WO2014136813A1 - 電池電極又はセパレーターコーティング膜組成物、これを用いて得られるコーティング膜を有する電池電極又はセパレーター、及びこの電池電極又はセパレーターを有する電池 - Google Patents

電池電極又はセパレーターコーティング膜組成物、これを用いて得られるコーティング膜を有する電池電極又はセパレーター、及びこの電池電極又はセパレーターを有する電池 Download PDF

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WO2014136813A1
WO2014136813A1 PCT/JP2014/055554 JP2014055554W WO2014136813A1 WO 2014136813 A1 WO2014136813 A1 WO 2014136813A1 JP 2014055554 W JP2014055554 W JP 2014055554W WO 2014136813 A1 WO2014136813 A1 WO 2014136813A1
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Prior art keywords
separator
particles
coating film
meth
battery
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PCT/JP2014/055554
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English (en)
French (fr)
Japanese (ja)
Inventor
嘉人 清水
太一 上村
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協立化学産業株式会社
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Priority to JP2015504351A priority Critical patent/JP6058783B2/ja
Priority to CN201480012044.4A priority patent/CN105027328B/zh
Priority to KR1020157026896A priority patent/KR102009736B1/ko
Publication of WO2014136813A1 publication Critical patent/WO2014136813A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a battery electrode or separator coating film composition, a battery electrode or separator having a coating film obtained by using the composition, and a battery having the battery electrode or separator.
  • Lithium ion secondary batteries that are lightweight, have high voltage and large capacity have been put into practical use as power sources for mobile devices such as mobile phones and laptop computers, power tools and power tools such as cars.
  • conventional batteries have low safety resulting from poor heat resistance and pressure collapse resistance, and there is a problem that conductive foreign substances that enter at the manufacturing stage penetrate the separator and cause a short circuit.
  • the lithium ion secondary battery has high internal resistance, charging and discharging characteristics at a high rate are not practically sufficient, charging and discharging capacities are not sufficient, and the active material layer is greatly deteriorated when used for a long time.
  • lithium ion secondary batteries cannot provide sufficient safety is that the insulation by the separator is broken due to contamination of conductive foreign matter, dent light, battery damage, etc. In this case, the mechanism for preventing the thermal runaway from proceeding and the heat resistance are insufficient.
  • Patent Document 1 a method for protecting the active material from falling off the electrode by forming a porous film made of alumina powder or silica powder on the active material coating layer applied to the current collector has been devised.
  • a porous protective film suppresses the generation of dentite, and the porous film also functions as a layer for holding the electrolyte solution.
  • the porous protective film serves as an ion supply source to lower internal resistance, and at a high rate. It also contributes to the improvement of discharge characteristics.
  • the porous protective film buffers and accelerates local degradation resulting from concentration of electrode reactions due to electrode surface non-uniformity, thereby preventing deterioration of the active material layer when used for a long period of time. There is also an effect.
  • Patent Documents 1 and 2 have a problem that curling occurs in the porous resin layer formed on the electrode or the separator.
  • curling occurs due to the generation of stress from the difference between the elastic modulus and the linear expansion coefficient between the electrode and the porous protective film.
  • curling occurs due to stress generated between the separator and the porous resin layer because the solvent evaporates and the coating film shrinks. This curl not only deteriorates handling during assembly, but also causes wrinkles. When wrinkles occur, the distance between the electrodes changes locally. As a result, localization of the electrochemical reaction occurs, and there is a problem that the charge / discharge characteristics and life of the battery are reduced.
  • an object of the present invention is to provide a battery electrode or separator coating film composition that can suppress the occurrence of curling and can form a coating film having high heat resistance.
  • the present inventor has studied to solve the above-mentioned problems of the prior art, and by using viscoelastic particles as a component contained in the composition forming the coating film, the occurrence of curling of the coating film can be suppressed and high.
  • a battery having a heat resistance and a battery electrode and / or a separator having a coating film obtained by using the coating film composition has a high heat resistance, a low internal resistance, and a charge and discharge cycle characteristic.
  • the present inventors have found that it is excellent, has a large charge and discharge capacity, has a small deterioration in the active material layer after long-term multicycle charge and discharge, and has a long life.
  • the gist of the present invention is as follows.
  • the present invention 1 is a battery electrode or separator coating film composition comprising a binder, a solvent, and viscoelastic particles.
  • the present invention 2 is the battery electrode or separator coating film composition of the present invention 1 in which the viscoelastic modulus of the viscoelastic particles is lower than the viscoelastic modulus of the binder.
  • the present invention 3 is the battery electrode or separator coating film composition of the present invention 1 or 2, wherein the viscoelastic particles have shape anisotropy.
  • the present invention 4 is a battery electrode or separator having a coating film obtained by using the battery electrode or separator coating film composition of any one of the present inventions 1 to 3.
  • Invention 5 is a battery according to Invention 4, wherein the viscoelastic particles have shape anisotropy, and the longest axis of the viscoelastic particles is oriented in parallel to the shrinkage direction of the base material of the battery electrode or separator. It is an electrode or a separator.
  • the present invention 6 is a battery having the battery electrode and / or separator of the present invention 5.
  • a battery electrode or separator coating film composition in which curling is suppressed and a battery electrode or separator coating film having high heat resistance is obtained.
  • the coating film of the present invention becomes an electrolyte holding layer on the electrode or separator surface or a desolvation layer of ions in the electrolyte, the ion conduction resistance is reduced. There is an effect that it is possible to prevent the deterioration of the battery characteristics after the multi-cycle charge and discharge for a period of time or when the battery is left at a high temperature in the charged state. Therefore, the battery of the present invention has high heat resistance, low internal resistance, excellent charge and discharge cycle characteristics, large charge and discharge capacity, and small deterioration of the active material layer after long-term multicycle charge and discharge. Long life.
  • the binder has a structure in which a porous structure is maintained by binding particles. Therefore, the stress relaxation ability of the binder is relatively weaker and the heat resistance is lower than when the particles are provided with a function of relaxing stress.
  • the method of the present invention using viscoelastic particles makes it difficult for the viscoelastic particles to be deformed beyond the deformation amount of the viscoelastic particles, so compared to the method of reducing the viscoelastic modulus of the binder, It is possible to obtain a coating film in which the occurrence of curling is suppressed and the heat resistance is high.
  • the coating film of the present invention can also be used as a solid electrolyte film or a gel electrolyte film by impregnating a porous structure with a solid or gel having ion conductivity.
  • FIG. 1 is a cross-sectional view of a battery electrode having a battery electrode or a separator coating film.
  • FIG. 2 is a cross-sectional view of a separator having a battery electrode or a separator coating film.
  • FIG. 3 is an optical micrograph of a separator having the coating film of Example 8. Arrows indicate the conveyance direction of the substrate.
  • the battery electrode or separator coating film composition has (1) viscoelastic particles, (2) a binder, and (3) a solvent.
  • the “viscoelastic particle” is a particle having a property of irreversibly plastically deforming with respect to stress and a property of reversibly elastically deforming.
  • the battery electrode or the separator coating film composition contains viscoelastic particles, the particles can be irreversibly deformed in the coating film, and the viscoelastic modulus of the resulting coating film is lowered. Thereby, the stress with a battery electrode or a separator base material can be reduced.
  • the base material is applied with tension applied and wound while being dried.
  • the tension at the time of coating is released, which causes curling. Since the viscoelastic particles in the coating film can reduce the occurrence of curling by relieving the stress with the base material, it is easy to handle even when manufacturing batteries by means of roll-to-roll. Occurrence is suppressed. Thereby, a high quality battery can be provided.
  • various polymers such as polyethylene, polypropylene, polystyrene, polycarbonate, polyacetal, polyphenylene sulfide, liquid crystal polymer, polyvinyl chloride, celluloid, polyvinyl alcohol, polyester, polyvinyl acetate, a polymer having a polyethylene glycol structure, Polymer having carbonate group, polyvinylidene fluoride, polytetrafluoroethylene, styrene / butadiene rubber, polyisoprene, chloroprene rubber, acrylic rubber, polymer having cyano group, urethane rubber, ethylene propylene rubber, epichlorohydrin rubber, butadiene rubber, Fluoro rubber, ethylene-vinyl alcohol copolymer, acrylic-vinyl alcohol copolymer, epoxy resin, oxetane resin, urethane resin , Acrylic resins, polysaccharides, polyimide, polyamide-imide, silicone
  • polymer derivative having a cyano group specifically, cyanoethylated vinyl alcohol, cyanoethylated carboxymethylcellulose, cyanoethylated pullulan, cyanoethylated cellulose, cyanoethylated starch, cyanoethylated esterified starch, cyanoethylated dextrin, cyanoethylated collagen, And nitrile rubber and the like.
  • polymer derivative having a polyethylene glycol structure include a polyethylene glycol acrylic acid amide styrene copolymer, a polyethylene glycol polylactic acid copolymer, and polyvinyl alcohol pendant with a polyethylene glycol chain.
  • a polymer having a carbonyl group there can be illustrated, for example, Nippon Polyvinyl acetate, PVA; D polymer (PVA having a carbonyl group);
  • a polymer having a ⁇ -diketone structure specifically, a polyacrylic compound having a ⁇ -diketone structure that can be prepared by radical copolymerization of a vinyl compound having a ⁇ -diketone structure such as allyl acetoacetate and an acrylate ester. Examples thereof include ester copolymers and polyvinyl alcohol copolymerized with vinyl acetate.
  • polymer having a carbonate group examples include polycarbonate and CO 2 -philic Co-polymer (CO 2 amphiphilic copolymer).
  • material of the viscoelastic particles urethane resin and polyethylene are preferable.
  • Viscoelastic particles may be used singly or in combination.
  • the viscoelastic particles may be in the form of a dispersion dispersed in a dispersion medium (for example, water).
  • the average particle diameter of the viscoelastic particles is preferably in the range of 0.001 to 100 ⁇ m, more preferably in the range of 0.01 to 50 ⁇ m, and still more preferably in the range of 0.05 to 10 ⁇ m. Since the porosity of the coating film can be further increased, it is preferable that the particle size distribution of the viscoelastic particles is narrow. That is, when the average particle diameter of viscoelastic particles is 1/5 times A and 5 times B, particles having a particle diameter in the range of A to B are 80% by volume of viscoelastic particles. It is preferable that the amount is 90% by volume or more.
  • the average particle size and particle size distribution can be measured by, for example, a laser diffraction / scattering particle size distribution measuring apparatus, and specifically, LA-920 manufactured by Horiba, Ltd. can be used.
  • Viscoelastic particles can be produced by various known methods, and can be produced by pulverization, emulsion polymerization, recrystallization, spraying, or using a forced thin film microreactor.
  • the shape of the viscoelastic particles is not particularly limited.
  • examples of the viscoelastic particles include viscoelastic particles having shape isotropy or shape anisotropy.
  • the viscoelastic particles preferably have shape anisotropy.
  • the viscoelastic particles have shape anisotropy
  • the electrode battery or separator coating film composition containing the viscoelastic particles having shape anisotropy is applied to the battery electrode or separator substrate
  • the shearing force can orient viscoelastic particles having shape anisotropy in the coating flow direction.
  • the viscoelastic particles can be oriented so that the longest axis is parallel to the contraction direction of the battery electrode or the separator substrate.
  • Examples of the shape of the viscoelastic particles having isotropy include a cubic shape and a spherical shape.
  • Examples of the shape of the viscoelastic particles having shape anisotropy include a flat shape (for example, a plate shape which is a rectangular parallelepiped), a fiber shape, a bent fiber shape, and a coil shape.
  • the separator has a direction that tends to shrink, the viscoelastic particles can be oriented in a direction effective to relieve the shrinkage stress.
  • plate-like viscoelastic particles can be prepared by tapping and crushing the particles, thinly slicing the fibers, or making it plate-like by self-organization. it can.
  • the fibrous particles can be produced by cutting a spun polymer shortly or by an electrospinning method.
  • Short fibers that can be used as particles having shape anisotropy can be produced by cutting the fibrous particles into short pieces or making short fibers by turning on and off the electric field when spinning by the electrospinning method.
  • the degree of elastic deformation of the viscoelastic particles can be expressed by an elastic modulus h3 determined by the following measurement method 1.
  • h3 of the viscoelastic particles is preferably 0.95 or less, and more preferably 0.9 or less.
  • the h3 of the viscoelastic particles is not particularly limited, but can be 0.5 or more, and preferably 0.6 or more.
  • the degree of plastic deformation of the viscoelastic particles can be expressed by the plastic deformation rate h6 determined by the following measurement method 2.
  • h6 is preferably 0.85 or less, and more preferably 0.75 or less.
  • h6 of the viscoelastic particles is not particularly limited, but is preferably 0.5 or more, and more preferably 0.6 or more.
  • h3 and h6 of the viscoelastic particles are equal to or less than the upper limit value, the stress relaxation ability is increased and curling can be effectively suppressed. If h3 and h6 of the viscoelastic particles are equal to or higher than the lower limit, the heat resistance is further improved. h3 and h6 are both parameters indicating ease of deformation, and both of them are easier to deform when the numerical value is smaller. Therefore, when h3 and h6 are smaller, curling is further suppressed. However, deformation due to elastic deformation leaves deformation stress. On the other hand, deformation due to plastic deformation does not leave deformation stress. Here, the deformation stress is a force that can cause curling. Therefore, the smaller the plastic deformation rate: h6, the more curling can be suppressed compared to the case where the elastic deformation rate: h3 is small.
  • Step of obtaining test particles (2) Packing the test particles obtained in step (1) into an acrylic cylinder having an inner diameter of 10 mm, an outer diameter of 110 mm, and a height of 150 mm so as to have a height of 100 mm.
  • Step of pushing in an iron bar having a length of 10 mm and a length of 200 mm using an autograph (3) Measuring height h1 when pushed in with 1 kgf and height h2 when pushing in with 0.5 kgf after loosening the pushing force.
  • Step (4) A step of obtaining the elastic modulus h3 of the viscoelastic particles by h1 / h2 h3.
  • the test object viscoelastic particles are sieved with a sieve having an opening of 50 ⁇ m to obtain test particles.
  • particles that are likely to be clogged are made into test particles by filtering in an aqueous dispersion.
  • the content of viscoelastic particles is 0.1 to 99.9% by weight or more of the components contained in the coating film composition excluding the solvent, preferably 0.5 to 99.5% by weight, more preferably Is from 1 to 99% by weight. If it is such a range, the stress relaxation ability accompanying deformation
  • the solvent includes a solvent for a binder described later and a dispersion medium when the viscoelastic particles are in the form of a dispersion.
  • the (2) binder of the present invention will be described.
  • the battery electrode or separator coating film composition of the present invention contains a binder.
  • the binder include a solid (for example, particulate) binder or a liquid binder.
  • the binder can be in a state dispersed in a solvent, a state dissolved in a solvent, a state dispersed in a solvent, and a state dissolved in a solvent.
  • Solid binder Various known solid binders can be used as the solid binder.
  • the solid binder include thermoplastic organic particles, organic crystals, and organic particles that crosslink during heat fusion.
  • the average particle size of the solid binder is not particularly limited, and can be 0.01 to 500 ⁇ m. Further, the solid binder does not include particles (that is, viscoelastic particles) having a property of plastically irreversibly with respect to stress and a property of elastically deforming reversibly.
  • thermoplastic organic particles are not particularly limited as long as they can be bonded by hot-melting the particles with a hot melt, and examples thereof include thermoplastic polymer particles.
  • thermoplastic polymers include viscoelastic particle materials.
  • the thermoplastic organic particles may be used alone or in combination of two or more.
  • thermoplastic organic particles polymer derivative particles having a cyano group, polymer derivative particles having a polyethylene glycol structure, and polymer derivatives having a carbonyl group are easy to interact with ions and from the viewpoint of ion conduction.
  • Particles preferably, polymer particles having a ⁇ -diketone structure
  • polymer particles having a carbonate group are preferable, particles of a polymer derivative having a cyano group, particles of a polymer having a polyethylene glycol structure, and Polymer particles having a carbonate group are more preferable.
  • Thermoplastic organic particles can be adjusted in molecular weight and crosslinking density to such an extent that they have a melting point and softening point in the range of -40 to 300 ° C.
  • thermoplastic organic particles can be used as a dry powder, or can be used as an aqueous emulsion by forming protective colloid particles using a surfactant or a water-soluble polymer. Further, for the purpose of adjusting the melting point, it is also possible to use a solvent with a high boiling point solvent having a boiling point of 80 ° C. or higher, such as ethylene glycol, glycerin, diethylene glycol, N-methylpyrrolidone, dimethyl sulfoxide, and isophorone.
  • a solvent with a high boiling point solvent having a boiling point of 80 ° C. or higher such as ethylene glycol, glycerin, diethylene glycol, N-methylpyrrolidone, dimethyl sulfoxide, and isophorone.
  • Organic crystals examples include hydrazide crystals, acid anhydride crystals, amine crystals, imidazole crystals, triazine crystals, and mixed crystals thereof.
  • the melting point of the organic crystal is preferably 40 ° C. or higher, more preferably 50 to 300 ° C.
  • hydrazide crystals As hydrazide crystals, adipic acid dihydrazide (melting point: 177 to 180 ° C.), 1,3-bis (hydrazinecarbonoethyl) -5-isopropylhydantoin (melting point: 120 ° C.), 7,11-octadecadien-1,18-di Examples thereof include carbohydrazide (melting point: 160 ° C.).
  • acid anhydride crystals include maleic anhydride (melting point 53 ° C.), phthalic anhydride (melting point 131 ° C.), pyromellitic anhydride (melting point 286 ° C.), and the like.
  • Examples of amine crystals include urea (melting point: 132 ° C.) and dicyandiamide (melting point: 208 ° C.).
  • Examples of imidazole crystals include imidazole (melting point 89 to 91 ° C.), 2-methylimidazole (melting point 140 to 148 ° C.), phenyl imidazole (melting point 174 to 184 ° C.), and the like.
  • triazine crystals examples include 2,4-diamino-6-vinyl-S-triazine (melting point 240 ° C.), 2,4-diamino-6-methacryloyloxyethyl-S-triazine (melting point 170 ° C.), and the like.
  • Organic crystals can be used in the form of a solid solution by mixing two or more kinds for the purpose of adjusting the melting point and the softening point.
  • Organic particles that crosslink during thermal fusion are various known latent curable solid resin particles.
  • latent curable solid resins include epoxy resins, mixtures of epoxy resins and oxirane compounds, (meth) acrylic acid esters, and prepolymers having active hydrogen groups.
  • a particle in which a latent thermal initiator is blended with a solid epoxy resin a particle in which a latent thermal initiator is blended in a mixture of a solid epoxy resin and an oxirane compound Particles that are a system containing a solid (meth) acrylic acid ester and a curing agent or an initiator; and particles that are a combination of a prepolymer having an active hydrogen group and a crosslinking agent.
  • (meth) acrylic acid ester refers to acrylic acid ester and methacrylic acid ester.
  • EPICLON 1050 bisphenol A type epoxy resin having a softening point of 64 to 74 ° C.
  • EPICLON N-660 cresol novolac type epoxy having a softening point of 62 to 70 ° C.
  • EPICLON N-770 phenol novolac type epoxy resin having a softening point of 65 to 75 ° C.
  • HP-7200HH dicyclopentadiene type epoxy resin having a softening point of 88 to 98 ° C.
  • EPICLON HP-4700 a naphthalene type epoxy resin having a softening point of 85 to 95 ° C.
  • EX-721 a monofunctional solid epoxy phthalimide skeleton having a melting point of 94 to 96 ° C.
  • EX- 71 melting point 40 ° C. of lauryl alcohol (EO) 15 glycidyl ether
  • oxirane compounds include oxetane compounds.
  • Specific examples of the oxirane compound include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-Ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ) Ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethy
  • thermal initiators for epoxy resins and oxirane compounds are catalysts for cationic polymerization, such as diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluoro).
  • Phenyl) borate bis (dodecylphenyl) iodonium / hexafluorophosphate, bis (dodecylphenyl) iodonium / hexafluoroantimonate, bis (dodecylphenyl) iodonium / tetrafluoroborate, bis (dodecylphenyl) iodonium / tetrakis (pentafluorophenyl) ) Borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluo Phosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) pheny
  • the amount of the thermal initiator is preferably 0.001 to 50 parts by weight, preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the solid epoxy resin or the mixture of the solid epoxy resin and the oxirane compound. More preferably, the amount is 0.1 to 10 parts by weight.
  • a crosslinking reaction can also be advanced at the time of heat fusion.
  • the cross-linking reaction can proceed simultaneously with the heat fusion, so that a mutually cross-linked and cross-linked structure can be obtained.
  • the blending amount of the curing agent is preferably 1 to 500 parts by weight, more preferably 2 to 200 parts by weight, based on 100 parts by weight of solid prepolymer particles described later.
  • Particles that are blended with a latent heat initiator in a solid epoxy resin, or particles that are blended with a latent heat initiator in a mixture of a solid epoxy resin and an oxirane compound are the solid epoxy resin.
  • Producing solid prepolymer particles by mixing a resin or a mixture of the solid epoxy resin and oxirane compound, a latent thermal initiator, and optionally a curing agent, and then grinding.
  • solid epoxy resin particles or particles of a mixture of the solid epoxy resin and the oxirane compound, initiator particles, and curing agent particles may be mixed to obtain solid prepolymer particles.
  • EBECRYL 740-40TP manufactured by Daicel Cytec Co., Ltd.
  • 1 -Hydroxy-cyclohexyl-phenyl-ketone 100: 5
  • crosslinking agent in the combination of the prepolymer having an active hydrogen group and the crosslinking agent examples include carboxylic acid, carboxylic acid anhydride, and metal chelate.
  • combinations of prepolymers having active hydrogen groups and crosslinking agents include boric acid such as a mixture of polyvinyl alcohol and polycarboxylic acid and derivatives thereof, a mixture of polyvinyl alcohol and derivatives thereof with metal chelates and alkoxides, and the like. Can do.
  • polycarboxylic acids examples include citric acid, butanetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, hexahydrophthalic acid, 1,3,3a, 4,5,9b-hexahydro-5 (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione (anhydride), glycerin bisanhydro trimellitate monoacetate (anhydride), 3 , 3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, ethylene glycol bisanhydrotrimellitate (anhydride), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, ethylene glycol bisanhydro Trimellitate, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, bicyclo [2.2.1] h
  • aromatic carboxylic acids are preferable from the viewpoint of reactivity, and those having three or more carboxyl groups in one molecule are preferable from the viewpoint of reactivity and crosslinking density.
  • those corresponding to acid anhydrides can also be used.
  • titanium chelates and alkoxides zirconium tetranormal propoxide, zirconium tetraacetyl acetonate, zirconium dibutoxy bis (ethyl acetoacetate), zirconium tributoxy monostearate, such as zirconium chelates and alkoxides, aluminum isopropoxide
  • Various known metal compounds such as aluminum chelate can be exemplified.
  • the combination of the prepolymer which has an active hydrogen group, and a crosslinking agent may contain the said hardening
  • Particles that are a combination of a prepolymer having active hydrogen groups and a crosslinker will not react with heat when mixing the prepolymer having active hydrogen groups, the crosslinker, and any hardeners and initiators present.
  • these are mixed in a good solvent, casted thinly and dried at room temperature, and can be produced by grinding while cooling and used as an organic particle type binder that crosslinks during thermal fusion. Can do.
  • An electrode battery or separator coating film composition containing organic particles that crosslink at the time of heat fusion as a binder, the composition and the battery electrode or separator are fused by evaporating the solvent after coating the composition.
  • crosslinking can be advanced by heating or irradiation with energy rays. Thereby, a protective film having excellent mechanical strength and high heat resistance can be obtained.
  • a liquid binder can be used as the binder of the present invention.
  • liquid binder various known liquid binders can be used.
  • specific examples of the liquid binder include a mixture of a liquid prepolymer and an initiator; a solid polymer substance dissolved in a solvent; a solid inorganic substance by a sol-gel reaction; and water glass It is done.
  • (Mixture of liquid prepolymer and initiator) As a mixture of a liquid prepolymer and an initiator, a combination of a photo radical initiator or a thermal radical generator and a compound having a (meth) acryl group, an allyl group, a vinyl group, a maleimide group, etc .; a photo cation initiator or A combination of a thermal cation initiator and a compound having an epoxy group, an oxirane ring such as an oxetane ring, a vinyl ether, a cyclic acetal, etc .; and a photoanion initiator, a compound having an epoxy group and / or a compound having a cyanoacrylate group And combinations thereof.
  • the (meth) acryl group includes an acryl group and a methacryl group.
  • a combination of a photo radical initiator or a thermal radical generator and a compound having a (meth) acryl group, an allyl group, a vinyl group, a maleimide group, etc. will be described.
  • photo radical initiators 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-Isopropylfeinyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2 Acetophenones such as -hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1; Benzoin, benzoin methyl ether, benzoin ethyl ether Benzoins such as ter, benzoin isopropyl ether, benzoin isobutyl
  • electron donors are used for intermolecular hydrogen abstraction type photoinitiators such as benzophenone, Michler ketone, dibenzosuberone, 2-ethylanthraquinone, camphorquinone, and isobutylthioxanthone.
  • electron donors include aliphatic amines and aromatic amines having active hydrogen.
  • Specific examples of the aliphatic amine include triethanolamine, methyldiethanolamine, and triisopropanolamine.
  • aromatic amine examples include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, and ethyl 4-dimethylaminobenzoate.
  • Thermal radical generators include 4-azidoaniline hydrochloride and azides such as 4,4′-dithiobis (1-azidobenzene); 4,4′-diethyl-1,2-dithiolane, tetramethylthiuram disulfide, And disulfides such as tetraethylthiuram disulfide; octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluyl peroxide Diacyl peroxides such as: di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, and di- (2-ethoxyethyl) B) Peroxydi
  • a decomposition accelerator can be used in combination with the above thermal radical generator.
  • the decomposition accelerator include thiourea derivatives, organometallic complexes, amine compounds, phosphate compounds, toluidine derivatives, and aniline derivatives.
  • examples include urea, N, N′-diphenylthiourea, and N, N′-dilaurylthiourea, preferably tetramethylthiourea or benzoylthiourea.
  • organometallic complex examples include cobalt naphthenate, vanadium naphthenate, copper naphthenate, iron naphthenate, manganese naphthenate, cobalt stearate, vanadium stearate, copper stearate, iron stearate, and manganese stearate.
  • amine compound primary or tertiary alkylamines or alkylenediamines represented by an integer of 1 to 18 carbon atoms of the alkyl group or alkylene group, diethanolamine, triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, Trisdiethylaminomethylphenol, 1,8-diazabicyclo (5,4,0) undecene-7, 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0)- Nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7, 2-methylimidazole, 2-ethyl-4-methylimidazole and the like can be exemplified.
  • Examples of the phosphate compound include methacrylic phosphate, dimethycyl phosphate, monoalkyl acid phosphate, dialkyl phosphate, trialkyl phosphate, dialkyl phosphate, and trialkyl phosphate.
  • Examples of toluidine derivatives include N, N-dimethyl-p-toluidine and N, N-diethyl-p-toluidine.
  • Examples of aniline derivatives include N, N-dimethylaniline and N, N-diethylaniline.
  • a compound having a (meth) acryl group, an allyl group, a vinyl group, or a maleimide group is a liquid prepolymer.
  • the compound having a (meth) acryl group include butanediol mono (meth) acrylate, t-butylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-diethylaminoethyl (meth).
  • Examples of the compound having a vinyl group include vinyl acetate, chloroethylene, vinyltrimethoxysilane, 1-vinyl-3,4-epoxycyclohexane, vinyl acetate, and the like.
  • Examples of the compound having an allyl group include allyl alcohol, 3-aminopropene, allyl bromide, allyl chloride, diallyl ether, diallyl sulfide, allicin, allyl disulfide, allyl isothiocyanate, and the like.
  • maleimide group maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 4,4′-diphenylmethanemaleimide, m-phenylenemaleimide, bisphenol A diphenylether bismaleimide, 3,3′-dimethyl-5,5′- Examples include diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, and 1,6′-bismaleimide- (2,2,4-trimethyl) hexane.
  • compounds having a (meth) acryl group and a vinyl group are preferable. These compounds can be cured with an electron beam even in the absence of a photoradical initiator.
  • a photo radical initiator and a thermal radical generator can be used in combination of two or more. These photoradical initiator and thermal radical generator are 0.01 to 50 parts by weight with respect to 100 parts by weight of a compound having a (meth) acryl group, an allyl group, a vinyl group, or a maleimide group as a liquid prepolymer. It is preferably added, more preferably 0.1 to 20 parts by weight, still more preferably 1 to 10 parts by weight.
  • the photoradical initiator and the thermal radical generator are used in combination, the above content is the total content of the photoradical initiator and the thermal radical generator.
  • the content of the electron donor is preferably 10 to 500 parts by weight with respect to 100 parts by weight of the photo radical initiator.
  • the content of the decomposition accelerator is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the thermal radical generator.
  • a combination of a photocationic initiator, a thermal cation initiator or a photoanion initiator and a compound having an epoxy group, an oxirane ring such as an oxetane ring, a vinyl ether, a cyclic acetal or the like will be described.
  • photocationic initiator examples include compounds other than the combination of silsesquioxane and aluminum acetylacetonate in the latent thermal initiator for the epoxy resin and oxirane compound described above.
  • a sensitizer can be used in combination with the photocationic initiator.
  • Such sensitizers include 9,10-butoxyanthracene, acridine orange, acridine yellow, benzoflavin, cetoflavin T, perylene, pyrene, anthracene, phenothiazine, 1,2-benzacetracene, coronene, thioxanthone, fluorenone, benzophenone And anthraquinone.
  • thermal cation initiator examples include latent thermal initiators for the epoxy resins and oxirane compounds described above.
  • Examples of the photoanion initiator include a 2-nitrobenzyl carbamate compound obtained by blocking a bifunctional or higher isocyanate with an o-nitrobenzyl alcohol compound, and a combination of a quinonediazide sulfonate compound and an N-alkylaziridine compound.
  • the photoanion initiator is used for polymerizing a compound having an epoxy group and a compound having a cyanoacrylate group.
  • a compound having an epoxy group, a cyanoacrylate group, an episulfide, an oxetane ring, a spiro ortho carbonate, or a vinyl ether group is a liquid prepolymer and is crosslinked with a photocationic initiator, a thermal cationic initiator, and / or a photoanionic initiator. It is a compound having a reactive substituent.
  • Examples of the compound having a cyanoacrylate group include methyl cyanoacrylate and ethyl cyanoacrylate.
  • the compound having episulfide is a compound in which the oxygen atom of the above-mentioned compound having an epoxy group is substituted with a sulfur atom.
  • Examples of the compound having an oxetane ring include the oxetane compounds described above.
  • Examples of the compound having spiro ortho carbonate include spiro glycol diallyl ether and bicycloorthoester.
  • Compounds having vinyl ether include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, allyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether , 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexane dimeta Over distearate ether, triethylene glycol divinyl ether, trimethyl propane trivinyl ether
  • the compound having an oxetane ring is preferable as the compound having an epoxy group, a cyanoacrylate group, an episulfide, an oxetane ring, a spiro ortho carbonate, or a vinyl ether group.
  • the photo cation initiator, the thermal cation initiator, and the photo anion initiator can be used in combination of two or more.
  • These photocationic initiator, thermal cationic initiator, and photoanion initiator are based on 100 parts by weight of a compound having an epoxy group, a cyanoacrylate group, an episulfide, an oxetane ring, a spiro orthocarbonate, or a vinyl ether group, which is a liquid prepolymer.
  • the addition amount is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, and still more preferably 1 to 10 parts by weight.
  • the above content is the total content of the photocationic initiator, the thermal cation initiator, and the photoanion initiator.
  • the content of the sensitizer is preferably 5 to 500 parts by weight with respect to 100 parts by weight of the photocation initiator.
  • liquid binder with solid polymer dissolved in solvent examples include those obtained by dissolving the above-described polymer particles in a solvent and those suspended in a solvent.
  • a solvent it can select suitably from the solvent which can melt
  • solid polymer substances include fully saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray Poval PVA-124, Nippon Vinegar Poval Co., Ltd .; JC-25), partially saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray Poval PVA-235, manufactured by Nihon Ventures & Poval Co., Ltd .; JP-33, etc.) Modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray K Polymer KL-118, Kuraray C Polymer CM-318, Kuraray R Polymer R-1130 Kuraray LM Polymer LM-10HD, manufactured by Nihon Vinegar Poval Co., Ltd .; D Polymer DF-20, anion-modified PVA AF-17, alkyl-modified PVA ZF-15, carboxymethyl cellulose (manufactured by Daicel Industries,
  • acrylic ester polymerization emulsion Showa Denko Co., Ltd .; Polysol F-361, F-417, S-65, SH-502
  • ethylene / vinyl acetate copolymer emulsion Kuraray Co., Ltd.
  • An emulsion such as Panflex OM-4000NT, OM-4200NT, OM-28NT, OM-5010NT) can be used in a state suspended in water.
  • polyvinylidene fluoride manufactured by Kureha Co., Ltd .; Kureha KF Polymer # 1120, Kureha KF Polymer # 9130
  • modified polyvinyl alcohol manufactured by Shin-Etsu Chemical Co., Ltd .; cyanoresin CR-V
  • modified pullulan Polymers such as (Shin-Etsu Chemical Co., Ltd .; cyanoresin CR-S) can be used in a state dissolved in N-methylpyrrolidone.
  • liquid binder obtained by dissolving a solid polymer substance in a solvent a liquid binder obtained by dissolving a water-soluble polymer in water, and a binder obtained by suspending an emulsion in water are preferable.
  • a liquid binder obtained by dissolving a solid polymer substance in a solvent can be solidified by removing the solvent by heating and / or reducing the pressure.
  • Such a binder can also improve the ionic conductivity of the coating film by impregnating the electrolytic solution in the coating film to form a gel electrolytic layer.
  • Liquid binder that becomes solid inorganic substance by sol-gel reaction Liquid binders that become solid inorganic substances by sol-gel reaction include triethoxysilane, trimethoxysilane, aluminum isopropoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxy.
  • the catalyst for sol-gel reaction can be added to these.
  • the catalyst for the sol-gel reaction is not particularly limited as long as it is a catalyst for a reaction in which an inorganic component is hydrolyzed and polycondensed.
  • Such catalysts include acids such as hydrochloric acid; alkalis such as sodium hydroxide; amines; or dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate
  • Organotin compounds such as tin octylate; organotitanate compounds such as isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraalkyl titanate;
  • the surfactant may form micelles.
  • a solid inorganic substance can be made into an inorganic porous body using micelles as a template.
  • a quaternary ammonium salt is preferable, and specific examples include butyltrimethylammonium chloride, hexyltrimethylammonium chloride, dibutyldimethylammonium chloride, dihexyldimethylammonium chloride and the like.
  • water glass In addition to the liquid binder that becomes a solid inorganic substance by the sol-gel reaction, water glass can be exemplified as the liquid binder from which the solid inorganic substance is obtained. Specifically, No. 1 water glass, No. 2, water glass, No. 3 water glass of JIS standard table K1408, 1 type of sodium metasilicate, 2 types of sodium metasilicate, 1 type of potassium silicate, 2 type of potassium silicate, and Lithium silicate or the like can be used.
  • the degree of the elastic deformation property and the plastic deformation property of the binder can be expressed by the elastic modulus (h3) and the plastic deformation rate (h6), similarly to the viscoelastic particles.
  • h3 of the binder is preferably 0.95 or less, and more preferably 0.9 or less.
  • the h3 of the binder is not particularly limited, but can be 0.5 or more, and preferably 0.6 or more.
  • h6 of the binder is preferably 0.90 or less, and preferably 0.85 or less.
  • h6 is not specifically limited, It is preferable that it is 0.5 or more, and it is more preferable that it is 0.6 or more.
  • h3 and h6 of a binder are below the said upper limit, it will be excellent in stress relaxation ability, and will be excellent in the adhesive force when a base material is bent. If h3 and h6 of a binder are more than the said lower limit, mechanical strength and heat resistance will improve more.
  • the viscoelastic modulus of the viscoelastic particles is lower than the viscoelastic modulus of the binder.
  • “the viscoelastic modulus of the viscoelastic particles is lower than the viscoelastic modulus of the binder” means that the h3 and h6 of the viscoelastic particles are smaller than the h3 and h6 of the binder.
  • the difference between h6 of the viscoelastic particles and the binder is preferably 0.01 to 0.3, and is preferably 0.05 to 0.2. Is more preferable. If the difference in h6 between the viscoelastic particles and the binder is 0.01 or more, it is possible to efficiently achieve both improved heat resistance and curl generation, and if it is 0.3 or less, the heat resistance is further improved. In addition, the occurrence of curling is further suppressed. Note that ⁇ h6 indicating the amount of plastic deformation is more dominant in suppressing the occurrence of curling.
  • the h3 and h6 of the binder can be measured in the same manner as that of the viscoelastic particles. That is, after solidifying into a film having a thickness of 50 ⁇ m under conditions using a binder, the particles are cooled with liquid nitrogen and then pulverized using a mill (manufactured by IKA; M20 general-purpose mill) to obtain binder particles. be able to.
  • This binder particle can be used as a test target particle in step (1) of [Measurement method 1] and [Measurement method 2]. Thereby, h3 and h6 of a binder can be calculated
  • the binder content is preferably a practically sufficient addition amount without filling the voids generated between the particles.
  • the content of the binder is preferably 0.01 to 49 parts by weight, more preferably 0.5 to 30 parts by weight, with respect to 100 parts by weight of the viscoelastic particles. Part by weight is more preferred.
  • the (3) solvent of the present invention will be described.
  • the battery electrode or separator coating film composition of the present invention has a solvent for generating voids due to transpiration and adjusting fluidity.
  • the solvent can be evaporated by heat drying, vacuum drying, freeze drying, or a combination thereof.
  • the binder is a resin that is cured with light or an electron beam, it can be made porous using a frosted shape by being lyophilized and then cured with light or an electron beam.
  • the electrolyte solution solvent used for a battery can be added in advance to assist the impregnation of the electrolyte.
  • Solvents include hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, amylbenzene, turpentine oil, pinene, etc.), halogenated hydrocarbons (chlorinated) Methyl, chloroform, carbon tetrachloride, ethylene chloride, methyl bromide, ethyl bromide, chlorobenzene, chlorobromomethane, bromobenzene, fluorodichloromethane, dichlorodifluoromethane, difluorochloroethane, etc.), alcohol (methanol, ethanol, n-propanol, (Isopropanol, n-amyl alcohol, isoamyl alcohol, n-hex
  • a solvent can be added to the battery electrode or separator coating film composition at an arbitrary ratio in order to adjust the viscosity in accordance with the coating apparatus.
  • the kind and content of the solvent for obtaining such a viscosity can be determined as appropriate. In the present invention, the viscosity is a value obtained with a cone plate type rotational viscometer.
  • the battery electrode or separator coating film composition is within the range not impairing the object of the present invention, other particles, core-shell type foaming agent, salt, ionic liquid, coupling agent, stabilizer, preservative, and interface.
  • An active agent can be included.
  • the battery electrode or separator coating film composition may further contain one or more particles selected from the group consisting of organic fillers, carbon-based fillers, and inorganic fillers as other particles.
  • the other particles do not include particles having the property of irreversibly plastically deforming with respect to stress and the property of reversibly elastically deforming (that is, viscoelastic particles).
  • organic filler examples include polymers such as acrylic resin, epoxy resin, and polyimide that are three-dimensionally cross-linked and not substantially plastically deformed, cellulose particles, silicone particles, polyolefin particles, and the like. Examples include fibers and flakes.
  • An organic filler can be used 1 type or in combination of 2 or more types.
  • the carbon filler examples include graphite, acetylene black, and carbon nanotube.
  • a carbon type filler can be used combining 1 type or 2 types or more.
  • the carbon-based filler is a particle that can be added to such an extent that the insulating property is not impaired.
  • inorganic fillers include powders of metal oxides such as alumina, silica, zirconia, beryllia, magnesium oxide, titania, and iron oxide; sols such as colloidal silica, titania sol, alumina sol, talc, kaolinite, and smectite.
  • metal oxides such as alumina, silica, zirconia, beryllia, magnesium oxide, titania, and iron oxide
  • sols such as colloidal silica, titania sol, alumina sol, talc, kaolinite, and smectite.
  • Clay minerals such as silicon carbide and titanium carbide; nitrides such as silicon nitride, aluminum nitride and titanium nitride; borides such as boron nitride, titanium boride and boron oxide; complex oxides such as mullite; water
  • examples include hydroxides such as aluminum oxide, magnesium hydroxide, and iron hydroxide; barium titanate, strontium carbonate, magnesium silicate, lithium silicate, sodium silicate, potassium silicate, and glass.
  • the inorganic filler that can be added to such an extent that the insulating properties are not impaired include lithium cobaltate and olivine-type lithium iron phosphate.
  • One kind of inorganic filler or two or more kinds of inorganic fillers can be used in appropriate combination.
  • the inorganic filler is preferably dried at a high temperature of about 200 ° C. for about 1 hour in order to activate the active hydrogen groups on the surface.
  • a high temperature of about 200 ° C. for about 1 hour in order to activate the active hydrogen groups on the surface.
  • activating the active hydrogen group adhesion to organic particles is improved, mechanical strength and heat resistance are improved, and ion conductivity is improved by stabilizing ions in the electrolyte.
  • the inorganic filler may be used in powder form, or in the form of a water-dispersed colloid such as silica sol or alumina sol or in a state dispersed in an organic solvent such as organosol. These may be contained in the organic particles to be thermally fused, or may be used in close contact with the surface of the organic particles to be thermally fused, or in a state independent of the organic particles to be thermally fused. May be added.
  • the size of other particles is preferably in the range of 0.001 to 100 ⁇ m, and more preferably in the range of 0.005 to 10 ⁇ m. Furthermore, it is also preferable to use a porous body of other particles from the viewpoint of increasing the porosity. Specifically, inorganic fillers such as silica gel, porous alumina, and various zeolites can be used as the other particles.
  • the surface of other particles can be modified with various coupling agents.
  • the coupling agent include a silane coupling agent and a titanium coupling agent.
  • silane coupling agent examples include (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane as a fluorine-based silane coupling agent, and (2-bromo) as a bromine-based silane coupling agent.
  • TESOX vinyltrimethoxysilane
  • vinyltriethoxysilane ⁇ -chloro Propyltrimethoxysilane
  • ⁇ -aminopropyltriethoxysilane N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane
  • N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane ⁇ -glycine Sidoxypropyltrimethoxysilane (city KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • ⁇ -glycidoxypropylmethyldimethoxysilane ⁇ -methacryloxypropyltrimethoxysilane
  • ⁇ -methacryloxypropylmethyldimethoxysilane ⁇ -mercaptopropyl
  • Examples include silane coupling agents such as trimethoxysilane and cyan
  • Titanium coupling agents include triethanolamine titanate, titanium acetylacetonate, titanium ethyl acetoacetate, titanium lactate, titanium lactate ammonium salt, tetrastearyl titanate, isopropyltricumylphenyl titanate, isopropyltri (N-aminoethyl-aminoethyl) ) Titanate, dicumylphenyloxyacetate titanate, isopropyl trioctanor titanate, isopropyl dimethacrylisostearoyl titanate, titanium lactate ethyl ester, octylene glycol titanate, isopropyl triisostearoyl titanate, triisostearyl isopropyl titanate, isopropyl tridodecyl benzene sulfonyl Titanate, tetra 2-ethylhexyl) titanate, butyl titanate dimer, isopropyliso
  • titanium coupling agents vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ - Aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -methacryloxypropylpropyl Methoxysilane, ⁇ -methacryloxyxypropylmethyldimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, and cyanohydrin silyl ether are preferred.
  • a silane coupling agent and a titanium coupling agent can be used alone or in combination of
  • Such a coupling agent can improve adhesion by causing interaction with the battery electrode surface or the separator surface. Also, by coating the surface of other particles with these coupling agents, gaps are created between the other particles due to the exclusion effect of the coupling agent molecules, and ions are conducted between them to improve ion conductivity. You can also. Moreover, since these particles can be hydrophobized by coating the surfaces of inorganic fillers, silicone particles, polyolefin particles and the like with a coupling agent, the defoaming property can be further improved.
  • the amount of water adsorbed on the surface can be reduced by substituting active hydrogen on the surface of other particles with a silane coupling agent, so that the amount of moisture that causes deterioration of characteristics in the non-aqueous battery can be reduced.
  • the other particles are preferably particles whose surfaces are coated with polymer chains formed by graft polymerization. Examples of the polymer chain include those described in the viscoelastic particle of the present invention, including preferable ones.
  • Titanium coupling agents can be more preferably applied to inorganic particles having an isoelectric point pH of 7 or more, and silane coupling agents can be more preferably applied to inorganic particles having an isoelectric point pH of less than 7.
  • pH of the isoelectric point of the inorganic particles the value measured by the method defined in JIS R1638 “Method for measuring the isoelectric point of fine ceramic powder” can be used.
  • Silica (pH about 1.8), kaolin (pH about 5.1), mullite (pH about 6.3; the pH of isoelectric point can be controlled by changing the ratio of silicon and aluminum), titania (anatase type) (pH about 6.2), tin oxide (pH About 6.9), boehmite (pH about 7.7), ⁇ -alumina (pH about 7.9), ⁇ -alumina (pH about 9.1), beryllia (pH about 10.1), iron hydroxide; Examples thereof include Fe (OH) 2 (pH about 12.0), manganese hydroxide (pH about 12.0), magnesium hydroxide (pH about 12.4), and the like.
  • the above-mentioned other particles can be added within a range that does not deteriorate the porosity and the continuity of the voids, and preferably 0 to 100 parts by weight of the viscoelastic particles. Up to 90 parts by weight can be contained, more preferably 0 to 50 parts by weight.
  • the content of the carbon-based filler and the inorganic filler that can be added to such an extent that the insulating property is not impaired is 0.01 to 10 parts by weight with respect to 100 parts by weight of the viscoelastic particles. The amount is preferably 0.1 to 5 parts by weight.
  • a combination of inorganic fillers having a large difference in pH at the isoelectric point is preferable because an acid-base interaction is likely to occur, and the amount of one active hydrogen is increased because the activity of the other active hydrogen is improved.
  • a combination is preferable, and a combination of silica and ⁇ -alumina or a combination of silica and magnesium hydroxide is more preferable.
  • the addition amount of silica having a low isoelectric point pH is preferably in the range of 0.1 to 100% by weight with respect to the inorganic filler having a high isoelectric point pH, and is 1 to 10% by weight.
  • the range of is more preferable.
  • the battery electrode or separator coating film composition of the present invention can contain a core-shell type foaming agent.
  • a foaming agent EXPANCEL (made by Nippon Philite Co., Ltd.) etc. can be used. Since the shell is organic, long-term reliability with respect to the electrolyte is poor. Therefore, what coat
  • metal oxides such as alumina, silica, zirconia, beryllia, magnesium oxide, titania and iron oxide
  • sols such as colloidal silica, titania sol and alumina sol
  • gels such as silica gel and activated alumina
  • Complex oxides hydroxides such as aluminum hydroxide, magnesium hydroxide, and iron hydroxide: and barium titanate can be exemplified.
  • These inorganic substances can be coated on the surface of the viscoelastic particles by sol-gel reaction or heating.
  • the surface is treated with a chromate treatment, a plasma treatment, a water-soluble polymer such as PVA, carboxymethyl cellulose, starch, or the like and a compound obtained by adding the above-described polycarboxylic acid to the ester and crosslinking.
  • a chromate treatment a plasma treatment
  • a water-soluble polymer such as PVA, carboxymethyl cellulose, starch, or the like
  • a compound obtained by adding the above-described polycarboxylic acid to the ester and crosslinking.
  • the adhesion can also be improved.
  • the foaming agent foams when the battery runs out of heat.
  • the distance between the electrodes can be increased, and thereby the shutdown function can be exhibited.
  • the shell portion expands greatly, the distance between the electrodes can be increased, thereby preventing a short circuit or the like. Further, since the expanded shell portion maintains its shape even after the heat generation has subsided, it is possible to prevent the electrodes from being narrowed again and short-circuiting again.
  • the battery electrode or separator coating film composition of the present invention preferably contains 1 to 99 parts by weight of the above core-shell type foaming agent with respect to 100 parts by weight of the total of the viscoelastic particles and the binder. More preferably, it is more preferably 20 to 97 parts by weight.
  • the battery electrode or separator protective film composition of the present invention can contain salts serving as various ion sources. Thereby, ion conductivity can be improved. It is also possible to add the electrolyte of the battery used.
  • a lithium ion battery as an electrolyte, lithium hydroxide, lithium silicate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (pentafluoro) Ethanesulfonyl) imide and lithium trifluoromethanesulfonate can be exemplified.
  • examples of the electrolyte include calcium hydroxide and calcium perchlorate.
  • examples of the electrolyte include magnesium perchlorate.
  • examples of the electrolyte include tetraethylammonium tetrafluoroborate, triethylmethylammonium bis (trifluoromethanesulfonyl) imide, and tetraethylammonium bis (trifluoromethanesulfonyl) imide.
  • the battery electrode or separator coating film composition of the present invention preferably contains 0.1 to 300 parts by weight, preferably 0.5 to 200 parts by weight of the above-mentioned salt with respect to 100 parts by weight as a total of the viscoelastic particles and the binder. More preferably, it is contained in an amount of 1 to 100 parts by weight.
  • the salt may be added as a powder, made porous, or dissolved in a compounding component.
  • the battery electrode or separator coating film composition of the present invention can contain an ionic liquid.
  • the ionic liquid may be a solution in which the salt is dissolved in a solvent or an ionic liquid.
  • examples of the solution in which the salt is dissolved in a solvent include a solution in which a salt such as lithium hexafluorophosphate or tetraethylammonium borofluoride is dissolved in a solvent such as dimethyl carbonate.
  • ionic liquids examples include imidazo such as 1,3-dimethylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide, 1-ethyl-3-methylimidazolium bromide, etc.
  • Pyridinium salt derivatives such as 3-methyl-1-propylpyridinium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide; tetrabutylammonium heptadeca Alkylammonium derivatives such as fluorooctane sulfonate and tetraphenylammonium methanesulfonate; phosphonium salt derivatives such as tetrabutylphosphonium methanesulfonate; Composite conductive agent complex such as a periodate such as lithium can show.
  • the content of the ionic liquid is preferably 0.01 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the viscoelastic particles. More preferred is 5 parts by weight.
  • the battery electrode or separator coating film composition of the present invention can further contain a coupling agent.
  • the coupling agent include those exemplified above, including preferred ones.
  • the content of the coupling agent is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the viscoelastic particles.
  • the battery electrode or separator coating film composition of the present invention may contain a stabilizer.
  • stabilizers include 2,6-di-tert-butyl-phenol, 2,4-di-tert-butyl-phenol, 2,6-di-tert-butyl-4-ethyl- Phenol-based antioxidants exemplified by phenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butyl-anilino) -1,3,5-triazine Agents: alkyldiphenylamine, N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-N'-isopropyl-p-phenylenediamine, etc.
  • Aromatic amine antioxidants exemplified by: dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, bis A sulfide hydroperoxide decomposer exemplified by [2-methyl-4- ⁇ 3-n-alkylthiopropionyloxy ⁇ -5-tert-butyl-phenyl] sulfide, 2-mercapto-5-methyl-benzimidazole and the like; (Isodecyl) phosphite, phenyl diisooctyl phosphite, diphenyl isooctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate diethyl ester, Phosphorus hydroperoxide decomposers exemplified by
  • Stabilizer benzophenone light stabilizer exemplified by 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, etc .; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like; Hindered amine light stabilizers exemplified by phenyl-4-piperidinyl carbonate, bis- [2,2,6,6-tetramethyl-4-piperidinyl] sebacate and the like; [2,2′-thio-bis (4-t-octylphenolate)]-2-ethylhexylamine-nickel- (II) Agent; cyanoacrylate light stabilizer; oxalic anilide-based light stabilizer; fullerenes, fullerene hydrogenated, mention may be made
  • the content of the stabilizer is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the viscoelastic particles. More preferably, it is part.
  • the battery electrode or separator coating film composition of the present invention can further contain a preservative, whereby the storage stability of the composition can be adjusted.
  • Preservatives include acids such as benzoic acid, salicylic acid, dehydroacetic acid, sorbic acid, salts such as sodium benzoate, sodium salicylate, sodium dehydroacetate, and potassium sorbate, 2-methyl-4-isothiazoline-3- ON, and isothiazoline-based preservatives such as 1,2-benzisothiazolin-3-one, alcohols such as methanol, ethanol, isopropyl alcohol, and ethylene glycol, parahydroxybenzoates, phenoxyethanol, benzalkonium chloride, And chlorhexidine hydrochloride.
  • acids such as benzoic acid, salicylic acid, dehydroacetic acid, sorbic acid, salts such as sodium benzoate, sodium salicylate, sodium dehydroacetate, and potassium sorbate, 2-methyl-4-isothiazoline-3- ON, and isothiazoline-based preservatives such as 1,2-benzisothiazolin-3-one, alcohols such as methanol, ethanol
  • preservatives can be used alone or in combination of two or more.
  • the content of the preservative is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight with respect to 100 parts by weight of the viscoelastic particles.
  • the battery electrode or separator coating film composition of the present invention can further contain a surfactant for the purpose of adjusting the wettability and antifoaming property of the composition.
  • the battery electrode or separator coating film composition of the present invention can contain an ionic surfactant for the purpose of further improving ionic conductivity.
  • Surfactants include anionic surfactants such as soap, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate (eg, dodecyl benzene sulfonate), polyoxyethylene alkyl ether phosphate, poly Oxyethylene alkyl phenyl ether phosphate, N-acyl amino acid salt, ⁇ -olefin sulfonate, alkyl sulfate ester salt, alkyl phenyl ether sulfate ester salt, methyl taurate, trifluoromethane sulfonate, pentafluoroethane sulfonate , Heptafluoropropane sulfonate, nonafluorobutane sulfonate, and the like.
  • anionic surfactants such as soap, lauryl sulfate, polyoxyethylene alkyl ether sulfate,
  • sodium ion, lithium ion, or the like can be used as the counter cation.
  • a lithium ion type surfactant is more preferable, and in the sodium ion battery, a sodium ion type surfactant is more preferable.
  • Amphoteric surfactants include alkyldiaminoethylglycine hydrochloride, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amide propyl betaine, fatty acid alkyl betaine, sulfobetaine , Amidoxide and the like.
  • Nonionic (nonionic) surfactants include alkyl ester compounds such as polyethylene glycol and acetylene glycol, alkyl ether compounds such as triethylene glycol monobutyl ether, ester compounds such as polyoxysorbitan esters, alkylphenol compounds, A fluorine type compound, a silicone type compound, etc. are mentioned.
  • Surfactant can be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the viscoelastic particles. More preferred are parts by weight.
  • the battery electrode or separator coating film composition of the present invention is used to protect the battery electrode or separator. That is, the composition of the present invention is used as a composition for a coating film formed on at least the surface of a battery electrode or a separator, and a part of the composition may enter the battery electrode or the separator.
  • the battery electrode or separator coating film composition of the present invention can be prepared by mixing and stirring the above components.
  • Stirring can be performed using a stirring device such as a propeller mixer, a planetary mixer, a hybrid mixer, a kneader, an emulsifying homogenizer, and an ultrasonic homogenizer.
  • a stirring device such as a propeller mixer, a planetary mixer, a hybrid mixer, a kneader, an emulsifying homogenizer, and an ultrasonic homogenizer.
  • it can also stir, heating or cooling as needed.
  • the method for producing viscoelastic particles whose surface is coated with a polymer formed by graft polymerization is the following process: mixing the viscoelastic particles of the present invention and a coupling agent having a reactive substituent.
  • a silane coupling agent having a reactive substituent is immobilized on the surface of the viscoelastic particles.
  • the graft polymerization can be performed using the reactive substituent immobilized on the surface as a reaction starting point.
  • immobilization means the state chemically bonded to the viscoelastic particle surface or the state physically adsorbed.
  • Examples of the coupling agent having a reactive substituent at one end include the above-mentioned silane coupling agents and titanium coupling agents, with fluorine-based silane coupling agents and bromine-based silane coupling agents being preferred, (2 -Bromo-2-methyl) propionyloxypropyltriethoxysilane is particularly preferred.
  • the amount of the coupling agent having a reactive substituent at one end is preferably 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, based on 100 parts by weight of the solid content of the viscoelastic particles. Is more preferable.
  • a step of washing the viscoelastic particles using the aforementioned solvent can be included.
  • reaction residues such as an unreacted coupling agent
  • the solvent used in the step of washing the viscoelastic particles is not particularly limited as long as it dissolves the reaction residue and does not peel off the surface-modified polymer, and the amount of the solvent used is an amount that can remove the reaction residue. If it does not specifically limit.
  • examples include compounds having a ring, vinyl ether, cyclic acetal, and the like, and those that react with and bind to the reactive substituents of the surface-modified viscoelastic particles can be selected.
  • the reactive substituent is a (2-bromo-2-methyl) propionyloxy group
  • a compound having a (meth) acryl group, an allyl group, and a vinyl group as the polymerizable compound Is mentioned.
  • the amount of the polymerizable compound is not particularly limited as long as viscoelastic particles coated with a desired polymer are obtained, and is 100 to 300 parts by weight with respect to 100 parts by weight of viscoelastic particles as a raw material. Is preferred.
  • Polymerization may be performed in the presence of an initiator.
  • An initiator can be used according to the kind of the polymerizable compound. Examples of such initiators include the latent thermal initiators, photocationic initiators, and thermal cationic initiators described above, and can be used depending on the type of polymerizable compound used. These initiators may be used alone or in combination of two or more. As for the usage-amount of an initiator, content of the latent thermal initiator mentioned above, a photocationic initiator, and a thermal cation initiator can be illustrated.
  • a step of washing viscoelastic particles coated with the polymer may be included after the step of obtaining viscoelastic particles coated with a polymer whose surface is formed by graft polymerization.
  • the solvent described above can be used for washing.
  • the battery electrode or separator surface protecting method of the present invention is a coating having voids by forming at least one layer of the battery electrode or separator coating film composition on the battery electrode or separator surface and evaporating the solvent. Forming a film. The surface of the battery electrode or separator is protected by the battery electrode or separator coating film of the present invention.
  • the present invention also relates to a coating film obtained by using the battery electrode or separator coating film composition of the present invention in the battery electrode or separator surface protecting method. That is, in the method for producing a coating film obtained using the battery electrode or separator coating film composition of the present invention, when the binder is dissolved in a solvent, the battery electrode or separator is formed on the surface of the battery electrode or separator. Including a step of forming at least one coating layer of the coating film composition and a step of evaporating the solvent.
  • the binder is a solid that does not dissolve in the solvent
  • a step of forming at least one coating layer of the battery electrode or separator coating film composition on the surface of the battery electrode or separator a step of evaporating the solvent
  • a step of heat-sealing the solid binder is included.
  • a gravure coater, a slit die coater, a spray coater, dipping or the like can be used to form a coating layer of the coating film composition on the battery electrode or separator.
  • the thickness of the coat layer is preferably in the range of 0.01 to 100 ⁇ m, and more preferably in the range of 0.05 to 50 ⁇ m from the viewpoint of electrical characteristics and adhesion.
  • the battery electrode or separator coating film composition of the present invention may have a structure in which at least a part of the battery electrode or separator is impregnated.
  • the dry thickness of the coating layer that is, the thickness of the coating film is preferably in the range of 0.01 to 100 ⁇ m, more preferably in the range of 0.05 to 50 ⁇ m. If the thickness of the coating film is 0.01 ⁇ m or more, the insulation against electronic conduction is good and the risk of a short circuit is suppressed. If the thickness of the coating film is 100 ⁇ m or less, the resistance increases in proportion to the thickness, so the resistance to ion conduction is low, and the charge / discharge characteristics of the battery are improved.
  • the amount of impregnation of the composition is an amount that does not completely fill the pore structure of the electrode or separator. That is, it is preferable that the porosity of the electrode or separator is more than 0%, preferably the amount of porosity of the electrode or separator is 50% or more, more preferably the porosity of the electrode or separator is 75% or more. Is the amount.
  • the viscoelastic particles are particles having shape anisotropy, the particles having shape anisotropy in the coating direction can be oriented by a shearing force during coating.
  • the solvent can be obtained by heat drying, vacuum drying, freeze drying, or a combination thereof. Heating and drying can be performed using a hot stove, an infrared heater, a heat roll, or the like.
  • the vacuum drying can be performed by putting a coating film of the coating film composition in a chamber and applying a vacuum. Freeze drying can be employed when a solvent having sublimation properties is used.
  • the heating temperature and heating time in heat drying are not particularly limited as long as the temperature and time at which the solvent evaporates, and can be, for example, 80 to 120 ° C. and 0.1 to 2 hours.
  • the components excluding the solvent of the battery electrode or separator coating film composition are in close contact with the battery electrode or the separator, and when the binder is hot melt particles, the components of the present invention are thermally fused. A coating film is formed.
  • the binders can be thermally fused to be solidified.
  • the particles can be solidified by heat fusion at a temperature at which the particles are completely melted, or the surfaces of the organic particles can be melted and welded and cooled in a state of being in close contact with each other. It can also be solidified in a state where it is in close contact with a gap. According to the former heat fusion solidification, there are many portions in a continuous phase, and ion conductivity, mechanical strength, and heat resistance are high.
  • the ion conductivity, mechanical strength and heat resistance through the fused organic particles are inferior. Impregnation can improve ion conductivity. Further, since the latter has a structure in which gaps are randomly opened, the effect of preventing a short circuit can be enhanced by preventing the linear growth when dentlite is generated.
  • Various known methods such as hot air, hot plate, oven, infrared ray, ultrasonic fusion can be used as the heat fusion method at the time of hot melt, and the density of the protective agent layer can be increased by pressing during heating. it can.
  • various known methods such as cooling gas and pressing against a heat sink can be used for cooling. Further, when heating to a temperature at which the binder is melted, the heating can be performed at a temperature at which the binder is melted for 0.1 to 1000 seconds.
  • the compounded material can be solidified in an oriented state using a magnetic field and / or an electric field.
  • a coating film having anisotropy in ion conductivity, mechanical strength, and heat resistance can be formed.
  • the stress relaxation ability can be enhanced by fixing the viscoelastic particles in a state in which they are oriented in a direction in which stress relaxation is easy using a magnetic field and / or an electric field.
  • anisotropy can be imparted to the magnetic susceptibility and / or the dielectric constant by stretching, so that the polymer material can be oriented by a magnetic field and / or an electric field.
  • fibers having anisotropy such as cellulose can also be used. Ion conductivity can be improved by pulverizing fibers and fibers produced by stretching such a polymer into particles and orienting the major axis so as to stand perpendicular to the electrode surface.
  • organic crystals those having crystal magnetic and / or dielectric anisotropy can be oriented by a magnetic field and / or an electric field, and the effects as described above can be exhibited.
  • the magnetic field and / or electric field may be a static magnetic field and / or an electric field or a time-varying magnetic field and / or an electric field such as a rotating magnetic field and / or an electric field, and the magnetic field and the electric field may be applied simultaneously.
  • the battery electrode or separator having a coating film on its surface can be obtained by the method for producing a battery electrode or separator coating film of the present invention including the above steps. Note that at least a part of the coating film may be formed so as to enter the inside of the battery electrode or the separator.
  • the porosity of the coating film is 40% or more, preferably 41 to 90%, and more preferably 41 to 80%.
  • the present invention relates to a battery electrode and / or separator having a coating film which is protected by the battery electrode or separator coating film or manufactured by the method for manufacturing the battery electrode or separator coating film.
  • the battery electrode or separator protected with the battery electrode or separator coating film of the present invention can be produced by coating the battery electrode or separator with the composition of the present invention and then evaporating the solvent.
  • a battery electrode the positive electrode and / or negative electrode of a well-known various battery and an electric double layer type capacitor can be illustrated,
  • a battery electrode or a separator coating film composition can be apply
  • the separator examples include a porous material made of polypropylene or polyethylene, a nonwoven fabric made of cellulose, polypropylene, polyethylene, or polyester, and can be applied or impregnated on both sides or one side.
  • the battery electrode or separator coating film composition of the present invention can be used in a state of being in close contact with the opposing separator or electrode. After the solvent is not evaporated, the separator and the electrode are in close contact and then dried or after battery assembly. These members can be brought into close contact with each other by hot pressing.
  • Electrodes and separators may have anisotropy in elastic modulus, linear expansion coefficient, and shrinkage when heated, depending on the application direction of the electrode active material layer, the stretching and winding directions of the separator, and the like.
  • a uniaxially stretched polyethylene separator relieves stress during stretching and increases the amount of shrinkage in the stretching direction when heated, resulting in an anisotropic increase in stress between the coating films.
  • the viscoelastic particles have shape anisotropy, and the longest axis of the viscoelastic particles is oriented parallel to the contraction direction (that is, the stretching direction) of the battery electrode or the separator base material.
  • a battery electrode or separator having a coating film obtained by using the battery electrode or separator coating film composition of the invention is preferred.
  • the longest axis of the viscoelastic particles refers to a line having the longest straight line connecting the end points of any two points of the viscoelastic particles.
  • the base material of a battery electrode or a separator means parts other than the coating film in the battery electrode or separator which have a coating film.
  • the stress relaxation ability between the coating film and the base material of the battery electrode or separator is increased, curling is further suppressed, and the heat resistance is further improved.
  • the present invention relates to a battery comprising a battery electrode and / or a separator protected with the battery electrode or separator coating film composition of the present invention.
  • the battery can be manufactured by a known method.
  • a battery can be manufactured using a coating film impregnated with ion conductivity by impregnating the coating film with an electrolytic solution.
  • the coating film composition itself can have ion conductivity and can be incorporated into a battery as a solid electrolyte film.
  • the amount of the binder with respect to the viscoelastic particles can be 20% by weight or less, and the ionic conductivity can be imparted by impregnating the electrolytic solution into the void formed by the volume exclusion effect of the particles. .
  • ion conductivity can be imparted by swelling the electrolyte in the binder.
  • Test Example 1 The elastic modulus and plastic deformation rate of the viscoelastic particles and binder used in Examples and Comparative Examples described later were evaluated by the following methods.
  • the dispersion of the viscoelastic particle to be used was filtered and dried to obtain test particles.
  • the binder was solidified into a film having a thickness of 50 ⁇ m under the conditions for using the binder used, cooled with liquid nitrogen, pulverized using a mill (made by IKA; M20 general-purpose mill), A test particle was obtained by sieving with an opening 50 ⁇ m sieve.
  • the test particles were packed into an acrylic cylinder having an inner diameter of 10 mm, an outer diameter of 110 mm, and a height of 150 mm so as to have a height of 100 mm, and an iron bar having an outer diameter of 10 mm and a length of 200 mm was pushed in using an autograph.
  • the battery was charged at a constant current of 0.005 mA until the voltage reached 4.2 V, and then charged at a constant voltage of 4.2 V for 2 hours. Thereafter, the battery was discharged at a constant current of 0.005 mA until the voltage reached 3.5V. This was repeated three times, and the third discharge capacity was set as the initial capacity.
  • the cell whose initial capacity was measured was set to a potential of 4.2 V, and an impedance of 1 kHz was measured with a voltage change of ⁇ 15 mV with the potential at the center.
  • the discharge rate was obtained from the initial capacity, and the discharge capacity for each discharge rate was measured.
  • the charge was increased to 4.2 V with a constant current over 10 hours each time, and then charged with a 4.2 V constant voltage for 2 hours. Thereafter, the battery was discharged at a constant current to 3.5 V over 10 hours, and the discharge capacity at this time was set to a discharge capacity of 0.1 C.
  • the battery was discharged at a current value at which discharge was completed in 1 hour from the discharge capacity determined at 0.1 C, and the discharge capacity at that time was determined to be the discharge capacity at 1 C.
  • the discharge dose at 3C, 10C, and 30C was determined, and the capacity retention rate was calculated when the discharge capacity at 0.1C was 100%.
  • the test method was the same as the heat-resistant insulation test described above, and the battery after the test was disassembled to confirm the internal state.
  • the evaluation criteria were as follows. ⁇ : There is no direct touch between the positive electrode and the negative electrode and the insulation state is maintained, and the battery electrode protective layer is in close contact with the electrode and / or the separator. ⁇ : There is no direct touch between the positive electrode and the negative electrode and the insulation state is maintained. Battery electrode protective layer is partially lifted but not peeled ⁇ : Desorption progresses and part of positive and negative electrodes is exposed ⁇ : Positive and negative electrodes are touched and short-circuited
  • Example 1 a negative electrode having a coating film obtained by coating a battery electrode or separator coating film composition comprising a solvent, a binder, and viscoelastic particles on a negative electrode and evaporating the solvent is used for lithium ion secondary. A method for manufacturing the secondary battery will be described.
  • composition of composition 20 kg of water is added to 50 kg of the dispersion, and 200 g of polyoxyethylene (manufactured by Meisei Chemical Co., Ltd .; Alcox E-30) is added and dissolved by stirring for 6 hours to obtain a battery electrode or separator coating film composition. It was. In the composition, the content of viscoelastic particles among the components excluding the solvent was 99.2% by weight.
  • the positive electrode and the negative electrode coated with the coating film are cut at 40 mm ⁇ 50 mm so as to include an area where the active material layer is not coated at both ends with a width of 10 mm on the short side, and in a portion where the metal is exposed
  • the positive electrode was joined with an aluminum tab, and the negative electrode was joined with a nickel tab by resistance welding.
  • a separator manufactured by Celgard Co., Ltd .; # 2400 was cut to a width of 45 mm and a length of 120 mm, folded back into three, and sandwiched so that the positive electrode and the negative electrode faced each other, and an aluminum laminate cell with a width of 50 mm and a length of 100 mm was obtained.
  • the sheet was sandwiched between two parts, and the sealant was sandwiched between the parts where the tabs hit, and then the sealant part and the side perpendicular to it were heat laminated to form a bag.
  • Example 2 a positive electrode having a coating film obtained by coating a battery electrode or separator coating film composition comprising a solvent, a binder, and viscoelastic particles on a positive electrode and evaporating the solvent is used to form a lithium ion catalyst.
  • a method for manufacturing the secondary battery will be described.
  • the positive electrode was manufactured by the method of Example 1.
  • Example 3 a battery electrode or separator coating film composition comprising a solvent, a binder and viscoelastic particles is coated on a separator, and a separator having a coating film obtained by evaporating the solvent is used to form lithium ion A method for manufacturing the secondary battery will be described.
  • a separator was produced in the same manner as in Example 1.
  • Example 4 a battery electrode or separator coating film composition comprising a solvent, a binder, and viscoelastic particles is coated on a separator, and a separator having a coating film obtained by evaporating the solvent is used to form a lithium ion solution.
  • a method for manufacturing the secondary battery will be described.
  • composition of composition 2 kg of water was added to 12 kg of the dispersion, 0.1 kg of ethylene / vinyl acetate copolymer emulsion (manufactured by Kuraray Co., Ltd .; Panflex OM-4000NT) was added and dissolved by stirring for 6 hours, and then lithium dodecylbenzenesulfonate was added. 0.01 kg of 55% aqueous solution was added and further stirred for 2 hours to obtain a battery electrode or separator coating film composition. In the composition, the content of viscoelastic particles among the components excluding the solvent was 99.2% by weight.
  • Example 5 a battery electrode comprising a solvent, a binder, and viscoelastic particles or a separator coating film composition is coated on a separator, and a separator having a coating film obtained by evaporating the solvent is used to form a lithium ion solution.
  • a method for manufacturing the secondary battery will be described.
  • composition of composition 2 kg of water was added to 12 kg of the dispersion, 0.1 kg of ethylene / vinyl acetate copolymer emulsion (manufactured by Kuraray Co., Ltd .; Panflex OM-4000NT) was added and dissolved by stirring for 6 hours, and then lithium dodecylbenzenesulfonate was added. 0.01 kg of 55% aqueous solution was added and further stirred for 2 hours to obtain a battery electrode or separator coating film composition. In the composition, the content of viscoelastic particles among the components excluding the solvent was 99.2% by weight.
  • Example 6 a separator having a coating film obtained by coating a battery electrode or separator coating film composition comprising a solvent, a binder and viscoelastic particles on a separator and evaporating the solvent, lithium ion A method for manufacturing the secondary battery will be described.
  • the finely pulverized slurry is filtered with a nylon mesh having an opening of 5 ⁇ m, stored in a 100 L polypropylene tank and allowed to stand for 2 days. Then, the supernatant layer of 1/5 of the volume is removed by a pump, and the remaining 3/5 is removed. An intermediate layer was collected by a pump and stored in a 100 L polypropylene tank, and 1/5 remaining at the bottom of the container was removed as a sedimentation layer. For the 3/5 sampled, the drained water was added to make 67%, then stored in a 50 L polypropylene tank and allowed to stand for 2 days, and the supernatant layer and the sedimented layer were similarly removed.
  • This operation of separating the intermediate layer was repeated three times after changing the capacity of the polypropylene tank to 20 L, and then the magnetic foreign matter was further removed from the finally separated intermediate layer with a 2T electromagnet, which was removed in the process.
  • Ion exchange water was added to prepare an inorganic particle-dispersed slurry containing 67% corundum particles.
  • composition of composition Add 1 kg of water to 3 kg of the inorganic particle-dispersed slurry, add 0.03 kg of polyoxyethylene (manufactured by Meisei Chemical Co., Ltd .; Alcox E-30) and stir for 6 hours to dissolve, and then add 100 g of CD-1200. The mixture was stirred for 2 hours to obtain a battery electrode or separator coating film composition.
  • the content of viscoelastic particles among the components excluding the solvent was 2.9% by weight.
  • Example 7 (Manufacture of lithium ion secondary batteries) Manufactured by the method of Example 1.
  • a battery electrode comprising a solvent, a binder, and viscoelastic particles or a separator coating film composition is coated on a separator, and a separator having a coating film obtained by evaporating the solvent is used to form a lithium ion solution.
  • a method for manufacturing the secondary battery will be described.
  • a polyethylene fishing line (manufactured by YKG Yotsuami; G-soul Pe 0.3) is cut to a width of 1 mm, and then dispersed in 50 g of water (5 kg). While cooling this, a bead mill (0.3 mm zirconia beads having a vessel volume of 0.6 L) The slurry was circulated and dispersed for one day using 80% filling and a peripheral speed of 10 m / s). Thereafter, the slurry was heated and stirred at 80 ° C. to remove moisture, and the concentration was increased to 60%. (Production of composition) A composition was prepared in the same manner as in Example 6 except that the above slurry was added instead of CD-1200 in Example 6.
  • Example 8 a battery electrode or a separator coating film composition comprising a solvent, a binder, and viscoelastic particles is coated on a separator, and a separator having a coating film obtained by evaporating the solvent is used.
  • a method for manufacturing the secondary battery will be described. (Manufacture of separator with coating film) Except that the cylinder / conveying speed ratio is set to 2, the cylinder is double the conveying speed, and the fiber is oriented so that the fiber is oriented parallel to the conveying direction of the substrate by the shearing force between the cylinder and the substrate. This was produced by the method of Example 3. The state of fiber orientation was observed with an optical microscope.
  • Example 1 A lithium ion secondary battery was produced in the same manner as in Example 1 except that a battery electrode or an electrode having no separator coating film and a separator were used.
  • the substrate electrode or separator coating film composition of the present invention even if the coating film is applied, the substrate electrode or separator suppresses the occurrence of curling and has high heat resistance. Since there is no deterioration in electrochemical durability due to the wrinkles of the base material, a battery with excellent long-term reliability can be provided.

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PCT/JP2014/055554 2013-03-05 2014-03-05 電池電極又はセパレーターコーティング膜組成物、これを用いて得られるコーティング膜を有する電池電極又はセパレーター、及びこの電池電極又はセパレーターを有する電池 WO2014136813A1 (ja)

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CN201480012044.4A CN105027328B (zh) 2013-03-05 2014-03-05 电池电极涂膜组合物或隔板涂膜组合物、具有使用该涂膜组合物得到的涂膜的电池电极或隔板、以及具有该电池电极或隔板的电池
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US11424435B2 (en) 2019-05-09 2022-08-23 New Jersey Institute Of Technology High oxidation state periodate battery
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US12051825B2 (en) 2019-06-19 2024-07-30 Lg Energy Solution, Ltd. Coated separator for secondary battery and method of manufacturing the same
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