. When the boiling point of the porogen is 50°C or higher, evaporation of the porogen at around room temperature is suppressed, making it easier to handle the first liquid composition and to control the porogen content in the first liquid composition. When the boiling point of the porogen is 250°C or less, the time required to remove the porogen in the step of drying the polymerized layer of the first liquid composition is shortened, thereby improving the productivity of the polymerized layer of the first liquid composition having a porous structure. In addition, since the amount of porogen remaining inside the polymerized layer of the first liquid composition can be reduced, the quality is improved when the polymerized layer of the first liquid composition is used as a functional layer such as a substance separation layer that separates substances or a reaction layer that serves as a reaction field.

[0055] The porogen is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ethylene glycols such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, and dipropylene glycol monomethyl ether; esters such as γ-butyrolactone and propylene carbonate; and amides such as N,N-dimethylacetamide. Liquids with relatively large molecular weights such as methyl tetradecanoate, methyl decanoate, methyl myristate, tetradecane, etc. Furthermore, liquids such as acetone, 2-ethylhexanol, and 1-bromonaphthalene can also be used.

[0056] It should be noted that not all of the liquids listed as examples are porogens. A porogen is a liquid that is compatible with a first polymerizable compound and that becomes incompatible (causes phase separation) with a polymer (resin) formed in the process of polymerizing the first polymerizable compound in the first liquid composition. In other words, whether a liquid is a porogen or not is determined by its relationship with the first polymerizable compound and the polymer (resin formed by polymerization of the first polymerizable compound). Furthermore, the first liquid composition only needs to contain at least one type of porogen that has a specific relationship with the first polymerizable compound. This allows for a wider range of material choices when preparing the first liquid composition, making it easier to design the first liquid composition. The wider range of material choices when preparing the first liquid composition allows for a wider range of options when the first liquid composition is required to have properties other than those required for the formation of a porous structure. For example, when the first liquid composition is ejected by an inkjet method, ejection stability and the like are required, and the wider range of material choices makes it easier to design the first liquid composition.

[0057] The content of the porogen is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 30.0 mass % or more and 95.0 mass % or less, more preferably 50.0 mass % or more and 90.0 mass % or less, and even more preferably 60.0 mass % or more and 80.0 mass % or less, relative to the total amount of the first liquid composition. When the porogen content is 30.0 mass% or more relative to the total amount of the first liquid composition, the size of the pores in the resulting polymerized layer of the first liquid composition is not too small, such as several nm or less, and the polymerized layer of the first liquid composition has an appropriate porosity, which is preferable because it is possible to suppress the tendency for liquids and gases to penetrate less easily. When the porogen content is 95.0% by mass or less, a three-dimensional network structure of the resin is sufficiently formed to obtain a porous structure, and the strength of the porous structure is also improved, which is preferable.

[0058] The content of the first solvent is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of the curl suppression effect, it is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total amount of the first liquid composition. Furthermore, from the viewpoint of film thickness control, it is preferably 70% by mass or less.

[0059] In the present invention, a plurality of solvents may be used in combination in order to provide a variety of polymerizable compounds.

[0060] [First Aspect of the First Liquid Composition] In a first aspect of the first liquid composition, the first solvent in the first liquid composition is a mixed solvent containing a good solvent and a poor solvent from the viewpoint of the effect of suppressing curling due to volume shrinkage, and satisfies formula (1).

[0061]

number

[0062] In this specification, a "good solvent" refers to a solvent in which the first polymerizable compound is soluble. In this specification, a "poor solvent" refers to a solvent in which the first polymerizable compound is insoluble. In addition, in this specification, a "mixed solvent" refers to a solvent containing a good solvent and a poor solvent. In this specification, the "mixing ratio X" is the content ratio of the good solvent in the mixed solvent expressed as a percentage based on the mass of the good solvent. In this specification, the "solubility point of the polymerizable compound" refers to the minimum content ratio, expressed as a percentage, based on the mass of a good solvent in a mixed solvent in which the first polymerizable compound is soluble.

[0063] Here, the term "soluble" in the first embodiment will be explained. "Soluble" refers to the property of not causing cloudiness or phase separation when a first solvent and a first polymerizable compound are mixed, ultrasonically stirred for 15 minutes using an ultrasonic stirrer (USS-1), and then allowed to stand 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 may be, for example, 25°C. The solubility / insolubility is determined depending on the composition of the first liquid composition, for example, the following patterns 1 to 5.

[0064] [Pattern 1] In the case of a first liquid composition containing two kinds (mixed compound) of first polymerizable compounds represented by general formula (1) or general formula (2) and one kind of first solvent, the solubility / insolubility is determined using a mixture of 10 g of the first solvent and 1 g of the mixed compound (monomer ratio (mass ratio) in the first liquid composition).

[0065] [Pattern 2] In the case of a first liquid composition containing one type of first polymerizable compound represented by general formula (1) or general formula (2), one type of polymerizable compound not satisfying general formula (1) or general formula (2), and one type of first solvent, the solubility / insolubility is determined using a mixture of 10 g of the first solvent and 1 g of a mixture of the polymerizable compound represented by general formula (1) or general formula (2) and the polymerizable compound not satisfying general formula (1) (monomer ratio (mass ratio) in the first liquid composition).

[0066] [Pattern 3] In the case of a first liquid composition containing one type of first polymerizable compound represented by general formula (1) or general formula (2) and two types of first solvents (mixed solvent), solubility / insolubility is determined using a mixture of 10 g of the mixed solvent (monomer ratio (mass ratio) in the first liquid composition) and 1 g of the first polymerizable compound represented by general formula (1) or general formula (2).

[0067] [Pattern 4] In the case of a first liquid composition containing two kinds of first polymerizable compounds (mixed compounds) represented by general formula (1) or general formula (2) and two kinds of first solvents (mixed solvents), the solubility / insolubility is determined using a mixture of 10 g of the mixed solvent (monomer ratio (mass ratio) in the first liquid composition) and 1 g of the mixed compounds (monomer ratio (mass ratio) in the first liquid composition).

[0068] [Pattern 5] In the case of a first liquid composition containing two first polymerizable compounds (mixed compound) represented by general formula (1) or general formula (2), a polymerizable compound that does not satisfy general formula (1) or general formula (2), and two first solvents (mixed solvent), solubility / insolubility is determined using a mixture of 10 g of the mixed solvent (monomer ratio (mass ratio) in the first liquid composition) and 1 g of the mixture of the mixed compound and the polymerizable compound that does not satisfy general formula (1) or general formula (2) (monomer ratio (mass ratio) in the first liquid composition).

[0069] Equation (1) can also be transformed into equation (1)'.

[0070]

number

[0071] When the first liquid composition of the first embodiment satisfies formula (1) or formula (1)', a polymerized layer of the first liquid composition having a high porosity can be formed based on the phase separation rate, and therefore volumetric shrinkage during hardening of the first liquid composition can be suppressed, allowing a high-quality polymerized layer of the first liquid composition to be formed. Furthermore, as the value of "mixing ratio X-solubility point of polymerizable compound" in formula (1)' approaches 0, curling due to volume shrinkage can be more effectively suppressed.

[0072] [Second embodiment of the first liquid composition] In a second aspect of the first liquid composition, the first polymerizable compound in the first liquid composition is a mixed compound containing a soluble polymerizable compound and an insoluble polymerizable compound, and preferably satisfies formula (2), from the viewpoint of the effect of suppressing curling due to volume shrinkage.

[0073]

number

[0074] As used herein, the term "soluble polymerizable compound" refers to a polymerizable compound that is soluble in a first solvent. As used herein, the term "insoluble polymerizable compound" refers to a polymerizable compound that is insoluble in a first solvent. Note that, as used herein, the term "mixed compound" refers to a polymerizable compound that includes a soluble polymerizable compound and an insoluble polymerizable compound. In this specification, the "mixing ratio Y" is the content ratio based on the mass of the insoluble polymerizable compound in the mixed compound, expressed as a percentage. In this specification, the "solvent solubility point" refers to the minimum content ratio, expressed as a percentage, based on the mass of the insoluble polymerizable compound in the mixed compound in which the first solvent is soluble.

[0075] Here, the term "soluble" in the second embodiment will be explained. "Soluble" refers to the property that the first polymerizable compound and the first solvent are mixed, ultrasonically stirred for 15 minutes using an ultrasonic stirrer (USS-1), and then left to stand at a predetermined temperature for 10 minutes without becoming cloudy or undergoing phase separation. The predetermined temperature is not particularly limited as long as it is the ambient temperature during actual use, and may be, for example, 25°C. The solubility / insolubility is determined depending on the composition of the first liquid composition, for example, the following patterns 6 to 8.

[0076] [Pattern 6] In the case of a first liquid composition containing one first polymerizable compound represented by general formula (1) or general formula (2) and two first solvents (mixed solvent), the solubility / insolubility is determined based on the monomer ratio (mass ratio) in the first liquid composition containing 10 g of the first polymerizable compound represented by general formula (1) or general formula (2) and 1 g of the mixed solvent.

[0077] [Pattern 7] In the case of a first liquid composition containing two kinds of first polymerizable compounds (mixed compounds) represented by general formula (1) or general formula (2) and two kinds of first solvents (mixed solvents), the solubility / insolubility is determined based on the solvent ratio (mass ratio) in the first liquid composition containing 10 g of the mixed compounds and 1 g of the mixed solvent.

[0078] [Pattern 8] In the case of a first liquid composition containing two first polymerizable compounds (mixed compound) represented by general formula (1) or general formula (2), a polymerizable compound that does not satisfy general formula (1) or general formula (2), and two first solvents (mixed solvent), the solubility / insolubility is determined based on the monomer ratio (mass ratio) in the first liquid composition containing 10 g of the mixture of the mixed compound and the polymerizable compound that does not satisfy general formula (1) or general formula (2), and 1 g of the mixed solvent.

[0079] Equation (2) can also be transformed into equation (2)'.

[0080]

number

[0081] When the first liquid composition of the second embodiment satisfies formula (2) or formula (2)', a polymerized layer of the first liquid composition having a high porosity can be formed based on the phase separation rate, and therefore volumetric shrinkage during hardening of the first liquid composition can be suppressed, allowing a high-quality polymerized layer of the first liquid composition to be formed. Furthermore, as the "mixing ratio Y-solvent solubility point" in formula (2)' approaches 0, curling due to volume shrinkage can be more effectively suppressed.

[0082] <<<<Polymerization initiator>>>> The polymerization initiator refers to a compound that is cleaved by heat, light, or the like to generate radicals, cations, or anions, and serves as the starting point for polymerization. In consideration of polymerization efficiency, etc., an ultraviolet-curing initiator is preferably used. Specific examples include photopolymerization initiators such as alkylphenone-based polymerization initiators, acylphosphine sulfite-based polymerization initiators, and oxime ester-based polymerization initiators. Specific examples of alkylphenone polymerization initiators include trade names such as Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV). Specific examples of the acylphosphine sulfite polymerization initiator include trade names such as Omnirad TPO and Omnirad 819 (both manufactured by IGM Resins BV). Specific examples of the oxime ester polymerization initiator include trade names such as Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 (all manufactured by BASF Japan).

[0083] The content of the polymerization initiator is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of obtaining a sufficient curing rate, the content 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, when the total amount of the polymerizable compounds is taken as 100.0% by mass.

[0084] <<<Method for producing first liquid composition>>> The method for producing the first liquid composition is not particularly limited and can be appropriately selected depending on the purpose. However, it is preferable to produce the first liquid composition through a step of mixing a first polymerizable compound, a step of mixing the first polymerizable compound with a first solvent, a step of dissolving a polymerization initiator in the solvent, and a step of stirring to obtain a uniform solution.

[0085] <<Step of forming a polymerized layer of first liquid composition and means for forming a polymerized layer of first liquid composition>> The first liquid composition polymer layer forming step is a step of polymerizing the first liquid composition applied in the first liquid composition applying step to form a first liquid composition polymer layer. The means for forming a polymerized layer of the first liquid composition is a means for polymerizing the first liquid composition applied in the first liquid composition application step to form a polymerized layer of the first liquid composition. The step of forming a layer of a polymer of the first liquid composition can be suitably carried out by a means for forming a layer of a polymer of the first liquid composition.

[0086] The step of forming a polymerized layer of the first liquid composition polymerizes the first polymerizable compound in the first liquid composition, and a polymerized layer of the first liquid composition having a porous structure is formed by polymerization-induced phase separation.

[0087] The means (step) for forming a polymerized product layer of the first liquid composition is not particularly limited and can be appropriately selected depending on the purpose, as long as it can impart the energy necessary to promote the polymerization reaction of the first polymerizable compound. Examples include light irradiation such as ultraviolet light, electron beams, α-rays, β-rays, γ-rays, X-rays, and infrared light; and heating. Among these, light irradiation is preferred, and ultraviolet light irradiation is more preferred. The light is preferably active energy rays. This allows the first liquid composition to be polymerized to form a polymerized product layer of the first liquid composition without removing the first solvent in the first liquid composition. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator.

[0088] The irradiation intensity of the active energy rays is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 1 W / cm 2 Less than 300mW / cm is preferable. 2 Less than 100 mW / cm is more preferable. 2 If the irradiation intensity of the active energy rays is too low, the phase separation will proceed excessively, which will tend to cause the porous structure to become uneven and coarse, and furthermore, the irradiation time will be long, which will reduce productivity. 2 More than 30mW / cm is preferable. 2 The above is more preferable.

[0089] <<<<Polymerized product layer of first liquid composition>>> In the present invention, the polymerized layer of the first liquid composition has a porous structure. The porous structure is preferably a co-continuous structure with a resin as the skeleton. Here, the term "co-continuous structure" refers to a structure in which two or more substances or phases each have a continuous structure and do not form an interface. In this embodiment, it refers to a structure in which both the resin phase and the pore phase are three-dimensional branched network continuous phases. The porous structure of the present invention also includes a structure in which the pore phase contains a solvent or the like. These structures can be formed by polymerization-induced phase separation (see, for example, JP 2003-1911628 A, WO 97-044363 A, JP 2005-298757 A, JP 2010-513589 A, JP 2001-163907 A, and JP 2001-138504 A).

[0090] [Polymerization-induced phase separation] Polymerization-induced phase separation refers to a state in which the first polymerizable compound and the first solvent are compatible before the start of polymerization, but after the start of polymerization, the polymer (resin) produced during the polymerization process of the first polymerizable compound is incompatible with the first solvent, resulting in phase separation. While there are other methods for obtaining porous structures through phase separation, the co-continuous porous structure obtained by polymerization-induced phase separation has the advantage of being highly resistant to chemicals and heat. Furthermore, compared to other methods, it has the advantage of shorter process time and easier surface modification.

[0091] Next, a process for forming a porous structure using a polymerization-induced phase separation method with a first liquid composition containing a first polymerizable compound will be described. The first polymerizable compound undergoes a polymerization reaction upon irradiation with light or the like to form a resin. During this process, the solubility of the growing resin in the first solvent decreases, causing phase separation between the resin and the first solvent. Ultimately, the resin forms a porous structure with a co-continuous structure due to the resin skeleton, with the first solvent or the like filling the pores. When this is dried, the first solvent or the like is removed, leaving behind a porous resin with a co-continuous structure of a three-dimensional network structure.

[0092] For this reason, the first liquid composition preferably contains a mixture of a polymerizable compound (monomer) and a solvent, and the resin after polymerization is insoluble in the solvent or does not form a gel or sol.

[0093] A method for confirming that the layer of the polymer of the first liquid composition has a co-continuous structure and that the pores are interconnected can be, for example, by observing an image of a cross section of the layer of the polymer of the first liquid composition using a scanning electron microscope (SEM) or the like to confirm that the pores are interconnected.

[0094] [An example of image observation using a scanning electron microscope (SEM)] After the polymerized layer of the first liquid composition is stained with osmium, it is vacuum impregnated with epoxy resin, and the internal cross-sectional structure is cut out using a focused ion beam (FIB) and observed using a scanning electron microscope (SEM).

[0095] The porosity of the polymer layer of the first liquid composition is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 30% or more, more preferably 50% or more, from the viewpoint of suppressing curling, and is preferably 70% or less, more preferably 60% or less, from the viewpoint of adhesion to the substrate. When the porosity of the layer of the polymer of the first liquid composition is 30% or more, the pressure applied from the layer of the polymer of the first liquid composition to the solid electrolyte layer can be reduced in the pressing step after the formation of the solid electrolyte layer, which is preferable. When the porosity of the polymerized layer of the first liquid composition is 90% or less, the strength of the polymerized layer of the first liquid composition is improved, and the shape of the polymerized layer of the first liquid composition can be sufficiently maintained when subjected to a pressing process, which is preferable.

[0096] The porosity of the layer of the polymer of the first liquid composition can be measured by the same method as described in the section [Example of method for observing images using a scanning electron microscope (SEM)].

[0097] The cross-sectional shape of the pores in the layer of the polymer of the first liquid composition is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a substantially circular shape, a substantially elliptical shape, and a substantially polygonal shape. Here, the pore size refers to the length of the longest part in the cross-sectional shape of the layer of polymerized material of the first liquid composition. The pore size of the layer of polymerized material of the first liquid composition can be determined, for example, from a cross-sectional photograph taken with a scanning electron microscope (SEM).

[0098] The size of the pores in the polymer layer of the first liquid composition is not particularly limited and can be appropriately selected depending on the purpose, but the ratio of the pore size to the median diameter of the solid electrolyte contained in the liquid composition for forming a solid electrolyte layer (liquid composition for forming a solid electrolyte layer) provided on the polymer layer of the first liquid composition is preferably 0.8 or more, and more preferably 1 or more. If the size of the pores in the layer of polymerized material of the first liquid composition is larger than the median diameter of the solid electrolyte, the solid electrolyte will be easily trapped in the pores in the layer of polymerized material of the first liquid composition. By making the size of the pores in the layer of polymerized material of the first liquid composition smaller than the median diameter of the solid electrolyte, a configuration can be achieved in which the solid electrolyte is less likely to be trapped in the layer of polymerized material of the first liquid composition, which is advantageous in terms of pressure distribution during pressing and relaxation of pressure applied from the layer of polymerized material of the first liquid composition to the solid electrolyte layer.

[0099] The method for controlling the size and porosity of the pores in the polymer layer of the first liquid composition is not particularly limited and can be appropriately selected depending on the purpose. Examples of the method include a method of adjusting the content of the first polymerizable compound in the first liquid composition, a method of adjusting the content of the first solvent in the first liquid composition, and a method of adjusting the light irradiation conditions.

[0100] The volume resistivity of the polymer layer of the first liquid composition is not particularly limited and can be appropriately selected depending on the purpose. 12 It is preferable that the electrical resistance is Ω·cm or more. It is also preferable that a conductive filler or the like is added to the material so that there is no conductive path.

[0101] The average thickness of the polymerized layer of the first liquid composition is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of excellent curl suppression effect, it is preferably 10 μm or more, more preferably 20 μm or more, and from the viewpoint of suppressing wetting and spreading, it is preferably 50 μm or less.

[0102] The method for measuring the average thickness of the polymer layer of the first liquid composition is not particularly limited and can be selected appropriately depending on the purpose. For example, it can be measured using a scanning electron microscope (SEM) device (phenompro-x, manufactured by Jusco International Co., Ltd.).

[0103] <<Second liquid composition application step and second liquid composition application means>> The second liquid composition application step is a step of applying a second liquid composition containing a second polymerizable compound and a second solvent onto the polymer layer of the first liquid composition. The second liquid composition applying means is a means for applying a second liquid composition containing a second polymerizable compound and a second solvent onto the polymer layer of the first liquid composition. The second liquid composition application step can be suitably carried out by a second liquid composition application means. The second liquid composition application step and the second liquid composition application means can be those described in the section <First liquid composition application step and first liquid composition application means>, and therefore redundant description will be omitted. In other words, the second liquid composition application step can be the first liquid composition application step, and the second liquid composition application means can be the first liquid composition application means.

[0104] <<<Second liquid composition>>> The second liquid composition contains a second polymerizable compound and a second solvent, and may contain a polymerization initiator and other components as necessary. The first polymerizable compound can be used as the second polymerizable compound, and the first solvent can be used as the second solvent.

[0105] The second liquid composition may have the same composition as the first liquid composition, or may have a different composition. When a second liquid composition having a different composition from the first liquid composition is used, the ratio of the content of the first polymerizable compound in the first liquid composition to the content of the second polymerizable compound in the second liquid composition (content of the first polymerizable compound in the first liquid composition / content of the second polymerizable compound in the second liquid composition) is preferably 1 or more from the viewpoint of improving adhesion to the substrate, and is preferably 1.5 or less from the viewpoint of suppressing interfacial peeling.

[0106] <<Step of forming a polymerized layer of second liquid composition and means for forming a polymerized layer of second liquid composition>> The second liquid composition polymer layer forming step is a step of polymerizing the second liquid composition applied in the second liquid composition application step to form a polymer layer of the second liquid composition. The means for forming a polymerized layer of the second liquid composition is a means for polymerizing the second liquid composition applied in the second liquid composition application step to form a polymerized layer of the second liquid composition. The step of forming a layer of a polymer of the second liquid composition can be suitably carried out by a means for forming a layer of a polymer of the second liquid composition. The step of forming a polymerized material layer of the second liquid composition and the means of forming a polymerized material layer of the second liquid composition can be those described in <Step of forming a polymerized material layer of the first liquid composition and means of forming a polymerized material layer of the first liquid composition>, so redundant description will be omitted. In other words, the step of forming a polymerized material layer of the second liquid composition can be the step of forming a polymerized material layer of the first liquid composition, the means of forming a polymerized material layer of the second liquid composition can be the means of forming a polymerized material layer of the first liquid composition, and the polymerized material layer of the second liquid composition can be the polymerized material layer of the first liquid composition.

[0107] <<Layer of polymerized product of second liquid composition>> The polymer layer of the second liquid composition may have a single layer structure or a laminate structure of two or more layers. Note that a polymer layer of the second liquid composition having a laminate structure of two or more layers is preferably formed by repeatedly carrying out a step of applying the second liquid composition and a step of forming a polymer layer of the second liquid composition after a step of forming a polymer layer of the first liquid composition. In this specification, for convenience, the step of applying a polymerized liquid composition layer, which is carried out after the second liquid composition application step, is referred to as the "third liquid composition application step", and the following steps will be referred to in the same manner. In this specification, for convenience, the step of forming a polymerized material layer of a liquid composition that is carried out after the step of forming a polymerized material layer of a second liquid composition will be referred to as the "step of forming a polymerized material layer of a third liquid composition," and the same will be used thereafter. For convenience, in this specification, a polymerized layer of a liquid composition formed after the polymerized layer of the second liquid composition is referred to as a "polymerized layer of a third liquid composition," and the same applies hereafter.

[0108] The average thickness of at least one layer constituting the polymer layer of the second liquid composition is preferably 100 μm or more, more preferably 110 μm or more, from the viewpoint of increasing the taper length and suppressing the occurrence of so-called coffee ring.

[0109] The porosity of the polymer layer of the second liquid composition is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably larger than the porosity of the polymer layer of the first liquid composition. By making the porosity of the polymer layer of the first liquid composition smaller than the porosity of the polymer layer of the second liquid composition, the adhesion of the polymer layer of the first liquid composition to the substrate is improved.

[0110] <<Step of drying the polymerized layer of the liquid composition, and means for drying the polymerized layer of the liquid composition>> The step of drying the polymerized layer of the liquid composition is a step of drying the polymerized layer of the first liquid composition and the polymerized layer of the second liquid composition. The means for drying the polymerized layer of the liquid composition is a means for drying the polymerized layer of the first liquid composition and the polymerized layer of the second liquid composition. The step of drying the polymerized layer of the liquid composition can be suitably carried out by a means for drying the polymerized layer of the liquid composition.

[0111] The means (step) for drying the polymerized layer of the liquid composition is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a method of drying the polymerized layer of the first liquid composition and the polymerized layer of the second liquid composition by heating. In this case, heating under reduced pressure is preferred because it further promotes removal of the solvent and can suppress the remaining liquid in the formed layer. Heating may be performed by a stage or by a heating mechanism other than a stage. The heating mechanism may be installed either above or below the substrate, or multiple heating mechanisms may be installed.

[0112] The heating mechanism is not particularly limited and can be appropriately selected depending on the purpose. Examples include a resistance heater, an infrared heater, and a fan heater. The heating temperature is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 70° C. or higher and 150° C. or lower from the viewpoint of energy use.

[0113] In the method for producing an electrode for an electrochemical device, it is preferable to carry out the step of applying the second liquid composition after the step of forming a polymerized layer of the first liquid composition without carrying out the step of drying the polymerized layer of the liquid composition, thereby eliminating the problem that the second liquid composition penetrates into the pores of the polymerized layer of the first liquid composition in the step of applying the second liquid composition, making it difficult to form a uniform film.

[0114] <Other steps and other means> The other steps are not particularly limited and can be appropriately selected depending on the purpose as long as they do not impair the effects of the present invention, and examples thereof include a transport step. The other means is not particularly limited and can be appropriately selected depending on the purpose as long as it does not impair the effects of the present invention, and examples thereof include conveying means.

[0115] <<Transportation process and transport means>> The transport step is a step of transporting the substrate, and the transport means is a means for transporting the substrate. The conveying step can be suitably carried out by a conveying means. The conveying step and conveying means are not particularly limited and can be appropriately selected depending on the purpose, as long as they can convey the material from the first liquid composition application step to the first liquid composition polymer layer forming step, from the first liquid composition polymer layer forming step to the second liquid composition application step, from the second liquid composition application step to the second liquid composition polymer layer forming step, and from the second liquid composition polymer layer forming step to the liquid composition polymer layer drying step. Examples of the conveying step and conveying means include a sheet-fed system and a roll-to-roll (rotary) system. The speed of the conveying step and conveying means is preferably 1 m / min or more and 100 m / min or less, more preferably 30 m / min or more and 60 m / min or less, from the viewpoint of productivity.

[0116] (Electrodes for electrochemical elements) One embodiment of the electrode for electrochemical elements of the present invention is an electrode for electrochemical elements having a substrate, an electrode mixture layer provided on the substrate, and a structure layer provided on at least a part of the peripheral edge of the electrode mixture layer, wherein the structure layer has a laminated structure of two or more layers including a first structure layer that is mainly in contact with the substrate and a second structure layer provided on the first structure layer, and the structure layer has a porous structure.

[0117] Another embodiment of the electrode for electrochemical devices of the present invention is an electrode for electrochemical devices having a substrate and a structural layer provided on at least a portion of the substrate, wherein the structural layer has a laminated structure of two or more layers including a first structural layer that is mainly in contact with the substrate and a second structural layer that is provided on the first structural layer and is mainly in contact with the first structural layer, the porosity of the second structural layer being larger than the porosity of the first structural layer, and the structural layer has a porous structure.

[0118] The electrode for an electrochemical device can be obtained by the method for producing an electrode for an electrochemical device of the present invention. In this specification, the negative electrode and the positive electrode are collectively referred to as "electrodes," the negative electrode electrode substrate and the positive electrode electrode substrate are collectively referred to as "substrates," and the negative electrode mixture layer and the positive electrode mixture layer are collectively referred to as "electrode mixture layers."

[0119] Here, one embodiment of an electrode for an electrochemical device obtained by the method for producing an electrode for an electrochemical device of the present invention will be described with reference to the drawings, although the present invention is not limited to these embodiments. In each drawing, the same components are denoted by the same reference numerals, and redundant explanations may be omitted. Furthermore, the number, position, shape, etc. of the components are not limited to the present embodiment, and the number, position, shape, etc. may be any number, position, shape, etc. that is preferable for implementing the present invention.

[0120] [Figure 1A] FIG. 1A is a schematic cross-sectional view showing an electrode for an electrochemical device obtained by a method for producing an electrode for an electrochemical device according to one embodiment of the present invention. The electrode for an electrochemical device has a substrate 1, a first structure layer 2 formed from a first liquid composition on at least a portion of the substrate 1, and a second structure layer 3 formed from a second liquid composition on the first structure layer 2. Although FIG. 1A illustrates a configuration in which the first structural layer 2 and the second structural layer 3 are provided on one side of the base 1, the first structural layer 2 and the second structural layer 3 may be provided on both opposing sides of the base 1.

[0121] [Figure 1B] FIG. 1B is a schematic cross-sectional view showing an electrode for an electrochemical device obtained by a method for producing an electrode for an electrochemical device according to another embodiment of the present invention. The electrode for an electrochemical device has a substrate 1, a first structural layer 2 formed from a first liquid composition on at least a portion of the substrate 1, a second structural layer 3 formed from a second liquid composition on the first structural layer 2, and a third structural layer 4 formed from the second liquid composition on the second structural layer. Note that, although Figure 1B illustrates a configuration in which the first structural layer 2, the second structural layer 3, and the third structural layer 4 are provided on one side of the base 1, the first structural layer 2, the second structural layer 3, and the third structural layer 4 may be provided on both opposing sides of the base 1. Furthermore, a fourth or subsequent structural layer may be further provided.

[0122] [Figure 2A] FIG. 2A is a schematic cross-sectional view showing an electrode for an electrochemical device according to one embodiment of the present invention. The electrode for an electrochemical device (25) has a substrate (21), an electrode mixture layer (20) disposed on the substrate (21), and a structure layer (10) disposed on the periphery of the electrode mixture layer (20). Although Figure 2A illustrates a configuration in which the electrode composite layer 20 and the structure layer 10 are provided on one side of the base 21, the electrode composite layer 20 and the structure layer 10 may be provided on both opposing sides of the base 21. In FIG. 2A, the laminated structure of the structural layer 10 is omitted.

[0123] <Base> As the substrate for the electrode for electrochemical devices, those described in the section (Method for manufacturing electrode for electrochemical devices and apparatus for manufacturing electrode for electrochemical devices) can be used. An electrode mixture layer may be provided on the substrate.

[0124] <Electrode composite layer> The electrode mixture layer (sometimes referred to as "active material layer") is composed mainly of an active material (negative electrode active material or positive electrode active material). In this specification, "composed mainly of an active material" means that the content of the active material is 70 mass % or more of the entire electrode mixture layer.

[0125] The electrode mixture layer is formed from an electrode mixture layer-forming liquid composition. The liquid composition for forming an electrode mixture layer is not particularly limited and can be appropriately selected depending on the purpose. For example, it contains an active material (negative electrode active material or positive electrode active material), and may contain, as necessary, a conductive auxiliary, a binder for the electrode mixture layer, a dispersant for the electrode mixture layer, a solid electrolyte, a gel electrolyte, a solvent for the electrode mixture layer, and other components.

[0126] <<Active material>> The active material may be a positive electrode active material or a negative electrode active material. The positive electrode active material or the negative electrode active material may be used alone or in combination of two or more.

[0127] -Cathode active material- The positive electrode active material is not particularly limited as long as it is a material that can reversibly store and release alkali metal ions, and alkali metal-containing transition metal compounds can be used. Examples of alkali metal-containing transition metal compounds include lithium-containing transition metal compounds such as composite oxides containing lithium and one or more elements selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium. Examples of lithium-containing transition metal compounds include lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide.

[0128] As the alkali metal-containing transition metal compound, a polyanionic compound having an XO4 tetrahedron (X=P, S, As, Mo, W, Si, etc.) in its crystal structure can be used. Among these, lithium-containing transition metal phosphate compounds such as lithium iron phosphate and lithium vanadium phosphate are preferred from the viewpoint of cycle characteristics, and lithium vanadium phosphate is more preferred from the viewpoint of lithium diffusion coefficient and output characteristics. When a polyanionic compound is used, it is preferable that the surface of the compound is coated with a conductive aid such as a carbon material to form a composite, in terms of electron conductivity.

[0129] The alkali metal-containing transition metal compound preferably has at least a portion of its surface coated with an ion-conductive oxide, preferably a lithium ion-conductive oxide. The lithium ion conductive oxide is not particularly limited and can be appropriately selected depending on the purpose. For example, x AO y (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). Specific examples of lithium ion conductive oxides include Li3BO3, LiBO2, Li2CO3, LiAlO2, Li4SiO4, Li2SiO3, Li3PO4, Li2SO4, Li2TiO3, and Li4Ti5O. 12 , Li2Ti2O5, Li2ZrO3, LiNbO3, LiTaO3, Li2MoO4, and Li2WO4. Among these, Li4Ti5O 12 , Li2ZrO3, or LiNbO3 are preferred. The lithium ion conductive oxide may be a composite oxide, which may be any combination of lithium ion conductive oxides, such as Li4SiO4-Li3BO3 and Li4SiO4-Li3PO4.

[0130] -Negative electrode active material- The negative electrode active material is not particularly limited as long as it is a material that can reversibly absorb and release alkali metal ions and can be appropriately selected depending on the purpose. For example, a carbon material containing graphite having a graphite-type crystal structure can be used. Examples of carbon materials include natural graphite, spherical or fibrous artificial graphite, non-graphitizable carbon (hard carbon), and easily graphitizable carbon (soft carbon). Examples of materials other than carbon materials include lithium titanate and titanium oxide. From the viewpoint of increasing the energy density of a lithium ion battery, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxide, silicon nitride, and tin oxide can also be suitably used as the negative electrode active material.

[0131] <<Conductive additives>> The conductive additive is not particularly limited and can be appropriately selected depending on the purpose. For example, carbon black produced by a furnace method, an acetylene method, a gasification method, or the like, or a carbon material such as carbon nanofiber, carbon nanotube, graphene, or graphite particles can be used. Examples of the conductive additive other than the carbon material include metal particles such as aluminum, metal fibers, etc. The conductive additive may be previously compounded with the active material.

[0132] The content of the conductive additive relative to the active material is not particularly limited and can be set appropriately depending on the purpose, but is preferably 10% by mass or less, more preferably 8% by mass or less, and is preferably 1% by mass or more from the viewpoint of reducing the resistance of the active material and imparting conductivity. If the content of the conductive assistant relative to the active material is 10% by mass or less, the stability of the electrode mixture layer-forming liquid composition is improved, which is preferable. If the content of the conductive auxiliary agent relative to the active material is 8% by mass or less, the stability of the electrode mixture layer-forming liquid composition is further improved, which is preferable.

[0133] <<Binder for electrode mixture layer>> The electrode mixture layer binder is not particularly limited and can be appropriately selected depending on the purpose, as long as it can bind negative electrode materials together, positive electrode materials together, a negative electrode material and a negative electrode substrate, or a positive electrode material and a positive electrode substrate. When the electrode mixture layer-forming liquid composition is used for inkjet ejection, it is preferable that the electrode mixture layer binder is one that does not easily increase the viscosity of the electrode mixture layer-forming liquid composition, from the viewpoint of suppressing nozzle clogging of the liquid ejection head. In this specification, the "insulating layer binder" in the insulating layer-forming liquid composition and the "electrode mixture layer binder" in the electrode mixture layer-forming liquid composition are distinguished.

[0134] As the binder for the electrode mixture layer, a polymer compound can be used. Examples of polymer compounds include thermoplastic resins such as polyvinylidene fluoride (PVDF), acrylic resin, polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, and 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), polymethylmethacrylate (PMMA), and polyethylene vinyl acetate (PEVA).

[0135] The content of the binder for the electrode mixture layer relative to the active material is not particularly limited and can be set appropriately depending on the purpose, but is preferably 1% by mass or more and 15% by mass or less, and more preferably 3% by mass or more and 10% by mass or less. If the content of the binder for the electrode mixture layer relative to the active material is 1% by mass or more, the active material can be firmly bound to the substrate, which is preferable.

[0136] <<Dispersant for electrode mixture layer>> The dispersant for the electrode mixture layer is not particularly limited as long as it is capable of improving the dispersibility of the active material in the liquid composition for forming the electrode mixture layer. Examples include polymer dispersants such as polyethylene oxides, polypropylene oxides, polycarboxylic acids, naphthalenesulfonic acid formalin condensation, polyethylene glycols, polycarboxylic acid partial alkyl esters, polyethers, and polyalkylene polyamines; low molecular weight dispersants such as alkyl sulfonic acids, quaternary ammonium higher alcohol alkylene oxides, polyhydric alcohol esters, and alkyl polyamines; and inorganic dispersants such as polyphosphate dispersants. In this specification, a distinction is made between the "dispersant for insulating layer" in the liquid composition for forming an insulating layer and the "dispersant for electrode mixture layer" in the liquid composition for forming an electrode mixture layer.

[0137] <<Solid electrolyte>> The solid electrolyte is not particularly limited as long as it is a solid substance that has electronic insulation properties and exhibits ionic conductivity, but sulfide solid electrolytes and oxide solid electrolytes are preferred from the viewpoint of high ionic conductivity.

[0138] Examples of sulfide solid electrolytes include Li 10 GeP2S 12 and Li6PS5X (X=F, Cl, Br, I) which has an argyrodite-type crystal structure. As an oxide-based solid electrolyte, for example, LLZ (Li7La3Zr2O 12 ), LATP (Li1+xAlxTi) with NASICON-type crystal structure 20 x(PO4)3) (0.1≦x≦0.4), LLT(Li 0.33 La 0.55 TiO3), amorphous LIPON (Li 2.9 PO 3.3 N 0.4 ) etc. These solid electrolytes may be used alone or in combination of two or more.

[0139] When the electrode mixture layer is a positive electrode mixture layer, the average thickness of the positive electrode mixture layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 μm or more and 300 μm or less, and more preferably 40 μm or more and 150 μm or less. When the average thickness of the positive electrode mixture layer is 10 μm or more, the energy density of the electrochemical device is improved. When the average thickness of the positive electrode mixture layer is 300 μm or less, the load characteristics of the electrochemical device are improved.

[0140] When the electrode mixture layer is a negative electrode mixture layer, the average thickness of the negative electrode mixture layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 μm or more and 450 μm or less, and more preferably 20 μm or more and 100 μm or less. When the average thickness of the negative electrode mixture layer is 10 μm or more, the energy density of the electrochemical device is improved. When the average thickness of the negative electrode mixture layer is 450 μm or less, the cycle characteristics of the electrochemical device are improved.

[0141] Here, an embodiment of an electrode according to the present invention will be described with reference to the drawings, although the present invention is not limited to these embodiments.

[0142] [Figure 2B] FIG. 2B is a schematic cross-sectional view showing an electrode for an electrochemical device according to another embodiment of the present invention. The electrode mixture layer may have openings 23 as shown in FIG. 2B. The number of openings 23 is preferably one or more, and more preferably two or more. The openings 23 may penetrate the electrode mixture layer from the surface of the electrode mixture layer to the surface of the substrate, or may not penetrate all the way to the surface of the substrate. The opening 23 may be hollow or filled with the material 24. When the opening 23 is filled with the material 24, the material 24 may be a single material or a mixture of two or more materials, but in either case, the material 24 is different from the material constituting the electrode mixture layer. From the viewpoint of improving ion conductivity, the material 24 is preferably a material having a solid electrolyte. The electrode mixture layer having the openings 23 can be suitably produced by using inkjet as the electrode mixture layer forming means, since application control is easy.

[0143] [Figure 2C] FIG. 2C is a schematic cross-sectional view showing an electrode for an electrochemical device according to another embodiment of the present invention. As shown in FIG. 2C, the electrode mixture layer may have an adhesive layer 22 between the substrate 21 and the electrode mixture layer 20, the adhesive layer 22 containing a metal that alloys with lithium.

[0144] <Structure layer> The structural layer has a laminated structure of two or more layers, including a first structural layer that is mainly in contact with the substrate, and a second structural layer that is provided on the first structural layer. The electrode for an electrochemical element is obtained by a method for manufacturing an electrode for an electrochemical element, and the first structure layer corresponds to a polymerized layer of the first liquid composition, and the second structure layer corresponds to a polymerized layer of the second liquid composition, so duplicated descriptions will be omitted. In this specification, the phrase "mainly in contact with the substrate" means that the contact area with the substrate is the largest in the structure layer.

[0145] In the electrode for electrochemical devices, the porosity of the second structure layer is greater than the porosity of the first structure layer, thereby improving the adhesion of the first structure layer to the substrate.

[0146] When an electrode mixture layer is provided on the substrate, the structure layer is preferably disposed on the periphery of the electrode mixture layer. In this specification, "disposed on the peripheral edge of the electrode mixture layer" means that the structure layer may be disposed on at least two sides of the peripheral edge of the electrode mixture layer, or may be disposed on three sides of the peripheral edge of the electrode mixture layer, or may be disposed on all four sides of the peripheral edge of the electrode mixture layer. In addition, the insulating layer may have a recess or a notch on any side to allow the electrode tab to protrude.

[0147] Here, the shape of the structural layer and the region in which it is provided will be described with reference to the drawings, but the present invention is not limited to these embodiments.

[0148] [Figure 3A] FIG. 3A is a schematic top view showing an electrode for an electrochemical device according to one embodiment of the present invention. In FIG. 3A, the structure layer 10 is provided adjacent to two sides of the periphery of the electrode mixture layer 20.

[0149] [Figure 3B] FIG. 3B is a schematic top view showing an electrode for an electrochemical device according to another embodiment of the present invention. In FIG. 3B, the structure layer 10 is provided adjacent to the two long sides and the two corners of the long sides at the periphery of the electrode mixture layer 20.

[0150] [Figure 3C] FIG. 3C is a schematic top view showing an electrode for an electrochemical device according to another embodiment of the present invention. 3C, the structure layer 10 is provided adjacently and continuously on all four sides of the peripheral edge of the electrode mixture layer 20. Note that the structure layer 10 may also be provided adjacently and discontinuously.

[0151] [Figure 3D-3F] 3D to 3F are schematic top views showing electrodes for electrochemical devices according to other embodiments of the present invention. 3D to 3F, the structure layer 10 is provided adjacent to and discontinuously arranged on all four sides of the peripheral edge of the electrode mixture layer 20. In FIG.

[0152] When the structure layers 10 are provided adjacent to each other discontinuously, as shown in Figures 3D to 3F, they may be provided adjacent to one or more sides of the electrode mixture layer 20 (Figure 3D), or they may be provided adjacent to one or more corners of the electrode mixture layer 20 (Figure 3E), or a combination thereof (Figure 3F).

[0153] [Figure 3G-3I] 3G to 3I are schematic top views showing electrodes for electrochemical devices according to other embodiments of the present invention. The inside of the outer edge of the electrode mixture layer 20 does not have to be coated entirely; that is, the electrode mixture layer 20 may have an opening or an uncoated portion, and the structure layer 10 may be provided on the outer and inner peripheries of the electrode mixture layer 20 (FIG. 3G), or an electrode mixture layer 20′ may be further provided on the inner periphery of the structure layer 20 provided on the inner periphery (FIG. 3H). Furthermore, even when the structure layer 10 is provided on the inner periphery of the electrode mixture layer 20 having an opening, the structure layer 10 may be provided discontinuously so as to be adjacent to one or more inner sides of the electrode mixture layer 20, or so as to be adjacent to one or more inner corners of the electrode mixture layer 20, or a combination thereof. Furthermore, the structure layer 10 may be provided only on the inner periphery of the electrode mixture layer 20 having an opening (FIG. 3I).

[0154] The structure layer preferably has insulating properties. In this specification, "having insulating properties" means that the volume resistivity of the structure layer is 1×10 12 (Ω·cm) or more. An example of a method for imparting insulating properties to the structure layer is a method of adding insulating inorganic particles to the first liquid composition and the second liquid composition. In this specification, a structural layer having insulating properties may be referred to as an "insulating layer," and a liquid composition that forms an insulating layer may be referred to as an "insulating layer-forming liquid composition."

[0155] <<Liquid composition for forming insulating layer>> The liquid composition for forming an insulating layer contains the "first liquid composition" or the "second liquid composition" described in the section (Method for manufacturing an electrode for an electrochemical element, and apparatus for manufacturing an electrode for an electrochemical element), and may contain insulating inorganic particles, a dispersant for the insulating layer, a binder for the insulating layer, a solvent for the insulating layer, and other components, as necessary.

[0156] <<Insulating inorganic particles>> As insulating inorganic particles, the volume resistivity is 10 8 As long as the resistivity is Ω·cm or more, there are no particular limitations and the material can be appropriately selected depending on the purpose, and examples include aluminum oxide (alumina), boehmite, silica, aluminum nitride, silicon nitride, cordierite, sialic acid, mullite, stearite, yttria, zirconia, silicon carbide, etc. Among these, inorganic oxides are preferred, and from the viewpoint of heat resistance, aluminum oxide and boehmite are more preferred, and α-alumina is even more preferred. Alpha-alumina is known to function as a scavenger for "junk" species, i.e., species that can cause capacity fade in lithium-ion secondary batteries. Furthermore, alumina particles have good wettability and affinity for electrolytes, improving the cycling performance of lithium-ion secondary batteries. The use of alpha-alumina as insulating inorganic particles improves the redispersibility and inkjet ejectability of insulating layer-forming liquid compositions, and improves the heat resistance of insulating layers. These insulating inorganic particles may be used alone or in combination of two or more kinds.

[0157] The shape of the insulating inorganic particles is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include rectangular, spherical, elliptical, cylindrical, oval, dogbone, amorphous, etc. Among these, from the viewpoint of improving ejection properties by inkjet, it is preferable that the insulating inorganic particles have a shape in which the aspect ratio of the long side to the short side is close to 1.

[0158] The median diameter of the insulating inorganic particles is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 200 nm or more and 1,000 nm or less. When the insulating inorganic particles have a median diameter of 200 nm or more, the particles can be prevented from floating in the air (generating mist) during inkjet ejection, and in the insulating layer, the insulating inorganic particles can be prevented from adhering to the substrate due to the loss of fine particles. When the median diameter of the insulating inorganic particles is 1,000 nm or less, nozzle clogging during inkjet ejection can be eliminated, improving ejection properties. In addition, in the case of an insulating layer, this is preferable because the thickness of the insulating layer is made uniform and homogenous (with less unevenness).

[0159] The method for measuring the median diameter of insulating inorganic particles is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include dynamic light scattering, photon correlation spectroscopy, laser diffraction, centrifugal sedimentation, induction diffraction, etc. More specifically, the liquid composition can be diluted so that the solid content is 10 mass % or less, and then measured using a concentrated particle size analyzer (FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.).

[0160] The insulating inorganic particles preferably include first insulating inorganic particles having a median diameter of 200 nm or more but less than 1,000 nm and second insulating inorganic particles having an average Stokes diameter of less than 30 nm, where the average Stokes diameter is the average value of the long diameters of the particles measured, for example, by observation with a transmission electron microscope (TEM). When the liquid composition contains second insulating inorganic particles having an average Stokes diameter of less than 30 nm, the energy barrier in the interaction potential energy between particles can be made sufficiently small, and the problem of the inorganic particles not being redispersed even when re-agitated after a long period of standing and causing the inorganic particles to aggregate can be eliminated.

[0161] The content of the insulating inorganic particles is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of achieving a uniform thickness of the insulating layer after drying, it is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total amount of the insulating layer-forming liquid composition. From the viewpoint of viscosity, it is preferably 60% by mass or less, based on the total amount of the insulating layer-forming liquid composition, and from the viewpoint of ejectability by inkjet, it is more preferably 55% by mass or less.

[0162] The insulating inorganic particles may be appropriately synthesized or commercially available. Examples of commercially available aluminum oxide insulating inorganic particles include, by trade name, AKP-15, AKP-20, AKP-30, AKP-50, AKP-53, AKP-700, AKP-3000, AA-03, AA-04, AA-05, AA-07, AA-1.5, AKP-G07, and AKP-G15 (high-purity alumina manufactured by Sumitomo Chemical Co., Ltd.), TM-DA, TM-DAR, and TM-5D (manufactured by Taimei Chemical Industry Co., Ltd.), CT-3000LSSG (manufactured by Almatis), LS-502, LS-711CB, and SLS-710 (manufactured by Nippon Light Metal Co., Ltd.), and SEPal-60 and SEPal-70 (manufactured by Alteo). An example of a commercially available product of boehmite as insulating inorganic particles is BMB-07 (Kawai Lime Industry Co., Ltd.).

[0163] <<Other ingredients>> The liquid composition for forming an insulating layer may contain, as other components, surfactants, pH adjusters, rust inhibitors, preservatives, antifungal agents, antioxidants, antireducing agents, evaporation promoters, chelating agents, etc., for the purposes of adjusting viscosity, adjusting particle size, adjusting surface tension, controlling evaporation of non-aqueous solvents, improving the solubility of additives, improving particle dispersibility, sterilization, etc. The content of other components is not particularly limited and can be set appropriately depending on the content of various components in the liquid composition for forming an insulating layer.

[0164] The average thickness of the insulating layer (structure layer) is not particularly limited and can be appropriately selected depending on various conditions such as the average thickness of the electrode mixture layer, but 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. If the insulating layer (structural layer) has an average thickness of 10.0 μm or more, the pressure load during pressing can be dispersed and short-circuiting between the positive electrode and the negative electrode can be prevented, which is preferable. When the average thickness of the insulating layer (structural layer) is 100.0 μm or less, an electrochemical device with high density and excellent battery characteristics can be produced.

[0165] The compression rate of the insulating layer (structure layer) after pressing at 500 MPa for 5 minutes is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 1% to 50%, more preferably 5% to 20%. When the compression ratio of the insulating layer (structural layer) is 50% or less, the shape of the insulating layer (structural layer) can be sufficiently maintained when subjected to a pressing step. If the insulating layer (structural layer) has a compressibility of 1% or more, the pressure applied from the insulating layer (structural layer) to the solid electrolyte layer can be reduced in the pressing step after the solid electrolyte layer is formed.

[0166] The insulating layer (structural layer) preferably has a bicontinuous structure. When the insulating layer (structure layer) has a co-continuous structure, the thickness of the insulating layer (structure layer) can be easily and precisely controlled by pressing when the thickness of the electrode mixture layer and the thickness of the insulating layer (structure layer) are to be made approximately equal. Furthermore, the insulating layer (structure layer) can be formed by a polymerization-induced phase separation method, which also makes it easy to control the thickness of the insulating layer (structure layer). A porous insulating layer (structure layer) with a co-continuous structure can efficiently release pressure generated during pressing, thereby suppressing defects such as damage to the insulating layer (structure layer) and unevenness in height, and enabling the production of a high-quality insulating layer (structure layer).

[0167] In electrochemical elements where short circuits due to dendrite precipitation may occur, the negative electrode composite layer is typically configured to be larger than the positive electrode composite layer. In this case, if the positive electrode current collector and the negative electrode current collector are approximately the same size, an excess portion where the positive electrode composite layer is not formed is generated on the positive electrode current collector in the region where the negative electrode composite layer of the negative electrode faces. From the viewpoint of electrical element characteristics, the insulating layer (structural layer) is preferably provided on the excess portion of the positive electrode, i.e., on the outer periphery of the positive electrode composite layer. Note that, if the electrochemical element is configured such that the negative electrode composite layer is smaller than the positive electrode composite layer, the insulating layer (structural layer) is preferably provided on the excess portion of the negative electrode, i.e., on the outer periphery of the negative electrode composite layer.

[0168] Here, an embodiment of the present invention will be described with reference to the drawings, but the present invention is not limited to these embodiments. In each drawing, the same components are denoted by the same reference numerals, and redundant explanations may be omitted. Furthermore, the number, position, shape, etc. of the components are not limited to the present embodiment, and the number, position, shape, etc. may be any number, position, shape, etc. that is preferable for implementing the present invention.

[0169] [FIG. 4: An embodiment in which a structural layer or an electrode for an electrochemical device is formed by applying a liquid composition to a substrate] FIG. 4 is a schematic diagram showing a method for producing an electrode for an electrochemical device according to one embodiment of the present invention. The electrochemical element electrode manufacturing apparatus 500 is an apparatus for manufacturing a structure layer using a liquid composition. The electrochemical element electrode manufacturing apparatus 500 includes a first printing unit 100 that performs a first liquid composition application step of applying a first liquid composition 7 onto a substrate 4 to form a first liquid composition film, a second printing unit 200 that performs a second liquid composition application step of applying a second liquid composition 8 to form a second liquid composition film, a polymerization unit 300 that performs a first liquid composition polymer layer formation step of applying heat or light to the first liquid composition film and the second liquid composition film to polymerize them, and a heating unit 400 that performs a liquid composition polymer layer drying step of heating a precursor of the structure layer and removing the solvent in its pores to obtain a structure layer.

[0170] The manufacturing apparatus 500 for electrodes for electrochemical elements includes a transport section 5 that transports the substrate 4, and the transport section 5 transports the substrate 4 at a preset speed through the first printing section 100, the polymerization section 300, the second printing section 200, and the heating section 400 in that order.

[0171] -First printing unit 100- The first printing unit 100 includes a printing device 1a that applies a first liquid composition 7 onto a substrate 4, a storage container 1b that stores the first liquid composition 7, and a supply tube 1c that supplies the first liquid composition 7 stored in the storage container 1b to the printing device 1a. The storage container 1b stores the first liquid composition 7, and the printing unit 100 ejects the first liquid composition 7 from the printing device 1a to apply the first liquid composition 7 onto the substrate 4. The storage container 1b may be integrated with the manufacturing apparatus for the electrochemical element electrode, or may be detachable from the manufacturing apparatus for the electrochemical element electrode. Alternatively, the storage container 1b may be a container used for adding a liquid to a storage container integrated with the manufacturing apparatus for the electrochemical element electrode or a storage container detachable from the manufacturing apparatus for the electrochemical element electrode. Any material can be selected for the storage container 1b and the supply tube 1c as long as they can stably store and supply the first liquid composition 7. The materials constituting the storage container 1b and the supply tube 1c preferably have a light-blocking property in the relatively short wavelength region of ultraviolet light and visible light, thereby preventing the initiation of polymerization of the first liquid composition 7 due to external light.

[0172] -Second printing unit 200- The second printing section 200 includes a printing device 2a that applies the second liquid composition 8 onto the substrate 4, a storage container 2b that stores the second liquid composition 8, and a supply tube 2c that supplies the second liquid composition 8 stored in the storage container 2b to the printing device 2a. The storage container 2b stores the second liquid composition 8, and the printing unit 200 ejects the second liquid composition 8 from the printing device 2a to apply the second liquid composition 8 onto the substrate 4. The storage container 2b may be integrated with the manufacturing apparatus for the electrochemical element electrode, or may be detachable from the manufacturing apparatus for the electrochemical element electrode. Alternatively, the storage container 2b may be a container used for adding to a storage container integrated with the manufacturing apparatus for the electrochemical element electrode or a storage container detachable from the manufacturing apparatus for the electrochemical element electrode. Any material can be selected for the storage container 2b and the supply tube 2c as long as they can stably store and supply the second liquid composition 8. The materials constituting the storage container 2b and the supply tube 2c preferably have a light-blocking property in the relatively short wavelength region of ultraviolet light and visible light, thereby preventing the second liquid composition 8 from being polymerized by external light.

[0173] - Polymerization section 300 - As shown in FIG. 4, in the case of photopolymerization, the polymerization unit 300 has a light irradiation device 3a that performs the step of forming a polymerized layer of the first liquid composition, and a polymerization inert gas circulation device 3b that circulates a polymerization inert gas. The light irradiation device 3a irradiates the first liquid composition film formed by the printing unit 100 with light in the presence of the polymerization inert gas, and photopolymerizes it to obtain a precursor of the structure layer. The light irradiation device 3a is appropriately selected depending on the absorption wavelength of the photopolymerization initiator contained in the first liquid composition, and is not particularly limited as long as it can initiate and progress the polymerization of the compound in the first liquid composition, and examples thereof include ultraviolet light sources such as high-pressure mercury lamps, metal halide lamps, hot cathode tubes, cold cathode tubes, and LEDs. However, since light with shorter wavelengths generally tends to reach deeper parts, it is preferable to select a light source depending on the thickness of the structure layer to be formed. Next, regarding the irradiation intensity of the light source of the light irradiation device 3a, if the irradiation intensity is too strong, polymerization will proceed rapidly before phase separation has fully occurred, making it difficult to obtain a porous structure. On the other hand, if the irradiation intensity is too weak, phase separation will proceed beyond the microscale, making it easy for porosity to vary or become coarse. In addition, the irradiation time will be long, which will tend to reduce productivity. Therefore, the irradiation intensity should be set to 10 mW / cm. 2 More than 1W / cm 2 Less than 30mW / cm is preferable. 2 More than 300mW / cm 2 The following is more preferred:

[0174] The polymerization inert gas circulation device 3b plays a role of reducing the concentration of polymerization-active oxygen contained in the atmosphere and allowing the polymerization reaction of the polymerizable compound near the surface of the liquid composition to proceed without being inhibited. Therefore, the polymerization inert gas used is not particularly limited as long as it satisfies the above function, and examples thereof include nitrogen, carbon dioxide, and argon. The O2 concentration of the polymerization inert gas is preferably less than 20% (an environment with a lower oxygen concentration than the atmosphere) in consideration of effectively obtaining the inhibition reduction effect, more preferably 0% to 15%, and even more preferably 0% to 5%. In addition, the polymerization inert gas circulation device 3b is preferably provided with a temperature control means capable of adjusting the temperature in order to realize stable polymerization progress conditions.

[0175] In the case of thermal polymerization, the polymerization section 300 may be a heating device. The heating device is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a base heater (e.g., a hot plate), an IR heater, and a hot air heater, and these may also be combined. The heating temperature and time, or the conditions for light irradiation, can be appropriately selected depending on the polymerizable compounds contained in the first liquid composition 7 and the second liquid composition 8, and the thickness of the formed film.

[0176] -Heating section 400- As shown in Fig. 4, the heating section 400 has a heating device 4a, and performs a step of drying the polymerized layer of the liquid composition by heating the precursor of the structure layer formed in the polymerization section 300 with the heating device 4a to dry and remove the remaining solvent. This allows the structure layer to be formed. The heating section 400 may be operated under reduced pressure. Furthermore, the heating unit 400 may also carry out a polymerization promotion step in which the precursor of the structure layer is heated by the heating device 4a to further promote the polymerization reaction carried out in the polymerization unit 300, and an initiator removal step in which the photopolymerization initiator remaining in the precursor of the structure layer is heated and dried by the heating device 4a to be removed. Note that these polymerization promotion step and initiator removal step do not have to be carried out simultaneously with the step of forming a polymerized material layer of the first liquid composition and the step of forming a polymerized material layer of the second liquid composition, but may be carried out before or after the step of forming a polymerized material layer of the first liquid composition and the step of forming a polymerized material layer of the second liquid composition.

[0177] [Figure 5] FIG. 5 is a schematic diagram showing a manufacturing apparatus (liquid ejection apparatus) for an electrochemical element member according to one embodiment of the present invention. The liquid ejection device 300 ′ is capable of circulating the liquid composition through the liquid ejection head 306 , the tank 307 and the tube 308 by controlling the pump 310 , the valve 311 and the valve 312 . In addition, the liquid ejection device 300' is provided with an external tank 313, and when the liquid composition in the tank 307 decreases, it is possible to supply the liquid composition from the external tank 313 to the tank 307 by controlling the pump 310, valve 311, valve 312, and valve 314. By using such an apparatus for manufacturing electrodes for electrochemical devices, it is possible to eject the liquid composition at a targeted location.

[0178] [Figure 6] FIG. 6 is a schematic diagram showing a manufacturing apparatus (liquid ejection apparatus) for an electrode for an electrochemical element according to another embodiment of the present invention. The method for producing an electrode for electrochemical devices 210 in which a structural layer is provided on a substrate includes a step of sequentially discharging the liquid composition 12A onto a substrate 211 using a liquid discharge device 300'. First, an elongated substrate 211 is prepared. Then, the substrate 211 is wound around a cylindrical core and set on a feed roller 304 and a take-up roller 305 so that the side on which the structure layer 212 is to be formed faces upward in FIG. 6. Here, the feed roller 304 and the take-up roller 305 rotate counterclockwise, and the substrate 211 is transported from right to left in FIG. 6. Then, droplets of the liquid composition 12A are ejected onto the substrate 211 that is being transported sequentially from a liquid ejection head 306 installed above the substrate 211 between the feed roller 304 and the take-up roller 305, in the same manner as in FIG. 6. Next, the substrate 211 onto which the droplets of the liquid composition 12A have been discharged is transported to a polymerization section 309 by a delivery roller 304 and a take-up roller 305. As a result, a structural layer 212 is formed, and an electrode for an electrochemical device 210 having a structural layer provided on the substrate is obtained. Thereafter, the substrate is cut to a desired size by punching or the like.

[0179] A plurality of liquid ejection heads 306 may be installed in a direction substantially parallel to or substantially perpendicular to the transport direction of the substrate 211 . The overlapping portion 309 may be provided on either the top or bottom of the base 211, or a plurality of overlapping portions may be provided. There are no particular limitations on the polymerization section 309 as long as it does not come into direct contact with the liquid composition 12A. For example, in the case of thermal polymerization, a resistance heater, an infrared heater, a fan heater, etc. can be used; in the case of photopolymerization, an ultraviolet ray irradiation device, etc. can be used. The conditions for heating or light irradiation are not particularly limited and can be appropriately selected depending on the purpose. The liquid composition 12A is polymerized by polymerization to form a structure layer.

[0180] [Figure 7] FIG. 7 is a schematic diagram showing a modified example of the manufacturing apparatus for an electrochemical element member according to one embodiment of the present invention. Liquid ejection device 300A' and liquid ejection device 300B' may be used in combination. That is, the liquid composition may be supplied from external tanks 313A and 313B connected to tanks 307A and 307B, and the liquid ejection head may have multiple heads 306A and 306B. Accordingly, tubes 308A and 308B, valves 311A, 311B, 312A, 312B, valves 314A and 314B, and pumps 310A and 310B may be provided.

[0181] [FIG. 8: An embodiment in which a structural layer or an electrode for an electrochemical device is formed by indirectly applying a liquid composition to a substrate] Fig. 8 is a structural diagram (part 1) showing an example of a printing unit employing an inkjet system and a transfer system as a liquid composition application means in an apparatus for manufacturing an electrochemical element member according to one embodiment of the present invention. The printing unit in Fig. 8 uses a drum-shaped intermediate transfer member. Printing unit 400' is an inkjet printer that transfers a liquid composition onto a substrate via intermediate transfer body 4001, thereby forming a structural layer on the substrate. The printing section 400 ′ includes an inkjet section 420 , a transfer drum 4000 , a pre-treatment unit 4002 , an absorption unit 4003 , a heating unit 4004 , and a cleaning unit 4005 .

[0182] The inkjet unit 420 includes a head module 422 that holds a plurality of heads 101 . The head 101 ejects a liquid composition onto an intermediate transfer body 4001 supported by a transfer drum 4000, forming a liquid composition film on the intermediate transfer body 4001. Each head 101 is a line head, and nozzles are arranged over a range that covers the width of the recording area of ​​a substrate of the largest usable size. The head 101 has a nozzle surface on its underside on which nozzles are formed, and the nozzle surface faces the surface of the intermediate transfer body 4001 via a minute gap. In this embodiment, the intermediate transfer body 4001 is configured to move cyclically on a circular orbit, so the multiple heads 101 are arranged radially.

[0183] The transfer drum 4000 faces the impression cylinder 621 and forms a transfer nip. The pretreatment unit 4002 applies, for example, a reaction liquid onto the intermediate transfer body 4001 to increase the viscosity of the liquid composition before the head 101 ejects the liquid composition.

[0184] The absorption unit 4003 absorbs liquid components from the liquid composition on the intermediate transfer member 4001 before transfer.

[0185] The heating unit 4004 heats the liquid composition on the intermediate transfer body 4001 before transfer. Heating the liquid composition forms a structure layer. In addition, the solvent is removed, improving transferability to the substrate.

[0186] A cleaning unit 4005 cleans the surface of the intermediate transfer body 4001 after transfer, and removes foreign matter such as ink and dust remaining on the intermediate transfer body 4001 .

[0187] The outer peripheral surface of the impression cylinder 621 is in pressure contact with the intermediate transfer body 4001, and the structure layer on the intermediate transfer body 4001 is transferred to the substrate when the substrate passes through the transfer nip between the impression cylinder 621 and the intermediate transfer body 4001. The impression cylinder 621 may be configured to have at least one gripping mechanism on its outer peripheral surface that holds the leading end of the substrate.

[0188] [Figure 9] 9 is a structural diagram (part 2) showing an example of a printing unit employing an inkjet system and a transfer system as a means for applying a first liquid composition and a means for applying a polymer layer of a second liquid composition in an apparatus for manufacturing an electrode for an electrochemical device according to one embodiment of the present invention. The printing unit in FIG. 9 uses an intermediate transfer member in the form of an endless belt. The printing unit 400 ″ is an inkjet printer that transfers a liquid composition onto a substrate via an intermediate transfer belt 4006 to form a structural layer. The printing section 400'' includes an inkjet section 420, a transfer roller 622, an intermediate transfer belt 4006, a heating unit 4007, a cleaning roller 4008, a drive roller 4009a, an opposing roller 4009b, a shape maintaining roller 4009c, a shape maintaining roller 4009d, a shape maintaining roller 4009e, and a shape maintaining roller 4009f.

[0189] The printing unit 400'' ejects droplets of the liquid composition from a plurality of heads 101 provided in the inkjet unit 420 onto the outer circumferential surface of the intermediate transfer belt 4006. The liquid composition on the intermediate transfer belt 4006 is heated by a heating unit 4007 and thermally polymerized to form a structure layer. At the transfer nip portion where the intermediate transfer belt 4006 faces the transfer roller 622, the structure layer on the intermediate transfer belt 4006 is transferred to the substrate. After transfer, the surface of the intermediate transfer belt 4006 is cleaned by a cleaning roller 4008.

[0190] Intermediate transfer belt 4006 is stretched over drive roller 4009a, opposing roller 4009b, multiple shape-maintaining rollers 4009c, shape-maintaining roller 4009d, shape-maintaining roller 4009e, shape-maintaining roller 4009f, and multiple support rollers 4009g, and moves in the direction of the arrow in Figure 9. Support roller 4009g, which is provided opposite head 101, maintains the tension state of intermediate transfer belt 4006 when the liquid composition is ejected from head 101.

[0191] (Electrode laminate for electrochemical devices) The electrode laminate for an electrochemical device of the present invention has an electrode for an electrochemical device and a solid electrolyte layer provided on an electrode mixture layer and a structure layer, and may contain other members as necessary. As the electrodes for electrochemical elements, those described in the section (Electrodes for electrochemical elements) can be used, and therefore redundant description will be omitted.

[0192] Here, an embodiment of an electrode laminate for an electrochemical device according to the present invention will be described with reference to the drawings, although the present invention is not limited to these embodiments.

[0193] [Figure 10] FIG. 10 is a schematic cross-sectional view showing an electrode laminate for an electrochemical device according to one embodiment of the present invention. The electrode laminate 35 for an electrochemical element has a base 21, an electrode composite layer 20 arranged on the base 21, a structure layer 10 arranged on the peripheral portion of the electrode composite layer 20, and a solid electrolyte layer 30 arranged on the electrode composite layer 20 and on the structure layer 10. Although FIG. 10 illustrates a configuration in which the electrode composite layer 20, the structure layer 10, and the solid electrolyte layer 30 are provided on one side of the base 21, the electrode composite layer 20, the structure layer 10, and the solid electrolyte layer 30 may be provided on both opposing sides of the base 21. In FIG. 10, the laminated structure of the structural layer 10 is omitted.

[0194] <Solid electrolyte layer> The solid electrolyte is not particularly limited and can be appropriately selected depending on the purpose, and those described in the section <<Solid Electrolyte>> can be used. The solid electrolyte layer is formed from a liquid composition for forming a solid electrolyte layer.

[0195] The solid electrolyte layer-forming liquid composition may contain a solid electrolyte layer binder. Examples of binders for the solid electrolyte layer include thermoplastic resins such as polyvinylidene fluoride (PVDF), acrylic resin, styrene-butadiene rubber, polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, and polybutylene terephthalate, 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), and polyethylene vinyl acetate (PEVA).

[0196] (electrochemical element) The electrochemical device of the present invention has electrodes for an electrochemical device, and may have an exterior and other members as necessary. As the electrodes for electrochemical devices, those described in the section (Electrodes for electrochemical devices) can be used, and therefore redundant description will be omitted.

[0197] (All-solid-state electrochemical device) The electrochemical device of the present invention has an electrode laminate for an electrochemical device, and may have an exterior and other members as necessary. As the electrode laminate for an electrochemical device, the one described in the section (Electrode laminate for an electrochemical device) can be used, and therefore a duplicate description will be omitted.

[0198] Here, an embodiment of the all-solid-state electrochemical device according to the present invention will be described with reference to the drawings, although the present invention is not limited to these embodiments.

[0199] [Figure 11] FIG. 11 is a schematic cross-sectional view showing an all-solid-state electrochemical device according to one embodiment of the present invention. The all-solid-state electrochemical element 45 has a substrate 21, an electrode mixture layer 20 disposed on the substrate 21, a structure layer 10 disposed on the peripheral edge of the electrode mixture layer 20, a solid electrolyte layer 30 disposed on the electrode mixture layer 20 and on the structure layer 10, a second electrode mixture layer 40 disposed on the solid electrolyte layer 30, and a second substrate 41 disposed on the second electrode mixture layer. The all-solid-state electrochemical element 45 is a single cell layer, which can be stacked to form a stacked battery. Although FIG. 11 illustrates a configuration in which the electrode mixture layer 20, the structure layer 10, and the solid electrolyte layer 30 are provided on one side of the base 21, the electrode mixture layer 20, the structure layer 10, and the solid electrolyte layer 30 may be provided on both opposing sides of the base 21, and a stacked battery may be formed by stacking these configurations. In FIG. 11, the laminated structure of the structural layer 10 is omitted.

[0200] [Figure 12] FIG. 12 is a schematic cross-sectional view showing an example of an all-solid-state electrochemical device according to one embodiment of the present invention. The all-solid-state battery shown in FIG. 12 includes a positive electrode (electrode mixture layer) 20, a negative electrode (electrode mixture layer) 40, a solid electrolyte layer 30, a lead wire 50, a lead wire 51, and an exterior 60. The positive electrode (electrode mixture layer) 20 includes a positive electrode substrate (substrate) 21 and a structure layer 10 disposed on the positive electrode substrate (substrate) 21 and on the periphery of the positive electrode (electrode mixture layer) 20. 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 casing 60. Here, the all-solid-state electrochemical element has a positive electrode (electrode mixture layer) 20 and a negative electrode (electrode mixture layer) 40 stacked with a solid electrolyte layer 30 interposed therebetween, and the positive electrode (electrode mixture layer) 20 is disposed on both sides of the negative electrode (electrode mixture layer) 40. There is no particular limit to the number of positive electrodes (electrode mixture layers) 20 and negative electrodes (electrode mixture layers) 40 stacked. Furthermore, the number of positive electrodes (electrode mixture layers) 20 and the number of negative electrodes (electrode mixture layers) 40 may be the same or different. In FIG. 12, the laminated structure of the structural layer 10 is omitted.

[0201] The exterior packaging is not particularly limited as long as it can seal the electrode laminate, and any known exterior packaging can be appropriately selected depending on the purpose.

[0202] The shape of the electrochemical element is not particularly limited and can be appropriately selected depending on the purpose. Examples include laminate type, cylinder type, and coin type.

[0203] (Method for manufacturing electrochemical elements and apparatus for manufacturing electrochemical elements) The method for manufacturing an electrochemical device according to the present invention preferably includes an insulating layer forming step, an electrode mixture layer forming step, a pressing step, a solid electrolyte layer forming step, an element forming step, and an electrode processing step, and may include other steps as necessary. The electrochemical element manufacturing apparatus according to the present invention preferably includes an insulating layer forming means, an electrode mixture layer forming means, a pressing means, a solid electrolyte layer forming means, an element forming means, and an electrode processing means, and may include other means as necessary. The method for producing an electrochemical device can be suitably carried out by an apparatus for producing an electrochemical device.

[0204] <Insulating layer forming step and insulating layer forming means> The insulating layer forming step is a step of forming an insulating layer on a substrate, and preferably includes a step of applying an insulating layer-forming liquid composition, a step of curing the insulating layer-forming liquid composition, and a step of removing a solvent. The insulating layer forming means is a means for forming an insulating layer on a substrate, and preferably includes a means for applying the insulating layer-forming liquid composition, a means for curing the insulating layer-forming liquid composition, and a means for removing the solvent. The insulating layer forming step can be suitably carried out by an insulating layer forming means.

[0205] <<Insulating layer forming liquid composition applying step and insulating layer forming liquid composition applying means>> The insulating layer-forming liquid composition application step is a step of applying the insulating layer-forming liquid composition onto a substrate. The insulating layer forming liquid composition applying means is a means for applying the insulating layer forming liquid composition onto a substrate. The step of applying the insulating layer-forming liquid composition can be suitably carried out by an insulating layer-forming liquid composition applying means. The insulating layer-forming liquid composition may be one described in the section <<Insulating layer-forming liquid composition>>, and the insulating layer-forming liquid composition application step and insulating layer-forming liquid composition application means may be one described in the section <First liquid composition application step and first liquid composition application means>.

[0206] <<Insulating layer forming liquid composition polymerization step and insulating layer forming liquid composition polymerization means>> The insulating layer forming liquid composition polymerizing step is a step of polymerizing the applied insulating layer forming liquid composition. The insulating layer forming liquid composition polymerizing means is a means for polymerizing the applied insulating layer forming liquid composition. The insulating layer forming liquid composition polymerizing step can be suitably carried out by an insulating layer forming liquid composition polymerizing means. The insulating layer-forming liquid composition polymerization step and the insulating layer-forming liquid composition polymerization means can be those described in the section <First liquid composition polymerized material layer formation step and first liquid composition polymerized material layer formation means>.

[0207] <<Solvent Removal Step and Solvent Removal Means>> The solvent removal step is a step of removing the solvent from the polymerized liquid composition for forming an insulating layer. The solvent removal means is a means for removing the solvent from the polymerized liquid composition for forming an insulating layer. The solvent removal step and solvent removal means may be those described in the section <Step of drying the polymerized layer of the liquid composition and means of drying the polymerized layer of the liquid composition>.

[0208] <Electrode mixture layer forming step and electrode mixture layer forming means> The electrode mixture layer forming step is a step of forming an electrode mixture layer on a substrate. The electrode mixture layer forming means is a means for forming an electrode mixture layer on a substrate. The electrode mixture layer forming step and the electrode mixture layer forming means are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a method in which the electrode mixture layer forming liquid composition is applied to a substrate, fixed, and dried. In this case, application methods such as spraying, dispenser, die coater, and lift-up coating can be suitably used.

[0209] In the method for producing an electrochemical device, the order of the insulating layer forming step and the electrode mixture layer forming step is not particularly limited. That is, the electrode mixture layer forming step may be performed before the insulating layer forming step, and the insulating layer may be formed on the periphery of the electrode mixture layer after the electrode mixture layer is formed. In this case, the method for producing an electrochemical device is performed in the order of the electrode mixture layer forming step, the insulating layer forming step, and the solvent removing step. Similarly, the electrode mixture layer forming step may be performed after the insulating layer forming step, and after a frame-shaped insulating layer is formed on the electrode substrate, the electrode mixture layer may be formed inside the insulating layer. In this case, the method for producing an electrochemical device is performed in the order of the insulating layer forming step, the electrode mixture layer forming step, and the solvent removing step.

[0210] <Solid electrolyte layer forming process, solid electrolyte layer forming means> The solid electrolyte layer forming step is a step of forming a solid electrolyte layer on the electrode mixture layer and the insulating layer. The solid electrolyte layer forming means is a means for forming a solid electrolyte layer on the electrode mixture layer and the insulating layer. The solid electrolyte layer forming step can be suitably carried out by a solid electrolyte layer forming means.

[0211] The solid electrolyte layer forming step (means) is not particularly limited and can be appropriately selected depending on the purpose. For example, a method of applying a liquid composition for forming a solid electrolyte layer, which contains a solid electrolyte and, if necessary, a binder for the solid electrolyte layer, onto an electrode mixture layer and an insulating layer, solidifying the liquid composition, and drying the liquid composition, can be mentioned.

[0212] The solid electrolyte layer forming step (means) is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include liquid ejection methods such as an inkjet method, a spray coating method, and a dispenser method, spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, and reverse printing.

[0213] <Pressing process, pressing method> The pressing step is a step of pressing the electrode mixture layer and the insulating layer. The pressing means is a means for pressing the electrode mixture layer and the insulating layer. The pressing step can be suitably carried out by a pressing means.

[0214] The pressing step and pressing means are not particularly limited and can be performed using a commercially available pressure molding device, as long as the electrode mixture layer and the insulating layer are pressed in the direction of the substrate, and examples thereof include uniaxial pressing, roll pressing, cold isostatic pressing (CIP), hot pressing, etc. Among these, cold isostatic pressing (CIP), which can apply isostatic pressure, is preferred.

[0215] The timing of performing the pressing step is not particularly limited and can be selected appropriately depending on the purpose. For example, the electrode mixture layer and the insulating layer may be pressed after being formed on the base, or, if the thickness of the insulating layer and the thickness of the electrode mixture layer before pressing are approximately the same, pressing may be performed after providing the solid electrolyte layer, or may be performed at both times. By performing a pressing step after forming the electrode mixture layer and the insulating 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 layer can be made approximately equal, and even if high pressure is applied when pressing the solid electrolyte layer provided on the electrode, the pressure load can be distributed.

[0216] The pressing pressure is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable to perform the pressing at a pressure that can compress the electrode mixture layer while pressing the substrate and the electrode mixture layer together, more specifically, a pressure of 1 MPa or more and 900 MPa or less is preferable, and a pressure of 50 MPa or more and 300 MPa or less is more preferable.

[0217] The pressing means is not particularly limited, and can be a commercially available pressure molding device, as long as it can press the electrode mixture layer and the insulating layer in the direction of the base, and examples thereof include uniaxial pressing, roll pressing, cold isostatic pressing (CIP), hot pressing, etc. Among these, cold isostatic pressing (CIP), which can apply isostatic pressure, is preferred.

[0218] The method for manufacturing the electrode laminate includes a series of steps from the insulating layer forming step to the pressing step. The method for manufacturing the electrode laminate includes each of the steps from the insulating layer forming step to the pressing step.

[0219] <Device Fabrication Process and Device Fabrication Means> The device fabrication step is a step of manufacturing an electrochemical device using the electrode stack. The device fabrication means is a means for producing an electrochemical device using the electrode laminate. The method for producing an electrochemical element using an electrode laminate is not particularly limited, and any known method for producing an electrochemical element can be appropriately selected depending on the purpose. For example, a method of at least one of providing a counter electrode, winding or laminating, or housing in a container can be used. The element fabrication step does not necessarily include all steps of fabrication, but may include only a part of the steps of fabrication.

[0220] <Electrode processing process and electrode processing section> The electrode processing step is a step of processing the electrode on which the insulating layer has been formed, which is performed after the step of applying the insulating layer-forming liquid composition in the insulating layer forming step, and may include at least one of a cutting step, a folding step, and a bonding step. The electrode processing means processes the electrode on which the insulating layer is formed, and may include at least one of cutting, folding, and laminating. The electrode processing means can, for example, cut the electrode on which the insulating layer is formed, or can wind or stack the electrode on which the insulating layer is formed. The electrode processing means has, for example, an electrode processing device, and performs cutting, zigzag folding, stacking, and winding of the electrode on which the insulating layer has been formed according to the desired battery configuration.

[0221] The use of the electrochemical element is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include mobile objects such as vehicles, smartphones, notebook computers, pen-input personal computers, mobile personal computers, electronic book players, mobile phones, mobile fax machines, mobile copiers, mobile printers, headphone stereos, video movie players, LCD televisions, handheld vacuum cleaners, portable CDs, minidiscs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, lighting equipment, toys, game devices, clocks, strobe lights, cameras, and other electrical equipment. Of these, vehicles and electrical equipment are preferred. Examples of the mobile body include a standard automobile, a large special-purpose automobile, a small special-purpose automobile, a truck, a large motorcycle, and a standard motorcycle.

[0222] Here, an embodiment of a moving body that is an electrochemical element according to the present invention will be described with reference to the drawings, although the present invention is not limited to these embodiments.

[0223] [Moving object] FIG. 13 is a schematic diagram showing an example of a moving body that is an electrochemical device according to one embodiment of the present invention. The moving object 70 is, for example, an electric vehicle. The moving object 70 includes a motor 71, an electrochemical device 72, and wheels 73.

[0224] The electrochemical element 72 is an electrochemical element according to the present invention. The electrochemical element 72 supplies power to the motor 71 to drive 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 is equipped with an electrochemical element 72, short circuits between the positive and negative electrodes are prevented, and the mobile object can be driven by power from the electrochemical element, which has excellent battery characteristics, allowing it to move safely and efficiently.

[0225] The mobile object 70 is not limited to an electric vehicle, but may also be a PHEV, HEV, or a locomotive or motorcycle that can run using a diesel engine and an electrochemical device in combination. Furthermore, the mobile object 70 may be a transport robot used in a factory or the like that can run using only an electrochemical device or a combination of an engine and an electrochemical device. Furthermore, the mobile object 70 may be an object that does not move as a whole, but only a part of it, such as an assembly robot that is arranged on a factory production line and that can operate an arm or the like using only an electrochemical device or a combination of an engine and an electrochemical device. [Example]

[0226] 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".

[0227] <Preparation of Liquid Composition 1> Liquid composition 1 was prepared by mixing 50 wt % polyethylene glycol (200) diacrylate (product name: PEG200DA, manufactured by Daicel Allnex Corporation) as a polymerizable compound, 24 wt % menthane and 26 wt % diethylene glycol diethyl ether (solvent mass ratio 48:52) as a solvent, and then mixing bis(2,4,6-trimethylbenzoyl)phenyl phosphate as a polymerization initiator in a proportion of 1 mass % relative to the polymerizable compound.

[0228] <Preparation of Liquid Composition 2> Liquid composition 2 was prepared by mixing 25 wt % CN2283 and 25 wt % HPPA as polymerizable compounds, and 38.5 wt % decane and 11.5 wt % 2-ethylhexyl acetate (solvent mass ratio 77:23) as solvents, and mixing bis(2,4,6-trimethylbenzoyl)phenyl phosphate as a polymerization initiator in a proportion of 1 mass % relative to the polymerizable compounds.

[0229] <Preparation of Liquid Composition 3> Liquid composition 3 was prepared by mixing 50 wt% polyethylene glycol (200) diacrylate (product name: PEG200DA, manufactured by Daicel Allnex Corporation) as a polymerizable compound and 50 wt% diethylene glycol diethyl ether as a solvent, and mixing bis(2,4,6-trimethylbenzoyl)phenyl phosphate as a polymerization initiator in a proportion of 1 mass% relative to the polymerizable compound.

[0230] <Preparation of Liquid Composition 4> Liquid composition 4 was prepared by mixing 50 wt % polyethylene glycol (200) diacrylate (product name: PEG200DA, manufactured by Daicel Allnex Corporation) as a polymerizable compound, 24 wt % menthane and 76 wt % diethylene glycol diethyl ether as a solvent, and mixing bis(2,4,6-trimethylbenzoyl)phenyl phosphate as a polymerization initiator in a proportion of 1 mass % relative to the polymerizable compound.

[0231] <Preparation of Liquid Composition 5> Liquid composition 5 was prepared by mixing 35 wt % polyethylene glycol (200) diacrylate (product name: PEG200DA, manufactured by Daicel Allnex Corporation) as a polymerizable compound, 31.2 wt % menthane, and 33.8 wt % diethylene glycol diethyl ether as a solvent (solvent mass ratio 48:52), and mixing bis(2,4,6-trimethylbenzoyl)phenyl phosphate as a polymerization initiator in a proportion of 1 mass % relative to the polymerizable compound.

[0232] <Preparation of Liquid Composition 6> Liquid composition 6 was prepared by mixing 100 wt% polyethylene glycol (200) diacrylate (product name: PEG200DA, manufactured by Daicel Allnex Corporation) as a polymerizable compound and bis(2,4,6-trimethylbenzoyl)phenyl phosphate as a polymerization initiator in a ratio of 1 mass% relative to the polymerizable compound.

[0233] [Table 1]

[0234] Example 1 <Preparation of electrodes for electrochemical devices> The obtained liquid composition 1 was filled into an ink jet ejection device equipped with MH5421F (manufactured by Ricoh Industry Co., Ltd.). Liquid composition 1 was applied to one side of an aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) using an inkjet device to a target film thickness of 10 μm and a shape of 50 mm × 30 mm in outer dimensions. Next, one second after application, the applied area was irradiated with ultraviolet light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm). 2 The coating was cured by irradiation for 20 seconds to obtain a polymerized layer of the first liquid composition. After UV irradiation, Liquid Composition 1 was again applied to the same coated area at a thickness of 140 μm, and similarly, 1 second after application, UV irradiation was carried out to harden the composition, thereby obtaining a polymerized layer of the second liquid composition. Next, the solvent was removed by heating at 120° C. for 10 minutes using a hot plate, and an electrode for electrochemical devices 1 of Example 1 having an average thickness of 150 μm was obtained.

[0235] [Measurement of the average thickness of each layer] The cross section of the electrode for electrochemical device 1 was observed using a scanning electron microscope (SEM) (phenompro-x, manufactured by Jusco International Co., Ltd.). The average thickness of the polymerized layer of the first liquid composition was calculated by measuring the thickness of the polymerized layer of the first liquid composition at three or more points, using the surface of the substrate as the reference, and then averaging the measured values. The average thickness of the polymerized layer of the second liquid composition was calculated by measuring the thickness of the polymerized layer of the second liquid composition at three or more points, using the interface between the polymerized layer of the first liquid composition and the polymerized layer of the second liquid composition as the reference point, and then averaging the measured values. The same measurement was carried out when a third or subsequent polymer layer of the liquid composition was present. The total thickness (average thickness) of the polymerized liquid composition layer was calculated by measuring the total thickness of the polymerized liquid composition layer at three or more points, using the substrate surface as the reference, and then averaging the measured values. The results are shown in Table 2.

[0236] [Porosity measurement] After staining the electrochemical element electrode 1 with osmium, it was vacuum-impregnated with epoxy resin, and the internal cross-sectional structure was cut out using a focused ion beam (FIB), and the porosity was measured using a scanning electron microscope (SEM). The results are shown in Table 2.

[0237] [Evaluation of wetting and spreading] The method for evaluating the wetting and spreading will be explained with reference to FIG. The shape of the electrode for electrochemical devices was measured using a Keyence laser microscope (VKX-3000). The Y-axis represents the thickness of the polymerized liquid composition layer, and the X-axis (Y = 0) corresponds to the substrate surface. Based on the total thickness (average thickness) obtained by [Measuring the average thickness of each layer], an imaginary line was drawn parallel to the X-axis. The intersections of the imaginary line and one end of the upper surface of the polymerized liquid composition layer were designated as points A and A'. The intersections of the polymerized liquid composition layer and the X-axis were designated as points B and B'. The horizontal distance between points A and B was designated as taper length C, and the horizontal distance between points A' and B' was designated as taper length C'. The average values ​​of taper length C and taper length C' were calculated and evaluated based on the evaluation criteria. A smaller taper length indicates a better wetting and spreading suppression effect. The results are shown in Table 2. -Evaluation criteria- ○: The average taper length is 5 mm or less ×: The average taper length exceeds 5 mm

[0238] [Flatness evaluation] The method for evaluating the flatness will be explained with reference to FIG. The shape of the electrode for electrochemical devices was measured using a Keyence laser microscope (VKX-3000). The Y axis represents the thickness of the polymerized liquid composition layer, and the X axis (Y = 0) corresponds to the substrate surface. Based on the total thickness (average thickness) obtained by [Measuring the average thickness of each layer], an imaginary line was drawn parallel to the X axis, and the intersections of the imaginary line and both ends of the upper surface of the polymerized liquid composition layer were designated as points A and A', respectively. The maximum and minimum thicknesses in the measurement range between points A and A' were measured. The difference between the obtained maximum and minimum thicknesses was calculated and evaluated based on the evaluation criteria. A grade of "△" or better was considered to be acceptable. The results are shown in Table 2. -Evaluation criteria- ○: Difference is less than 5 μm △: Difference is 5 μm or more and less than 10 μm ×: Difference is 10 μm or more

[0239] [Carl's Rating] With the electrode for electrochemical elements placed on a horizontal surface, the maximum height (mm) of the warpage at one end of the electrode for electrochemical elements was measured as "warpage" and evaluated based on the evaluation criteria. A grade of "△" or better was considered to be acceptable. The results are shown in Table 2. -Evaluation criteria- ◎: Maximum warpage is 0 mm or more and less than 1 mm 〇: Maximum warpage is 1mm or more and less than 3mm △: Maximum warpage is 3mm or more and less than 5mm ×: Maximum warpage is 5 mm or more

[0240] [Evaluation of peel strength] The base surface of the electrode 1 for electrochemical elements was adhered to a stainless steel plate, and one end of the tape was attached to a force gauge (ZTA-5N) manufactured by Imada Co., Ltd. The other end of the tape attached to the force gauge was attached to the polymerized layer of the liquid composition on the electrode for electrochemical elements, and the 90-degree peel strength was measured. Evaluation was performed based on the evaluation criteria. A grade of "△" or better was considered to be acceptable. The results are shown in Table 2. -Evaluation criteria- ○: Peel strength is 100N / m or more △: Peel strength is 30N / m or more and less than 100N / m ×: Peel strength is less than 30 N / m

[0241] Examples 2 to 5 An electrode for an electrochemical device was prepared in the same manner as in Example 1, except that the conditions were changed as shown in Table 2, and measurements and evaluations were carried out. The results are shown in Table 2.

[0242] Example 6 The obtained liquid composition 3 was filled into an ink jet ejection device equipped with MH5421F (manufactured by Ricoh Industry Co., Ltd.). Liquid composition 3 was applied to one side of an aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) using an inkjet device to a target film thickness of 10 μm and a shape of 50 mm × 30 mm in outer dimensions. Next, one second after application, the applied area was irradiated with ultraviolet light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm). 2 The coating was cured by irradiation for 20 seconds to obtain a polymerized layer of the first liquid composition. After UV irradiation, Liquid Composition 3 was again applied to the same coated area at a thickness of 45 μm, and similarly, 1 second after application, UV irradiation was carried out to harden the composition, thereby obtaining a polymerized layer of the second liquid composition. After UV irradiation, Liquid Composition 3 was again applied to the same coated area at a thickness of 95 μm, and similarly, 1 second after application, UV irradiation was carried out to harden the composition, thereby obtaining a polymerized layer of the third liquid composition. Next, the solvent was removed by heating at 120° C. for 10 minutes using a hot plate, and an electrode 6 for an electrochemical device of Example 6 having an average thickness of 150 μm was obtained.

[0243] (Examples 7 to 22) An electrode for an electrochemical device was prepared in the same manner as in Example 1, except that the conditions were changed as shown in Table 2, and measurements and evaluations were carried out. The results are shown in Table 2. In Examples 14 and 15, a copper foil substrate (50 mm×50 mm, average thickness: 15 μm) was used as the substrate, and in Examples 16 and 17, a stainless steel foil substrate (50 mm×50 mm, average thickness: 15 μm) was used as the substrate.

[0244] (Comparative Example 1) The obtained liquid composition 1 was filled into an ink jet ejection device equipped with MH5421F (manufactured by Ricoh Industry Co., Ltd.). Liquid composition 1 was applied to one side of an aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) using an inkjet device to a target film thickness of 150 μm and a shape of 50 mm × 30 mm in outer dimensions. Next, one second after application, the applied area was irradiated with ultraviolet light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm). 2 The coating was cured by irradiation for 20 seconds to obtain a polymerized layer of the first liquid composition. Next, the solvent was removed by heating at 120° C. for 10 minutes using a hot plate, and a comparative electrode for electrochemical devices 1 of Comparative Example 1 having an average thickness of 150 μm was obtained.

[0245] (Comparative Examples 2 to 3) Comparative electrodes 2 and 3 for electrochemical elements were prepared in the same manner as in Comparative Example 1, except that the conditions were changed as shown in Table 2, and measurements and evaluations were carried out. The results are shown in Table 2.

[0246] [Table 2]

[0247] From the results of Examples 1 to 22, it is clear that the present invention can provide an excellent effect of suppressing wetting and spreading if the preferred embodiments described in this specification are adopted. The results of Examples 2, 21, and 22 show that if the average thickness of the polymerized layer of the first liquid composition is less than 10 μm, a sufficient wetting and spreading suppression effect cannot be obtained. Examples 3, 6, 7, 8, 20, and 21 show that when the average thickness of the polymerized layer of the second liquid composition and the polymerized layer of the third liquid composition is less than 100 μm, flatness is lost and coffee ring occurs. From Examples 5 and 10, it can be seen that when Liquid Compositions 3 and 4, which do not satisfy either Formula (1) or Formula (2), are used, a sufficient curl suppression effect and sufficient peel strength cannot be obtained. From Example 11, it can be seen that if the step of drying the polymerized liquid composition layer is carried out before (during) the step of applying the second liquid composition, flatness is lost and coffee rings occur. From Example 12, it can be seen that if the step of drying the polymerized liquid composition layer is carried out before (during) the step of applying the third liquid composition, flatness is lost and coffee rings occur. From Example 13, it can be seen that when Liquid Composition 5, which contains a low proportion of the polymerizable compound relative to the total amount of the liquid composition, is used as the first liquid composition, the peel strength decreases.

[0248] In Comparative Examples 1 and 2, a layer of the polymerized product of the second liquid composition was not formed, and therefore a sufficient effect of suppressing wetting and spreading was not obtained. In Comparative Example 3, liquid composition 6, which does not form a porous structure, was used, and therefore curling occurred, making it impossible to carry out various evaluations.

[0249] The present invention includes, for example, the following aspects. <1> A method for manufacturing an electrode for an electrochemical element, the method comprising: a substrate; an electrode mixture layer provided on the substrate; and a structure layer provided on at least a portion of a peripheral edge of the electrode mixture layer, the method comprising: The method for manufacturing an electrode for an electrochemical device includes a structural layer forming step, The structural layer forming step includes: a first liquid composition application step of applying a first liquid composition containing a first polymerizable compound and a first solvent onto a substrate; a first liquid composition polymer layer forming step of polymerizing the first liquid composition applied in the first liquid composition application step to form a polymer layer of the first liquid composition; a second liquid composition applying step of applying a second liquid composition containing a second polymerizable compound and a second solvent onto the polymer layer of the first liquid composition, The method for producing an electrode for an electrochemical device is characterized in that the polymer layer of the first liquid composition has a porous structure. <2> a second liquid composition polymerized layer forming step of polymerizing the second liquid composition applied in the second liquid composition applying step to form a polymerized layer of the second liquid composition, <1> 1. A method for producing an electrode for an electrochemical element according to claim 1. <3> a liquid composition polymer layer drying step of drying the polymer layer of the first liquid composition and the polymer layer of the second liquid composition; <2> 1. A method for producing an electrode for an electrochemical element according to claim 1. <4> the average thickness of the polymerized layer of the first liquid composition is 10 μm or more; <1> from <3> 10. A method for producing an electrode for an electrochemical element according to any one of the preceding claims. <5> the polymerized layer of the second liquid composition has a single-layer structure; <2> from <4> 10. A method for producing an electrode for an electrochemical element according to any one of the preceding claims. <6> the polymerized layer of the second liquid composition has a laminated structure of two or more layers; <2> from <4> 10. A method for producing an electrode for an electrochemical element according to any one of the preceding claims. <7> At least one layer constituting the polymerized product layer of the second liquid composition has an average thickness of 100 μm or more. <2> from <6> 10. A method for producing an electrode for an electrochemical element according to any one of the preceding claims. <8> The first polymerizable compound is represented by the following general formula (1) or the following general formula (2): <1> from <7> 10. A method for producing an electrode for an electrochemical element according to any one of the preceding claims. [ka] (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.) [ka] (In the general formula (2), R3 and R4 represent a hydrogen atom or a methyl group.) <9> the first solvent is a mixed solvent containing a good solvent in which the first polymerizable compound is soluble and a poor solvent in which the first polymerizable compound is insoluble, The first solvent satisfies the following formula (1): <1> from <8> 10. A method for producing an electrode for an electrochemical element according to any one of the preceding claims.

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[0250] <1> from <13> The method for producing an electrode for an electrochemical element according to any one of the preceding claims. <14> from <16> The electrode for an electrochemical element according to any one of <17> The electrode laminate for an electrochemical element according to <18> The electrochemical element according to claim 1, <19> The all-solid-state electrochemical device described in the above can solve the various problems encountered in the past and achieve the object of the present invention. [Explanation of symbols]

[0251] 1 Base 2. Polymer layer of first liquid composition 3. Polymerized layer of second liquid composition 4. Polymerized layer of third liquid composition [Prior art documents] [Patent documents]

[0252] [Patent Document 1] Patent No. 4730038

Claims

1. A method for manufacturing an electrode for an electrochemical element, the method comprising: a substrate; an electrode mixture layer provided on the substrate; and a structure layer provided on at least a portion of a peripheral edge of the electrode mixture layer, the method comprising: The method for manufacturing an electrode for an electrochemical device includes a structural layer forming step, The structural layer forming step includes: a first liquid composition application step of applying a first liquid composition containing a first polymerizable compound and a first solvent onto a substrate; a first liquid composition polymer layer forming step of polymerizing the first liquid composition applied in the first liquid composition application step to form a polymer layer of the first liquid composition; a second liquid composition applying step of applying a second liquid composition containing a second polymerizable compound and a second solvent onto the polymer layer of the first liquid composition, A method for producing an electrode for an electrochemical element, wherein the polymer layer of the first liquid composition has a porous structure.

2. 2. The method for manufacturing an electrode for an electrochemical element according to claim 1, further comprising a second liquid composition polymer layer forming step of polymerizing the second liquid composition applied in the second liquid composition application step to form a polymer layer of the second liquid composition.

3. 3. The method for producing an electrode for an electrochemical element according to claim 2, further comprising a step of drying a polymer layer of the liquid composition, the polymer layer of the first liquid composition and the polymer layer of the second liquid composition.

4. 3. The method for producing an electrode for an electrochemical element according to claim 1, wherein the layer of the polymer of the first liquid composition has an average thickness of 10 [mu]m or more.

5. 3. The method for producing an electrode for an electrochemical element according to claim 2, wherein the layer of the polymer of the second liquid composition has a single layer structure.

6. 3. The method for producing an electrode for an electrochemical element according to claim 2, wherein the layer of the polymer of the second liquid composition has a laminated structure of two or more layers.

7. 7. The method for producing an electrode for an electrochemical element according to claim 5, wherein at least one layer constituting the layer of the polymer of the second liquid composition has an average thickness of 100 [mu]m or more.

8. 3. The method for producing an electrode for an electrochemical element according to claim 1, wherein the first polymerizable compound is represented by the following general formula (1) or (2): 【Chemical 1】 (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.) 【Chemistry 2】 (In the general formula (2), R3 and R4 represent a hydrogen atom or a methyl group.)

9. the first solvent is a mixed solvent containing a good solvent in which the first polymerizable compound is soluble and a poor solvent in which the first polymerizable compound is insoluble, The method for producing an electrode for an electrochemical element according to claim 1 or 2, wherein the first solvent satisfies the following formula (1): [Equation 1] (The mixing ratio X in the formula (1) is the content ratio of the good solvent in the mixed solvent expressed as a percentage based on the mass of the good solvent, and the solubility point of the polymerizable compound is the minimum content ratio of the good solvent in the mixed solvent in which the first polymerizable compound is soluble expressed as a percentage based on the mass of the good solvent.)

10. the first polymerizable compound is a mixed compound containing a soluble polymerizable compound that is soluble in the first solvent and an insoluble polymerizable compound that is insoluble in the first solvent, The method for producing an electrode for an electrochemical element according to claim 1 or 2, wherein the first polymerizable compound satisfies the following formula (2): [Equation 2] (The mixing ratio Y in the formula (2) is the content ratio of the insoluble polymerizable compound in the mixed compound expressed as a percentage based on the mass of the insoluble polymerizable compound, and the solvent solubility point is the minimum content ratio of the insoluble polymerizable compound in the mixed compound soluble in the first solvent expressed as a percentage based on the mass of the insoluble polymerizable compound.)

11. 3. The method for producing an electrode for an electrochemical device according to claim 1, wherein the first solvent contains a porogen.

12. 3. The method for producing an electrode for an electrochemical element according to claim 1, wherein the layer of the polymer of the first liquid composition has a bicontinuous structure with a resin as a skeleton.

13. the substrate has an electrode mixture layer provided on the substrate and containing an active material, the first liquid composition applying step includes applying the first liquid composition onto the substrate and to a peripheral edge portion of the electrode mixture layer; 3. The method for producing an electrode for an electrochemical element according to claim 1, wherein the first liquid composition applying step and the second liquid composition applying step are carried out by an inkjet system.

14. An electrode for an electrochemical device, comprising: a substrate; an electrode mixture layer provided on the substrate; and a structure layer provided on at least a portion of a peripheral edge of the electrode mixture layer, the structural layer has a laminated structure of two or more layers including a first structural layer that is mainly in contact with the substrate and a second structural layer that is provided on the first structural layer; The electrode for an electrochemical element, wherein the structural layer has a porous structure.

15. a substrate; an electrode for an electrochemical element having a structural layer provided on at least a portion of the substrate, the structural layer has a laminated structure of two or more layers including a first structural layer that is mainly in contact with the substrate and a second structural layer that is provided on the first structural layer; the porosity of the second structural layer is greater than the porosity of the first structural layer; The electrode for an electrochemical element, wherein the structural layer has a porous structure.

16. an electrode mixture layer including an active material provided on the substrate; The electrode for an electrochemical element according to claim 15 , wherein the structure layer is provided on the periphery of the electrode mixture layer.

17. The electrode for an electrochemical device according to claim 14 or 16; a solid electrolyte layer provided on the electrode mixture layer and on the structure layer.

18. An electrochemical device comprising the electrode for an electrochemical device according to claim 14 or 15.

19. An all-solid-state electrochemical device comprising the electrode laminate for an electrochemical device according to claim 17.

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