Method for manufacturing battery laminates, apparatus for manufacturing battery laminates

Abstract

To suppress the occurrence of damage to a laminate for a battery during an electrode manufacturing process.SOLUTION: A method for manufacturing a laminate for a battery includes an insulating layer forming step of applying a liquid composition on a first electrode to form an insulating layer, and an electrode installation step of installing a second electrode on the first electrode on which the insulating layer is formed, and the insulating layer forming step and the electrode installation step are carried out by a series of conveyances.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a battery laminate and an apparatus for manufacturing a battery laminate. [Background technology]

[0002] In recent years, there has been a rapidly increasing demand for higher output, higher capacity, and longer lifespan in energy storage elements such as batteries and power generation elements such as fuel cells. However, various challenges related to the safety of these elements still remain in order to achieve these goals. For example, short circuits between electrodes caused by misalignment or damage to the insulating layer between electrodes can lead to battery explosions and fires, so further improvements are needed. In this context, an electrode-integrated insulating layer has been proposed, as shown in Patent Document 1. [Overview of the Initiative] [Problems that the invention aims to solve]

[0003] However, the insulating layer integrated with the electrode had room for improvement in that, if the strength of the electrode base material was low, the insulating layer was prone to cracking or other damage during the electrode manufacturing process due to deformation of the electrode base material when subjected to impacts such as bending. [Means for solving the problem]

[0004] The manufacturing method for this battery laminate comprises an insulating layer forming step of forming an insulating layer on a first electrode, and an electrode setting step of setting a second electrode on the first electrode on which the insulating layer has been formed, An electrode processing step for processing the first electrode is performed after the insulating layer formation step, The insulating layer formation step includes a step of applying a liquid composition, and the insulating layer formation step and the electrode installation step are carried out by a series of transports. Furthermore, in the electrode processing step, the first electrode on which the second electrode is installed is wound or stacked. . [Effects of the Invention]

[0005] According to the disclosed technology, it is possible to suppress the occurrence of damage to the battery laminate during the electrode manufacturing process. [Brief explanation of the drawing]

[0006] [Figure 1] It is a diagram (part 1) illustrating a manufacturing apparatus for a battery laminate according to this embodiment. [Figure 2] It is a diagram (part 2) illustrating a manufacturing apparatus for a battery laminate according to this embodiment. [Figure 3] It is a diagram (part 3) illustrating a manufacturing apparatus for a battery laminate according to this embodiment. [Figure 4] It is a diagram (part 4) illustrating a manufacturing apparatus for a battery laminate according to this embodiment. [Figure 5] It is a diagram (part 5) illustrating a manufacturing apparatus for a battery laminate according to this embodiment. [Figure 6] It is a diagram (part 6) illustrating a manufacturing apparatus for a battery laminate according to this embodiment. [Figure 7] It is a diagram (part 7) illustrating a manufacturing apparatus for a battery laminate according to this embodiment. [Figure 8] It is an example of a main hardware block diagram of a control unit. [Figure 9] It is an example of a main functional block diagram of a control unit. [Figure 10] It is a plan view and a cross-sectional view illustrating a first electrode with an insulating layer formed thereon. [Figure 11] It is a plan view illustrating a first electrode with an insulating layer formed thereon. [Figure 12] It is a plan view (part 1) illustrating a state where a second electrode is installed on a first electrode with an insulating layer formed thereon. [Figure 13] It is a plan view (part 2) illustrating a state where a second electrode is installed on a first electrode with an insulating layer formed thereon. [Figure 14] It is a cross-sectional view illustrating a battery laminate. [Figure 15] It is a diagram summarizing examples and comparative examples.

Modes for Carrying Out the Invention

[0007] The embodiments for carrying out the invention will be described below with reference to the drawings. In each drawing, the same reference numerals are used for identical components, and redundant explanations may be omitted.

[0008] There are no particular limitations on the batteries to which this embodiment can be applied; it can be suitably applied to secondary batteries, capacitors, and especially lithium-ion secondary batteries, which are generally energy storage elements. Furthermore, the battery laminate according to this embodiment includes a structure in which a negative electrode and a positive electrode are laminated with an insulating layer in between, and the negative electrode and positive electrode are insulated from each other by the insulating layer. The battery is formed by the battery laminate, an electrolyte injected into the battery laminate, an outer casing that seals the battery laminate and the electrolyte, etc.

[0009] <Electrodes (first electrode, second electrode)> The term "electrode" refers to the negative electrode and positive electrode as described below, and one may be referred to as the first electrode and the other as the second electrode. In other words, if the first electrode is a component used as the negative electrode, the second electrode refers to the positive electrode, and if the first electrode is a component used as the positive electrode, the second electrode refers to the negative electrode. Furthermore, the negative electrode substrate and the positive electrode substrate are collectively referred to as the electrode substrate, and the negative electrode composite layer and the positive electrode composite layer are collectively referred to as the electrode composite layer.

[0010] <<Electrode base>> The negative electrode substrate and the positive electrode substrate are not particularly limited as long as they are conductive substrates, and can generally be aluminum foil, copper foil, stainless steel foil, titanium foil, and etched foil obtained by etching these materials to create fine holes, or perforated electrode substrates used in lithium-ion capacitors, which are suitable for use in secondary batteries, capacitors, and especially lithium-ion secondary batteries, which are energy storage elements.

[0011] Furthermore, carbon paper used in power generation elements such as fuel cells, fibrous electrodes that are non-woven or woven and flattened, and perforated electrode substrates with fine holes can also be used. In addition, in the case of solar cells, in addition to the above, transparent semiconductor thin films such as indium-titanium oxide or zinc oxide formed on a flat substrate such as glass or plastic, or conductive electrode films that have been thinly deposited can be used.

[0012] <<Electrode composite layer>> The negative electrode composite layer and the positive electrode composite layer are not particularly limited and can be appropriately selected depending on the purpose. For example, they may contain at least an active material (negative electrode active material or positive electrode active material) and optionally one or more binders, thickeners, conductive agents, dispersants, non-aqueous electrolytes, solid electrolytes, gel electrolytes, or monomers that become gel electrolytes through a polymerization process. The negative electrode composite layer contains the negative electrode active material, and the positive electrode composite layer contains the positive electrode active material.

[0013] The negative electrode composite layer and the positive electrode composite layer can be formed by dispersing powdered active material or catalyst composition in a liquid, and then coating, fixing, and drying the liquid on an electrode substrate. Typically, printing using spray, dispenser, die coater, or pull coating is used, and the layer can be formed by drying after coating.

[0014] The negative electrode active material is not particularly limited as long as it is a material capable of reversibly intercalating and releasing alkali metal ions. Typically, carbon materials containing graphite having a graphite-type crystal structure can be used as the negative electrode active material. Examples of such carbon materials include natural graphite, spherical or fibrous artificial graphite, non-graphitizable carbon (hard carbon), and easily graphitizable carbon (soft carbon). Lithium titanate is an example of a material other than carbon. Furthermore, from the viewpoint of increasing the energy density of lithium-ion batteries, high-capacity materials such as silicon, tin, silicon alloys, tin alloys, silicon oxide, silicon nitride, and tin oxide can also be suitably used as negative electrode active materials.

[0015] Examples of hydrogen storage alloys used as active materials in nickel-metal hydride batteries include Zr-Ti-Mn-Fe-Ag-V-Al-W and Ti 15 Zr 21 V 15 Ni 29 C r5 Examples include AB2 or A2B hydrogen storage alloys, such as Co5Fe1Mn8.

[0016] The positive electrode active material is not particularly limited as long as it is a material capable of reversibly intercalating and releasing alkali metal ions. Typically, alkali metal-containing transition metal compounds can be used as positive electrode active materials. For example, lithium-containing transition metal compounds include composite oxides containing lithium and at least one element selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium.

[0017] Examples of composite oxides include lithium-containing transition metal oxides such as lithium cobaltate, lithium nickelate, and lithium manganate; olivine-type lithium salts such as LiFePO4; chalcogen compounds such as titanium disulfide and molybdenum disulfide; and manganese dioxide.

[0018] Lithium-containing transition metal oxides are metal oxides containing lithium and a transition metal, or metal oxides in which a portion of the transition metal in the metal oxide is substituted with a heterogeneous element. Examples of heterogeneous elements include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B, with Mn, Al, Co, Ni, and Mg being particularly preferred. There may be one heterogeneous element or two or more. These positive electrode active materials can be used individually or in combination of two or more. Examples of the above active materials in nickel-metal hydride batteries include nickel hydroxide.

[0019] For the negative or positive electrode binder, for example, PVDF, PTFE, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamide-imide, polyacrylonitrile, polyacrylic acid, polyacrylate methyl ester, polyacrylate ethyl ester, polyacrylate hexyl ester, polymethacrylic acid, polymethacrylate methyl ester, polymethacrylate ethyl ester, polymethacrylate hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene-butadiene rubber, carboxymethylcellulose, etc. can be used.

[0020] Alternatively, copolymers of two or more materials selected from tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene may be used. Furthermore, two or more materials selected from these may be mixed and used.

[0021] The conductive agents included in the electrode composite layer include, for example, graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black, conductive fibers such as carbon fibers and metal fibers, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and organic conductive materials such as phenylene derivatives and graphene derivatives.

[0022] In fuel cells, the active material generally used as a catalyst for the cathode or anode electrode is a metal nanoparticle such as platinum, ruthenium, or platinum alloy supported on a catalyst support such as carbon. To support catalyst particles on the surface of the catalyst support, for example, the catalyst support is suspended in water, and a precursor of catalyst particles (for example, containing alloy components such as chloroplatinic acid, dinitrodiaminoplatinum, dicplatinum chloride, platinum monochloride, bisacetylacetonate platinum, dichlorodiammineplatinum, dichlorotetramineplatinum, dicplatinum sulfate ruthenium chloride, iridium chloride, rhodium chloride, ferric chloride, cobalt chloride, chromium chloride, gold chloride, silver nitrate, rhodium nitrate, palladium chloride, nickel nitrate, iron sulfate, copper chloride, etc.) is added and dissolved in the suspension, and an alkali is added to generate metal hydroxides, thereby obtaining a catalyst support supported on the surface of the catalyst support. This catalyst support is coated onto an electrode substrate and reduced under a hydrogen atmosphere to obtain an electrode composite layer with catalyst particles (active material) coated on its surface.

[0023] In the case of solar cells and the like, the active material can be tungsten oxide powder or titanium oxide powder, as well as oxide semiconductor layers such as SnO2, ZnO, ZrO2, Nb2O5, CeO2, SiO2, and Al2O3. Dyes are supported on the semiconductor layer, and examples of such compounds include ruthenium-tris type transition metal complexes, ruthenium-bis type transition metal complexes, osmium-tris type transition metal complexes, osmium-bis type transition metal complexes, ruthenium-cis-diqua-bipyridyl complexes, phthalocyanines and porphyrins, and organic-inorganic perovskite crystals.

[0024] <Insulating layer> The insulating layer is a component that physically separates the positive and negative electrodes and ensures ionic conductivity between them, and is provided on the current collector, the electrode composite layer, or both. The insulating layer is not particularly limited, but has a volume resistivity of 1 × 10⁻⁶. 12 It is preferable that the layer exhibits a volume resistivity of (Ω·cm) or higher. 12If the thickness is (Ω·cm) or greater, electrical short circuits between the positive and negative electrodes will not occur. The thickness of the insulating layer is not particularly limited as long as the insulating properties between the positive and negative electrodes are maintained, but it is preferably 1 μm to 50 μm, and particularly preferably 5 μm to 20 μm. If the thickness is thinner than the above, it is difficult to maintain good insulating properties between the positive and negative electrodes. Also, if the thickness is thicker than the above, it is difficult to ensure good ionic conductivity.

[0025] Furthermore, the insulating layer is a porous insulating layer having pores, and the size of the pores is not particularly limited as long as they have ionic conductivity, but from the viewpoint of electrolyte permeability, it is preferable that they be between 0.01 μm and 10 μm. In addition, the porosity of the insulating layer is preferably 30% or more, and more preferably 50% or more.

[0026] Furthermore, as shown in Figure 10, which will be used in a later explanation, a thick film region may be formed around the electrode in the insulating layer. In Figure 10, 9 is the current collector of the first electrode, 10 is the active material of the first electrode, 11a is the thin film region of the insulating layer, and 11b is the thick film region of the insulating layer. Here, the periphery of the electrode is preferably the outer circumference of the surface on which the electrode composite layer of the first electrode is provided, and more preferably, it is within the region on the surface of the electrode composite layer of the first electrode where the second electrode does not face the first electrode when a second electrode having a different polarity from the first electrode is laminated to form an electrode laminate. By forming a thick film region, distortion of the electrodes at the edges can be prevented when the first electrode and the second electrode are laminated, and misalignment during lamination can be suppressed. The thick film region is formed from a material having a melting point and glass transition temperature (Tg), so that the thick film regions of the first electrode located above and below the laminate can be heat-bonded after lamination.

[0027] <Liquid composition for forming an insulating layer> The insulating layer forming liquid composition is a liquid applied to form an insulating layer and includes organic and / or inorganic compounds, and a solvent or dispersion. The above organic and / or inorganic compounds and solvent or dispersion can be appropriately selected as needed, as long as the final formed organic and / or inorganic layer has insulating properties.

[0028] For example, examples of insulating inorganic materials include metal oxides, metal nitrides, and other metal nanoparticles. Preferred metal oxides include Al2O3 (alumina), TiO2, BaTiO3, and ZrO2. Preferred metal nitrides include aluminum nitride and silicon nitride. Preferred other metal nanoparticles include sparingly soluble ionic crystalline nanoparticles such as aluminum fluoride, calcium fluoride, barium fluoride, and barium sulfate, or mineral resource-derived materials such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, and bentonite, or artificial products thereof. Another example of an insulating inorganic material is glass ceramic powder. Preferred glass ceramic powders include crystalline glass ceramics using ZnO-MgO-Al2O3-SiO2 crystalline glass, BaO-Al2O3-SiO2 crystalline ceramic powder, and non-glass ceramics using Al2O3-CaO-SiO2-MgO-B2O3 crystalline ceramic powder.

[0029] Among these, aluminum oxide and silica are preferred in terms of insulation and heat resistance, and α-alumina is more preferred. α-alumina can function as a scavenger for "junk" chemical species, i.e., chemical species that can cause capacity fade in lithium-ion secondary batteries.

[0030] Furthermore, solid electrolytes such as oxides or ceramics such as sulfides can be used. Examples of oxides include LISICON-type oxides such as γ-Li3PO4, Li3BO4, 0.75Li4GeO4-0.25Li2ZnGeO4 solid solution, Li4SiO4-Zn2SiO4 solid solution, Li4GeO4-Li3VO4 solid solution, and NASICON-type oxides such as Li 1.3 Al0.3 Ti 1.7 (PO4)3 or Li 1.6 Al 0.6 Ge 0.8 Ti 0.6 (PO4)3, (Li, La)TiO3 with a perovskite structure, La5Li3Nb2O which is a garnet-type oxide 12 , Li5La3TaO 12 , or Li7La3Zr2O 12 may be mentioned.

[0031] As sulfides, Li4GeS4-Li3PS4 solid solution, Li4SiS4-Li3PS4 solid solution, Li3PS4-Li2S solid solution, Li2S-P2S5 solid solution, Li2S-SiS2, Li 10 GeP2S 12 , Argyrodite-type Li6PS5X (X = Cl, Br, I), or L7P3S 11 crystals may be mentioned.

[0032] (Ceramic solid electrolyte for sodium ion secondary battery) As oxides, NASICON-type Na 1+x Zr2SixP 3-x O 12 (0 ≦ x ≦ 1), or β-alumina-type Na2O-11A l2 O3 may be mentioned. As sulfides, Na2S-P2S5, Na3PS4, Na3SbS4, Na2S-SiS2, or Na2S-GeS2, etc. may be mentioned. As selenides, Na3PSe4, etc. may be mentioned. These may be used as composite electrolytes with polymers.

[0033] The particle size of these inorganic materials is preferably 10 μm or less, more preferably 3 μm or less. By setting the particle size as above, it is possible to form a dense porous structure, and a porous structure having good ion permeability without local unevenness inside the porous structure can be obtained. Disperse the above inorganic materials in a liquid to obtain a liquid composition for producing an inorganic layer. The liquid is selected as a liquid suitable for the inorganic materials to be dispersed.

[0034] When the inorganic material is dispersed in a liquid, a binder is added. The binder has the function of fixing the inorganic material particles together so that the inorganic material can be held in place as an insulating layer. Acrylic resins, styrene-butadiene resins, polyvinylidene fluoride resins, etc., can be used as binders.

[0035] When preparing the ink for the inorganic layer, it may be dispersed using a homogenizer. The homogenizer can be a high-speed rotary shear stirring type, a high-pressure jet dispersion type, an ultrasonic dispersion type, a media stirring mill type, or the like.

[0036] When preparing the ink for the inorganic layer, additives such as dispersants and surfactants may be used as needed. Examples of dispersants and surfactants include Megafac (DIC Corporation), Marialim (NOF Oil Co., Ltd.), Esream (NOF Oil Co., Ltd.), Solspers (Lubrizol), and Polyflow (Kyoeisha Chemical Co., Ltd.). Other additives that can be used to adjust viscosity include propylene glycol and carboxymethylcellulose, which are thickeners.

[0037] Furthermore, resins can be used as insulating organic and / or inorganic materials. To form the resin, a liquid composition for producing a resin layer is used, which is obtained by dissolving or dispersing at least one of the resin and / or the resin precursor (the resin and / or the resin precursor) in a liquid. The liquid is selected to be suitable for the resin to be dissolved or dispersed. Specifically, water, hydrocarbon liquids, alcohol liquids, ketone liquids, ester liquids, and ether liquids can be used.

[0038] Preferably, such resins and resin precursors are resins or oligomers that have a crosslinkable structure within the molecule due to ionizing radiation or infrared radiation (heat) dissolved in a liquid. Preferably, such resins and resin precursors are low molecular weight oligomer precursors among polyimide resins, polyester resins, polyamide resins, polyolefin resins, and acrylic resins, or those modified in part with hydrocarbon groups having aliphatic unsaturated bonds, for example. Preferably, some acrylic copolymers have unsaturated bonds such as allyl groups, allyloxy groups, acryloyl groups, butenyl groups, cinnamyl groups, cinnamoyl groups, crotomail groups, cyclohexagenyl groups, impropenyl groups, methacryloyl groups, pentenyl groups, propenyl groups, styryl groups, vinyl groups, and butagenyl groups in the side chains.

[0039] Furthermore, for materials such as polybutylene terephthalate, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyether ketone, polyethylene naphthalate, polysulfone, polyimide, polyester, polypropylene, polyoxymethylene, polyamide, polyvinylpyrrolidone, and cellulose, relatively low molecular weight dispersion precursors or cellulose nanofibers with a molecular weight of 10,000 or less can be used, and their insolubility and crosslinkability after fixation can be enhanced by heating them with ionizing radiation or infrared radiation.

[0040] Furthermore, these precursors may contain up to 30 parts by weight of an azide compound to enhance crosslinking. For example, 3,3′-dichloro-4,4′-diazidediphenylmethane, 4,4′-diazidediphenyl ether, 4,4′-diazidediphenyl disulfide, 4,4′-diazidediphenyl sulfide, 4,4′-diazidediphenyl sulfone, 4-azidocalcone, 4-azido-4′-hydroxychalcone, 4-azido-4′-methoxychalcone, 4-azido-4′-morpholinochalcone, 4-dimethylamino-4′-azidocalcone, 2,6-bis(4′-azidobenzal)-4-methylcyclohexano 2,6-bis(4′-azidobenzal)-cyclohexanone, cinnamyridene-4-azidoacetophenone, 4-azidocinnamyrideneacetophenone, 4-azido-4′-dimethylaminocinnamyrideneacetophenone, cinnamyridene-4-azidocinnamyrideneacetone, 2,6-bis(4′-azidocinnamyridene)-4-methylcyclohexanone, 2,6-bis(4′-azidocinnamyridene)-cyclohexanone, 1,4′-azidobenzylideneindene, 1,4′-azidobenzylideneindene 1,4′-azidobenzylidene-3-α-hydroxy-4″-azidobenzylindene, 9,4′-azidobenzylidenefluorene, 9,4′-azidocinnamyridenefluorene, 4,4′-diazidostilbene-2,2′-disulfonyl-N-(p-methoxyphenyl)amide, 4,4′-diazidostilbene-2,2′-disulfonyl-N-(p-hydroxyethylphenyl)amide, 4,4′-diazidostilbene-2,2′-disulfonyl-N-(p-hydroxyphenyl)amide, 4,4′-dia Examples include zidostilbene-2,2′-disulfonylamide, 4,4′-diazidobenzophenone, 4,4′-diazidostilbene, 4,4′-diazidochalcone, 4,4′-diazidobenzalacetone, 6-azido-2-(4'-azidostyryl)benzimidazole, 3-azidobenzylidenaniline-N-oxyp~(4-azidobenzylidenamid)benzoic acid, 1,4-bis(3′-azi1ζstyryl)benzene, 3,3′-diazidodiphenylsulfone, and 4,4′-diazidodiphenylmethane.

[0041] In particular, 2,6-bis-(4′azidobenzal)-4-methylcyclohexanone can be preferably used. The solvent in which these materials are dissolved is not particularly specified, but a solvent that can dissolve the above compounds and has a boiling point and surface tension suitable for subsequent coating and drying processes can be prepared and used, either alone or in mixtures. When the resin layer formed from the resin has voids inside, it is preferable because it allows for the passage of ions such as electrolytes, thereby providing a separator function and a thermal runaway prevention function.

[0042] From the viewpoint of electrolyte permeability and liquid retention, it is desirable to have not only ion permeability but also fine openings. It is even more desirable when the resin contains a material such as a foaming agent and is heated after coating, or when it contains soluble salts such as electrolytes and is immersed in an electrolyte after coating, the salts dissolve, forming openings and pores, thereby exhibiting ion permeability. Alternatively, a block-like molecular skeleton can form specific phase separation or microphase separation after coating, creating fine openings and thus exhibiting ion permeability. Or, by including a volatile solvent in the ink composition, solid-liquid phase separation can be induced by polymerization following printing, and then a fine mesh-like opening can be obtained by removing (drying) the solvent. Liquid compositions that induce solid-liquid phase separation by polymerization (hereinafter also referred to as "polymerization-induced phase separation") are particularly preferred because a porous resin structure with high ion permeability can be obtained in a short time.

[0043] From the viewpoint of ensuring good permeability of liquids and gases, the porous insulating layer preferably has a three-dimensional branched network structure of cured resin or inorganic solid material as its framework, with multiple pores in the porous insulating layer being continuously connected. In other words, it is preferable that the porous insulating layer has many pores, and that one pore has communication with other pores around it, extending three-dimensionally. This communication between pores facilitates the penetration of liquids and gases.

[0044] One method for confirming that pores are interconnected is to observe an image of the cross-section of the porous structure using a scanning electron microscope (SEM) or the like to confirm that the connections between pores are continuous. One of the physical properties obtained when pores are interconnected is air permeability. The air permeability of a porous structure is measured according to JIS P8117, for example, and is preferably 1000 seconds / 100 mL or less, more preferably 500 seconds / 100 mL or less, and even more preferably 300 seconds / 100 mL or less. In this case, the air permeability is measured using, for example, a Gurley densometer (manufactured by Toyo Seiki Seisakusho). Therefore, as an example, it may be determined that pores are interconnected if the air permeability is 1000 seconds / 100 mL or less.

[0045] The cross-sectional shape of the pores is not particularly limited and can be various shapes such as approximately circular, approximately elliptical, or approximately polygonal. The size of the pores is also not particularly limited. Here, the size of the pores refers to the length of the longest straight line that can be drawn in the cross-sectional shape. The size of the pores can be determined from cross-sectional images taken with a scanning electron microscope (SEM), etc. The size of the pores in the porous structure is preferably between 0.1 μm and 10 μm, and more preferably between 0.1 μm and 1 μm. A pore size of 0.1 μm to 10 μm allows for sufficient penetration of liquids and gases in the porous structure, enabling efficient expression of functions such as substance separation and reaction fields.

[0046] Furthermore, as will be described later, when a porous structure is used as an insulating layer for an energy storage element, if the size of the pores is 10 μm or less, it is possible to prevent short circuits between the positive and negative electrodes caused by lithium dendrites generated inside the energy storage element, thereby improving safety. The porosity of the porous structure is preferably 30% or more, and more preferably 50% or more.

[0047] Furthermore, the porosity of the porous structure is preferably 90% or less, and more preferably 85% or less. When the porosity is 30% or more, sufficient penetration of liquids and gases occurs in the porous structure, allowing functions such as substance separation and reaction fields to be efficiently expressed. In addition, when the porous structure is used as an insulating layer in an energy storage element, the permeability of the electrolyte and ion permeability are improved, and reactions inside the energy storage element proceed efficiently.

[0048] Furthermore, a porosity of 90% or less improves the strength of the porous structure. While there are no particular limitations on the method for measuring the porosity of a porous structure, one example is to fill the porous structure with unsaturated fatty acids (commercial butter), stain it with osmium, then cut out the internal cross-sectional structure using FIB, and measure the porosity using SEM.

[0049] A porous insulating layer formed from resin is a porous resin structure comprising a resin-formed skeletal structure and areas where the skeletal structure is not formed as pores. Preferably, the resin structure is a co-continuous structure or a monolithic structure, where the resin portion and the pore portion are continuous.

[0050] The term "continuous resin portion" refers to a configuration in which there are no interfaces within the resin portion. In other words, it is distinct from a configuration in which multiple resin particles are bound and connected by a binder or other material made of a different resin. Such a structure can be formed, for example, by the polymerization-induced phase separation method described above and below.

[0051] The aforementioned resin may contain a resin and a non-aqueous electrolyte, an ionic liquid, a grime, or an electrolyte salt as a gel electrolyte.

[0052] --Polymerizable compound-- Polymerizable compounds form resins by polymerization, and when polymerized in a liquid composition that undergoes polymerization-induced phase separation, they form porous resins. The resins formed by polymerizable compounds are preferably resins having a network structure formed by the application of active energy rays (for example, by irradiation with light or application of heat), and for example, 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 are preferred. Furthermore, from the viewpoint of productivity, acrylate resins, methacrylate resins, and urethane acrylate resins, which are resins formed by polymerizable compounds having (meth)acryloyl groups, and vinyl ester resins, which are resins formed by polymerizable compounds having vinyl groups, are more preferred because it is easy to form structures using highly reactive radical polymerization. These may be used individually or in combination of two or more. When two or more types are used in combination, there are no particular restrictions on the combination of polymerizable compounds, and they can be appropriately selected according to the purpose. For example, to impart flexibility, it is preferable to mix other resins with urethane acrylate resin as the main component. In this disclosure, polymerizable compounds having an acryloyl group or a methacryloyl group are referred to as polymerizable compounds having a (meth)acryloyl group.

[0053] Polymerizable compounds preferably have at least one radical polymerizable functional group. Examples include monofunctional, difunctional, trifunctional or more radical polymerizable compounds, functional monomers, and radical polymerizable oligomers. Among these, difunctional or more radical polymerizable compounds are preferred.

[0054] Examples of monofunctional radical polymerizable compounds 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 individually or in combination of two or more.

[0055] Examples of bifunctional radical polymerizable compounds 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, and tricyclodecanedimethanol diacrylate. These can be used individually or in combination of two or more.

[0056] Examples of radical polymerizable compounds with three or more functions 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 tri Examples include 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 ethoxytetraacrylate, EO-modified phosphate triacrylate, and 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate. These can be used individually or in combination of two or more.

[0057] The content of polymerizable compounds in the liquid composition that induces polymerization-induced phase separation is preferably 5.0% by mass or more and 70.0% by mass or less, more preferably 10.0% by mass or more and 50.0% by mass or less, and even more preferably 20.0% by mass or more and 40.0% by mass or less, based on the total amount of the liquid composition. When the content of polymerizable compounds is 70.0% by mass or less, the size of the pores in the resulting porous resin does not become too small (less than a few nanometers), the porous resin has an appropriate porosity, and the tendency for liquid and gas penetration to be difficult to occur is suppressed, which is preferable. Furthermore, when the content of polymerizable compounds is 5.0% by mass or more, a three-dimensional network structure of the resin is sufficiently formed, a sufficiently porous structure is obtained, and the strength of the resulting porous structure tends to improve, which is also preferable.

[0058] --Pologen-- The solvent used to induce polymerization-induced phase separation (hereinafter also referred to as "pologen") is a liquid that is compatible with the polymerizable compound. Furthermore, pologen is a liquid that becomes incompatible with the polymer (resin) formed during the polymerization process of the polymerizable compound in the liquid composition (resin undergoing phase separation). The presence of the solvent in the liquid composition allows the polymerizable compound to form a porous resin when polymerized within the liquid composition—in other words, when the liquid composition is sequentially irradiated with a first active energy ray and then a second active energy ray. It is also preferable that the solvent be able to dissolve compounds that generate radicals or acids upon exposure to light or heat (polymerization initiators, described later). The solvent may be used alone or in combination of two or more types. Note that pologen itself is not polymerizable.

[0059] The boiling point of a single pologen or a combination of two or more pologens is preferably 50°C to 250°C at atmospheric pressure, and more preferably 70°C to 200°C. A boiling point of 50°C or higher suppresses the vaporization of pologen near room temperature, making it easier to handle the liquid composition and to control the pologen content in the liquid composition. Furthermore, a boiling point of 250°C or lower shortens the drying time for the pologen after polymerization, improving the productivity of the porous resin. In addition, the amount of pologen remaining inside the porous resin can be suppressed, improving the quality when the porous resin is used as a functional layer such as a substance separation layer for separating substances or a reaction layer as a reaction field.

[0060] Furthermore, the boiling point of a single pologen or a combination of two or more pologens is preferably 120°C or higher at normal pressure.

[0061] Examples of pologenes 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 NN-dimethylacetamide. Liquids with relatively large molecular weights, such as methyl tetradecanoate, methyl decanoate, methyl myristate, and tetradecane, can also be used. Furthermore, liquids such as acetone, 2-ethylhexanol, and 1-bromonaphthalene can also be used.

[0062] It should be noted that not all of the liquids exemplified above are necessarily pologenes. As described above, a pologen is a liquid that is miscible with polymerizable compounds and becomes miscible (undergoes phase separation) with the polymerized product (resin) produced during the polymerization process of the polymerizable compound in the liquid composition. In other words, whether or not a liquid is a pologen depends on its relationship with the polymerizable compound and the polymerized product (the resin formed by the polymerization of the polymerizable compound).

[0063] Furthermore, since the liquid composition only needs to contain at least one pologen that has the specific relationship described above with the polymerizable compound, the range of material selection when preparing the liquid composition is broadened, and the design of the liquid composition becomes easier. This broader range of material selection allows for greater versatility in addressing properties required of the liquid composition other than the formation of a porous structure. For example, when a liquid composition is ejected using an inkjet method, it is required to have ejection stability and other properties besides porous formation. The broader range of material selection makes the design of the liquid composition easier.

[0064] As stated above, the liquid composition only needs to contain at least one pologen that has the specific relationship described above with the polymerizable compound; therefore, it may also contain additional liquids that do not have the specific relationship described above with the polymerizable compound (liquids that are not pologens). However, the content of liquids that do not have the specific relationship described above with the polymerizable compound (liquids that are not pologens) is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, even more preferably 1.0% by mass or less, and particularly preferably not included, based on the total amount of the liquid composition.

[0065] The pologen content in the liquid composition is preferably 30.0% by mass or more and 95.0% by mass or less, more preferably 50.0% by mass or more and 90.0% by mass or less, and even more preferably 60.0% by mass or more and 80.0% by mass or less, based on the total amount of the liquid composition. When the pologen content is 30.0% by mass or more, it is preferable because the size of the pores in the resulting porous material does not become too small (less than a few nanometers), the porous material has an appropriate porosity, and the tendency for liquid and gas penetration to be difficult to occur can be suppressed. Furthermore, when the pologen content is 95.0% by mass or less, a three-dimensional network structure of the resin is sufficiently formed, a sufficiently porous structure is obtained, and the strength of the resulting porous structure tends to improve, which is also preferable.

[0066] The mass ratio of polymerizable compound content to pologen content (polymerizable compound: pologen) in the liquid composition is preferably 1.0:0.4 to 1.0:19.0, more preferably 1.0:1.0 to 1.0:9.0, and even more preferably 1.0:1.5 to 1.0:4.0.

[0067] ---Polymerization-induced phase separation--- Porous resins can be formed by polymerization-induced phase separation. In polymerization-induced phase separation, polymerizable compounds and pologenes are miscible, but the polymers (resins) produced during the polymerization process of the polymerizable compounds are miscible with pologenes (phase separation occurs). While other methods exist for obtaining porous resins through phase separation, using the polymerization-induced phase separation method allows for the formation of porous materials with a network structure, resulting in porous materials with high resistance to chemicals and heat. Furthermore, compared to other methods, it offers advantages such as shorter process time and easier surface modification.

[0068] Next, the process of forming porous resins using polymerization-induced phase separation will be described. Polymerizable compounds undergo a polymerization reaction upon irradiation with light or other means to form a resin. During this process, the solubility of the growing resin for porogen decreases, and phase separation occurs between the resin and porogen. Finally, the resin forms a porous structure in which porogen and other substances fill the pores. When this is dried, the porogen and other substances are removed, leaving behind the porous resin. Therefore, in order to form a porous resin with an appropriate porosity, the compatibility between porogen and polymerizable compounds, and the compatibility with the resin formed by the polymerization of porogen and polymerizable compounds, are investigated.

[0069] The compatibility between pologenes and polymerizable compounds is determined as follows:

[0070] First, the liquid composition is injected into a quartz cell and stirred at 300 rpm using a stirring bar, while measuring the transmittance of light (visible light) at a wavelength of 550 nm of the liquid composition. In this disclosure, a light transmittance of 30% or more is considered to indicate that the polymerizable compound and pologen are miscible, and a light transmittance of less than 30% is considered to indicate that the polymerizable compound and pologen are miscible. The conditions for measuring the light transmittance are shown below.

[0071] • Quartz cell: Special microcell with screw cap (Product name: M25-UV-2) ·Transmittance measurement device: Ocean Optics USB4000 • Stirring speed: 300 rpm ·Measurement wavelength: 550nm • Reference: Obtained by measuring the transmittance of light at a wavelength of 550 nm inside a quartz cell with air inside (transmittance: 100%).

[0072] The compatibility of resins formed by the polymerization of pologens and polymerizable compounds is determined as follows.

[0073] First, resin fine particles are uniformly dispersed on an alkali-free glass substrate by spin coating to form a gap filler. Next, the substrate coated with the gap filler is bonded to an alkali-free glass substrate without the gap filler, with the gap filler-coated side sandwiched between them. Then, the liquid composition is filled between the bonded substrates using capillary action to create a "pre-UV irradiation haze measurement element". Subsequently, the pre-UV irradiation haze measurement element is irradiated with UV light to cure the liquid composition. Finally, the "haze measurement element" is fabricated by sealing the periphery of the substrate with a sealant. The conditions during fabrication are shown below.

[0074] • Alkali-free glass substrate: Nippon Electric Glass Co., Ltd., 40mm, t=0.7mm, OA-10G • Gap filler: Sekisui Chemical Co., Ltd., resin microparticle Micropearl GS-L100, average particle size 100 μm Spin coating conditions: Dispersion drop volume 150 μL, rotation speed 1000 rpm, rotation time 30 s • Amount of liquid composition filled: 160 μL • UV irradiation conditions: UV LED used as light source, light source wavelength 365nm, irradiation intensity 30mW / cm 2 , irradiation time 20s • Sealant: TB3035B (manufactured by Three Bond)

[0075] Next, the haze value (degree of cloudiness) is measured using the fabricated pre-UV irradiation haze measurement element and the haze measurement element. The measurement value from the pre-UV irradiation haze measurement element is used as a reference (haze value 0), and the rate of increase of the measurement value (haze value) from the haze measurement element to the measurement value from the pre-UV irradiation haze measurement element is calculated. The haze value from the haze measurement element increases as the compatibility between the resin formed by the polymerization of the polymerizable compound and the pologen decreases, and decreases as the compatibility increases. Furthermore, a higher haze value indicates that the resin formed by the polymerization of the polymerizable compound is more likely to form a porous structure. In this disclosure, a rate of increase of 1.0% or more in the haze value is judged to be in a state of incompatibility between the resin and the pologen, and a rate of increase of less than 1.0% is judged to be in a state of compatibility between the resin and the pologen. The apparatus used for measurement is shown below.

[0076] • Haze measuring device: Haze meter NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.

[0077] --Polymerization initiator-- Polymerization initiators are materials that can generate active species such as radicals and cations in response to energy such as light or heat, thereby initiating the polymerization of polymerizable compounds. Known polymerization initiators such as radical polymerization initiators, cationic polymerization initiators, and base generators can be used individually or in combination of two or more, and among these, the use of photoradical polymerization initiators is preferred.

[0078] As photoradical polymerization initiators, photoradical generators can be used. For example, photoradical polymerization initiators such as Michler ketone and benzophenone, known by trade names Irgacure and Darocure, and more specifically, benzophenone, acetophenone derivatives, such as α-hydroxy- or α-aminocetophenone, 4-aloyl-1,3-dioxolane, benzyl ketal, 2,2-diethoxyacetophenone, p-dimethylaminoacetophen, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, and pp'-dichlorobenzophenone. Phen, pp'-bis-diethylaminobenzophenone, Michler ketone, benzyl, benzoin, benzyldimethyl ketal, tetramethylthiuram monosulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutyronitrile, benzoin peroxide, di-tert-butyl peroxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-(4-isopropylphenyl)-2-hydroxy -2-Methylpropan-1-one, methylbenzoylformate, benzoin isopropyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin n-propyl, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1 ,2-diphenylethane-1-one, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-methyl-1[4-(methylthio)phenyl]-2-molifolinopropan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one monoacylphosphine oxide, bisacylphosphine oxide or titanocene, fluorescene, anthraquinone, thioxanthone or xanthone, rhofin dimer, trihalomethyl or dihalomethyl compounds, active ester compounds, organoboron compounds, etc. are preferably used.

[0079] Furthermore, photocrosslinking radical generators such as bisazide compounds may be included simultaneously. Also, when polymerization is carried out solely by heat, conventional radical generators such as azobisisobutyronitrile (AIBN) or other thermal polymerization initiators can be used.

[0080] The polymerization initiator content is preferably 0.05% by mass or more and 10.0% by mass or less, and more preferably 0.5% by mass or more and 5.0% by mass or less, when the total mass of the polymerizable compound is 100.0% by mass, in order to obtain a sufficient curing rate.

[0081] -Physical properties of liquid compositions- From the viewpoint of workability when applying the liquid composition, the viscosity of the liquid composition is preferably 1.0 mPa·s to 150.0 mPa·s at 25°C, more preferably 1.0 mPa·s to 30.0 mPa·s, and particularly preferably 1.0 mPa·s to 25.0 mPa·s. A viscosity of 1.0 mPa·s to 30.0 mPa·s ensures good ejection performance even when the liquid composition is applied to an inkjet system. Here, viscosity can be measured using, for example, a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.).

[0082] <<Manufacturing method for battery laminates>> The method for manufacturing a battery laminate according to this embodiment includes an insulating layer formation step of applying a liquid composition to a first electrode to form an insulating layer, and an electrode installation step of installing a second electrode on the first electrode on which the insulating layer has been formed, wherein the insulating layer formation step and the electrode installation step are carried out by a series of transport operations.

[0083] Here, "on the first electrode" includes on the current collector, on the electrode composite layer, or both. For example, if the first electrode is formed only from the current collector, an insulating layer is formed on the current collector. If the first electrode is formed from the current collector and an electrode composite layer formed on the current collector, an insulating layer may be formed only on the electrode composite layer, or an insulating layer may be formed on the current collector and the electrode composite layer that are exposed from the electrode composite layer.

[0084] In this way, by performing the insulating layer formation process and the electrode installation process in a single transport operation, the occurrence of damage to the battery laminate during the electrode manufacturing process can be suppressed. That is, since the insulating layer is a component that is prone to damage such as cracks, it is preferable to install the second electrode on the insulating layer at an early stage after the insulating layer has been formed. By performing the insulating layer formation process and the electrode installation process in a single transport operation, the second electrode can be installed on the insulating layer at an early stage after the insulating layer has been formed, so the second electrode functions as a protective member that protects the insulating layer, thereby suppressing the occurrence of damage to the battery laminate.

[0085] In this specification and in the claims, a series of conveyances refers to a process carried out by a single conveyance. For example, if the first electrode is being conveyed by roll, it means that the insulating layer formation process and the installation process are carried out within a single conveyance process. Furthermore, from the viewpoint of suppressing the occurrence of damage to the battery laminate described above, the case may also include a case in which the installation process is carried out immediately after conveyance that includes an insulating layer formation process in which the effect can be demonstrated. Moreover, roll conveyance as used herein refers to a method of conveying while maintaining tension between the conveyance start point and the conveyance end point, and the conveyed member may be supported using support members such as guide rolls as needed. Roll conveyance includes, but is not limited to, a roll-to-roll conveyance. Roll conveyance also includes, for example, a case in which the conveyed member is wound into a roll at the conveyance start point, but is not wound into a roll at the conveyance end point.

[0086] Furthermore, when the first electrode is transported using a belt, whether there is one belt or multiple belts is not a factor in determining whether it constitutes a series of transports. For example, even if there are multiple belts, if the first electrode moves continuously from one belt to another, it is included in a series of transports.

[0087] The manufacturing method for the battery laminate according to this embodiment may optionally include an electrode composite layer formation step of forming an electrode composite layer on a current collector, an irradiation step of irradiating a liquid composition with active energy rays, a removal step of removing a solvent contained in the liquid composition, and an electrode processing step of processing the electrode for cell formation after the installation of the second electrode. In this case, for example, the irradiation step may be performed between the insulating layer formation step and the electrode installation step, as long as the insulating layer formation step and the installation step are a series of steps.

[0088] Preferably, the first electrode is the negative electrode and the second electrode is the positive electrode. Placing the positive electrode on top of the negative electrode is advantageous because it eliminates wasted space on each electrode, thus increasing productivity, and also because it enhances the safety of the battery.

[0089] <Insulation layer formation process> The insulating layer formation step is a step of forming an insulating layer consisting of an organic layer and / or an inorganic layer on the object to be applied, which is the first electrode. The insulating layer formation step includes an insulating layer formation liquid application step of applying a liquid composition to the object to be applied, which is the first electrode, to form an insulating layer formation liquid composition layer, and may optionally include an irradiation step of irradiating the liquid composition with active energy rays, or a removal step of removing the solvent contained in the liquid composition. As for the insulating layer, an organic layer is preferred in terms of lightness and imparting functions due to temperature changes, while an inorganic layer is preferred in terms of robustness and heat resistance.

[0090] In the insulating layer formation process, the insulating layer may be formed in a shape having an uneven pattern including recesses and protrusions, as shown in Figure 10. In this case, it is preferable that the protrusions are formed outside the area where the second electrode is installed. In the example in Figure 10, the thick film region 11b of the insulating layer is the protrusion, and the thin film region 11a of the insulating layer exposed inside the thick film region 11b is the recess.

[0091] <Process for applying liquid for forming an insulating layer> The step of applying the insulating layer-forming liquid is a step of applying an insulating layer-forming liquid composition containing an organic and / or inorganic compound and a solvent or dispersion to the object to be applied, which is the first electrode. Preferably, the applied liquid composition forms a liquid composition layer, which is a liquid film of the liquid composition, on the object to be applied. There are no particular limitations on the method of applying the liquid composition, and examples include 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, liquid ejection methods such as inkjet printing are preferred from the viewpoint of being able to control the position in which the liquid composition is applied.

[0092] <Irradiation process> The irradiation step involves irradiating the liquid composition applied in the liquid application step with active energy rays. In particular, in the case of a liquid composition that undergoes polymerization-induced phase separation, the first irradiation step improves the porosity of the insulating layer, which is the porous resin ultimately produced, thereby improving the fluid uptake capacity of the porous resin, such as liquid or gas. Specifically, by irradiating the liquid composition with active energy rays, a porous precursor having a porous structure that forms the basis for creating a porous resin with high porosity is formed.

[0093] The active energy ray can be any ray capable of providing the necessary energy to advance the polymerization reaction of the polymerizable compound, and is not particularly limited. Examples include ultraviolet rays, electron beams, alpha rays, beta rays, gamma rays, and X-rays. Among these, ultraviolet rays are preferred. In particular, when using a high-energy light source, the polymerization reaction can proceed without the use of a polymerization initiator.

[0094] The following explanation focuses specifically on cases where the liquid composition undergoes polymerization-induced phase separation, and describes why the irradiation process forms a porous precursor.

[0095] As described above, when forming porous resins by polymerization-induced phase separation, the structure and properties of the porous resin change depending on the polymerization conditions. For example, when forming a porous resin under conditions where a liquid composition is irradiated with highly intensified active energy rays to promote the polymerization of polymerizable compounds, polymerization tends to proceed before sufficient phase separation occurs, making it difficult to produce a porous resin with a high porosity.

[0096] Therefore, in order to form a porous resin with a high porosity, the irradiation intensity of the activated energy rays is set so as not to be too high. Specifically, the irradiation intensity of the activated energy rays is set to 1 W / cm². 2 The following is preferable: 300 mW / cm² 2 The following is more preferable: 100 mW / cm² 2The following is even more preferable. However, if the irradiation intensity of the active energy rays is too low, phase separation will proceed excessively, which can easily lead to variations and coarsening of the porous structure, and furthermore, the irradiation time will be longer, reducing productivity, therefore 10 mW / cm² is preferable. 2 Preferably, it is 30 mW / cm² or higher. 2 It is more preferable that the above conditions are met.

[0097] <Removal process> The removal step is a step of removing the solvent or dispersion from the liquid composition. The method for removing the solvent or dispersion is not particularly limited, and one example is a method of removing the solvent or dispersion from the porous resin by heating. In this case, heating under reduced pressure is preferable because it further promotes the removal of the solvent or dispersion and suppresses the residue of the solvent or dispersion in the insulating layer that is formed.

[0098] <Electrode installation process> The electrode installation process involves installing a second electrode on a first electrode, which has an insulating layer formed on it, for example, as shown in Figure 12. In Figure 12, 9 represents the current collector of the first electrode, 11b represents the thick film region of the insulating layer, 12 represents the current collector of the second electrode, and 13 represents the active material of the second electrode. There are no particular limitations on the method of installing the second electrode, but if the installation area is not in a suitable location, a short circuit will occur between the first electrode and the second electrode. Therefore, it is preferable that the electrode installation process includes an alignment process to adjust the installation position of the second electrode after forming an insulating layer on the first electrode. In addition, to prevent displacement after the installation of the second electrode, an adhesive or tack may be applied to the first electrode and / or the second electrode before installation of the second electrode.

[0099] <Electrode composite material layer formation process> The electrode composite layer formation process is a process of forming an electrode composite layer on an object to be applied, which is the first electrode. The electrode composite layer formation process includes an electrode composite layer formation liquid application step of forming an electrode composite layer on an object to be applied, which is the first electrode, and a removal step of removing the solvent contained in the liquid composition.

[0100] <Process for applying liquid for electrode composite layer formation> The step of applying the liquid for electrode composite layer formation is a step of applying a liquid composition for electrode composite layer formation, which contains a powdered active material, a catalyst composition, a dispersion, etc., to the object to be applied, which is the first electrode. Preferably, the applied liquid composition forms a liquid composition layer, which is a liquid film of the liquid composition, on the object to be applied. There are no particular limitations on the method of applying the liquid composition, and examples include 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, liquid ejection methods such as inkjet printing are preferred from the viewpoint of being able to control the position in which the liquid composition is applied.

[0101] <Conveying Process> The conveying process is the process of conveying the first electrode. As for the conveying process, it is preferable to use roll conveying without using a conveying belt, from the viewpoint of suppressing damage to the first electrode and insulating layer caused by friction between the first electrode and insulating layer and the conveying device, by reducing the contact area between the first electrode and insulating layer and the conveying device during the conveying process.

[0102] <Electrode processing process> The electrode processing step is a step in which the first electrode is processed after the insulating layer formation step. In the electrode processing step, for example, the first electrode on which the second electrode is installed can be cut to create an electrode laminate in which the second electrode is installed on the first electrode on which the insulating layer has been formed. In the electrode processing step, it is preferable to cut the first electrode so that its area is larger than the area of ​​the second electrode. This prevents the cut end of the first electrode from short-circuiting with the end of the second electrode.

[0103] If the insulating layer contains a material having a melting point or glass transition temperature, the electrode processing step involves, for example, creating multiple electrode stacks in which a second electrode is placed on a first electrode on which an insulating layer has been formed, and at least a portion of one electrode stack is bonded to another by heating. For example, if the electrode stack has a thick film region 11b of the insulating layer as shown in Figure 10, the upper and lower electrode stacks may be arranged facing each other, and the thick film regions of the opposing electrode stacks may be heat-bonded together.

[0104] In the electrode processing process, for example, a first electrode with a second electrode installed can be laminated or wound to produce a laminated or wound body. When laminating or winding a first electrode with a second electrode installed, the first electrode may be cut at an appropriate time.

[0105] One method of lamination is to cut the first electrode, on which the second electrode is installed, into multiple sheets to create multiple electrode stacks, and then stack the multiple electrode stacks. Another method, as shown in Figure 13, is to stack the second electrode in a zigzag structure by folding over the first electrode, which is installed at intervals. In Figure 13, 9 is the current collector of the first electrode, 11b is the thick film region of the insulating layer, 12 is the current collector of the second electrode, and 13 is the active material of the second electrode.

[0106] Winding can be performed, for example, using a battery laminate manufacturing apparatus (described later) as shown in Figure 2. That is, a roll-shaped second electrode is supplied onto the first electrode 6 while it is being transported by a second electrode transport device 4b, and the second electrode is continuously stacked on the first electrode 6, and then wound by an electrode processing unit 500 located downstream of the electrode installation unit 400.

[0107] Furthermore, when the number of layers in a zigzag structure or the number of turns in a wound structure reaches the desired number, the desired laminated or wound body can be obtained by cutting.

[0108] Furthermore, an electrode processing step may be performed between the insulating layer formation step and the installation step. That is, the electrode installation step may be performed immediately after the electrode processing step. For example, in the electrode processing step, the first electrode can be cut before the second electrode is installed, and the electrode installation step can be performed immediately after cutting. Here, "immediately after" means that the electrode processing step and the electrode installation step are in a continuous flow, and the cut first electrode is not temporarily moved to another location between the electrode processing step and the electrode installation step. In other words, providing an electrode processing step between the insulating layer formation step and the installation step, and performing the electrode installation step immediately after the electrode processing step, is included in the series of transport according to the present invention. The process flow described here can be realized, for example, by a battery laminate manufacturing apparatus (described later) shown in Figure 3.

[0109] Alternatively, an electrode processing step may be performed between the insulating layer formation step and the installation step, and a second electrode processing step may be performed after the installation step. For example, an electrode laminate in which a second electrode is placed on the insulating layer of a cut first electrode may be laminated in the second electrode processing step. Or, an electrode laminate in which multiple second electrodes are placed on the insulating layer of a cut first electrode may be wound in the second electrode processing step.

[0110] By performing the electrode installation process immediately after the electrode processing process, the second electrode can be installed on the insulating layer at an early stage after the insulating layer has been formed. As a result, the second electrode functions as a protective member that protects the insulating layer, thereby suppressing damage to the battery laminate.

[0111] <<Manufacturing equipment for battery laminates>> The battery laminate manufacturing apparatus according to this embodiment includes an insulating layer forming unit that applies a liquid composition onto a first electrode to form an insulating layer, and an electrode setting unit that places a second electrode on the first electrode on which the insulating layer has been formed. The insulating layer forming unit and the electrode setting unit are arranged in a series of transport areas on which the first electrode is transported. The battery laminate manufacturing apparatus according to this embodiment may also include, if necessary, an irradiation unit that irradiates the liquid composition with active energy rays, a removal unit that removes solvents contained in the liquid composition, and an electrode processing unit that processes the electrode for cell formation after the placement of the second electrode.

[0112] Details of the manufacturing equipment for battery laminates will be explained with reference to Figures 1 to 9. Figure 1 is a schematic diagram showing an example of a manufacturing equipment for battery laminates.

[0113] A battery laminate manufacturing apparatus 1, which is an example of a battery laminate manufacturing apparatus, is an apparatus for manufacturing electrodes using the above-mentioned liquid composition. The battery laminate manufacturing apparatus 1 includes an insulating layer forming section 600 consisting of a liquid application section 100 that applies the liquid composition 7 to a first electrode 6 to form an insulating layer, an electrode installation section 400 that installs a second electrode on the formed insulating layer by a series of conveying operations, and a control unit 800 that controls the insulating layer forming section 600 and the electrode installation section 400. The battery laminate manufacturing apparatus 1 further includes a roll section 8. If the battery laminate manufacturing apparatus 1 includes a plurality of roll sections 8, some or all of the roll sections 8 may rotate under the control of the control unit 800 and function as a conveying section that conveys the first electrode 6 at a predetermined speed. In addition, some of the roll sections 8 may function as guide rolls that are support members.

[0114] Furthermore, as shown in the schematic diagrams of an example of a battery laminate manufacturing apparatus in Figures 2-7, in addition to the configuration shown in the battery laminate manufacturing apparatus 1, it may also include an irradiation unit 200 that performs a step of activating the polymerization initiator in the liquid composition to obtain an insulating layer by polymerization of polymerizable compounds, a removal unit 300 that performs a step of heating the liquid composition to remove the solvent, and an electrode processing unit 500 that processes the electrode toward cell formation after the installation of the second electrode. The irradiation unit 200, the removal unit 300, and the electrode processing unit 500 are controlled by a control unit 800. Note that the battery laminate manufacturing apparatus shown in Figures 6 and 7 can apply the liquid composition to both sides of the first electrode 6.

[0115] <Insulating layer formation section> The insulating layer forming section 600 includes at least a liquid application section 100 and may optionally include an irradiation section 200 and / or a removal section 300. The insulating layer forming section 600 may form the insulating layer in a shape having an uneven pattern including recesses and protrusions as shown in Figure 10. In this case, it is preferable that the protrusions are formed outside the area where the second electrode is installed.

[0116] <Liquid application section> The liquid application unit 100 includes a printing device 1a that performs an application process of applying a liquid composition onto the first electrode 6, a storage container 1b that contains the liquid composition, and a supply tube 1c that supplies the liquid composition stored in the storage container 1b to the printing device 1a.

[0117] The containment container 1b contains the liquid composition 7, and the liquid dispensing unit 100 dispenses the liquid composition 7 from the printing device 1a and applies it to the first electrode 6 to form a thin film layer of the liquid composition. The containment container 1b may be integrated with the battery laminate manufacturing apparatus 1, or it may be detachable from the battery laminate manufacturing apparatus 1. It may also be a container used for adding to a containment container integrated with the battery laminate manufacturing apparatus 1 or a containment container detachable from the battery laminate manufacturing apparatus 1.

[0118] The printing apparatus 1a is not particularly limited as long as it can apply the liquid composition 7. For example, any printing apparatus can be used that is suitable for 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.

[0119] The containment container 1b and the supply tube 1c can be arbitrarily selected as long as they can stably store and supply the liquid composition 7. The materials constituting the containment container 1b and the supply tube 1c are preferably light-shielding in the relatively short wavelength regions of ultraviolet and visible light. This prevents polymerization from being initiated by ambient light if the liquid composition 7 contains polymerizable compounds.

[0120] <Irradiation area> The irradiation unit 200 includes, for example, a light irradiation device 2a that polymerizes polymerizable compounds by irradiating the liquid composition with active energy rays such as heat and light, and a polymerization inert gas circulation device 2b that circulates polymerization inert gas. When the liquid composition formed by the liquid application unit 100 contains polymerizable compounds, the light irradiation device 2a irradiates light in the presence of polymerization inert gas to form an insulating layer.

[0121] The light irradiation device 2a 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 promote the polymerization of the compound in the liquid composition layer. Examples include high-pressure mercury lamps, metal halide lamps, hot cathode tubes, cold cathode tubes, and ultraviolet light sources such as LEDs. However, since shorter wavelength light generally tends to penetrate deeper, it is preferable to select a light source according to the thickness of the porous film to be formed.

[0122] Next, the polymerization inert gas circulator 2b plays a role in reducing the concentration of polymerization-active oxygen in the atmosphere, thereby allowing the polymerization reaction of polymerizable compounds near the surface of the liquid composition layer to proceed without being inhibited. Therefore, there are no particular restrictions on the polymerization inert gas used as long as it satisfies the above function, and examples include nitrogen, carbon dioxide, and argon.

[0123] Furthermore, considering the effective reduction of inhibition, the flow rate of the polymerization inert gas is preferably such that the O2 concentration is less than 20% (an environment with a lower oxygen concentration than the atmosphere), more preferably between 0% and 15%, and even more preferably between 0% and 5%. In addition, the polymerization inert gas circulation device 2b is preferably equipped with a temperature control means that can adjust the temperature in order to achieve stable polymerization conditions.

[0124] <Removal part> The removal unit 300, as shown in Figure 4, for example, has a heating device 3a, and removes any solvent remaining on the formed insulating layer by heating and drying it with the heating device 3a. The removal unit 300 may also perform the solvent removal process under reduced pressure.

[0125] In addition, the removal section 300 may be removed by heating and drying the photopolymerization initiator remaining in the insulating layer using the heating device 3a.

[0126] The heating device 3a is not particularly limited as long as it satisfies the above functions, and examples include IR heaters and hot air heaters.

[0127] Furthermore, the heating temperature and heating time can be appropriately selected depending on the boiling point of the solvent contained in the insulating layer and the thickness of the resulting film.

[0128] <Electrode installation part> As shown in Figures 1-7, the electrode installation section 400 has a second electrode container 4a, and the second electrode is installed onto the insulating layer formed on the first electrode by a second electrode transport device 4b. The second electrode container 4a may be a wound electrode or a sheet electrode. The second electrode transport device 4b is not particularly limited as long as it can transport the electrode, but examples include a device that transports the electrode using a suction mechanism. The electrode installation section 400 may also have an alignment mechanism, if necessary, which may be equipped with a camera or the like to adjust the installation position of the second electrode.

[0129] <Electrode processing section> The electrode processing unit 500 processes the first electrode on which an insulating layer has been formed. The electrode processing unit 500 has, for example, an electrode processing apparatus 5 as shown in Figure 2. The electrode processing unit 500 winds or stacks, for example, the first electrode on which the second electrode is installed. The electrode processing unit 500 also cuts the first electrode on which the second electrode is installed. At this time, it is preferable that the electrode processing unit 500 cuts the first electrode so that the area of ​​the first electrode is larger than the area of ​​the second electrode. This prevents the cut end of the first electrode from short-circuiting with the end of the second electrode. When the electrode processing unit 500 winds or stacks the first electrode on which the second electrode is installed, it may cut the first electrode at an appropriate timing.

[0130] If the insulating layer contains a material having a melting point or glass transition temperature, the electrode processing unit 500 may, for example, produce a plurality of electrode laminates in which a second electrode is placed on a first electrode on which an insulating layer is formed, and heat one electrode laminate to another to bond at least a portion of it. The electrode processing unit may also cut the first electrode before the second electrode is placed. In this case, the second electrode processing unit may be provided after the second electrode has been placed to perform lamination or winding.

[0131] In this way, the electrode processing unit 500 can perform tasks such as cutting electrodes, zigzag folding of the first electrodes, lamination and winding, and thermal bonding between the first electrodes after lamination and winding, according to the desired battery configuration.

[0132] <Department Head> Figure 8 is an example of a main hardware block diagram of the control unit. As shown in Figure 8, the control unit 800 includes, for example, a CPU 801, a ROM 802, a RAM 803, an NVRAM 804, an ASIC 805, an I / O 806, and an operation panel 807.

[0133] The CPU 801 controls the entire battery laminate manufacturing apparatus. The ROM 802 stores programs executed by the CPU 801 and other fixed data. The RAM 803 temporarily stores data related to the manufacturing of battery laminates. The NVRAM 804 is a non-volatile memory that retains data even when the power to the apparatus is cut off. The ASIC 805 processes image processing and input / output signals for controlling the entire apparatus. The I / O 806 is an interface for inputting and outputting signals to the insulating layer forming unit 600, electrode installation unit 400, etc. The operation panel 807 inputs and displays information necessary for the control unit 800.

[0134] Figure 9 is an example of a main functional block diagram of the control unit. As shown in Figure 9, the control unit 800 has, as functional blocks, an insulating layer formation control unit 851, an electrode placement control unit 852, and an electrode processing control unit 853.

[0135] The insulating layer formation control unit 851 controls the insulating layer formation unit 600. For example, the insulating layer formation control unit 851 issues commands to the liquid application unit 100 to control the timing and amount of liquid composition to be applied. For example, when forming an insulating layer by inkjet printing, the insulating layer formation control unit 851 instructs the liquid application unit 100 to apply the liquid composition at predetermined waveform data, discharge conditions such as discharge frequency, and predetermined timing and number of drops.

[0136] Furthermore, for example, the insulating layer formation control unit 851 issues commands to the irradiation unit 200 to control the timing and amount of irradiation when irradiating the liquid composition with active energy rays. Also, for example, the insulating layer formation control unit 851 issues commands to the removal unit 300 to control the timing and amount of heating when heating and drying to remove the solvent remaining in the insulating layer.

[0137] The electrode placement control unit 852 issues commands to the electrode placement unit 400, for example, to control the timing of electrode suction and the speed at which the suctioned electrodes are transported. If the electrode placement unit 400 has an alignment mechanism, the electrode placement control unit 852 controls the alignment mechanism to adjust the placement position of the second electrode based on position information from an image sensor such as a camera.

[0138] The electrode processing control unit 853, for example, when cutting the first electrode using a laser, issues commands to the electrode processing unit 500 to control the amount of laser light emitted or to scan the laser based on position information from an image sensor such as a camera. Furthermore, the electrode processing control unit 853 also issues commands to the electrode processing unit 500 to control the start and end timings for processes such as zigzag folding, lamination, and winding of the first electrode. Additionally, the electrode processing control unit 853 issues commands to the electrode processing unit 500 to control the heating temperature and heating time when performing thermal bonding between the first electrodes after lamination or winding.

[0139] The present invention will be described in more detail below with reference to examples and comparative examples of batteries, etc., but the present invention is not limited in any way to these examples.

[0140] [Examples] First, the negative and positive electrodes used in each example and comparative example were prepared.

[0141] <Fabrication of the negative electrode> To form the negative electrode composite layer, a negative electrode coating was prepared by adding 97.0% by mass of graphite, 1.0% by mass of a thickener (carboxymethylcellulose), 2.0% by mass of a polymer (styrene-butadiene rubber), and 100.0% by mass of water as a solvent. This negative electrode coating was applied to both sides of a copper foil substrate and dried, resulting in a basis weight of 9.0 mg / cm² on one side of the negative electrode composite layer. 2 A negative electrode was obtained with the following characteristics. Next, a roll press was used to obtain an electrode deposition density of 1.6 g / cm³. 3 The negative electrode was obtained by pressing it to the desired shape. At this time, the total film thickness of the negative electrode was 112.0 μm.

[0142] <Fabrication of the positive electrode> A cathode coating was prepared by dispersing 92.0% by mass of lithium nickelate (NCA) as the cathode active material, 3.0% by mass of acetylene black as the conductive material, and 5.0% by mass of polyvinylidene fluoride (PVDF) as the binder in N-methylpyrrolidone (NMP). This cathode coating was applied to both sides of an aluminum foil substrate and dried, resulting in a basis weight of 15.0 mg / cm² on each side of the cathode composite layer. 2 A positive electrode was obtained with the following characteristics. Next, the volume density of the electrode was measured in a roll press machine to 2.8 g / cm³. 3 The positive electrode was obtained by pressing it in the manner described. At this time, the total film thickness of the positive electrode was 132.0 μm. Finally, the positive electrode was punched out using a die punching machine (punching area: 47.0 mm × 27.0 mm).

[0143] [Example 1] -Preparation of insulating layer forming liquid composition- An insulating layer-forming liquid composition was prepared by mixing the materials in the proportions shown below. Tricyclodecanedimethanol diacrylate (manufactured by Daicel Ornex Co., Ltd.) was mixed at a ratio of 29.0% by mass as polymerizable compound A, dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Industry Co., Ltd.) was mixed at a ratio of 70.0% by mass as the solvent (pologen), and Irgacure 184 (manufactured by BASF) was mixed at a ratio of 1.0% by mass as the polymerization initiator to obtain an insulating layer-forming liquid composition.

[0144] <Formation of insulating layer, installation of second electrode> The insulating layer was formed and the second electrode was installed using the battery laminate manufacturing apparatus shown in Figure 6.

[0145] -Formation of the insulating layer- First, a liquid composition for forming the functional layer was filled into a die-coating printing apparatus. The negative electrode, which would serve as the first electrode, was prepared in a roll shape with a current collector width of 60 mm and a composite layer width of 50 mm. The liquid composition was discharged onto the negative electrode, which was transported at 50 mm / sec, and an insulating layer was formed on both sides of the negative electrode composite layer to a thickness of 20.0 μm. Immediately thereafter, the coated area was irradiated with UV light under an N2 atmosphere (light source: UV-LED (Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm²). 2 The material was cured by irradiation for 20 seconds. Next, the solvent was removed by heating the cured material at 120°C for 1 minute using a hot air drying oven, and a first electrode with an insulating layer was obtained.

[0146] -Installation of the second electrode- After forming the insulating layer, the positive electrode was placed as the second electrode, positioned on the insulating layer (thin film region) of the first electrode with the insulating layer. Subsequently, the first electrode with the insulating layer on which the second electrode was placed was cut to a size of 60.0 mm × 30.0 mm to obtain the first electrode set.

[0147] [Evaluation 1: Membrane impact resistance test] The obtained first electrode set was subjected to intensity tests according to the evaluation procedures 1-1 to 1-3 below. The results are shown in Figure 15.

[0148] Step 1-1: Applying the load A load was applied to the obtained first electrode set by pressing a pin against it from above.

[0149] In the case of Comparative Examples 1 to 8, since the second electrode was not installed, the strength test was performed on the first electrode with an insulating layer that did not have the second electrode installed, instead of the first electrode set.

[0150] Step 1-2: Battery preparation before electrolyte injection In Comparative Examples 1-8 only, the positive electrodes were first stacked facing each other. A laminate outer casing was used to seal the battery, and the battery before electrolyte injection, as shown in Figure 14, was fabricated.

[0151] Steps 1-3: Short-circuit evaluation between positive and negative electrodes The obtained batteries were checked using a digital multimeter to see if a short circuit occurred between the positive and negative terminals. The criteria for determining a short circuit were as follows, based on the resistance value displayed on the digital multimeter.

[0152] a: No short circuit (30MΩ or more) b: Short circuit present (less than 30MΩ)

[0153] [Evaluation 2: Battery operation confirmed] The batteries obtained in Evaluation 1, before electrolyte injection, were subjected to battery operation tests according to the evaluation procedures 2-1 to 2-2 below. However, if a short circuit was determined in Evaluation 1, Evaluation 2 was not performed. Figure 15 shows the results.

[0154] Step 2-1: Making the battery The batteries obtained in Evaluation 1, before electrolyte injection, were vacuum-dried at 120°C for 12 hours, and then the electrolyte was injected. In Example 4 and Comparative Example 4, the thick film regions of the first electrodes located above and below the stack at the electrode ends were heat-bonded. The electrolyte used was a solution in which LiPF6, the electrolyte, was added to a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) (a mixture with a mass ratio of "EC:DMC = 1:1") to a concentration of 1.5 mol / L.

[0155] Step 2-2: Measuring the initial battery capacity The positive and negative lead wires of the fabricated battery were connected to a charge / discharge test device, and the battery was charged at a constant current and voltage of 4.2V and a current rate of 0.2C for 5 hours. After charging was complete, it was left to stand in a 40°C constant temperature bath for 5 days. After that, it was discharged at a constant current of 0.2C down to 2.5V. Then, it was charged at a constant current and voltage of 4.2V and a current rate of 0.2C for 5 hours, with a 10-minute break in between, and then discharged at a constant current of 0.2C down to 2.5V. The discharge capacity at this time was defined as the initial capacity.

[0156] a: Confirm that the initial capacity is less than ±10% of the theoretical capacity. b: Confirm that the initial capacity is at least ±10% of the theoretical capacity.

[0157] [Comparative Example 1] In Example 1, the first electrode with an insulating layer was obtained in the same manner as in Example 1, except that the installation of the second electrode was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0158] -Installation of the second electrode- After forming the insulating layer, the positive electrode was not installed as the second electrode. Instead, the first electrode was cut to a size of 60.0 mm x 30.0 mm to obtain the first electrode.

[0159] [Example 2] In Example 1, a first electrode set with an insulating layer and a second electrode was obtained in the same manner as in Example 1, except that the procedure for forming the insulating layer was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0160] -Formation of the insulating layer- The insulating layer was formed and the second electrode was installed using the manufacturing apparatus shown in Figure 7. First, the liquid composition for forming the functional layer was filled into an inkjet ejector equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). Then, by controlling the amount of liquid composition ejected to the negative electrode, insulating layers (thin film region) and insulating layers (thick film region) were formed on both sides of the negative electrode composite layer to form the pattern image shape shown in Figure 11. The area of ​​the insulating layer (thin film region) was 47.0 mm × 27.0 mm and the film thickness was 20.0 μm, and the film thickness of the insulating layer (thick film region) was 26.0 μm. Immediately thereafter, the coated area was irradiated with UV light under an N2 atmosphere (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm²). 2 The material was cured by irradiation for 20 seconds. Next, the cured material was heated in a hot air drying oven at 120°C for 1 minute to remove pologen and obtain an insulating layer.

[0161] [Comparative Example 2] In Example 2, the first electrode with an insulating layer was obtained in the same manner as in Example 2, except that the installation of the second electrode was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0162] -Installation of the second electrode- After forming the insulating layer, the positive electrode was not installed as the second electrode. Instead, the first electrode was cut to a size of 60.0 mm x 30.0 mm to obtain the first electrode.

[0163] [Example 3] In Example 1, a first electrode set with an insulating layer and a second electrode was obtained in the same manner as in Example 1, except that the procedure for forming the insulating layer-forming liquid composition was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0164] -Formation of insulating layer- A liquid composition for forming an insulating layer was obtained by mixing EBECRYL8402 (manufactured by Daicel Ornex Co., Ltd.) as polymerizable compound B at a ratio of 39.0% by mass, diisobutyl ketone (manufactured by Kanto Chemical Industry Co., Ltd.) as pologen at a ratio of 60.0% by mass, and Irgacure819 (manufactured by BASF) as a polymerization initiator at a ratio of 1.0% by mass.

[0165] [Comparative Example 3] In Example 3, the first electrode with an insulating layer was obtained in the same manner as in Example 3, except that the installation of the second electrode was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0166] -Installation of the second electrode- After forming the insulating layer, the positive electrode was not installed as the second electrode. Instead, the first electrode was cut to a size of 60.0 mm x 30.0 mm to obtain the first electrode.

[0167] [Example 4] In Example 3, a first electrode set with an insulating layer and a second electrode was obtained in the same manner as in Example 3, except that the procedure for forming the insulating layer was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0168] -Formation of the insulating layer- The insulating layer was formed and the second electrode was installed using the manufacturing apparatus shown in Figure 7.

[0169] A liquid composition for forming a functional layer was filled into an inkjet ejector equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). By controlling the amount of liquid composition ejected to the negative electrode, insulating layers (thin film region) and insulating layers (thick film region) were formed on both sides of the negative electrode composite layer to form the pattern image shape shown in Figure 11. The area of ​​the insulating layer (thin film region) was 47.0 mm × 27.0 mm and the film thickness was 20.0 μm, while the film thickness of the insulating layer (thick film region) was 26.0 μm. Immediately thereafter, the coated area was irradiated with UV light under an N2 atmosphere (light source: UV-LED (Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm²). 2 The material was cured by irradiation for 20 seconds. Next, the cured material was heated in a hot air drying oven at 120°C for 1 minute to remove pologen and obtain an insulating layer.

[0170] [Comparative Example 4] In Example 4, the first electrode with an insulating layer was obtained in the same manner as in Example 4, except that the installation of the second electrode was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0171] -Installation of the second electrode- After forming the insulating layer, the positive electrode was not installed as the second electrode. Instead, the first electrode was cut to a size of 60.0 mm x 30.0 mm to obtain the first electrode.

[0172] [Example 5] In Example 1, a first electrode set with an insulating layer and a second electrode was obtained in the same manner as in Example 1, except that the procedure for forming the insulating layer-forming liquid composition was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0173] -Formation of insulating layer- As an inorganic solid, α-alumina (primary particle size (D50) is 0.5 μm, specific surface area is 7.8 g / m²) 2 A pre-dispersion was prepared by mixing 40.0% by mass of ) with 58.0% by mass of a mixed solution of dimethyl sulfoxide and ethylene glycol (DMSO-EG) and 2.0% by mass of Marialim HKM-150A (manufactured by NOF Corporation) as a dispersant. This pre-dispersion was placed in a container together with zirconia beads (Φ2 mm) and dispersed using a cryogenic nano-pulverizer NP-100 (manufactured by Sinky Corporation) at 1500 rpm for 3 minutes to obtain a dispersion. The zirconia beads were removed from the obtained dispersion using a 25 μm mesh filter to prepare an insulating layer forming liquid composition.

[0174] [Comparative Example 5] In Example 5, the first electrode with an insulating layer was obtained in the same manner as in Example 5, except that the installation of the second electrode was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0175] -Installation of the second electrode- After forming the insulating layer, the positive electrode was not installed as the second electrode. Instead, the first electrode was cut to a size of 60.0 mm x 30.0 mm to obtain the first electrode.

[0176] [Example 6] In Example 1, a first electrode set with an insulating layer and a second electrode was obtained in the same manner as in Example 1, except that the procedure for forming the insulating layer was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0177] -Formation of the insulating layer- The insulating layer was formed and the second electrode was installed using the manufacturing apparatus shown in Figure 7. The liquid composition for forming the functional layer was filled into an inkjet ejector equipped with a GEN5 head (manufactured by Ricoh Printing Systems Co., Ltd.). By controlling the amount of liquid composition ejected to the negative electrode, a patterned coated area was formed on both sides of the negative electrode as shown in Figure 11, so that the insulating layer (thin film region) and insulating layer (thick film region) had the following configuration. The area of ​​the insulating layer (thin film region) was 47.0 mm × 27.0 mm and the film thickness was 20.0 μm, and the film thickness of the insulating layer (thick film region) was 26.0 μm. Immediately thereafter, the coated area was irradiated with UV light in an N2 atmosphere (light source: UV-LED (manufactured by Phoseon, product name: FJ800), wavelength: 365 nm, irradiation intensity: 30 mW / cm²). 2 The material was cured by irradiation for 20 seconds. Next, the cured material was heated in a hot air drying oven at 120°C for 1 minute to remove pologen and obtain an insulating layer.

[0178] [Comparative Example 6] In Example 6, the first electrode with an insulating layer was obtained in the same manner as in Example 6, except that the installation of the second electrode was changed to the procedure shown below. Subsequently, evaluations 1 and 2 were performed in the same manner as in Example 1. The results are shown in Figure 15.

[0179] -Installation of the second electrode- After forming the insulating layer, the positive electrode was not installed as the second electrode. Instead, the first electrode was cut to a size of 60.0 mm x 30.0 mm to obtain the first electrode.

[0180] Figure 15 shows that in all of the examples, an "a" rating was obtained in both Evaluation 1 and Evaluation 2. In other words, the results in Figure 15 indicate that by installing a second electrode, the resistance of the film to impact is improved, and good battery characteristics are obtained. Furthermore, this result depends only on whether or not a second electrode was installed, and not on the type of material used to form the insulating layer. That is, the insulating layer can be made of an organic or inorganic material, as long as it is a material capable of forming an insulating layer, and by installing a second electrode, the resistance of the film to impact is improved, and good battery characteristics are obtained.

[0181] Furthermore, it was confirmed that when polymerizable compound B, which has a low glass transition temperature (Tg), is used as the insulating layer material, the thick film regions of the first electrode located above and below the laminate at the electrode edge are heat-bonded by heating after the second electrode is installed and the laminate is laid, and it was also shown that a laminate less prone to electrode misalignment after lamination can be obtained.

[0182] Although preferred embodiments have been described in detail above, the invention is not limited to the embodiments described above, and various modifications and substitutions can be made to the embodiments described above without departing from the scope of the claims. [Explanation of Symbols]

[0183] 1a Printing device 1b Containment container 1c supply tube 2a Light irradiation device 2b Polymerization inert gas circulation system 3a Heating device 4a Second electrode container 4b Second electrode transport device 5 Electrode processing equipment 6. First electrode 7 Liquid composition 8 Roll section 9. Current collector of the first electrode 10 Active material of the first electrode 11a Thin film region of the insulating layer 11b Thick film region of the insulating layer 12 Current collector of the second electrode 13 Active material of the second electrode 100 Liquid application unit 200 Irradiation section 300 Removal section 400 Electrode installation section 500 Electrode processing department 600 Insulating layer forming section 800 Control Unit 801 CPU 802 ROM 803 RAM 804 NVRAM 805 ASIC 806 I / O 807 Control Panel 851 Insulation layer formation control unit 852 Electrode Installation Control Unit 853 Electrode Processing Control Unit [Prior art documents] [Patent Documents]

[0184] [Patent Document 1] Japanese Patent Publication No. 2013-191550

Claims

1. An insulating layer formation step in which an insulating layer is formed on the first electrode, An electrode installation step of installing a second electrode on the first electrode on which the insulating layer is formed, The process includes, after the insulating layer formation step, an electrode processing step for processing the first electrode, The insulating layer formation step includes a step of applying a liquid composition, The insulating layer formation step and the electrode installation step are carried out by a series of transports. A method for manufacturing a battery laminate, wherein the electrode processing step involves winding or stacking the first electrode on which the second electrode is installed.

2. An insulating layer formation step in which an insulating layer is formed on the first electrode, An electrode installation step of installing a second electrode on the first electrode on which the insulating layer is formed, The process includes, after the insulating layer formation step, an electrode processing step for processing the first electrode, The insulating layer formation step includes a step of applying a liquid composition, The insulating layer formation step and the electrode installation step are carried out by a series of transports. A method for manufacturing a battery laminate, wherein the electrode processing step involves cutting the first electrode on which the second electrode is installed.

3. The insulating layer comprises a material having a melting point or glass transition point. The method for manufacturing a battery laminate according to claim 2, wherein in the electrode processing step, a plurality of electrode laminates are manufactured in which the second electrode is placed on the first electrode on which the insulating layer is formed, and at least a portion of one electrode laminate and another electrode laminate are bonded together by heating.

4. An insulating layer formation step in which an insulating layer is formed on the first electrode, An electrode installation step of installing a second electrode on the first electrode on which the insulating layer is formed, The process includes, after the insulating layer formation step, an electrode processing step for processing the first electrode, The insulating layer formation step includes a step of applying a liquid composition, The insulating layer formation step and the electrode installation step are carried out by a series of transports. In the electrode processing step, the first electrode is cut before the second electrode is installed. A method for manufacturing a battery laminate, wherein the electrode installation step is performed immediately after the electrode processing step.

5. An insulating layer formation step in which an insulating layer is formed on the first electrode, The process includes an electrode placement step of placing a second electrode on the first electrode on which the insulating layer is formed, The insulating layer formation step includes a step of applying a liquid composition, The insulating layer formation step and the electrode installation step are carried out by a series of transports. A method for manufacturing a laminate for a battery, wherein in the insulating layer forming step, the insulating layer is formed to have a shape having an uneven pattern including recesses and protrusions.

6. An insulating layer formation step in which an insulating layer is formed on the first electrode, The process includes an electrode placement step of placing a second electrode on the first electrode on which the insulating layer is formed, The insulating layer formation step includes a step of applying a liquid composition, The insulating layer formation step and the electrode installation step are carried out by a series of transports. A method for manufacturing a battery laminate, wherein the electrode installation step includes an alignment step for adjusting the installation position of the second electrode.

7. A method for manufacturing a battery laminate according to any one of claims 1 to 6, wherein the first electrode is a negative electrode and the second electrode is a positive electrode.

8. The method for manufacturing a battery laminate according to claim 5, wherein the protrusion is formed outside the region where the second electrode is installed.

9. An insulating layer forming unit that applies a liquid composition onto a first electrode to form an insulating layer, An electrode installation section for installing a second electrode on the first electrode on which the insulating layer is formed, It has an electrode processing unit for processing the first electrode on which the insulating layer is formed, The insulating layer forming section and the electrode installation section are arranged in a series of transport areas where the first electrode is transported. The electrode processing unit is a manufacturing apparatus for a battery laminate, which winds or stacks the first electrode on which the second electrode is installed.

10. An insulating layer forming unit that applies a liquid composition onto a first electrode to form an insulating layer, An electrode installation section for installing a second electrode on the first electrode on which the insulating layer is formed, It has an electrode processing unit for processing the first electrode on which the insulating layer is formed, The insulating layer forming section and the electrode installation section are arranged in a series of transport areas where the first electrode is transported. The electrode processing unit is a manufacturing apparatus for a battery laminate, which cuts the first electrode at the first electrode on which the second electrode is installed.

11. The insulating layer comprises a material having a melting point or glass transition point. The electrode processing unit produces a plurality of electrode stacks in which the second electrode is placed on the first electrode on which the insulating layer is formed, and heats one electrode stack to bond at least a portion of the other electrode stacks, the apparatus for manufacturing a battery stack according to claim 10.

12. An insulating layer forming unit that applies a liquid composition onto a first electrode to form an insulating layer, An electrode installation section for installing a second electrode on the first electrode on which the insulating layer is formed, It has an electrode processing unit for processing the first electrode on which the insulating layer is formed, The insulating layer forming section and the electrode installation section are arranged in a series of transport areas where the first electrode is transported. The electrode processing unit cuts the first electrode before the second electrode is installed. The electrode placement section is a manufacturing apparatus for a battery laminate, which places the second electrode on the cut first electrode.

13. An insulating layer forming unit that applies a liquid composition onto a first electrode to form an insulating layer, It has an electrode mounting section for installing a second electrode on the first electrode on which the insulating layer is formed, The insulating layer forming section and the electrode installation section are arranged in a series of transport areas where the first electrode is transported. The insulating layer forming unit is a manufacturing apparatus for a battery laminate, which forms the insulating layer into a shape having an uneven pattern including recesses and protrusions.

14. An insulating layer forming unit that applies a liquid composition onto a first electrode to form an insulating layer, It has an electrode mounting section for installing a second electrode on the first electrode on which the insulating layer is formed, The insulating layer forming section and the electrode installation section are arranged in a series of transport areas where the first electrode is transported. The electrode installation section has an alignment mechanism for adjusting the installation position of the second electrode, and is a manufacturing apparatus for battery laminates.

15. The apparatus for manufacturing a battery laminate according to any one of claims 9 to 14, wherein the first electrode is a negative electrode and the second electrode is a positive electrode.

16. The apparatus for manufacturing a battery laminate according to claim 13, wherein the insulating layer forming portion forms the protrusion outside the region where the second electrode is installed.

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