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

Abstract

To provide a method for manufacturing an electrode, which has a simplified process, is excellent in productivity, and is capable of manufacturing an electrode in which curling of the electrode substrate is suppressed.SOLUTION: A method for manufacturing an electrode includes a first application step of applying a first liquid composition containing a polymerizable compound and a first solvent onto an electrode substrate to form a first liquid composition layer, a polymerization step of polymerizing the polymerizable compound to form a resin structure layer, a second application step of applying a second liquid composition containing an active material and a second solvent onto the electrode substrate to form a second liquid composition layer, and a removal step of removing the first solvent and the second solvent.SELECTED DRAWING: Figure 7A

Description

[Technical field]

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

[0002] Compared to conventional lithium-ion secondary batteries, all-solid-state secondary batteries are more resistant to temperature changes and have a smaller risk of fire, which is a major advantage in terms of safety, as well as the ability to rapidly charge, and so demand is expected to grow for their use in electric vehicles, etc. In addition, 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 becoming more diverse.

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

[0004] In order to prevent damage such as cracks in the solid electrolyte in such an all-solid-state battery, a positive electrode for a solid battery has been reported that includes a positive electrode current collector and a positive electrode active material layer containing a positive electrode active material formed on the positive electrode current collector, in which positive electrode guides are disposed on at least two adjacent sides of the outer periphery of the positive electrode active material layer on the surface having the positive electrode active material layer (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, which has a simplified process, excellent productivity, and is capable of producing an electrode in which curling of the electrode substrate is suppressed. [Means for solving the problem]

[0006] The electrode manufacturing method of the present invention as a means for solving the above-mentioned problems includes a first application step of applying a first liquid composition containing a polymerizable compound and a first solvent onto an electrode substrate to form a first liquid composition layer, a polymerization step of polymerizing the polymerizable compound to form a resin structure layer, a second application step of applying a second liquid composition containing an active material and a second solvent onto the electrode substrate to form a second liquid composition layer, and a removal step of removing the first solvent and the second solvent. Effect of the Invention

[0007] According to the present invention, it is possible to provide a method for producing an electrode which simplifies the process, has excellent productivity, and is capable of producing an electrode in which curling of the electrode substrate is suppressed. [Brief description of the drawings]

[0008] [Figure 1A] FIG. 1A is a cross-sectional view showing an example of an electrode of the present embodiment. [Figure 1B] FIG. 1B is a cross-sectional view showing another example of the electrode of the present embodiment. [Diagram 2] FIG. 2 is a cross-sectional view showing an example of the electrode laminate of the present embodiment. [Diagram 3] FIG. 3 is a cross-sectional view showing an example of the electrochemical device of this embodiment. [Figure 4] FIG. 4 is a top view showing a manufacturing process of an example of the electrode of this embodiment. [Diagram 5] FIG. 5 is a top view showing a manufacturing process of another example of the electrode of the present embodiment. [Figure 6] FIG. 6 is a top view showing a manufacturing process of another example of the electrode of the present embodiment. [Figure 7A] FIG. 7A is a schematic diagram showing an example of an apparatus for manufacturing an electrode according to this embodiment. [Figure 7B] FIG. 7B is a schematic diagram showing another example of the electrode manufacturing apparatus of this embodiment. [Figure 8]FIG. 8 is a schematic diagram showing an example of a liquid ejection apparatus which is an apparatus for producing the resin structure layer of this embodiment. [Figure 9] FIG. 9 is a schematic diagram showing another example of a liquid ejection apparatus which is an apparatus for producing a resin structure layer of the present embodiment. [Figure 10] FIG. 10 is a schematic diagram showing a modification of the liquid ejection device of FIG. [Figure 11] FIG. 11 is a configuration diagram showing an example of a printing unit using a drum-shaped intermediate transfer body as a manufacturing device for a resin structure layer of this embodiment. [Figure 12] FIG. 12 is a configuration diagram showing an example of a printing unit using an endless belt-like intermediate transfer body as a manufacturing device for a resin structure layer of this embodiment. [Figure 13] FIG. 13 is a cross-sectional view showing an example of an all-solid-state battery which is an electrochemical device of this embodiment. [Figure 14] FIG. 14 is a schematic diagram showing an example of a mobile object equipped with an all-solid-state battery that is an electrochemical device according to this embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] (Electrode manufacturing method and electrode manufacturing device) The method for producing an electrode of the present invention includes a first application step of applying a first liquid composition containing a polymerizable compound and a first solvent onto an electrode substrate to form a first liquid composition layer, a polymerization step of polymerizing the polymerizable compound to form a resin structure layer, a second application step of applying a second liquid composition containing an active material and a second solvent onto the electrode substrate to form a second liquid composition layer, and a removal step of removing the first solvent and the second solvent. The electrode manufacturing apparatus of the present invention has a first storage container containing a first liquid composition containing a polymerizable compound and a first solvent, a second storage container containing a second liquid composition containing an active material and a second solvent, a first application means for applying the first liquid composition onto an electrode substrate to form a first liquid composition layer, a polymerization means for polymerizing the polymerizable compound to form a resin structure layer, a second application means for applying the second liquid composition onto the electrode substrate to form a second liquid composition layer, and a removal means for removing the first solvent and the second solvent. The method for producing an electrode of the present invention includes a first application step, a polymerization step, a second application step, and a removal step, and may further include other steps as necessary. The electrode manufacturing apparatus of the present invention has a first storage container, a second storage container, a first application means, a polymerization means, a second application means, and a removal means, and may further have other means as necessary.

[0010] The electrode manufacturing method of the present invention is an invention based on the fact that the present inventors have found the following problems in the conventional art. That is, in a conventional method for producing an all-solid-state battery using a positive electrode for a solid-state battery, in order to prevent a short circuit between the positive electrode and the negative electrode in the all-solid-state battery, a positive electrode guide is arranged on the outer periphery of the surface of the positive electrode active material layer that faces the solid electrolyte layer, and stacking and pressing are performed. However, since extremely high pressure is applied during the production of an all-solid-state battery, cracks in the positive electrode guide and pressure load are applied to the electrode, and there is still a problem that damage due to the pressure load occurs to the electrode and the solid electrolyte layer. In addition, the positive electrode guide is preferably made of resin because it needs to have a certain degree of viscoelasticity so that it can withstand pressing, and in consideration of productivity and the diversity of shapes of the active material layer, it is considered preferable to form a coating film by applying a liquid composition using a coater. However, Patent Document 1 (International Publication No. 2020-022111) discloses insulating materials such as insulating resins and inorganic oxides, and laminated sheets as one form of materials for the positive electrode guide, but does not disclose that the resin structure layer is produced from a liquid composition.

[0011] In recent years, the inkjet method has been attracting attention as an industrial coater because it can handle minute amounts to precise pattern coating, can minimize material loss, and can coat precise patterns from CAD data without plate making (masks). Furthermore, inkjet printing has high film thickness uniformity, allows highly accurate landing and separate coating, and is capable of irregular coating, fine wiring, and wiring drawing such as microscopic pieces, so it is expected that a resin active material layer guide will be formed using a photocurable liquid composition.

[0012] In general, photocurable liquid compositions are often composed of a photoinitiator and an acrylic polyfunctional monomer. In the case of photocuring using such a polyfunctional monomer, a large number of monomers are polymerized to form one molecule, which causes a volume shrinkage (hereinafter referred to as "curing shrinkage") due to the gap from the van der Waals distance to the covalent bond distance, and there is a problem that phenomena such as curling and peeling from the substrate often occur. When a resin structure layer is formed by applying and curing a liquid composition as an active material layer guide, the active material layer is thicker than the electrode substrate (current collector foil) serving as the base material from the viewpoint of the energy density of the battery, and the thickness of the resin structure layer is inevitably thicker. Therefore, the curing shrinkage of the resin structure layer has a large effect, and curling of the electrode substrate appears particularly prominently. Therefore, it has been found that there is a problem that handling in the pressurizing step and lamination step becomes difficult, and defects and short circuits occur during lamination due to cracks occurring in the guide during the pressurizing step and peeling between the active material and the resin structure layer, resulting in poor yield and reduced productivity.

[0013] Means for Solving the Problems The present inventors conducted intensive research to achieve the above object, and as a result, discovered that the electrode manufacturing method of the present invention simplifies the process, is highly productive, and makes it possible to manufacture an electrode in which curling of the electrode substrate is suppressed, thereby completing the present invention.

[0014] <First Containment Container> The first storage container includes a first liquid composition containing a polymerizable compound and a first solvent, and a container in which the first liquid composition is stored. Examples of containers include glass bottles, plastic containers, plastic bottles, stainless steel bottles, one-gallon cans, drums, and the like.

[0015] <Second Containment Container> The second storage container includes a second liquid composition containing an active material and a second solvent, and a container in which the second liquid composition is stored. Examples of containers include glass bottles, plastic containers, plastic bottles, stainless steel bottles, one-gallon cans, drums, and the like.

[0016] <First Application Step, First Application Means> The first application step is a step of applying a first liquid composition containing a polymerizable compound and a first solvent onto an electrode substrate to form a first liquid composition layer, and can be suitably performed by a first application means. The first application means is a means for applying the first liquid composition onto an electrode substrate to form a first liquid composition layer. The first liquid composition contains a polymerizable compound and a first solvent, and may further contain other components such as a binder, a conductive material, etc. The aspects of the first liquid composition will be described later. It is preferable that the resin structure layer formed from the first liquid composition has pores of 0.01 μm or more and 10 μm or less, and the viscosity of the first solvent at 25° C. is 1 mPa·s or more and 150 mPa·s or less. In addition, it is preferable that the first solvent and the second solvent are different from each other.

[0017] The application step and application means are not particularly limited as long as they can apply the liquid composition, and can be appropriately selected according to the purpose. For example, any printing device can be used according to various printing methods such as 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, and inkjet printing. Among these, inkjet printing is preferred. This allows the resin layer to be formed accurately in the required area.

[0018] <Polymerization process, polymerization means> The polymerization step is a step of forming a resin structure layer by polymerizing the polymerizable compound, and can be suitably carried out by a polymerization means. The polymerization means is a means for polymerizing the polymerizable compound to form a resin structure layer. By the polymerization, the polymerizable compound in the liquid composition is polymerized, and a porous resin is formed by polymerization-induced phase separation, and a resin structure layer can be produced on the electrode substrate.

[0019] The polymerization step and polymerization means are not particularly limited and can be appropriately selected according to the purpose as long as they can provide the energy required to advance the polymerization reaction of the polymerizable compound, and examples of the polymerization method include light irradiation such as ultraviolet rays, electron beams, α rays, β rays, γ rays, X-rays, and infrared rays; and heating. Among these, light irradiation is preferred, and ultraviolet irradiation is more preferred. This allows the first liquid composition layer to be polymerized without removing the first solvent in the first liquid composition, thereby forming a co-continuous structure (resin skeleton) of the porous insulating layer. In other words, the resin structure layer obtained by the polymerization step is a layer containing the first solvent in the resin skeleton. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator.

[0020] The irradiation intensity of the active energy rays is 1W / cm 2 Less than 300mW / cm is preferable. 2 Less than 100 mW / cm is more preferable. 2 However, 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 decrease productivity. 2 More than 30mW / cm is preferable. 2 The above is more preferable.

[0021] <Second Application Step, Second Application Means> The second application step is a step of applying a second liquid composition containing an active material and a second solvent onto the electrode substrate to form a second liquid composition layer, and can be suitably carried out by a second application means. The second application means is a means for applying the second liquid composition onto an electrode substrate to form a second liquid composition layer. The second liquid composition contains an active material and a solvent, and further contains other components such as a binder and a conductive material, as required.

[0022] -Second liquid composition- The second liquid composition is a composition for forming an electrode mixture layer (sometimes referred to as an "active material layer"), and contains an active material and a dispersion medium, and may further contain other components, as necessary, such as a dispersant, a conductive assistant, a binder, a non-aqueous electrolyte, a solid electrolyte, a gel electrolyte, or a monomer that becomes a gel electrolyte through a polymerization process. The negative electrode mixture layer and the positive electrode mixture layer are collectively referred to as "electrode mixture layers", and the negative electrode active material and the positive electrode active material are collectively referred to as "active materials".

[0023] --Active material-- As the active material, a positive electrode active material or a negative electrode active material can be used. The positive electrode active material or the negative electrode active material may be used alone or in combination of two or more kinds.

[0024] The positive electrode active material is not particularly limited as long as it is a material capable of reversibly absorbing and releasing alkali metal ions, and an alkali metal-containing transition metal compound can be used. Examples of the alkali metal-containing transition metal compound include lithium-containing transition metal compounds such as composite oxides containing lithium and one or more elements selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium. Examples of the lithium-containing transition metal compound include lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide. As the alkali metal-containing transition metal compound, a polyanion-based compound having an XO4 tetrahedron (X=P, S, As, Mo, W, Si, etc.) in the crystal structure can also be used. Among these, lithium-containing transition metal phosphate compounds such as lithium iron phosphate and lithium vanadium phosphate are preferred in terms of cycle characteristics, and lithium vanadium phosphate is particularly preferred in terms of lithium diffusion coefficient and output characteristics. From the viewpoint of electronic conductivity, the polyanion-based compound is preferably composited by coating the surface with a conductive assistant such as a carbon material.

[0025] Examples of sodium-containing transition metal compounds include NaMO2-type oxides, sodium chromite (NaCrO2), sodium ferrate (NaFeO2), sodium nickelate (NaNiO2), sodium cobaltate (NaCoO2), sodium manganate (NaMnO2), and sodium vanadate (NaVO2). A part of M may be substituted with a metal element other than M and Na, for example, at least one selected from the group consisting of Cr, Ni, Fe, Co, Mn, V, Ti, and Al. In addition, as a sodium-containing metal oxide, NaF e PO4F, NaVPO4F, NaCoPO4, NaNiPO4, NaMnPO4, NaMn 1.5 Ni 0.5 O4, or Na2V2(PO4)3, etc. can also be used.

[0026] The negative electrode active material may be a material capable of absorbing and desorbing metals that are alloyed with alkali metal ions such as Li ions or Na ions. Examples of such materials include composite oxides of transition metals and Li, metal oxides, alloy materials, inorganic compounds such as transition metal sulfides, carbon materials, organic compounds, Li metal, and Na metal.

[0027] The composite oxides include LiMnO2, LiMn2O4, and lithium titanate (Li4Ti5O 12 , Li2Ti3O7), Lithium manganese titanate (LiMg 1 / 2 Ti 3 / 2 O4), lithium cobalt titanate (LiCo 1 / 2 Ti 3 / 2 O4), Lithium Zinc Titanate (LiZn 1 / 2 Ti 3 / 2 O4), lithium iron titanate (LiFeTiO4), lithium chromium titanate (LiCrTiO4), lithium strontium titanate (Li2SrTi6O 14 ), or lithium barium titanate (Li2BaTi6O 14 ) etc.

[0028] The sodium composite oxide includes sodium titanate, for example, Na2Ti3O7 or Na4Ti5O 12 A part of Ti or Na in sodium titanate may be substituted with another element, for example, at least one selected from the group consisting of Ni, Co, Mn, Fe, Al, and Cr.

[0029] Examples of metal oxides include TiO2, Nb2TiO7, WO3, MoO2, MnO2, V2O5, SiO2, SiO, and SnO2.

[0030] Examples of alloy materials include Al, Si, Sn, Ge, Pb, As, and Sb. Examples of transition metal sulfides include FeS and TiS. Examples of carbon materials include graphite, non-graphitizable carbon, and easily graphitizable carbon. The inorganic compound may be a compound in which the transition metal of the above composite oxide is replaced with a different element.

[0031] --Second solvent (dispersion medium)-- The second solvent (dispersion medium) is not particularly limited as long as it can disperse the active material, and can be appropriately selected according to the purpose, and examples thereof include aqueous dispersion media such as water, ethylene glycol, or propylene glycol; organic dispersion media such as N-methyl-2-pyrrolidone, 2-pyrrolidone, cyclohexanone, ethyl lactate, butyl acetate, mesitylene, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dibutyl ether, diethyl ether, di-tert-butyl ether, 2-n-butoxymethanol, 2-dimethylethanol, N,N-dimethylacetamide, anisole, diethoxyethane, normal hexane, heptane, octane, nonane, decane, and p-menthane; and the like. These may be used alone or in combination of two or more.

[0032] The boiling point of the second solvent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 70° C. or higher in terms of storage stability. If the boiling point is 70° C. or higher, for example, when stored at room temperature, the occurrence of precipitation due to the concentration effect caused by the volatilization of the solvent can be suppressed, and the storage stability is excellent. In addition, the boiling point of the second solvent is preferably 210° C. or lower in terms of battery characteristics. The content of the second solvent is preferably 10% by mass or more with respect to the total amount of the second liquid composition. By making the content 10% by mass or more, it is possible to suppress the occurrence of spots during film formation and form a liquid layer of the second liquid composition with high uniformity. Furthermore, the content of the second solvent is preferably 80% by mass or more with respect to the total amount of the second liquid composition. By making the content 80% by mass or less, it is possible to obtain a liquid composition with a viscosity that easily forms a liquid layer with high uniformity.

[0033] --Other ingredients-- ---Conductive additive--- The conductive assistant may be previously compounded with the active material, or may be added when the dispersion liquid is prepared. As the conductive assistant, for example, conductive carbon black formed by a furnace method, an acetylene method, a gasification method, or the like, as well as carbon materials such as carbon nanofibers, carbon nanotubes, graphene, or graphite particles can be used. As the conductive assistant other than the carbon material, for example, metal particles such as aluminum or metal fibers can be used. The mass ratio of the conductive assistant to the active material is preferably 10% by mass or less, and more preferably 8% by mass or less. When the mass ratio of the conductive assistant to the active material is 10% by mass or less, the stability of the dispersion is improved.

[0034] ---Dispersant--- The dispersant is not particularly limited as long as it is capable of improving the dispersibility of the active material, polymer particles, or conductive assistant in the dispersion medium. Examples of the dispersant include polymer types such as polycarboxylic acid, naphthalenesulfonic acid-formalin condensation, polyethylene glycol, polycarboxylic acid partial alkyl ester, polyether, and polyalkylene polyamine; surfactant types such as alkylsulfonic acid, quaternary ammonium, higher alcohol alkylene oxide, polyhydric alcohol ester, and alkyl polyamine; and inorganic types such as polyphosphate.

[0035] ---binder--- The binder can be added when the dispersant or electrolyte material is not sufficient to bond the positive electrode materials together or the negative electrode materials together, or to bond the positive electrode materials or the negative electrode materials to the electrode substrate, to ensure the binding force. The binder is not particularly limited as long as it can provide binding force, but from the viewpoint of inkjet ejection properties, a compound that does not increase viscosity is preferable. The binder can be polymerized after the monomer compound is applied, or polymer particles can be used. In addition, a polymer compound that can be dispersed in a dispersion medium can be used as a material that does not increase the viscosity of the liquid composition. Furthermore, when a polymer compound that can be dissolved in a dispersion medium is used, the liquid composition in which the polymer compound is dissolved in the dispersion medium only needs to have a viscosity that allows it to be ejected from a liquid ejection head.

[0036] Examples of using a monomer compound include a method of applying a dispersion liquid containing a compound having a polymerizable moiety and a polymerization initiator or catalyst, in which the compound having a polymerizable moiety is dissolved, followed by heating; and a method of irradiating with non-ionizing radiation, ionizing radiation, or infrared radiation. In a compound having a polymerizable site, the polymerizable site may be one in the molecule, or may be polyfunctional. Note that a polyfunctional polymerizable compound means a compound having two or more polymerizable groups. There is no particular limitation on the polyfunctional polymerizable compound, so long as it can be polymerized by heating or irradiation with non-ionizing radiation, ionizing radiation, or infrared radiation. Examples of the polyfunctional polymerizable compound include acrylate resins, methacrylate resins, urethane acrylate resins, vinyl ester resins, unsaturated polyesters, epoxy resins, oxetane resins, vinyl ethers, and resins utilizing ene-thiol reactions, etc. Among these, from the viewpoint of productivity, acrylate resins, methacrylate resins, urethane acrylate resins, and vinyl ester resins are preferred.

[0037] Examples of materials that make up the polymer particles include polyvinylidene fluoride, acrylic resin, polyamide compounds, polyimide compounds, polyamideimide, ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene copolymer, nitrile butadiene rubber (HNBR), isoprene rubber, polyisobutene, polyethylene glycol (PEO), polymethyl methacrylic acid (PMMA), polyethylene vinyl acetate (PEVA), polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, and polybutylene terephthalate.

[0038] Examples of polymer compounds include polyamide compounds, polyimide compounds, polyamideimide, ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), nitrile butadiene rubber (NBR), isoprene rubber, polyisobutene, polyethylene glycol (PEO), polymethyl methacrylic acid (PMMA), and polyethylene vinyl acetate (PEVA).

[0039] The mass ratio of the binder to the active material is preferably 10% or less, more preferably 5% or less. When the mass ratio of the binder to the active material is 10% or less, the binding strength during electrode formation is improved without impairing the ejection properties.

[0040] The method for forming the second liquid composition layer is not particularly limited and may be appropriately selected depending on the purpose. For example, a method may be used in which a powdered active material, a binder, a conductive material, etc. are dispersed in a liquid, and the obtained second liquid composition is applied onto an electrode substrate, fixed, and dried. Examples of the application method include spraying, dispenser, die coater, and pull-up coating.

[0041] <Removal process, removal means> The removal step is a step of removing the first solvent and the second solvent, and can be suitably carried out by a removal means. The removal means is a means for removing the first solvent and the second solvent. The method for removing the first solvent and the second solvent is not particularly limited, and examples thereof include a method of removing liquids such as a solvent and a dispersion liquid from the first liquid composition layer and the second liquid composition layer by heating. In this case, heating under reduced pressure is preferable because it can further promote the removal of the solvent and suppress the remaining of the liquid in the formed resin structure layer. When heating, heating may be performed by a stage, or by a heating mechanism other than the stage. The heating mechanism may be installed either above or below the substrate, or multiple heating mechanisms may be installed. There are no particular limitations on the heating mechanism, and examples of the heating mechanism include a resistance heater, an infrared heater, and a fan heater. The heating temperature is not particularly limited, but is preferably 70° C. to 150° C. from the viewpoint of energy usage.

[0042] <Other processes and other means> The other steps in the method for producing the electrode are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected depending on the purpose. Other means in the electrode manufacturing apparatus are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected depending on the purpose.

[0043] In one embodiment, the method for manufacturing an electrode preferably includes the first application step, the polymerization step, and the second application step in this order, and the second application step is a step of applying the second liquid composition adjacent to the resin structure layer on the electrode substrate. As a result, the electrode mixture layer is formed inside the frame formed by the insulating resin layer using a wet-on-wet process, so that the interface between the electrode mixture layer and the insulating resin layer has a cross-sectional shape in which the electrode mixture layer rides on top of the insulating resin layer (see FIG. 1B). Therefore, the area of ​​the surface of the electrode mixture layer that is not in contact with the electrode substrate becomes equal to or greater than the area of ​​the surface of the electrode mixture layer that is in contact with the electrode substrate, and the electrode mixture layer and the insulating resin layer are in contact and continuous with each other. The heights of the electrode mixture layer and the insulating resin layer may or may not be approximately equal to each other. They can be made approximately equal by performing a pressing process.

[0044] In another embodiment, it is preferable that the first application step and the second application step are carried out simultaneously or sequentially, and then the polymerization step is carried out, and the first liquid composition and the second liquid composition are applied adjacent to each other. This prevents unnecessary wetting and spreading of the first liquid composition and the second liquid composition, and allows the desired interface between the resin structure layer and the electrode mixture layer to be formed. Specifically, when the second liquid composition is applied to form a second liquid composition layer before the formation of the resin structure layer, and then dried to form the electrode mixture layer, there is a possibility that the wetting and spreading may cause unevenness in the end of the resulting electrode mixture layer, but this embodiment can effectively prevent unevenness in the end of the electrode mixture layer. Therefore, the electrode mixture layer is in contact with the end face of the resin structure layer and is continuous, covering the end of the resin structure layer that is in contact with the electrode base, and good adhesion can be obtained. The heights of the electrode mixture layer and the insulating resin layer may or may not be approximately equal to each other. They can be made approximately equal by performing a pressing process.

[0045] -First liquid composition- The first liquid composition (sometimes referred to as "liquid composition") is a liquid composition for forming a resin structure layer, and contains a polymerizable compound and a first solvent, and further contains other components such as a polymerization initiator, as necessary. The first liquid composition is not particularly limited and can be appropriately selected depending on the purpose, and preferable examples thereof include the following first embodiment, second embodiment, and third embodiment.

[0046] [First embodiment] The first liquid composition as a first embodiment contains a polymerizable compound represented by the following general formula (1) and a non-aqueous solvent represented by the following general formula (2) as a first solvent, and further contains other components such as a polymerization initiator as necessary. When A in the general formula (2) is a hydroxyl group, the difference in Millikan charge between the hydrogen atom and the oxygen atom in the hydroxyl group is 0.520 or more, and when A in the general formula (2) is an amino group, the difference in Millikan charge between the hydrogen atom and the nitrogen atom in the amino group is 0.470 or more.

[0047] [ka] (In the above general formula (1), R 1 represents an n-valent functional group having 2 or more carbon atoms which may have an oxygen atom, and n represents an integer of 2 to 6.

[0048] [ka] (In the above general formula (2), R 2 , R 3 and R 4 each independently represents a hydrocarbon group; R 2 , R 3 and R 4 The total number of carbon atoms is 4 or more, and A is a hydroxyl group or -NR 5 H represents an amino group, and R 5 represents a hydrogen atom, a methyl group, or an ethyl group.

[0049] The first liquid composition according to the first embodiment can suppress the decrease in ionic conductivity of the sulfide solid electrolyte, and can form a resin structure layer with less warping.

[0050] The polymerizable compound is not particularly limited and can be appropriately selected depending on the purpose. Examples of the polymerizable compound include bifunctional acrylates such as 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, and bifunctional acrylic acid polymer ester acrylates; trifunctional acrylates such as trifunctional trimethylolpropane acrylates, trifunctional alkoxylated glycerin acrylates, and trifunctional isocyanate acrylates; and tetrafunctional to hexafunctional acrylates such as tetrafunctional pentaerythritol acrylates, tetrafunctional ditrimethylolpropane acrylates, tetrafunctional diglycerin tetraacrylates, and hexafunctional dipentaerythritol hexaacrylates. These may be used alone or in combination of two or more.

[0051] [Second embodiment] The first liquid composition according to the second embodiment contains a polymerizable compound having an average molecular weight of less than 700 and represented by the following general formula (3), and a solvent that is a non-aromatic compound as a first solvent, and further contains other components such as a polymerization initiator as necessary. The Hansen solubility parameter (HSP) of the polymerizable compound is (δ D A , δ P A , δ H A ), the volume fraction of the polymerizable compound is X A The HSP of the solvent is (δ D B , δ P B , δ H B ), the volume fraction of the solvent is X B The HSP of the liquid composition is (δ D C , δ P C , δ H C ), the volume fraction of the liquid composition is XA +X B = 1, ΔHSP 2 is represented by the following formula (I), and ΔHSP is the compatibility limit between the polymerizable compound and the solvent. 2 ΔHSP 2 SL When 2 and ΔHSP 2 SL The relationship satisfies the following formula (II). Formula (I) ΔHSP 2 =(δ D A -δ D C ) 2 +(δ P A -δ P C ) 2 +(δ H A -δ H C ) 2 Formula (II) 0.51≦ΔHSP 2 ≦ΔHSP 2 SL

[0052] [ka] (In the general formula (3), R represents at least one of an acyclic alkylene group and an acyclic alkylene oxide group, and Y represents a hydrogen atom or a -O-COCH=CH2 group.)

[0053] The first liquid composition according to the second embodiment can simultaneously reduce the curing shrinkage and swelling shrinkage that occur during the formation of a resin layer, and can form a resin layer with suppressed warping even when the resin layer has a thickness on the scale of 100 μm.

[0054] When Y is a hydrogen atom, the polymerizable compound is a difunctional acrylate, and when Y is a -O-COCH=CH2 group (i.e., a group in which an oxygen atom is bonded to an acrylic group), the polymerizable compound is a trifunctional acrylate. Examples of the bifunctional acrylate include bifunctional acyclic alkyl acrylates; and bifunctional acyclic polyalkylene oxide acrylates such as bifunctional acyclic polyethylene glycol acrylate, bifunctional acyclic polypropylene glycol acrylate, and bifunctional acyclic polytetramethylene glycol acrylate. Examples of the trifunctional acrylate include a trifunctional acyclic alkyl acrylate and a trifunctional acyclic polyalkylene oxide acrylate. These may be used alone or in combination of two or more.

[0055] The solvent is not particularly limited as long as it is a non-aromatic compound and can be appropriately selected depending on the purpose. Examples of the solvent include alcohol-based solvents, amine-based solvents, hydrocarbon-based solvents, ester-based solvents, ketone-based solvents, aldehyde-based solvents, and thiol-based solvents. These may be used alone or in combination of two or more.

[0056] [Third embodiment] The first liquid composition according to the third embodiment contains a polymerizable compound and a liquid as a first solvent, and further contains other components such as a polymerization initiator as necessary. The liquid composition forms a porous resin, and the light transmittance at a wavelength of 550 nm measured while stirring the liquid composition is 30% or more, and the increase rate of the haze value in a haze measurement element produced by polymerizing the liquid composition is 1.0% or more. For the polymerizable composition as the third embodiment, the matters described in JP 2021-088691 A can be appropriately selected. Below, matters common to the first to third embodiments and matters relating to each embodiment (mainly the third embodiment) will be described.

[0057] The liquid composition forms a porous structure, that is, a resin structure having a porous structure with a resin skeleton (also referred to as a "porous resin" or a "porous structure") is formed by polymerization and curing of the polymerizable compound in the liquid composition. Here, "the liquid composition forms a porous resin" refers not only to the case where a porous resin is formed in the liquid composition, but also to the case where a precursor of the porous resin (e.g., the skeletal part of the porous resin) is formed in the liquid composition, and the porous resin is formed by subsequent treatment (e.g., heat treatment, etc.).

[0058] --Polymerizable compound-- The polymerizable compound forms a resin by polymerization, and forms a porous resin depending on the composition and characteristics of the liquid composition. The polymerizable compound is not particularly limited as long as it forms a polymer (resin) by polymerization, and any known polymerizable compound can be appropriately selected depending on the purpose, but it is preferable that the polymerizable compound has at least one radically polymerizable functional group. Suitable examples of the polymerizable compound include radical polymerizable compounds such as monofunctional, bifunctional, trifunctional or higher functional radical polymerizable monomers and oligomers; functional monomers and oligomers having a functional group other than the polymerizable functional group. Among these, bifunctional or higher functional radical polymerizable compounds are preferred. The polymerizable group of the polymerizable compound is preferably at least one of a (meth)acryloyl group and a vinyl group, and more preferably a (meth)acryloyl group. The polymerizable compound is preferably polymerizable by irradiation with active energy rays, and more preferably polymerizable by heat or light.

[0059] The resin formed from the polymerizable compound is preferably a resin having a mesh-like structure formed by application of active energy rays (for example, by irradiation with light or heating), etc. Suitable examples thereof include acrylate resins, methacrylate resins, urethane acrylate resins, vinyl ester resins, unsaturated polyester resins, epoxy resins, oxetane resins, vinyl ether resins, and resins formed by ene-thiol reactions. Among these, acrylate resins, methacrylate resins, and urethane acrylate resins, which are resins formed from polymerizable compounds having a (meth)acryloyl group, are more preferred because they can be easily used to form a structure by utilizing highly reactive radical polymerization, and from the viewpoint of productivity, vinyl ester resins, which are resins formed from polymerizable compounds having a vinyl group, are more preferred. These may be used alone or in combination of two or more. When using two or more, the combination of polymerizable compounds is not particularly limited and can be appropriately selected according to the purpose, but for example, in order to impart flexibility, it is preferable to mix other resins with urethane acrylate resin as the main component. Note that a polymerizable compound having at least one of an acryloyl group and a methacryloyl group is referred to as a polymerizable compound having a (meth)acryloyl group.

[0060] The active energy ray is not particularly limited as long as it can provide the energy required for the polymerization reaction of the polymerizable compound in the liquid composition, and can be appropriately selected according to the purpose, and examples thereof include ultraviolet rays, electron beams, α rays, β rays, γ rays, and X-rays. Among these, ultraviolet rays are preferred. In particular, when a high-energy light source is used, the polymerization reaction can be promoted without using a polymerization initiator. The irradiation intensity of the active energy rays is 1W / cm 2 Less than 300mW / cm is preferable. 2 Less than 100 mW / cm is more preferable. 2However, 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 decrease productivity. 2 More than 30mW / cm is preferable. 2 The above is more preferable.

[0061] Examples of the monofunctional radical polymerizable compound include 2-(2-ethoxyethoxy)ethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, and styrene monomer. These may be used alone or in combination of two or more.

[0062] Examples of the bifunctional radical polymerizable compound include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, etc. These may be used alone or in combination of two or more.

[0063] Examples of the trifunctional or higher radical polymerizable compound include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, HPA-modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH-modified glycerol triacrylate, EO-modified glycerol triacrylate, PO-modified glycerol triacrylate, and trimethylolpropane triacrylate. Examples of the acrylates include thi(acryloxyethyl)isocyanurate, dipentaerythritol hexaacrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxy tetraacrylate, EO-modified phosphoric acid triacrylate, and 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate. These may be used alone or in combination of two or more.

[0064] The content of the polymerizable compound is preferably from 5.0% by mass to 70.0% by mass, more preferably from 10.0% by mass to 50.0% by mass, and even more preferably from 20.0% by mass to 40.0% by mass, based on the total amount of the liquid composition. When the content is 70.0% by mass or less, the size of the pores in the resulting porous body is not too small, such as a few nm or less, and the porous body has an appropriate porosity, which is preferable because it can suppress the tendency for liquids and gases to become less likely to penetrate. Also, when the content is 5.0% by mass or more, the three-dimensional network structure of the resin is sufficiently formed, a sufficient porous structure is obtained, and the strength of the resulting porous structure also tends to be improved, which is preferable.

[0065] --liquid-- The liquid contains a porogen and, if necessary, further contains other liquids other than the porogen. The porogen is a liquid that is compatible with the polymerizable compound and becomes incompatible with the polymer (resin) (causes phase separation) during the polymerization of the polymerizable compound in the liquid composition. By including a porogen in the liquid composition, a porous resin is formed when the polymerizable compound is polymerized. In addition, it is preferable that the porogen can dissolve a compound (a polymerization initiator described later) that generates a radical or an acid by light or heat. The liquid or porogen may be used alone or in combination of two or more kinds. In this embodiment, the liquid is not polymerizable.

[0066] The boiling point of one type of porogen alone or two or more types of porogen in combination is preferably 50°C to 250°C, more preferably 70°C to 200°C, and even more preferably 120°C to 190°C at normal pressure. By having a boiling point of 50°C or more, vaporization of the porogen at around room temperature is suppressed, making the liquid composition easy to handle and making it easy to control the content of the porogen in the liquid composition. In addition, by having a boiling point of 250°C or less, the time required for the process of removing the porogen after polymerization is shortened, improving the productivity of the porous resin. In addition, since the amount of porogen remaining inside the porous resin can be suppressed, the quality is improved when the porous resin is used as a functional layer such as a material separation layer that separates substances or a reaction layer as a reaction field.

[0067] Examples of the porogen 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. In addition, liquids with relatively large molecular weights such as methyl tetradecanoate, methyl decanoate, methyl myristate, and tetradecane can also be used. In addition, liquids such as acetone, 2-ethylhexanol, and 1-bromonaphthalene can also be used.

[0068] It should be noted that not all of the above-listed liquids are porogens. As described above, a porogen is a liquid that is compatible with a polymerizable compound and is incompatible with (subjects to phase separation from) a polymerized product (resin) produced in the course of polymerization of the polymerizable compound in a liquid composition. In other words, whether or not a liquid corresponds to a porogen is determined by its relationship with the polymerizable compound and the polymerized product (resin formed by polymerization of the polymerizable compound). In addition, since the liquid composition only needs to contain at least one type of porogen having the above-mentioned specific relationship with the polymerizable compound, the range of material selection when preparing the liquid composition is broadened, and the liquid composition can be easily designed. By broadening the range of material selection when preparing the liquid composition, the range of response is broadened when there are characteristics required for the liquid composition from a viewpoint other than the formation of a porous structure. For example, when the liquid composition is discharged by the inkjet method, the liquid composition is required to have discharge stability and the like from a viewpoint other than the formation of a porous structure, and the wide range of material selection makes it easy to design the liquid composition.

[0069] The content of the liquid or porogen is preferably from 30.0% by mass to 95.0% by mass, more preferably from 50.0% by mass to 90.0% by mass, and even more preferably from 60.0% by mass to 80.0% by mass, based on the total amount of the liquid composition. When the content of the liquid or porogen is 30.0% by mass or more, the size of the pores in the resulting porous body is not too small, such as several nm or less, and the porous body has an appropriate porosity, which is preferable because it is possible to suppress the tendency for liquid or gas to penetrate less easily. Also, when the content of the liquid or porogen is 95.0% by mass or less, the three-dimensional network structure of the resin is sufficiently formed, a porous structure is sufficiently obtained, and the strength of the resulting porous structure also tends to be improved, which is preferable.

[0070] As described above, the liquid composition is required to contain at least one type of porogen having the above-mentioned specific relationship with the polymerizable compound, and may additionally contain other liquids (liquids that are not porogens) that do not have the above-mentioned specific relationship with the polymerizable compound. The content of the other liquids is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, still more preferably 1.0% by mass or less, and particularly preferably 0% by mass (not included), based on the total amount of the liquid composition.

[0071] The mass ratio of the polymerizable compound content to the porogen content in the liquid composition (polymerizable compound:porogen) is preferably from 1.0:0.4 to 1.0:19.0, more preferably from 1.0:1.0 to 1.0:9.0, and even more preferably from 1.0:1.5 to 1.0:4.0.

[0072] [Polymerization-induced phase separation] Porous resins are formed by polymerization-induced phase separation. Polymerization-induced phase separation refers to a state in which the polymerizable compound and porogen are compatible, but the polymer (resin) that is generated during the polymerization process of the polymerizable compound and the porogen are not compatible (phase separation occurs). Although there are other methods for obtaining porous bodies by phase separation, the polymerization-induced phase separation method can form a porous body with a network structure, which is expected to be highly resistant to chemicals and heat. In addition, compared to other methods, it has the advantage of a shorter process time and easier surface modification.

[0073] Next, a process for forming a porous resin using polymerization-induced phase separation with a liquid composition containing a polymerizable compound will be described. The polymerizable compound undergoes a polymerization reaction by light irradiation or the like to form a resin. During this process, the solubility of the porogen in the growing resin decreases, and phase separation occurs between the resin and the porogen. Finally, the resin forms a porous structure having a co-continuous structure due to the resin skeleton, with the porogen filling the pores. When this is dried, the porogen is removed, leaving a porous resin having a co-continuous structure of a three-dimensional network structure. Therefore, in order to form a porous resin with an appropriate porosity, the compatibility of the porogen with the polymerizable compound and the compatibility of the porogen with the resin formed by polymerization of the polymerizable compound are examined.

[0074] [Light transmittance] The liquid composition has a light transmittance of 30% or more at a wavelength of 550 nm, measured while being stirred. The compatibility between the porogen and the polymerizable compound can be judged by the light transmittance. When the light transmittance is 30% or more, it is determined that the liquid contains porogen and that the polymerizable compound and the porogen are in a compatible state, and when the light transmittance is less than 30%, it is determined that the polymerizable compound and the liquid are in an incompatible state.

[0075] Specifically, the light transmittance can be measured by the following method. First, the liquid composition is poured into a quartz cell, and while stirring with a stirrer at 300 rpm, the transmittance of the liquid composition to light (visible light) at a wavelength of 550 nm is measured under the following conditions. Quartz cell: Special microcell with screw cap (product number: 42016, manufactured by Mitrica Co., Ltd.) ·Transmittance measurement device: Ocean Optics USB4000 ·Stirring speed: 300rpm ·Measurement wavelength: 550nm Reference: Obtained by measuring the light transmittance at a wavelength of 550 nm when the quartz cell is filled with air (transmittance: 100%)

[0076] [Haze value increase rate] The increase rate of the haze value in a haze measuring element prepared by polymerizing the liquid composition is 1.0% or more. The compatibility between the porogen and the resin formed by polymerization of the polymerizable compound can be judged by the rate of increase in the haze value. When the increase in the haze value is 1.0% or more, it is determined that the liquid contains porogen and the resin and the porogen are incompatible with each other, and when the increase in the haze value is less than 1.0%, it is determined that the resin and the liquid are compatible with each other. The haze value in the haze measuring element increases as the compatibility between the porogen and the resin formed by polymerization of the polymerizable compound decreases, and decreases as the compatibility increases. Also, the higher the haze value, the easier it is for the resin formed by polymerization of the polymerizable compound to form a porous structure.

[0077] Specifically, the rate of increase in haze value is the rate of increase in haze value before and after polymerization of a haze measurement element having an average thickness of 100 μm produced by polymerizing the liquid composition, and can be measured by the following method. - Fabrication of haze measurement element - First, resin particles as a gap agent are uniformly dispersed on a non-alkali glass substrate by spin coating. Then, the substrate coated with the gap agent is bonded to a non-alkali glass substrate not coated with the gap agent, with the surfaces coated with the gap agent sandwiched between them. Next, a liquid composition is filled between the bonded substrates by utilizing capillary action to prepare a "pre-UV haze measurement element". Next, the pre-UV haze measurement element is irradiated with UV light to harden the liquid composition. Finally, the periphery of the substrate is sealed with a sealant to prepare a "haze measurement element". The size of the gap agent (average particle diameter 100 μm) corresponds to the average thickness of the haze measurement element. The various conditions during preparation are shown below. Non-alkali glass substrate: Nippon Electric Glass, 40mm, t=0.7mm, OA-10G Gap agent: Sekisui Chemical Co., Ltd., resin microparticle Micropearl GS-L100, average particle size 100 μm Spin coating conditions: Dispersion drop amount 150 μL, rotation speed 1000 rpm, rotation time 30 s Filled liquid composition volume: 160μL UV irradiation conditions: UV-LED is used as the light source, light source wavelength is 365 nm, irradiation intensity is 30 mW / cm 2 , irradiation time 20s Sealant: TB3035B (Three Bond)

[0078] - Haze value (cloudiness) measurement - Next, the haze value (cloudiness) is measured using the prepared haze measurement element before UV irradiation and the haze measurement element. The measured value in the haze measurement element before UV irradiation is set as a reference (haze value 0), and the increase rate of the measured value (haze value) in the haze measurement element relative to the measured value in the haze measurement element before UV irradiation is calculated. The equipment used for the measurements is shown below. Haze measuring device: Haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.

[0079] --Surfactant-- The liquid composition preferably contains a surfactant. The surfactant can be used for the purpose of orienting itself at the gas-liquid interface, eliminating foaming, lowering surface tension, and smoothing and averaging the upper part of the liquid film, that is, so-called leveling of the liquid film. The surfactant is not particularly limited and can be appropriately selected depending on the purpose. Suitable examples of the surfactant include silicon-based surfactants, acrylic-based surfactants, and fluorine-based surfactants. These may be used alone or in combination of two or more.

[0080] Examples of the silicone surfactant include Polyflow series KL-400HF, KL-401, KL-402, and KL-406 (all manufactured by Kyoeisha Chemical Co., Ltd.); BYK series UV3500, UV3505, UV3510, UV3530, UV3570, UV3575, and UV3576 (all manufactured by BYK Japan KK); and Disparlon series UVX-272, NSH-8430HF, 1711EF, LS-001, LS-460, and LS-480 (all manufactured by Kusumoto Chemical Co., Ltd.).

[0081] Examples of the acrylic surfactant include Polyflow series No. 7, No. 36, No. 50E, No. 56, No. 75, No. 77, No. 85, No. 85HF, No. 90, No. 90D-50, No. 95, and No. 99C (all manufactured by Kyoeisha Chemical Co., Ltd.); BYK TM Series 3440, 3560 (all manufactured by BYK Japan KK); Disparlon Series 1970, 230, 230HF, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, UVX-36 (all manufactured by Kusumoto Chemicals Co., Ltd.).

[0082] Examples of the fluorosurfactant include the Surflon series (manufactured by ACG Seimi Chemical Co., Ltd.); Megafac series RS-56, RS-75, RS-72-K, RS-76-E, RS-76-NS, RS-78, and RS-90 (all manufactured by DIC Corporation). Other structures include, for example, BYK TM -UV3535 (manufactured by BYK Japan Co., Ltd.), Disparlon series LHP-90, LHP-91, LHP-95, LHP-96 (all manufactured by Kusumoto Chemicals Co., Ltd.), etc.

[0083] --Other ingredients-- ---Polymerization initiator--- The liquid composition may contain other components, such as a polymerization initiator. The polymerization initiator is a material capable of generating active species such as radicals and cations by energy such as light and heat, and initiating polymerization of a polymerizable compound. Examples of the polymerization initiator include known radical polymerization initiators, cationic polymerization initiators, and base generators. These may be used alone or in combination of two or more. Among these, photoradical polymerization initiators are preferred.

[0084] The photoradical polymerization initiator is not particularly limited, and a known photoradical generator can be appropriately selected depending on the purpose. Examples of the photoradical polymerization initiator include Michler's ketone and benzophenone, known under the trade names Irgacure and Darocur, and acetophenone derivatives. Specific examples of the compounds include α-hydroxy-acetophenone, α-aminoacetophenone, 4-aroyl-1,3-dioxolane, benzil ketal, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, pp'-dichlorobenzophenone, pp'-bisdiethylaminobenzophenone, Michler's ketone, benzil, benzoin, benzil dimethyl ketal, tetramethylthiuram monosulfide, thioxanthone, and 2-chlorothioxanthone. benzoin peroxide, di-tert-butyl peroxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methyl benzoyl formate, benzoin isopropyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin Zoin n-propyl, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-methyl-1[4-(methylthio) )phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one monoacylphosphine oxide, bisacylphosphine oxide; titanocene, fluorescene, anthraquinone, thioxanthone; xanthone, lophine dimer, trihalomethyl compounds;Examples include dihalomethyl compounds, active ester compounds, and organic boron compounds.

[0085] Furthermore, a photocrosslinking radical generator such as a bisazide compound may be simultaneously contained. When polymerization is performed by heat alone, a thermal polymerization initiator such as azobisisobutyronitrile (AIBN), which is a typical radical generator, can be used.

[0086] The content of the polymerization initiator is preferably from 0.05% by mass to 10.0% by mass, and more preferably from 0.5% by mass to 5.0% by mass, based on the total mass of the polymerizable compounds being 100.0% by mass, in terms of obtaining a sufficient curing rate.

[0087] The liquid composition may be a non-dispersion type composition that does not contain a dispersed substance in the liquid composition, or a dispersion type composition that contains a dispersed substance in the liquid composition, but is preferably a non-dispersion type composition.

[0088] [viscosity] The viscosity of the first liquid composition is preferably 5 mPa·s or more from the viewpoint of the stability of the thickness of the first liquid composition layer, and more preferably 8 mPa·s or more and 20 mPa·s or less when considering use as an inkjet ink. Here, the viscosity is measured at 25°C at a rotation speed of 100 rpm, and specifically, a value measured using a TV25 type viscometer (cone plate) at a rotation speed of 100 rpm can be used.

[0089] [Hansen Solubility Parameter (HSP)] The compatibility between the porogen and the polymerizable compound, and the compatibility between the porogen and the resin formed by polymerization of the polymerizable compound, can be predicted through Hansen Solubility Parameter (HSP). Hansen Solubility Parameter (HSP) is a useful tool for predicting the compatibility of two substances, and was discovered by Charles M. Hansen. Hansen Solubility Parameter (HSP) is expressed by combining the following three experimentally and theoretically derived parameters (δD, δP, and δH). The unit of Hansen Solubility Parameter (HSP) is MPa0.5 or (J / cm 3 ) 0.5 In this embodiment, (J / cm 3 ) 0.5 was used. · δD: Energy resulting from London dispersion forces. · δP: Energy resulting from dipole-dipole interactions. · δH: Energy derived from hydrogen bonding forces.

[0090] Hansen Solubility Parameter (HSP) is a vector quantity expressed as (δD, δP, δH) and is plotted in a three-dimensional space (Hansen space) with three parameters as coordinate axes. The Hansen Solubility Parameter (HSP) of commonly used substances is available from publicly known information sources such as databases, so the Hansen Solubility Parameter (HSP) of a desired substance can be obtained, for example, by referring to the database. For substances whose Hansen Solubility Parameter (HSP) is not registered in the database, the Hansen Solubility Parameter (HSP) can be calculated from the chemical structure of the substance or the Hansen Solubility Sphere method described below, for example, by using computer software such as Hansen Solubility Parameters in Practice (HSPiP). The Hansen Solubility Parameter (HSP) of a mixture containing two or more substances is calculated as the vector sum of the Hansen Solubility Parameter (HSP) of each substance multiplied by the volume ratio of each substance to the entire mixture. In this embodiment, the Hansen Solubility Parameter (HSP) of a liquid (porogen) obtained based on a known information source such as a database is referred to as the "Hansen Solubility Parameter of a liquid."

[0091] In addition, the relative energy difference (RED) based on the Hansen solubility parameters (HSP) of a solute and a solution is expressed by the following formula:

number

[0092] -Hansen dissolving ball method- First, prepare the substance for which Ro is to be obtained and several dozen types of evaluation liquids (liquids whose meaning is different from the above-mentioned "liquid (porogen)") whose Hansen solubility parameters (HSP) are known, and perform a compatibility test of the target substance with each evaluation liquid. In the compatibility test, the Hansen solubility parameters (HSP) of the evaluation liquids that showed compatibility and the Hansen solubility parameters (HSP) of the evaluation liquids that showed no compatibility are plotted on the Hansen space. Based on the plotted Hansen solubility parameters (HSP) of each evaluation liquid, create a virtual sphere (Hansen sphere) in the Hansen space that includes the Hansen solubility parameters (HSP) of the evaluation liquids that showed compatibility and does not include the Hansen solubility parameters (HSP) of the evaluation liquids that showed no compatibility. The radius of the Hansen sphere is the interaction radius R0 of the substance, and the center is the Hansen solubility parameter (HSP) of the substance. The evaluation criteria (criteria for determining whether or not compatibility exists) between the substance for which the interaction radius R0 and the Hansen solubility parameter (HSP) are to be calculated and the liquid for evaluation whose Hansen solubility parameter (HSP) is known are set by the evaluator himself / herself. The evaluation criteria in this embodiment will be described later.

[0093] -Hansen Solubility Parameter (HSP) and Interaction Radius of Polymerizable Compounds- The Hansen solubility parameter (HSP) of the polymerizable compound in this embodiment and the interaction radius of the polymerizable compound are determined by the Hansen dissolved ball method. As described above, the evaluation criteria for compatibility in the Hansen dissolved ball method are set by the evaluator himself, so the Hansen solubility parameter (HSP) of the polymerizable compound in this embodiment obtained by the following criteria is represented as the "Hansen solubility parameter C of the polymerizable compound", and the interaction radius of the polymerizable compound is represented as the "interaction radius D of the polymerizable compound". In other words, the "Hansen solubility parameter C of the polymerizable compound" and the "interaction radius D of the polymerizable compound" are obtained based on the Hansen solubility parameter of the liquid, which is obtained based on a publicly known information source such as a database, and are obtained based on the Hansen dissolved ball method including the evaluation criteria for compatibility set by the evaluator himself.

[0094] The Hansen solubility parameter C and the interaction radius D of the polymerizable compound are determined by evaluating the compatibility of the polymerizable compound with the evaluation liquid in accordance with the following [1-1] and the above-mentioned method for measuring light transmittance (based on "the light transmittance at a wavelength of 550 nm of the transmittance measurement composition, which is measured while stirring the transmittance measurement composition containing the polymerizable compound and the evaluation liquid").

[0095] [1-1] Preparation of composition for transmittance measurement First, prepare a polymerizable compound for which the Hansen Solubility Parameter (HSP) is to be calculated and several dozen types of evaluation liquids with known Hansen Solubility Parameter (HSP), and mix the polymerizable compound, each evaluation liquid, and polymerization initiator in the ratio shown below to prepare a composition for transmittance measurement. As several dozen types of evaluation liquids with known Hansen Solubility Parameter (HSP), the following 21 types of evaluation liquids are used. ~Composition ratio for transmittance measurement~ Polymerizable compound for which Hansen Solubility Parameter (HSP) is to be calculated: 28.0% by mass Liquid for evaluation with known Hansen Solubility Parameters (HSP): 70.0% by mass Polymerization initiator (Irgacure 819, manufactured by BASF): 2.0% by mass ~Evaluation liquid group (21 types)~ Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether, N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, 1-bromonaphthalene

[0096] -Hansen solubility parameter (HSP) and interaction radius of resin formed by polymerization of polymerizable compounds- The Hansen solubility parameter (HSP) of the resin formed by polymerization of the polymerizable compound and the interaction radius of the resin formed by polymerization of the polymerizable compound are determined by the Hansen solubility parameter (HSP) of the resin formed by polymerization of the polymerizable compound in this embodiment obtained by the following criteria is represented as "Hansen solubility parameter A of the resin", and the interaction radius of the resin formed by polymerization of the polymerizable compound is represented as "interaction radius B of the resin". In other words, "Hansen solubility parameter A of the resin" and "interaction radius B of the resin" are obtained based on the Hansen solubility parameter of the liquid, which is obtained based on a publicly known information source such as a database, and are obtained based on the Hansen solubility parameter of the resin including the evaluation criteria of compatibility set by the evaluator himself.

[0097] The Hansen solubility parameter A of the resin and the interaction radius B of the resin are determined by evaluating the compatibility of the resin with the evaluation liquid in accordance with the following [2-1] and the above-mentioned method for measuring the rate of increase in haze value (evaluation based on "the rate of increase in haze value (cloudiness) in a haze measurement element prepared using a haze measurement composition containing a polymerizable compound and an evaluation liquid").

[0098] [2-1] Preparation of composition for haze measurement First, prepare a precursor (polymerizable compound) of the resin for which the Hansen Solubility Parameter (HSP) is to be calculated, and several dozen types of evaluation liquids with known Hansen Solubility Parameter (HSP), and mix the polymerizable compound, each evaluation liquid, and polymerization initiator in the ratio shown below to prepare a composition for haze measurement. As several dozen types of evaluation liquids with known Hansen Solubility Parameter (HSP), the following 21 types of evaluation liquids are used. ~Composition ratio for haze measurement~ Precursor of the resin for which you want to calculate the Hansen Solubility Parameter (HSP) (polymerizable compound): 28.0% by mass Liquid for evaluation with known Hansen Solubility Parameters (HSP): 70.0% by mass Polymerization initiator (Irgacure 819, manufactured by BASF): 2.0% by mass ~Evaluation liquid group (21 types)~ Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether, N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethylhexanol, diisobutyl ketone, benzyl alcohol, 1-bromonaphthalene

[0099] -Relative Energy Difference (RED) based on Hansen Solubility Parameters (HSP) of resin and liquid (porogen)- As described above, the relative energy difference (RED) calculated based on the Hansen solubility parameter A of the resin formed by polymerization of the polymerizable compound, which is determined based on the rate of increase in the haze value (cloudiness) in a haze measurement element prepared using a composition for haze measurement containing a polymerizable compound and an evaluation liquid, the interaction radius B of the resin, and the Hansen solubility parameter of the porogen according to the following formula 1 is preferably 1.00 or more, more preferably 1.10 or more, even more preferably 1.20 or more, and particularly preferably 1.30 or more.

number

[0100] -Relative Energy Difference (RED) based on Hansen Solubility Parameters (HSP) of polymerizable compounds and liquids (porogens)- As described above, the relative energy difference (RED) calculated based on the Hansen solubility parameter C of the polymerizable compound, which is determined based on the light transmittance at a wavelength of 550 nm of the transmittance measurement composition containing the polymerizable compound and the evaluation liquid, measured while stirring the transmittance measurement composition containing the polymerizable compound and the evaluation liquid, the interaction radius D of the polymerizable compound, which is determined based on the compatibility between the polymerizable compound and the evaluation liquid, and the Hansen solubility parameter of the liquid, based on the following formula 2, is preferably 1.05 or less, more preferably 0.90 or less, even more preferably 0.80 or less, and particularly preferably 0.70 or less.

number

[0101] [Method for producing the 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 prepare the first liquid composition through a process including a step of dissolving a polymerization initiator in a polymerizable compound, a step of further dissolving a porogen and other components, and a step of stirring to obtain a homogeneous solution.

[0102] (electrode) The electrode of the present invention has an electrode substrate, an electrode mixture layer provided on the electrode substrate, and a resin structure layer provided adjacent to the electrode mixture layer and formed by polymerizing a liquid composition containing a polymerizable compound. Moreover, the electrode as one embodiment of the present invention preferably satisfies at least one of the following (1) to (3), and more preferably satisfies all of (1) to (3). (1) The electrode mixture layer is in contact with and continuous with the end face of the resin structure layer, and covers the end of the resin structure layer that is in contact with the electrode substrate. (2) The area of ​​the surface of the electrode mixture layer that is not in contact with the electrode substrate is equal to or greater than the area of ​​the surface of the electrode mixture layer that is in contact with the electrode substrate. (3) The ratio (B / A) of the average thickness B of the resin structure layer to the average thickness A of the electrode mixture layer is 0.97 or more and 1.03 or less.

[0103] The average thickness A of the electrode mixture layer means the average thickness of the plateau surface of the electrode mixture layer, and can be calculated by measuring the thickness at any three or more points on the plateau surface and averaging the thicknesses. The average thickness B of the resin structure layer means the average thickness of the resin structure layer on the plateau surface, and can be calculated by measuring the thickness at any three or more points and averaging the thicknesses.

[0104] The electrode of the present invention can be suitably manufactured by the electrode manufacturing method of the present invention, and the process is simplified, resulting in excellent productivity, and an electrode in which curling of the electrode substrate is suppressed can be manufactured. An electrode satisfying the above-mentioned (1) to (3) as one embodiment of the present invention can be suitably produced by an embodiment of the electrode production method of the present invention, which comprises the first application step, the polymerization step, and the second application step in this order, and the second application step is a step of applying the second liquid composition adjacent to the resin structure layer on the electrode substrate. Moreover, an electrode satisfying the above-mentioned (1) to (3) as one embodiment of the present invention can be suitably produced by an embodiment of the electrode production method of the present invention, in which the first application step and the second application step are carried out simultaneously or sequentially, and then the polymerization step is carried out, and the first liquid composition and the second liquid composition are applied adjacent to each other.

[0105] (Electrode laminate) The electrode laminate of the present invention comprises the electrode of the present invention described above and a solid electrolyte layer provided on the electrode. In other words, the electrode laminate of the present invention has an electrode substrate, an electrode mixture layer provided on the electrode substrate, a resin structure layer provided adjacent to the electrode mixture layer and formed by polymerizing a liquid composition containing a polymerizable compound, and a solid electrolyte layer provided on the electrode mixture layer and the resin structure layer. It is preferable that the electrode mixture layer is continuous with and in contact with an end face of the resin structure layer, covers the end of the resin structure layer that is in contact with the electrode substrate, the area of ​​the surface of the electrode mixture layer that is not in contact with the electrode substrate is equal to or greater than the area of ​​the surface of the electrode mixture layer that is in contact with the electrode substrate, and the ratio (B / A) of an average thickness B of the resin structure layer to an average thickness A of the electrode mixture layer is 0.97 or more and 1.03 or less.

[0106] An example of an electrode of the present invention is shown in Fig. 1A. Fig. 1A is a cross-sectional view of an electrode 25. The electrode 25 has a first electrode having a first electrode substrate 21 and an electrode mixture layer 20 on the first electrode substrate 21, and a resin structure layer 10 on the outer periphery of the first electrode mixture layer 20, and the electrode mixture layer 20 is in contact with and continuous with an end face of the resin structure layer 10, covering the end of the resin structure layer 10 that is in contact with the electrode substrate 21. In addition, FIG. 1A illustrates a configuration in which an electrode mixture layer 20 and a resin structure layer 10 are provided on one side of the first electrode substrate 21, but an electrode mixture layer 20 and a resin structure layer 10 may be provided on both opposing sides of the first electrode substrate 21.

[0107] Another example of the electrode of the present invention is shown in Fig. 1B. In the electrode of Fig. 1B, the electrode mixture layer 20 is in contact with and continuous with the end face of the resin structure layer 10, covers the end of the resin structure layer 10 in contact with the electrode substrate 21, the area of ​​the surface of the electrode mixture layer 20 not in contact with the electrode substrate 21 is equal to or greater than the area of ​​the surface of the electrode mixture layer 20 in contact with the electrode substrate 21, and the ratio (B / A) of the average thickness B of the resin structure layer 10 to the average thickness A of the electrode mixture layer 20 is 0.97 or more and 1.03 or less.

[0108] An example of the electrode laminate of the present invention is shown in Fig. 2. Fig. 2 is a cross-sectional view of an electrode laminate 35, which has a first electrode substrate 21, a first electrode mixture layer 20 on the first electrode substrate 21, a resin structure layer 10 on the outer periphery of the first electrode mixture layer 20, and a solid electrolyte layer 30 on the first electrode mixture layer 20 and the resin structure layer 10, and the resin structure layer 10 is continuous with the electrode mixture layer 20 in contact with an end face of the resin structure layer 10, and covers the end of the resin structure layer 10 in contact with the electrode substrate 21. In addition, FIG. 2 illustrates a configuration in which the electrode mixture layer 20, the resin structure layer 10, and the solid electrolyte layer 30 are provided on one side of the first electrode substrate 21, but the electrode mixture layer 20, the resin structure layer 10, and the solid electrolyte layer 30 may be provided on both opposing sides of the first electrode substrate 21.

[0109] An example of an electrochemical element of the present invention, which will be described later, is shown in Fig. 3. Fig. 3 is a cross-sectional view of an electrochemical element 45, which has a second electrode on an electrode laminate 35, the second electrode having a second electrode substrate 41 and an electrode mixture layer 40 on the second electrode substrate 41, and the solid electrolyte layer 30 and the electrode mixture layer 40 face each other. The electrochemical element 45 is a single cell layer, which can be stacked to form a stacked battery. In addition, FIG. 3 illustrates a configuration in which the electrode mixture layer 20, the resin structure layer 10, and the solid electrolyte layer 30 are provided on one side of the first electrode substrate 21, but the electrode mixture layer 20, the resin structure layer 10, and the solid electrolyte layer 30 may be provided on both opposing sides of the first electrode substrate 21, and this configuration may be stacked to form a stacked battery.

[0110] The shape of the resin structure layer or the first liquid composition layer, the shape of the electrode mixture layer or the second liquid composition layer, and the regions in which they are provided will be described with reference to the drawings. The shapes of the resin structure layer and the electrode mixture layer will be described. Since the resin structure layer 10 is formed by polymerizing the first liquid composition layer 11 and the electrode mixture layer 20 is formed from the second liquid composition layer 12, the matters described for the resin structure layer 10 can be applied to the first liquid composition layer 11, and the matters described for the electrode mixture layer 20 can be applied to the second liquid composition layer 12. 4 to 6 are top views showing the manufacturing process of the electrode 25 shown in FIG. 1 and top views showing the manufacturing process of an electrode according to another embodiment. In Fig. 4, the resin structure layer 10 is provided adjacent to two sides of the electrode mixture layer 20. In Fig. 5, the resin structure layer 10 in two regions is provided adjacent to one long side of the electrode mixture layer 20 and two corners of the long side. As shown in FIG. 6, the resin structure layer 10 may be provided continuously adjacent to all four sides of the electrode mixture layer 20, or may be provided discontinuously adjacent thereto (not shown).

[0111] Here, the resin structure layer being provided in the "portion adjacent to the electrode mixture layer" means that the resin structure layer and the electrode mixture layer are provided adjacent to each other. The resin structure layer may be provided on the outer periphery of the electrode mixture layer, or when the electrode mixture layer has an opening or an uncoated portion, the resin structure layer may be provided on the inner periphery of the electrode mixture layer, or a combination thereof may be used. When a resin structure layer is provided on the "periphery of the electrode mixture layer", the resin structure layer may be provided on at least two sides of the outer periphery of the electrode mixture layer, and the resin structure layer may be provided on three sides or four sides (all sides) of the outer periphery of the electrode mixture layer. In addition, the resin structure layer may have a recess or a notch on any side for allowing an electrode tab to protrude. In addition, being provided on "the outer periphery of the electrode substrate" may mean that the resin structure layer is provided so as to include the end portion of the electrode substrate, or the resin structure layer may be provided around the resin structure layer with a margin of the electrode substrate as shown in Figs. 4 to 6.

[0112] In addition, "the electrode mixture layer is continuous and in contact with the end face of the resin structure layer" means that a continuous area of ​​90% or more of one end face of the electrode mixture layer is in contact with the end face of the resin structure layer, and specifically means that a continuous area of ​​one end face of the electrode mixture layer 20, excluding the ends (corners) of each side of the electrode mixture layer, is in contact with the end face of the adjacent resin structure layer. That is, "a continuous region of 90% or more of one end face of the electrode mixture layer" is, for example, the region represented by the hatched portion of the electrode mixture layer 20 in FIGS. Furthermore, when the resin structure layer is provided intermittently adjacent to one end face of the electrode mixture layer 20, the area in which the resin structure layer is not provided, which is caused by the resin structure layer being provided intermittently, is not included in "a continuous area of ​​90% or more of one end face of the electrode mixture layer."

[0113] As described above, the resin structure layer is provided on at least two of the four sides of the end face of the outer periphery of the electrode mixture layer, and may be provided on three sides or all four sides. However, it is sufficient that at least one side of the electrode mixture layer satisfies the requirement that "the electrode mixture layer is in contact with and continuous with the end face of the resin structure layer," and it is preferable that two sides of the electrode mixture layer satisfy this requirement. Furthermore, when the resin structure layer is provided on all three or four sides of the electrode mixture layer, it is more preferable that all three or four sides of the electrode mixture layer satisfy the condition that "the electrode mixture layer is in contact with and continuous with an end face of the resin structure layer."

[0114] <Electrodes (first electrode, second electrode)> The electrode includes an electrode substrate, an electrode mixture layer, and a resin structure layer. The negative electrode and positive electrode are collectively referred to as "electrodes", the negative electrode substrate and positive electrode substrate are collectively referred to as "electrode substrate", and the negative electrode mixture layer and positive electrode mixture layer are collectively referred to as "electrode mixture layer". Moreover, when the first electrode is a negative electrode, the second electrode refers to a positive electrode, and when the first electrode is a positive electrode, the second electrode refers to a negative electrode.

[0115] <Electrode base> The electrode substrate is not particularly limited as long as it is a conductive substrate that is stable against an applied potential. Examples of the electrode substrate include aluminum foil, copper foil, stainless steel foil, titanium foil, etched foils obtained by etching these foils to form fine holes, and perforated electrode substrates used in lithium ion capacitors.

[0116] <Electrode composite layer> The electrode mixture layer is formed from the first liquid composition and the first liquid composition layer, contains an active material, and may further contain other components such as a dispersion medium, a dispersant, a conductive assistant, a binder, a non-aqueous electrolyte, a solid electrolyte, a gel electrolyte, etc. Each component can be appropriately selected from the items described in the manufacturing method of the electrode of the present invention.

[0117] <Resin structure layer> The resin structure layer is provided on the outer periphery of the electrode mixture layer provided on the electrode substrate, and is also provided on the outer periphery of the electrode substrate. The resin structure layer is a resin structure layer formed by polymerizing a first liquid composition containing a polymerizable compound and a first solvent. The resin structure layer is preferably porous, and more preferably has a bicontinuous structure with a resin skeleton. The resin structure layer preferably has pores having a size of 0.01 μm or more and 10 μm or less. The resin structure layer preferably has insulating properties. In the present specification and claims, the term "insulating properties" means that the volume resistivity of the resin structure layer is 1×10 12 (Ω cm) or more. 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, and in this embodiment, refers to a structure in which both the resin phase and the pore phase are three-dimensional branched network continuous phases. Such a structure can be formed, for example, by polymerizing the liquid composition described below by a polymerization induced phase separation method.

[0118] The compression ratio of the resin structure layer after pressing at 500 MPa for 5 minutes is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1% to 50%, more preferably 5% to 20%. When the compression ratio is 50% or less, the shape of the resin structure layer can be sufficiently maintained when undergoing a pressing step from the viewpoint of the strength of the resin structure layer, and when the compression ratio is 1% or more, the pressure applied from the resin structure layer to the solid electrolyte layer can be alleviated in the pressing step after the formation of the solid electrolyte layer.

[0119] Since the resin structure layer has a cocontinuous structure, when the thickness of the electrode mixture layer and the thickness of the resin structure layer are to be made substantially equal, the thickness of the resin structure layer can be easily and accurately controlled by pressing. In addition, the thickness of the resin structure layer can be easily controlled by forming the resin structure layer by coating and polymerization induced phase separation as described later. If the resin structure layer is a porous resin layer having a cocontinuous structure, it is possible to efficiently release the pressure generated during pressing, thereby suppressing the occurrence of defects such as destruction of the resin layer and unevenness in height difference, and a resin layer of good quality can be obtained.

[0120] In electrochemical elements where a short circuit due to dendrite precipitation may occur, the negative electrode mixture layer is generally larger than the positive electrode mixture layer. In this case, if the positive electrode current collector and the negative electrode current collector are approximately the same size, a surplus portion where the positive electrode mixture layer is not formed is generated in the region on the positive electrode current collector where the negative electrode mixture layer of the negative electrode faces. From the viewpoint of electrical element characteristics, the resin structure layer is preferably provided on the surplus portion of the positive electrode, i.e., on the outer periphery of the positive electrode mixture layer. Note that, if the negative electrode mixture layer is configured to be smaller than the positive electrode mixture layer when the electrochemical element is formed, the resin structure layer is preferably provided on the surplus portion of the negative electrode, i.e., on the outer periphery of the negative electrode mixture layer.

[0121] A method for confirming that the porous structure has a bicontinuous structure and that the pores are interconnected can be, for example, by observing the cross section of the porous structure using a scanning electron microscope (SEM) or the like to confirm that the pores are interconnected. Air permeability is one of the physical properties that can be obtained by interconnecting pores.

[0122] [Image observation using a scanning electron microscope (SEM) and measurement of porosity] The porosity of the porous structure is preferably 30% or more, more preferably 50% or more, and is preferably 90% or less, more preferably 85% or less. When the porosity is 30% or more, the pressure applied from the resin structure layer to the solid electrolyte layer in the pressing step after the formation of the solid electrolyte layer can be alleviated, and when the porosity is 90% or less, the shape of the resin structure layer can be sufficiently maintained after the pressing step from the viewpoint of the strength of the resin structure layer. The method for evaluating the porosity of the porous structure is not particularly limited and can be appropriately selected depending on the purpose. For example, a method can be used in which the porous structure is stained with osmium, then vacuum-impregnated with an epoxy resin, the internal cross-sectional structure is cut out with a focused ion beam (FIB), and the porosity is measured using a scanning electron microscope (SEM).

[0123] [Air permeability] The air permeability of the porous structure is preferably 1,000 sec / 100 mL or less, more preferably 500 sec / 100 mL or less, and even more preferably 300 sec / 100 mL or less. The air permeability is measured in accordance with JIS P8117, and can be measured, for example, by using a Gurley densometer (manufactured by Toyo Seiki Seisakusho, Ltd.). As an example, it may be determined that the pores are interconnected when the air permeability is 1,000 sec / 100 mL or less.

[0124] The cross-sectional shape of the pores of the porous resin may be various shapes and sizes, such as a substantially circular shape, a substantially elliptical shape, a substantially polygonal shape, etc. Here, the size of the pores refers to the length of the longest part in the cross-sectional shape. The size of the pores can be obtained from a cross-sectional photograph taken with a scanning electron microscope (SEM). The size of the pores of the porous resin 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 the solid electrolyte layer provided on the resin structure layer is preferably smaller than 1, more preferably 0.8 or less. If the pore size is larger than the median diameter of the solid electrolyte, the solid electrolyte is easily contained in the pores of the resin structure layer. By setting the size in the above range, a configuration in which the solid electrolyte is not easily contained in the resin structure layer can be obtained, which is advantageous in terms of pressure dispersion during pressing and relaxation of pressure applied from the resin structure layer to the solid electrolyte. The method for adjusting the pore size and porosity of the porous resin to fall within these ranges is not particularly limited, and examples thereof include a method of adjusting the content of the polymerizable compound in the liquid composition to fall within the above-mentioned range, a method of adjusting the content of the porogen in the liquid composition to fall within the above-mentioned range, and a method of adjusting the irradiation conditions of active energy rays.

[0125] The average thickness of the resin 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 to 150.0 μm, and more preferably 10.0 μm to 100.0 μm. An average thickness of 10.0 μm or more can distribute pressure load and prevent short circuit between the positive electrode and the negative electrode, while an average thickness of 100.0 μm or less can produce an electrochemical element with high density and excellent battery characteristics. The average thickness can be determined by measuring the thickness at any three or more points and calculating the average.

[0126] <Solid electrolyte layer> As the solid electrolyte of the solid electrolyte layer, any of the materials described as the solid electrolyte of the electrode mixture layer can be appropriately selected and used. The solid electrolyte layer may contain a binder. Examples of the binder include thermoplastic resins such as polyvinylidene fluoride (PVDF), acrylic resin, styrene butadiene rubber, polyethylene, polypropylene, polyurethane, nylon, polytetrafluoroethylene, polyphenylene sulfide, polyethylene terephthalate, 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).

[0127] (Method of manufacturing electrode laminate and device for manufacturing electrode laminate) The method for producing an electrode laminate of the present invention includes an electrode production step of producing an electrode by the above-described electrode production method of the present invention, and a solid electrolyte layer formation step, and may further include other steps such as a pressing step as necessary. In other words, the method for producing an electrode laminate of the present invention includes at least a first applying step, a polymerization step, a second applying step, and a removal step. The electrode laminate manufacturing apparatus of the present invention has an electrode manufacturing means for manufacturing an electrode by the electrode manufacturing apparatus of the present invention described above, and a solid electrolyte layer forming means, and further has other means such as a pressing means as necessary. In other words, the electrode laminate manufacturing apparatus of the present invention has at least a first storage container, a second storage container, a first application means, a polymerization means, a second application means, and a removal means. The first applying step, the polymerization step, the second applying step, the removal step, the first storage container, the second storage container, the first applying means, the polymerization means, the second applying means, and the removal means can be appropriately selected from those described in the electrode manufacturing method and the electrode manufacturing apparatus of the present invention described above.

[0128] <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 resin structure layer, and can be suitably performed by a solid electrolyte layer forming means. The solid electrolyte layer forming means is a means for forming a solid electrolyte layer on the electrode mixture layer and the resin structure layer. The method for forming the solid electrolyte layer is not particularly limited and can be appropriately selected depending on the purpose. For example, a method in which a liquid composition containing the solid electrolyte and, if necessary, the binder is applied onto the electrode mixture layer and the resin structure layer, solidified, and dried can be mentioned.

[0129] The coating method is not particularly limited, and 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.

[0130] <Pressing process, pressing method> The pressing step is a step of pressing the electrode mixture layer and the resin structure layer, and can be suitably performed by a pressing means. The pressing means is a means for pressing the electrode mixture layer and the resin structure layer. By performing the pressing, the average thickness of the electrode mixture layer and the average thickness of the resin structure layer can be made substantially equal. Therefore, even if high pressure is applied when pressing the solid electrolyte layer provided on the electrode, the pressure load can be dispersed excellently. The timing of performing the pressing step is not particularly limited and can be appropriately selected depending on the purpose. For example, the electrode mixture layer and the resin structure layer may be formed on the electrode base, and then the electrode mixture layer and the resin structure layer may be pressed. Alternatively, if the thickness of the resin structure layer before pressing and the thickness of the electrode mixture layer are approximately equal, a solid electrolyte layer may be further provided and then pressing may be performed. Alternatively, both of these may be performed.

[0131] The pressing method is not particularly limited and can be performed using a commercially available pressure molding device, and can be performed by pressing the electrode mixture layer and the resin structure layer in the direction of the electrode substrate, and examples of the method 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. The pressing pressure is preferably a pressure capable of compressing the electrode mixture layer while bonding the electrode substrate and the electrode mixture layer together, and is preferably 1 MPa to 900 MPa, and more preferably 50 MPa to 300 MPa.

[0132] [Embodiments in which a resin structure layer or an electrode is formed by applying a liquid composition to a substrate] 7A and 7B are schematic diagrams showing an example of a method for producing an electrode of this embodiment. The electrode manufacturing apparatus 500 is an apparatus for manufacturing a resin structure layer using the above-mentioned first liquid composition. The electrode manufacturing apparatus includes a first printing unit 100 for carrying out a first application process of applying a first liquid composition onto a printing substrate 4 to form a first liquid composition layer, a second printing unit 200 for carrying out a second application process of applying a second liquid composition onto the printing substrate 4 to form a second liquid composition layer, a polymerization unit 300 for carrying out a polymerization process of applying heat or light to the first liquid composition layer to polymerize it, and a heating unit 400 for carrying out a heating process of heating the resin structure layer 10 containing the first solvent and removing the first solvent in the pores to obtain the resin structure layer 10 and removing the second solvent contained in the electrode mixture layer. The resin structure layer manufacturing apparatus includes a conveying unit 5 for conveying the printing substrate 4, and the conveying unit 5 conveys the printing substrate 4 at a preset speed in the order of the first printing unit 100, the second printing unit 200, the polymerization unit 300, and the heating unit 400. The printing substrate 4 is an electrode substrate.

[0133] -First printing unit 100- The first printing unit 100 includes a printing device 1a, which is an example of an application means for realizing a first application step of applying a first liquid composition 7 for forming a resin structure layer on the printing substrate 4, a storage container 1b for storing the first liquid composition 7, and a supply tube 1c for supplying 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 and applies the first liquid composition 7 onto the printing substrate 4 to form a first liquid composition layer 11 in a thin film form. The storage container 1b may be integrated with an apparatus for producing a resin structure layer, or may be removable from the apparatus for producing a resin structure layer. Alternatively, the storage container 1b may be a container used for adding to a storage container integrated with an apparatus for producing a resin structure layer or a storage container removable from the apparatus for producing a resin structure layer. The storage container 1b and the supply tube 1c can be arbitrarily selected 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 and visible light. This prevents the first liquid composition 7 from being polymerized by external light.

[0134] -Second printing unit 200- The second printing unit 200 includes a printing device 2a, which is an example of an application means for realizing a second application step of applying a second liquid composition 8 for forming an electrode mixture layer on the printing substrate 4, a storage container 2b for storing the second liquid composition 8, and a supply tube 2c for supplying 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 7 from the printing device 2a and applies the second liquid composition 8 onto the printing substrate 4 to form a thin film of the second liquid composition layer. The storage container 2b may be integrated with the production device for the resin structure layer, or may be removable from the production device for the resin structure layer. Alternatively, the storage container 2b may be a container used for adding to a storage container integrated with the production device for the resin structure layer or a storage container removable from the production device for the resin structure layer. The container 2b and the supply tube 2c may be selected from any materials as long as they can stably store and supply the second liquid composition 8. The materials constituting the container 2b and the supply tube 2c preferably have a light blocking property in the relatively short wavelength region of ultraviolet and visible light. This prevents the second liquid composition 7 from being polymerized by external light.

[0135] As shown in FIG. 7A, the first printing unit 100 (first application unit) and the second printing unit 200 (second application unit) may be performed sequentially or simultaneously, followed by polymerization in the polymerization unit 300; as shown in FIG. 7B, the first printing unit 100 (first application unit), the polymerization unit 300, and the second printing unit 200 (second application unit) may be provided in this order.

[0136] - Polymerization section 300 - As shown in FIGS. 7A and 7B, in the case of photopolymerization, the polymerization unit 300 has a light irradiation device 3a which is an example of a polymerization means for carrying out a polymerization step, and a polymerization inert gas circulation device 3b which circulates a polymerization inert gas. The light irradiation device 3a irradiates the first liquid composition layer 11 formed by the printing unit 100 with light in the presence of the polymerization inert gas, and photopolymerizes the layer to obtain a resin structure layer 10 containing a first solvent. The light irradiation device 3a is appropriately selected according to the absorption wavelength of the photopolymerization initiator contained in the liquid composition layer, and is not particularly limited as long as it can initiate and advance the polymerization of the compound in the liquid composition layer, 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 a shorter wavelength generally tends to reach deeper parts, it is preferable to select a light source according to the thickness of the porous film 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 sufficiently occurred, and it will tend to be difficult to obtain a porous structure. On the other hand, if the irradiation intensity is too weak, phase separation will proceed to a microscale or greater, and porosity will tend to vary and become coarse. In addition, the irradiation time will also be long, and productivity will tend to decrease. For this reason, the irradiation intensity is 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:

[0137] The polymerization inert gas circulation device 3b plays a role of lowering the concentration of polymerization active oxygen contained in the atmosphere and allowing the polymerization reaction of the polymerizable compound near the surface of the first liquid composition layer 11 to proceed without being hindered. Therefore, the polymerization inert gas used is not particularly limited as long as it satisfies the above-mentioned functions, 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 2b is preferably provided with a temperature control means capable of controlling the temperature in order to realize stable polymerization progress conditions.

[0138] In the case of thermal polymerization, the polymerization section 300 may be a heating device. The heating device is not particularly limited and may be appropriately selected depending on the purpose. Examples of the heating device include a substrate heater (e.g., a hot plate), an IR heater, and a hot air heater, and these may be combined. Moreover, the heating temperature, time, and light irradiation conditions can be appropriately selected depending on the polymerizable compound contained in the first liquid composition 7 and the thickness of the formed film.

[0139] -Removal part 400- 7A and 7B, the removal unit 400 has a heating device 4a, and performs a removal step in which the resin structure layer 10 containing the first solvent and formed by the polymerization unit 300 and the electrode mixture layer are heated by the heating device 4a to dry and remove the remaining first solvent and second solvent. This allows the resin structure layer 10 to be formed. The removal unit 400 may remove the liquid under reduced pressure. The removal unit 400 also carries out a polymerization promotion step of heating the resin structure layer 10 containing the first solvent with the heating device 4a to further promote the polymerization reaction carried out in the polymerization unit 300, and an initiator removal step of heating, drying and removing the photopolymerization initiator remaining in the resin structure layer 10 with the heating device 4a. Note that the polymerization promotion step and the initiator removal step do not necessarily need to be carried out simultaneously with the liquid removal step, but may be carried out before or after the liquid removal step. Furthermore, after the liquid removing step, the removal unit 400 performs a polymerization completion step of heating the porous material under reduced pressure. The heating device 4a is not particularly limited as long as it satisfies the above-mentioned functions, and examples thereof include an IR heater and a hot air heater. The heating temperature and time can be appropriately selected depending on the boiling points of the first solvent contained in the resin structure layer 10 and the second solvent contained in the electrode mixture layer, and the thickness of the formed film.

[0140] FIG. 8 is a schematic diagram showing another example of a resin structure layer manufacturing apparatus (liquid ejection apparatus) for implementing the electrode manufacturing method of the present embodiment. 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 and the valves 311 and 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 also possible to supply a first liquid composition from the external tank 313 to the tank 307 by controlling the pump 310 and the valves 311, 312, and 314. By using the above-mentioned resin structure layer producing device, the first liquid composition can be discharged onto a targeted location on an object to which the composition is to be applied.

[0141] Another example of the method for producing the resin structure layer of the present embodiment is shown in FIG. The method for producing an electrode 210 having a porous resin provided on a substrate includes a step of sequentially discharging a first liquid composition 12A onto a substrate 211 using a liquid discharger 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 porous resin 212 is formed faces upward in FIG. 9. 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. 9. Then, droplets of the first liquid composition 12A are ejected from a liquid ejection head 306 installed above the substrate 211 between the feed roller 304 and the take-up roller 305 onto the substrate 211 that is being transported in sequence, in the same manner as in FIG. 8. A plurality of liquid ejection heads 306 may be installed in a direction substantially parallel to or substantially perpendicular to the transport direction of substrate 211. Next, substrate 211 onto which droplets of first liquid composition 12A have been ejected is transported to polymerization section 309 by delivery roller 304 and take-up roller 305. As a result, porous resin 212 is formed, and electrode 210 having porous resin provided on substrate 210 is obtained. Thereafter, electrode 210 having polymer electrolyte provided thereon is cut to a desired size by punching or the like.

[0142] The overlapping portion 309 may be provided either above or below the base material 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 first liquid composition 12A, and examples of the polymerization section 309 include, in the case of thermal polymerization, a resistance heater, an infrared heater, a fan heater, etc., and in the case of photopolymerization, an ultraviolet ray irradiation device, etc. Note that a plurality of polymerization sections 309 may be installed.

[0143] The conditions for heating or light irradiation are not particularly limited and can be appropriately selected depending on the purpose. The first liquid composition 12A is polymerized by polymerization to form a porous resin. As shown in FIG. 10, the tank 307A may be supplied with the liquid composition from a tank 313A connected to the tank 307A, and the liquid ejection head 306 may have a plurality of liquid ejection heads 306A and 306B.

[0144] [Embodiments in which a resin structure layer or an electrode is formed by indirectly applying a liquid composition to a substrate] 11 and 12 are configuration diagrams showing an example of a printing unit employing an inkjet system and a transfer system as an application means, as a manufacturing apparatus for a resin structure layer of this embodiment. FIG. 11 is a configuration diagram showing a printing unit using a drum-shaped intermediate transfer body, and FIG. 12 is a configuration diagram showing a printing unit using an endless belt-shaped intermediate transfer body. The printing unit 400' shown in FIG. 11 is an inkjet printer that transfers a liquid composition or a porous resin to a substrate via an intermediate transfer body 4001, thereby forming a porous resin on the substrate.

[0145] The printing section 400 ′ includes an inkjet section 420 , a transfer drum 4000 , a pretreatment unit 4002 , an absorption unit 4003 , a heating unit 4004 and a cleaning unit 4005 . The inkjet unit 420 includes a head module 422 that holds a plurality of heads 101. The heads 101 eject a liquid composition onto an intermediate transfer body 4001 supported by a transfer drum 4000, and form a liquid composition layer on the intermediate transfer body 4001. Each head 101 is a line head, and nozzles are arranged in a range that covers the width of a recording area of ​​a substrate of the maximum size that can be used. The head 101 has a nozzle surface on its lower surface on which nozzles are formed, and the nozzle surface faces the surface of the intermediate transfer body 4001 via a minute gap. In the case of this embodiment, the intermediate transfer body 4001 is configured to circulate on a circular orbit, so the plurality of heads 101 are arranged radially.

[0146] The transfer drum 4000 faces the impression cylinder 621 and forms a transfer nip. The pretreatment unit 4002 applies, for example, a reaction liquid for increasing the viscosity of the liquid composition onto the intermediate transfer body 4001 before the liquid composition is discharged by the head 101. The absorption unit 4003 absorbs liquid components from the liquid composition layer on the intermediate transfer body 4001 before transfer. The heating unit 4004 heats the liquid composition layer on the intermediate transfer body 4001 before transfer. By heating the liquid composition layer, the liquid composition is thermally polymerized to form a porous resin. In addition, the solvent is removed, improving the transferability to the substrate. The cleaning unit 4005 cleans the intermediate transfer body 4001 after transfer and removes foreign matter such as ink and dust remaining on the intermediate transfer body 4001. The outer peripheral surface of the impression cylinder 621 is in pressure contact with the intermediate transfer body 4001, and the porous resin on the intermediate transfer body 4001 is transferred to the substrate when the substrate passes through a 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 for holding the leading end of the substrate on its outer peripheral surface.

[0147] The printing unit 400 ″ shown in FIG. 12 is an inkjet printer that transfers a liquid composition or a porous resin onto a substrate via an intermediate transfer belt 4006 to form a porous resin on the substrate. The printing section 400'' ejects droplets of the liquid composition from a plurality of heads 101 provided in the inkjet section 420 to form a liquid composition layer on the outer circumferential surface of the intermediate transfer belt 4006. The liquid composition layer formed on the intermediate transfer belt 4006 is heated by a heating unit 4007 and thermally polymerized to form a porous resin, which is then turned into a film on the intermediate transfer belt 4006.

[0148] The porous resin film on the intermediate transfer belt 4006 is transferred to the substrate in the transfer nip where the intermediate transfer belt 4006 faces the transfer roller 622. The surface of the intermediate transfer belt 4006 after transfer is cleaned by a cleaning roller 4008. The intermediate transfer belt 4006 is stretched over a drive roller 4009a, an opposing roller 4009b, multiple (four in this example) shape maintaining rollers 4009c, 4009d, 4009e, and 4009f, and multiple (four in this example) support rollers 4009g, and moves in the direction of the arrow in the figure. The support roller 4009g, which is provided opposite the head 101, maintains the tension state of the intermediate transfer belt 4006 when ink droplets are ejected from the head 101.

[0149] (Electrochemical element) The electrochemical device of the present invention is an electrochemical device having at least the above-mentioned electrode laminate of the present invention and further having an exterior. The electrochemical device is preferably an all-solid-state battery having a solid electrolyte layer. The exterior packaging is not particularly limited as long as it can seal the electrodes and the electrode structure, and any known exterior packaging can be appropriately selected depending on the purpose. FIG. 13 shows an example of an all-solid-state battery which is an electrochemical device of the present invention. 13, a positive electrode 20 and a negative electrode 40 are laminated with a solid electrolyte 30 interposed therebetween. Here, the positive electrode 20 is laminated on both sides of the negative electrode 40. Further, 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 . There is no particular limit to the number of stacked positive electrodes 20 and negative electrodes 40. The number of positive electrodes 20 and the number of negative electrodes 40 may be the same or different. The lead wires 50 and 51 are led out to the outside of the exterior 60 . The shape of the electrochemical element is not particularly limited, and examples thereof include a laminate type, a cylinder type, and a coin type.

[0150] (Electrochemical element manufacturing method and electrochemical element manufacturing apparatus) The method for manufacturing an electrochemical element of the present invention includes an electrode manufacturing step of manufacturing an electrode laminate by the above-mentioned method for manufacturing an electrode laminate of the present invention, and an element fabrication step of manufacturing an electrochemical element using the electrode laminate, and may further include other steps as necessary. The electrochemical element manufacturing apparatus of the present invention has an electrode manufacturing section that manufactures an electrode laminate using the above-mentioned electrode laminate manufacturing apparatus of the present invention, and an element production section that manufactures an electrochemical element using the electrode laminate, and may further have other means as necessary.

[0151] <Electrode manufacturing process and electrode manufacturing department> The electrode manufacturing process includes the application process, polymerization process, electrode mixture layer forming process, pressing process, and solid electrolyte layer forming process, which are explained in the above-mentioned manufacturing method of the electrode laminate of the present invention, and further includes other means such as an electrode processing process, as necessary. The electrode manufacturing section has a container, an application means, a polymerization means, an electrode mixture layer forming means, a pressing means, and a solid electrolyte layer forming means, all of which are described in the electrode laminate manufacturing apparatus of the present invention, and further has other means, such as an electrode processing means, as necessary. The electrode manufacturing process and the electrode manufacturing unit can manufacture an electrode having an electrode substrate, an electrode mixture layer on the electrode substrate, a resin structure layer on the outer periphery of the electrode mixture layer, and a solid electrolyte layer on the electrode mixture layer and the resin structure layer.

[0152] <Device Fabrication Process and Device Fabrication Department> The device fabrication step is a step of manufacturing an electrochemical device using the electrode laminate. The device production section is a means for producing an electrochemical device using the electrode laminate. The method for producing an electrochemical element using the electrode laminate is not particularly limited, and a publicly known method for producing an electrochemical element can be appropriately selected depending on the purpose. For example, a method of forming an energy storage element by at least one of providing a counter electrode, winding or stacking, and housing in a container can be mentioned. The element fabrication step does not need to include all steps of element fabrication, and may include only a part of the steps.

[0153] <Electrode processing process and electrode processing section> The electrode processing unit is a means for processing the electrode on which the resin layer is formed downstream of the application unit. The electrode processing unit may perform at least one of cutting, folding, and lamination. The laminated electrode processing unit can, for example, cut the laminated electrode on which the resin layer is formed to prepare a laminate of laminated electrodes. The electrode processing unit can wind or stack the laminated electrode on which the resin layer is formed. The electrode processing section has, for example, an electrode processing device, and cuts, folds, stacks, or winds the laminated electrode on which the porous resin layer is formed, according to the desired battery form. The electrode processing step performed by the electrode processing unit is, for example, a step of processing a laminated electrode on which a resin layer has been formed downstream of the application step. The electrode processing step may include at least one of a cutting step, a folding step, and a bonding step.

[0154] <Applications of electrochemical elements> Applications of the electrochemical element are not particularly limited, 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 machines, liquid crystal televisions, handy cleaners, portable CDs, mini discs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power sources, motors, lighting equipment, toys, game devices, clocks, strobes, cameras, and other electric devices. Among these, vehicles and electric devices are particularly preferred. Examples of the mobile body include ordinary automobiles, large special purpose automobiles, small special purpose automobiles, trucks, large motorcycles, ordinary motorcycles, and the like.

[0155] [Mobile object] 14 shows an example of a mobile body equipped with an all-solid-state battery that is an electrochemical element of the present invention. Mobile body 70 is, for example, an electric vehicle. Mobile body 70 includes a motor 71, an electrochemical element 72, and wheels 73 that are an example of a means of transportation. Electrochemical element 72 is the electrochemical element of the present invention described above. Electrochemical element 72 drives motor 71 by supplying power to motor 71. Driven motor 71 can drive wheels 73, and as a result, mobile body 70 can move. According to the above-mentioned configuration, short-circuiting between the positive and negative electrodes is prevented, and the vehicle is driven by electric power from an electrochemical element having excellent battery characteristics, so that the vehicle can be moved safely and efficiently. The moving body 70 is not limited to an electric vehicle, but may be a PHEV or HEV, or a locomotive or motorcycle that can run using a diesel engine and an electrochemical device in combination. The moving body may also 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. The moving body may also be an object that does not move in its entirety, but only a part of it, such as an assembly robot that is arranged on a factory production line and whose arms, etc., can operate using only an electrochemical device or a combination of an engine and an electrochemical device. EXAMPLES

[0156] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0157] <Synthesis of solid electrolyte 1> As the solid electrolyte 1, an argyrodite-type sulfide solid electrolyte Li6PS5Cl (LPSC) was synthesized according to the known literature 1 “J. Power Sources. 2018, 396, 33-40”. The solid electrolyte paint was prepared as follows. The solvent used was octane (manufactured by Tokyo Chemical Industry Co., Ltd.) The dehydrated solvent used was confirmed to have a moisture content of 100 ppm or less using a Karl Fischer moisture concentration meter. 100 parts by mass of the solvent was mixed with 100 parts by mass of the above-synthesized solid electrolyte and a dispersant (Solspersetm, manufactured by Lubrizol). TM 21000) was added and mixed to obtain a solid electrolyte coating material.

[0158] <Surface coating of ion-conductive oxide on active material> A nickel-based positive electrode active material (lithium nickel cobalt manganese oxide, hereinafter sometimes referred to as "NCM1"; average primary particle diameter 3.5 μm, manufactured by Toshima Manufacturing Co., Ltd.) was used as the positive electrode active material. LiNbO3 was used as the ion conductive oxide for surface coating the NCM1 particles. The LiNbO3 layer was formed by hydrolyzing an alkoxide solution containing lithium and niobium on the surface of the NCM1 powder particles, with reference to the publicly known document 2 "J. Mater. Chem. A. 2021, 9, 4117-4125". First, metallic lithium (manufactured by Honjo Metals Co., Ltd.) was dissolved in anhydrous ethanol (manufactured by Kanto Chemical Co., Ltd.) to prepare an ethanol solution of lithium ethoxide. Furthermore, niobium pentaethoxide (Nb(OC2H5)5) (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was added to this solution to prepare an alkoxide solution containing lithium and niobium. The NCM1 powder was made into a fluidized bed using a rolling fluidizer (MP-01, Powrex Corporation), and the alkoxide solution was sprayed onto the fluidized bed to obtain a precursor powder in which the surface of the NCM1 powder particles was coated with alkoxide. This powder was heated at 350°C in a dry air atmosphere to synthesize LNO / NCM1, which had a LiNbO3 layer formed on the NCM1 surface.

[0159] <Method of making negative electrode> <Negative electrode 1> A lithium metal (manufactured by Honjo Metals Co., Ltd.) with an average thickness of 50 μm was attached onto a stainless steel foil substrate (50 mm × 50 mm, average thickness: 20 μm) as an electrode substrate, and then an indium foil (manufactured by Nilaco Corporation) with a thickness of 50 μm was attached to obtain a negative electrode 1 with a size of 22 mm × 22 mm.

[0160] <Negative electrode 2> Negative electrode paint 2 was prepared by dispersing 45.5 mass% of graphite (Gr, manufactured by Sigma-Aldrich Corporation) as a negative electrode active material, 1.4 mass% of acetylene black (Denka Black, manufactured by Denka Co., Ltd.) as a conductive material, 1.8 mass% of acrylonitrile butadiene rubber (NBR, manufactured by Sigma-Aldrich Corporation) as a binder, and 14.8 mass% of solid electrolyte 1 in 36.5 mass% anisole. The negative electrode coating material 2 was applied to both sides of a stainless steel foil substrate (50 mm×50 mm, average thickness: 20 μm) and then dried to obtain a negative electrode 2 of 25 mm×25 mm. The average thickness of the negative electrode 2 is 61 μm, and the battery capacity per unit area is 3.38 mAh / cm 2 It was.

[0161] <Negative electrode 3> Negative electrode paint 3 was prepared by dispersing 45.5 mass% of silicon (Si, manufactured by Sigma-Aldrich Corporation) as a negative electrode active material, 1.4 mass% of acetylene black (Denka Black, manufactured by Denka Co., Ltd.) as a conductive material, 1.8 mass% of acrylonitrile butadiene rubber (NBR, manufactured by Sigma-Aldrich Corporation) as a binder, and 14.8 mass% of solid electrolyte 1 in 36.5 mass% anisole. The negative electrode coating material 3 was applied to both sides of a stainless steel foil substrate and then dried to obtain a negative electrode 3 of 25 mm×25 mm. The average thickness of the negative electrode 3 was 21 μm, and the battery capacity per unit area was 3.61 mAh / cm 2 .

[0162] <Preparation of First Liquid Composition for Forming Resin Structure Layer> The materials were mixed in the ratio shown below to prepare a first liquid composition for forming an insulating layer. <First liquid composition 1> A first liquid composition 1 for forming a resin structure layer was obtained by mixing 49.5 mass% of tetrahydrolinalool (manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent, 50.0 mass% of polyethylene glycol (200) diacrylate (manufactured by Daicel Allnex Corporation) as a polymerizable compound, and 0.5 mass% of bis(2,4,6-trimethylbenzoyl)phenylphosphate (manufactured by IGM Resins BV) as a polymerization initiator.

[0163] <First liquid composition 2> A first liquid composition 2 was obtained by mixing 49.5 mass% cyclohexanone (manufactured by Kanto Chemical Industry Co., Ltd.) as a solvent, 50.0 mass% polyethylene glycol (200) diacrylate (manufactured by Daicel Allnex Corporation) as a polymerizable compound, and 0.5 mass% bis(2,4,6-trimethylbenzoyl)phenylphosphate as a polymerization initiator.

[0164] <Preparation of second liquid composition for forming positive electrode mixture layer> A second liquid composition 1 for forming a positive electrode mixture layer was prepared by dispersing 45.3 mass% of LNO / NMC1 as a positive electrode active material, 2.2 mass% of acetylene black (Denka Black, manufactured by Denka Co., Ltd.) as a conductive material, 1.4 mass% of polybutyl methacrylate (PBMA, manufactured by Aldrich Chemical Industries) as a binder, and 14.7 mass% of solid electrolyte 1 in 36.4 mass% of anisole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0165] Example 1 <Preparation of positive electrode> The first liquid composition 1 for forming the resin structure layer was filled into an inkjet discharge device equipped with an inkjet head (MH5421F, manufactured by Ricoh Industry Co., Ltd.). An aluminum foil substrate (50 mm × 50 mm, average thickness: 15 μm) was placed on a stage, and the first liquid composition 1 was discharged and applied so as to have an outer dimension of 40 mm × 40 mm, a width of the resin structure layer of 10 mm, and an opening of 20 mm × 20 mm in which the current collector was exposed inside. Immediately afterwards, the coated area was irradiated with UV light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm) in a nitrogen atmosphere. 2 The resin was then cured by irradiation for 20 seconds. Next, the second liquid composition 1 was applied by discharging it using an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of an opening of 20 mm×20 mm. Next, the substrate was heated at 120° C. for 1 minute using a hot plate to remove the solvent, thereby obtaining an electrode 1 having a positive electrode mixture layer-resin structure layer on an electrode substrate (see FIGS. 1B and 6). For the obtained electrode 1, the surface size of the positive electrode layer was 21 mm × 21 mm, and the amount of warping of the substrate was 0 mm. The average thicknesses of the resin structure layer and the positive electrode layer were measured using a laser microscope (Keyence Corporation, VKX-3000), and both were 95 μm. The positive electrode was in contact with and covered the top of the end of the resin structure layer, forming a continuous positive electrode composite layer-resin structure layer. The battery capacity per unit area was 2.91 mAh / cm 2 It was.

[0166] [Warpage evaluation method] With the electrode substrate of the obtained electrode placed on a horizontal surface, the maximum height (mm) of the warpage at the end of the electrode substrate was measured as "warpage" and evaluated according to the following evaluation criteria. -Evaluation criteria- ◎: Warpage is 0mm to 1mm, and is in excellent condition with no warpage. ◯: Warpage is 1mm to 3mm, and is good with little warpage. △: Warpage is 3mm to 5mm. There is some warpage, but it does not affect use. ×: Warpage of 5 mm or more is so large that there is a problem in use.

[0167] <Battery Construction> The electrode 1 of Example 1 was sealed with an aluminum laminate, and then pressurized at 500 MPa for 5 minutes using a cold isostatic press (CIP). After pressing, the electrode 1 was removed from the aluminum laminate. A solid electrolyte layer was applied to the positive electrode by a bar coating method to form an electrode laminate (see FIG. 2). After coating, the electrode was sealed again with an aluminum laminate, and pressurized at 500 MPa for 5 minutes using a CIP. The electrode 1 and the negative electrode 1 were placed opposite each other to form a single cell layer (see FIG. 3). After each electrode had a lead wire attached, the laminate was vacuum sealed to produce the all-solid-state battery 1 of Example 1.

[0168] The battery voltage of the all-solid-state battery 1 produced by the following procedure was measured and found to be 2.08 V. Thereafter, the capacity per unit area was able to be charged without any problems at a constant current up to 3.6 V at a current value that was 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0169] [Method of measuring the capacitance per unit area of ​​an electrode] The capacity per unit area of ​​the electrode was measured using a charge / discharge measuring device (TOSCAT3001, manufactured by Toyo Systems Co., Ltd.) according to the following procedure. First, the prepared electrode was punched out into a circular shape with a diameter of 10 mm. Next, the capacity of the electrode containing a solid electrolyte in the positive electrode was evaluated by the following method. In an argon atmosphere, the positive electrode was punched out to a capacity per unit area of ​​a round electrode having a diameter of 10 mm. 80 mg of solid electrolyte 1 was placed in a polyethylene terephthalate (PET) tube of a bipolar cell (manufactured by Hosen Co., Ltd.), a press pin was placed on it, and the cell was molded for 1 minute at a nominal pressure of 10 MPa using a uniaxial press (P-6, manufactured by Riken Seiki Co., Ltd.). Next, the surface of the positive electrode composite layer of the positive electrode punched to a diameter of 10 mm was placed in contact with the surface of the solid electrolyte in the PET tube, a press pin was set, and the positive electrode was molded for 1 minute at a nominal pressure of 30 MPa using a uniaxial press (P-6, manufactured by Riken Seiki Co., Ltd.). On the opposite side of the pressed positive electrode composite layer, a 10 μm SUS foil with an average thickness of 50 μm of lithium attached (manufactured by Honjo Metals Co., Ltd.) was layered with an average thickness of 50 μm of indium (manufactured by Nilaco Corporation). It was then molded for 3 seconds at a nominal pressure of 12 MPa using a uniaxial press (P-6, manufactured by Riken Seiki Co., Ltd.). With the press pin still attached, the PET tube was placed into the bipolar cell and sealed at a nominal pressure of 25 N·m using a digital torque ratchet (KTC Tool). This electrochemical element was initially charged and discharged at a constant current of 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material to 3.6 V at room temperature (25° C.), and then discharged at a constant current to 2.4 V. This charge and discharge was then carried out twice, and the second discharge capacity was measured as the initial capacity per unit area of ​​the positive electrode. Similarly, the negative electrode was charged and discharged in the range of −0.55 V to 1.4 V at a current value that was 20% of the capacity per unit area calculated from the theoretical capacity of the negative electrode active material, and the capacity per unit area of ​​the negative electrode was calculated.

[0170] Example 2 <Preparation of positive electrode> The first liquid composition 1 for forming the resin layer and the second liquid composition 1 for forming the positive electrode composite layer were each filled into an inkjet discharge device equipped with a separate GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm x 50 mm, average thickness: 15 μm) serving as a current collector was placed on a stage, and the first liquid composition 1 was applied by discharging the positive electrode paint into the 20 mm x 20 mm area in a shape having an outer dimension of 40 mm x 40 mm, a resin structure layer width of 10 mm, and an opening of 20 mm x 20 mm through which the current collector was exposed. Immediately afterwards, the coated area was irradiated with UV light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm) in a nitrogen atmosphere. 2 The resin was then cured by irradiation for 20 seconds. Next, the substrate was heated at 120° C. for 1 minute using a hot plate to remove the solvent, thereby obtaining an electrode 2 having a positive electrode mixture layer-resin structure layer on an electrode substrate (see FIG. 1B and 6). For the obtained electrode 2, the surface size of the positive electrode layer was 20.5 mm × 20.5 mm, and the amount of warping of the substrate was 0 mm. The average thicknesses of the resin structure layer and the positive electrode layer were both 95 μm when measured using a laser microscope (Keyence Corporation, VKX-3000), and the positive electrode was in contact with and covered the top of the end of the resin structure layer, forming a continuous positive electrode composite layer-resin structure layer. In addition, the battery capacity per unit area was 2.91 mAh / cm 2 It was.

[0171] <Battery Construction> An all-solid-state battery 2 of Example 2 was produced in the same manner as in Example 1, except that an electrode 2 was used instead of the electrode 1 in Example 1. The battery voltage of the fabricated all-solid-state battery 2 was measured and found to be 2.07 V. Thereafter, the capacity per unit area was able to be charged without any problems at a constant current up to 3.6 V at a current value that was 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0172] Example 3 <Preparation of positive electrode> The first liquid composition 1 for forming a resin layer was filled into an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm x 50 mm, average thickness: 15 μm) serving as a current collector was placed on a stage, and the first liquid composition 1 was applied by discharging the positive electrode paint into the 20 mm x 20 mm area in a shape having an outer dimension of 40 mm x 40 mm, a resin structure layer width of 10 mm, and an opening of 20 mm x 20 mm through which the current collector was exposed. Immediately afterwards, the coated area was irradiated with UV light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm) in a nitrogen atmosphere. 2 The resin was then cured by irradiation for 20 seconds. Next, the second liquid composition 1 was applied by discharging it using an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of an opening of 20 mm×20 mm. Next, the substrate was heated at 120° C. for 1 minute using a hot plate to remove the solvent, thereby obtaining an electrode 3 having a positive electrode mixture layer-resin structure layer on an electrode substrate (see FIGS. 1B and 6). For the obtained electrode 3, the surface size of the positive electrode layer was 21 mm × 21 mm, and the amount of warping of the substrate was 1 mm. The average thickness of the resin structure layer was measured using a laser microscope (Keyence Corporation, VKX-3000) and found to be 110 μm. At this time, the positive electrode was in contact with and covered the end of the resin structure layer up to a height of 97 μm, forming a continuous positive electrode composite layer-resin structure layer. In addition, the battery capacity per unit area was 2.91 mAh / cm 2 It was.

[0173] <Battery Construction> An all-solid-state battery 3 of Example 3 was produced in the same manner as in Example 1, except that an electrode 3 was used instead of the electrode 1 in Example 1. The battery voltage of the fabricated all-solid-state battery 3 was measured and found to be 2.08 V. Thereafter, the capacity per unit area was able to be charged without any problems at a constant current up to 3.6 V at a current value that was 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0174] Example 4 <Preparation of positive electrode> The first liquid composition 2 for forming a resin layer was filled into an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm x 50 mm, average thickness: 15 μm) serving as a current collector was placed on a stage, and the first liquid composition 1 was applied by discharging the positive electrode paint into the 20 mm x 20 mm area in a shape having an outer dimension of 40 mm x 40 mm, a resin structure layer width of 10 mm, and an opening of 20 mm x 20 mm through which the current collector was exposed. Immediately afterwards, the coated area was irradiated with UV light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm) in a nitrogen atmosphere. 2 The resin was then cured by irradiation for 20 seconds. Next, the second liquid composition 1 was applied by discharging it using an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of an opening of 20 mm×20 mm. Next, the substrate was heated at 120° C. for 1 minute using a hot plate to remove the solvent, thereby obtaining an electrode 4 having a positive electrode mixture layer-resin structure layer on an electrode substrate (see FIGS. 1B and 6). For the obtained electrode 4, the surface size of the positive electrode layer was 21 mm × 21 mm, and the warpage of the substrate was 3 mm. The average thicknesses of the resin structure layer and the positive electrode layer were both 95 μm when measured using a laser microscope (Keyence Corporation, VKX-3000). The positive electrode was in contact with and covered the top of the end of the resin structure layer, forming a continuous positive electrode composite layer-resin structure layer. The battery capacity per unit area was 2.91 mAh / cm 2 It was.

[0175] <Battery Construction> An all-solid-state battery 4 of Example 4 was produced in the same manner as in Example 1, except that an electrode 4 was used instead of the electrode 1 in Example 1. The battery voltage of the fabricated all-solid-state battery 4 was measured and found to be 2.01 V. Thereafter, the capacity per unit area was able to be charged without any problems at a constant current up to 3.6 V at a current value that was 20% of the capacity per unit area calculated from the theoretical capacity of the positive electrode active material, and no short circuit was observed.

[0176] Comparative Example 1 The first liquid composition 2 for forming a resin layer was filled into an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). An aluminum foil substrate (50 mm x 50 mm, average thickness: 15 μm) serving as a current collector was placed on a stage, and the first liquid composition 1 was applied by discharging the positive electrode paint into the 20 mm x 20 mm area in a shape having an outer dimension of 40 mm x 40 mm, a resin structure layer width of 10 mm, and an opening of 20 mm x 20 mm through which the current collector was exposed. Immediately afterwards, the coated area was irradiated with UV light (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm) in a nitrogen atmosphere. 2 The substrate was then heated at 120° C. for 1 minute using a hot plate to remove the solvent. Next, the second liquid composition 1 was applied by discharging it using an inkjet discharge device equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.) so as to fill the inside of an opening of 20 mm×20 mm. Next, the base material was heated at 120° C. for 1 minute using a hot plate to remove the solvent, thereby obtaining an electrode a having a positive electrode mixture layer-resin structure layer on an electrode substrate. For the obtained electrode a, the surface size of the positive electrode layer was 21 mm × 21 mm, and the warpage of the substrate was 5 mm. The average thicknesses of the resin structure layer and the positive electrode layer were both 97 μm when measured using a laser microscope (Keyence Corporation, VKX-3000). The positive electrode was in contact with and covered the top of the end of the resin structure layer, forming a continuous positive electrode composite layer-resin structure layer. The battery capacity per unit area was 2.91 mAh / cm 2 It was.

[0177] [Table 1]

[0178] For example, aspects of the present invention are as follows. <1> a first application step of applying a first liquid composition containing a polymerizable compound and a first solvent onto an electrode substrate to form a first liquid composition layer; a polymerization step of polymerizing the polymerizable compound to form a resin structure layer; a second application step of applying a second liquid composition containing an active material and a second solvent onto the electrode substrate to form a second liquid composition layer; a removing step of removing the first solvent and the second solvent; The method for producing an electrode is characterized by comprising the steps of: <2> The method includes the first applying step, the polymerization step, and the second applying step in this order, The second applying step is a step of applying the second liquid composition adjacent to the resin structure layer on the electrode substrate. <1> 2 is a method for producing the electrode according to the present invention. <3> The first application step and the second application step are carried out simultaneously or sequentially, and then the polymerization step is carried out; The first liquid composition and the second liquid composition are applied adjacent to each other. <1> 2 is a method for producing the electrode according to the present invention. <4> The polymerization step is a photopolymerization step by light irradiation. <1> from <3> 13. The method for producing the electrode according to claim 12, <5> The resin structure layer is porous. <1> from <4> 13. The method for producing the electrode according to claim 12, <6> the resin structure layer has pores having a size of 0.01 μm or more and 10 μm or less, The viscosity of the first solvent at 25° C. is 1 mPa·s or more and 150 mPa·s or less. <5> 2 is a method for producing the electrode according to the present invention. <7> The first solvent and the second solvent are different from each other. <1> from <6> 13. The method for producing the electrode according to claim 12, <8> An electrode substrate; an electrode mixture layer provided on the electrode substrate; a resin structure layer provided adjacent to the electrode mixture layer and obtained by polymerizing a liquid composition containing a polymerizable compound and a first solvent; the electrode mixture layer is in contact with and continuous with an end face of the resin structure layer and covers an end of the resin structure layer that is in contact with the electrode base, an area of ​​a surface of the electrode mixture layer that is not in contact with the electrode substrate is equal to or greater than an area of ​​a surface of the electrode mixture layer that is in contact with the electrode substrate; The electrode is characterized in that the ratio (B / A) of the average thickness B of the resin structure layer to the average thickness A of the electrode mixture layer is 0.97 or more and 1.03 or less. <9> a first storage container containing a first liquid composition including a polymerizable compound and a first solvent; a second storage container containing a second liquid composition including an active material and a second solvent; a first applying means for applying the first liquid composition onto an electrode substrate to form a first liquid composition layer; a polymerization means for polymerizing the polymerizable compound to form a resin structure layer; a second applying means for applying the second liquid composition onto an electrode substrate to form a second liquid composition layer; a removal means for removing the first solvent and the second solvent; The electrode manufacturing apparatus is characterized by comprising: <10> The above <1> from <7> an electrode manufacturing process for manufacturing an electrode by the electrode manufacturing method according to any one of the above; and a device forming step of manufacturing an electrochemical device using the electrode. <11> The above <9> an electrode manufacturing means for manufacturing an electrode by the electrode manufacturing apparatus according to the present invention; and an element forming means for producing an electrochemical element using the electrode.

[0179] The above <1> from <7> The method for producing an electrode according to any one of the preceding claims. <8> The electrode according to <9> The electrode manufacturing apparatus according to the <10> The method for producing the electrochemical element according to the present invention <11> The manufacturing apparatus for an electrochemical element described above can solve the above-mentioned problems in the prior art and achieve the object of the present invention. [Explanation of symbols]

[0180] 1a: Printing device 1b: Ink container 1c: Ink supply tube 2a: Light irradiation device 2b: Polymerization inert gas circulation device 3a: Heating device 4: Printing base material 5: Transport section 6: Porous resin precursor (resin structure layer precursor) 7: First liquid composition 8: Second liquid composition 10: Resin structure layer 11: First liquid composition layer 12: Second liquid composition layer 20: First electrode mixture layer 21: First electrode substrate 25: Electrode 35: Electrode laminate 40: Second electrode mixture layer 41: Second electrode substrate 45: Electrochemical element 100:Printing Department 200: Polymerization section 300:Removal section 500: Resin structure layer manufacturing equipment [Prior art documents] [Patent documents]

[0181] [Patent Document 1] International Publication No. 2020-022111

Claims

1. a first application step of applying a first liquid composition containing a polymerizable compound and a first solvent onto an electrode substrate to form a first liquid composition layer; a polymerization step of polymerizing the polymerizable compound to form a resin structure layer; a second application step of applying a second liquid composition containing an active material and a second solvent onto the electrode substrate to form a second liquid composition layer; a removing step of removing the first solvent and the second solvent; A method for manufacturing an electrode, comprising:

2. The method includes the first applying step, the polymerization step, and the second applying step in this order, 2. The method for producing an electrode according to claim 1, wherein the second applying step is a step of applying the second liquid composition adjacent to the resin structure layer on the electrode substrate.

3. the first applying step and the second applying step are carried out simultaneously or sequentially, and then the polymerization step is carried out; The method for manufacturing an electrode according to claim 1 , wherein the first liquid composition and the second liquid composition are applied adjacent to each other.

4. The method for manufacturing an electrode according to claim 1 or 2, wherein the polymerization step is a photopolymerization step using light irradiation.

5. The method for producing an electrode according to claim 1 or 2, wherein the resin structure layer is porous.

6. the resin structure layer has pores of 0.01 μm or more and 10 μm or less, 6. The method for manufacturing an electrode according to claim 5, wherein the viscosity of the first solvent at 25°C is 1 mPa·s or more and 150 mPa·s or less.

7. The method for producing an electrode according to claim 1 , wherein the first solvent and the second solvent are different from each other.

8. an electrode substrate; an electrode mixture layer provided on the electrode substrate; a resin structure layer provided adjacent to the electrode mixture layer and formed by polymerizing a liquid composition containing a polymerizable compound and a first solvent, the electrode mixture layer is continuous with and in contact with an end face of the resin structure layer, and covers an end of the resin structure layer that is in contact with the electrode base, an area of ​​a surface of the electrode mixture layer that is not in contact with the electrode substrate is equal to or greater than an area of ​​a surface of the electrode mixture layer that is in contact with the electrode substrate; An electrode characterized in that a ratio (B / A) of an average thickness B of the resin structure layer to an average thickness A of the electrode mixture layer is 0.97 or more and 1.03 or less.

9. a first storage container containing a first liquid composition including a polymerizable compound and a first solvent; a second storage container containing a second liquid composition containing an active material and a second solvent; a first applying means for applying the first liquid composition onto an electrode substrate to form a first liquid composition layer; a polymerization means for polymerizing the polymerizable compound to form a resin structure layer; a second applying means for applying the second liquid composition onto an electrode substrate to form a second liquid composition layer; a removal means for removing the first solvent and the second solvent; An electrode manufacturing apparatus comprising:

10. an electrode manufacturing process for manufacturing an electrode by the electrode manufacturing method according to claim 1; and a device fabrication step of fabricating an electrochemical device using the electrode.

11. an electrode manufacturing unit that manufactures an electrode using the electrode manufacturing apparatus according to claim 9; and element forming means for producing an electrochemical element using the electrode.

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