KR20150125700A - Coating film composition for battery electrodes or separators, battery electrode or separator provided with coating film obtained by using same, and battery provided with battery electrode or separator - Google Patents

Abstract

It is an object of the present invention to provide a cell electrode or separator coating film composition which can suppress the generation of curl and form a coating film having high heat resistance. The present invention is a cell electrode or separator coating film composition containing a binder, a solvent and viscoelastic particles.

Description

TECHNICAL FIELD [0001] The present invention relates to a battery electrode or a separator coating composition, a battery electrode or separator having a coating film obtained using the same, and a battery having the battery electrode or the separator. BACKGROUND ART [0002] , AND BATTERY PROVIDED WITH BATTERY ELECTRODE OR SEPARATOR}

The present invention relates to a battery electrode or a separator coating film composition, a battery electrode or separator having a coating film obtained by using the same, and a battery having the battery electrode or the separator.

Lithium ion secondary batteries, which are light in weight, high in voltage and large in capacity, are partly put to practical use as power supplies for mobile tools such as cellular phones, notebook computers, and power tools such as power tools and cars. However, in the conventional battery, safety derived from poor heat resistance and breakdown resistance is low, and there is also a problem that a conductive foreign matter entering in the production step penetrates through the separator and is short-circuited. In addition, the lithium ion secondary battery has a high internal resistance, a sufficient charging and discharging characteristic at a high rate, a sufficient charging and discharging capacity, and a poor deterioration of the active material layer when used for a long period of time.

As one of the reasons why the lithium ion secondary battery can not provide sufficient safety as described above, when the insulating property by the separator is destroyed due to incorporation of conductive foreign matter, generation of dentrite, breakage of the battery, A structure for preventing breakage from progressing due to thermal runaway and an insufficient heat resistance.

As a remedy for the above problem, there has been proposed a method of forming a porous film containing alumina powder or silica powder on the active material applied layer applied to the collector to protect the active material from falling off from the electrode (Patent Document 1). Such a porous protective film suppresses the generation of dentrite or acts as a layer for holding the electrolyte, and the porous protective film serves as an ion source, thereby reducing the internal resistance and contributing to improvement of discharge characteristics at high rates. In addition, acceleration of local deterioration resulting from concentration of an electrode reaction due to non-uniformity of the surface of the electrode is buffered uniformly by the porous protective film, thereby preventing deterioration of the active material layer when used for a long period of time.

On the other hand, in a cell in which an electrode and a separator are adhered to each other with an adhesive layer, a method in which the adhesive layer is a porous resin layer and a continuous porous protective layer is formed using a path when the solvent is evaporated (Patent Document 2). Since the liquid electrolyte is held in the through-hole of the porous resin layer, good ion conductivity at the electrode electrolyte interface can be secured.

Japanese Patent Laid-Open No. 7-220759 International Publication No. 1999/026307

However, in Patent Documents 1 and 2, there is a problem that curling is generated on a porous resin layer formed on an electrode or a separator. In the method described in Patent Document 1, the stress is generated due to the difference between the elastic modulus and the linear expansion coefficient of the electrode and the porous protective film, and curl is generated. Further, in the method described in Patent Document 2, since the solvent evaporates and the coating film shrinks, stress is generated between the separator and the porous resin layer to generate curl. This curl not only deteriorates handling at the time of assembly but also causes a cause of wrinkles. When wrinkles occur, the distance between electrodes changes locally. As a result, localization of the electrochemical reaction occurs and there is a problem that the charge-discharge characteristics and the life of the battery are deteriorated.

Accordingly, an object of the present invention is to provide a cell electrode or separator coating film composition capable of forming a coating film having a suppressed generation of curl and having a high heat resistance.

The inventors of the present invention have studied to solve the above problems of the prior art. As a result, the present inventors have found that by using viscoelastic particles as a component contained in a composition for forming a coating film, curling of the coating film is suppressed and high heat resistance is obtained, A battery having a coating film obtained by coating a battery with a coating film and / or a separator has a high heat resistance, a low internal resistance, an excellent charging and discharging cycle characteristic, a large charging and discharging capacity, It was found that the deterioration of the active material layer thereafter was small and the lifetime was long.

The gist of the present invention is as follows.

The present invention 1 is a cell electrode or separator coating film composition containing a binder, a solvent and viscoelastic particles.

The present invention 2 is the cell electrode or separator coating film composition of the present invention 1 in which the viscoelastic particles have a viscoelasticity lower than that of the binder.

The present invention 3 is the cell 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 the separator coating film composition of any one of the inventions 1 to 3.

Invention 5 is a battery electrode or separator according to the fourth aspect of the present invention in which the viscoelastic particles have shape anisotropy and the longest axis of the viscoelastic particles is oriented parallel to the shrinking direction of the base of the battery electrode or the separator.

The present invention 6 is a cell having the battery electrode and / or the separator according to the fifth aspect of the present invention.

According to the present invention, there is provided a battery electrode or a separator coating film composition in which generation of curling is suppressed and a battery electrode or separator coating film having high heat resistance is obtained. By using a battery electrode or a separator having a coating film of the present invention in a battery, it is possible to prevent a short circuit of the positive electrode due to the collapse of the battery due to an accident or the melting of the separator due to mixing of conductive foreign matter and thermal runaway.

In addition, since the coating film of the present invention is an electrolyte-retaining layer on the surface of an electrode or a separator, or a desolvation layer of ions in an electrolyte solution, the ion conduction resistance can be reduced. Therefore, charging and discharging can be performed at high rates, It is possible to prevent deterioration of the battery characteristics when the battery is left at high temperature in a 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, small deterioration of the active material layer after charging and discharging a large number of cycles for a long period of time, to be.

On the other hand, as a method for suppressing the generation of curl, there is a method of lowering the viscoelasticity of the binder. However, the binder has a structure in which a porous structure is retained by binding between particles. As a result, the stress relieving ability of the binder is relatively weak and the heat resistance is lower than that in the case of adding the function of relaxing the stress to the particles. On the other hand, in the method of the present invention using the viscoelastic particles, the viscoelastic particles are less likely to be deformed than the deformation amount of the viscoelastic particles, so that the occurrence of curl is suppressed as compared with a method of decreasing the viscoelasticity of the binder, Can be obtained.

The coating film of the present invention can also be used as a solid electrolyte membrane or a gel electrolyte membrane by impregnating the porous structure with a solid or gel having ionic conductivity.

1 is a sectional view of a battery electrode or a battery electrode having a separator coating film.
2 is a sectional view of a separator having a battery electrode or a separator coating film.
3 is an optical microscope photograph of a separator having a coating film of Example 8. Fig. The arrow indicates the transport direction of the substrate.

The battery electrode or separator coating film composition has (1) viscoelastic particles, (2) a binder, and (3) a solvent.

[Viscoelastic particles]

(1) Viscoelastic particles of the present invention will be described. The " viscoelastic particles " in the present invention are particles having a property of irreversibly plastic deformation against stress and a property of reversibly elastic deformation. When the battery electrode or the separator coating film composition contains viscoelastic particles, the particles can be irreversibly deformed in the coating film, and the resulting coating film has a low modulus of viscoelasticity. Thereby, the stress with the battery electrode or the separator base can be reduced. When a gravure coater or the like is used to coat a battery with a roll-to-roll process in the production of a battery, the battery is coated with a tensile force applied thereto, and wound while being dried. If the wound substrate is cut in a later step, the tension at the time of coating is opened, which is also a cause of curling. The viscoelastic particles in the coating film relax the stress with the base material to reduce the generation of curl. Therefore, even when the battery is produced by the roll-to-roll means, the handling property is good and the occurrence of wrinkles is suppressed. Thus, a high-quality battery can be provided.

As viscoelastic particles, various polymers such as polyethylene, polypropylene, polystyrene, polycarbonate, polyacetal, polyphenylene sulfide, liquid crystal polymer, polyvinyl chloride, celluloid, polyvinyl alcohol, Polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber, polyisoprene, chloroprene rubber, acrylic rubber, polymer having cyano group, urethane (meth) acrylate, A polyvinyl alcohol copolymer, an acrylic-vinyl alcohol copolymer, an epoxy resin, an oxetane resin, a urethane resin, an acrylic resin, a polysaccharide, a polyimide, Polyamideimide, silicon, a polymer having a carbonyl group (for example,? -Di Polymer having a metric tons), and there can be mentioned a copolymer thereof.

Specific examples of the polymer derivative having a cyano group include cyanoethylated vinyl alcohol, cyanoethylated carboxymethyl cellulose, cyanoethylated pullulan, cyanoethylated cellulose, cyanoethylated starch, cyanoethylated ester Modified starch, hydrogenated starch, cyanoethylated dextrin, cyanoethylated collagen and nitrile rubber. Specific examples of the polymer derivative having a polyethylene glycol structure include a polyethylene glycol acrylamide styrene copolymer, a polyethylene glycol polylactic acid copolymer, and a polyvinyl alcohol pendant of a polyethylene glycol chain. Examples of the polymer having a carbonyl group include, for example, D polymer (PVA having a carbonyl group) manufactured by Kuraray Co., Ltd.; Isobenzene and the like. Specific examples of the polymer having a? -diketone structure include a polyacrylic ester copolymer having a? -diketone structure, which can be produced by radical copolymerization of a vinyl compound having a? -diketone structure such as allyl acetoacetate with an acrylate ester Or polyvinyl alcohol copolymerized with vinyl acetate, and the like. A polymer having a carbonate, specifically, there may be mentioned, such as polycarbonate, CO ₂ copolymer (CO ₂ -philic Co-polymer) solvent friendly. As the material of the viscoelastic particles, urethane resin and polyethylene are preferable.

The viscoelastic particles may be used alone or in a plurality of combinations. Further, the viscoelastic particles may be in the form of a dispersion liquid 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 mu m, more preferably in the range of 0.01 to 50 mu m, and still more preferably in the range of 0.05 to 10 mu m. It is preferable that the particle size distribution of the viscoelastic particles be narrow in that the porosity of the coating film can be made higher. That is, it is preferable that particles having a particle diameter in the range of A to B are 80% by volume or more of the viscoelastic particles when A is 1/5 of the average particle diameter of the viscoelastic particles and B is 5 times thereof, More preferably 90 vol% or more. The average particle diameter and the 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 Seisakusho Co., Ltd. can be used. The 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. Viscoelastic particles include viscoelastic particles having shape isotropy or shape anisotropy. In the present invention, the viscoelastic particles preferably have shape anisotropy.

When the viscoelastic particles have shape anisotropy, when the electrode cell or the separator coating film composition containing viscoelastic particles having shape anisotropy is applied to the substrate of the battery electrode or the separator, the shear force at the time of coating causes shape anisotropy The viscoelastic particles can be oriented. In addition, a magnetic field or an electric field can be applied so that the longest axis of the viscoelastic particles becomes parallel to the contraction direction of the base material of the battery electrode or the separator. As a result, the stress relaxation ability due to the deformation of the particles can be made higher, the pores in the coating layer can be oriented, and the battery characteristics can be further improved.

The shape of the viscoelastic particles having shape isotropy includes a cubic shape and a spherical shape. The shape of the viscoelastic particles having shape anisotropy may be a flat shape (for example, a plate shape that is a rectangular parallelepiped), a fiber shape, a bent fiber shape, or a coil shape. When the separator has a tendency to shrink, the viscoelastic particles can be oriented in an effective direction to relax the shrinkage stress. Of the flat viscoelastic particles, the plate-shaped viscoelastic particles can be produced by tapping and crushing the particles, slicing the fibers thinly, or making them self-organized into a plate shape. The fibrous particles can be produced by cutting the spinning polymer shortly, or by electrospinning. By shortening the fibrous particles or spinning them by electrospinning, short fibers can be formed by turning the electric field on and off, so that short fibers that can be used as particles having shape anisotropy can be produced.

The degree of the elastic deforming property of the viscoelastic particles can be expressed by the elastic modulus h3 determined by the following measurement method 1. In the present invention, h3 of viscoelastic particles is preferably 0.95 or less, more preferably 0.9 or less. The h3 of the viscoelastic particles is not particularly limited, but may 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 strain h6 determined by the following method 2. In the present invention, h6 is preferably 0.85 or less, more preferably 0.75 or less. The h6 of the viscoelastic particles is not particularly limited, but is preferably 0.5 or more, more preferably 0.6 or more. When h3 and h6 of the viscoelastic particles are not more than the upper limit value, the stress relaxation ability is increased and the curling can be effectively suppressed. When h3 and h6 of the viscoelastic particles are not lower than the above lower limit value, the heat resistance is further improved. Both h3 and h6 are parameters indicating ease of deformation, and either of them is liable to be deformed when the numerical value is small. Therefore, when h3 and h6 are smaller, curl is further suppressed. However, deformation due to elastic deformation leaves deformation stress. On the other hand, deformation caused by plastic deformation does not leave deformation stress. Here, the strained stress becomes a force capable of generating curl. Therefore, when the plastic strain: h6 is smaller, the occurrence of curl is further suppressed as compared with the case where the elastic strain: h3 is small.

[Measurement method 1]

(2) The test particles obtained in the step (1) were filled in an acrylic tube having an inner diameter of 10 mm, an outer diameter of 110 mm and a height of 150 mm to a height of 100 mm, and an iron rod having an outer diameter of 10 mm and a length of 200 mm (3) a step of measuring a height h1 when press-fitted with 1 kgf and a height h2 when the press-in force is reduced by press-fitting to 0.5 kgf, (4) a step of pressing h1 / h2 = h3 To obtain the modulus of elasticity of the viscoelastic particles: h3.

[Measurement method 2]

(1) Step of obtaining test particles (2) The test particles are filled in an acrylic tube having an inner diameter of 10 mm, an outer diameter of 110 mm and a height of 150 mm to a height of 100 mm, and iron bars having an outer diameter of 10 mm and a length of 200 mm are press- (3) After the weight of 1 kgf is applied, the height h4 when the load is returned to 0.5 kgf is determined. Subsequently, the iron rod is pressed at 100 kgf, and the height h5 is obtained when the load is returned to 0.5 kgf . (4) A step of obtaining plastic strain h6 of viscoelastic particles by h5 / h4 = h6.

When the average particle diameter of the viscoelastic particles is 50 μm or more, the viscoelastic particles to be tested are sieved with a sieve of 50 μm in size to obtain test particles. Further, the particles which are likely to be clogged are filtered as an aqueous dispersion to obtain test particles.

The content of the viscoelastic particles is 0.1 to 99.9% by weight or more, preferably 0.5 to 99.5% by weight, more preferably 1 to 99% by weight, of the components contained in the coating film composition excluding the solvent. In such a range, the stress relaxation performance accompanying the deformation of the viscoelastic particles and the low elastic modulus is increased, and curling can be effectively suppressed. Further, 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.

[Binder]

The binder (2) of the present invention will be described. The battery electrode or separator coating film composition of the present invention contains a binder. As the binder, a solid (e.g., particulate) binder or a liquid binder may be mentioned. The binder may be in a state of being dispersed in a solvent, a state of being dissolved in a solvent, a state of being dispersed in a solvent, or a state of being dissolved in a solvent.

[Solid binder]

As the solid binder, various known solid binders can be used. Examples of the solid binder include thermoplastic organic particles, organic crystals, and organic particles that are crosslinked at the time of heat fusion. The average particle diameter of the solid binder is not particularly limited and may be 0.01 to 500 mu m. In addition, the solid binder does not include particles that are irreversibly plastically deformed against stress and particles having reversibly elastic deformability (i.e., viscoelastic particles).

The thermoplastic organic particles are not particularly limited as long as they can be bonded together by hot melt bonding of the particles by hot melt, and thermoplastic polymer particles can be mentioned.

As the thermoplastic polymer, a material of viscoelastic particles can be exemplified. The thermoplastic organic particles may be used alone or in a plurality of combinations. Particles of a polymer derivative having a cyano group, particles of a polymer derivative having a polyethylene glycol structure, particles of a polymer derivative having a carbonyl group (preferably, a particle of a polymer having a β- Particles of a polymer having a diketone structure) and a polymer 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 particles of a polymer having a carbonate group desirable.

The thermoplastic organic particles can adjust the molecular weight or crosslinking density to the extent that they have a melting point or softening point in the range of -40 to 300 캜.

The thermoplastic organic particles may be used as a dry powder, or may be used as an aqueous emulsion by forming a protective colloid particle with a surfactant or a water-soluble polymer. Further, for the purpose of adjusting the melting point, a high boiling point solvent such as ethylene glycol, glycerin, diethylene glycol, N-methylpyrrolidone, dimethylsulfoxide and isophorone and having a boiling point of 80 ° C or higher may be further added.

[Determination of organic matter]

Examples of the crystals of the organic substance include hydrazide crystals, acid anhydride crystals, amine crystals, imidazole crystals and triazine crystals, or mixed crystals thereof. The melting point of the organic material crystal is preferably 40 캜 or higher, more preferably 50 to 300 캜.

(Hydrazinecarbonoethyl) -5-isopropylhydantoin (melting point 120 占 폚), 7,11-octadecadienes (having a melting point of 177 to 180 占 폚), hydrazine dihydrazide -1,18-dicarbohydrazide (melting point 160 캜), and the like. Examples of the 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 캜), dicyandiamide (melting point 208 캜), and the like. As the imidazole crystal, imidazole (melting point 89 to 91 ° C), 2-methylimidazole (melting point 140 to 148 ° C), phenylimidazole (melting point 174 to 184 ° C) and the like can be mentioned. 6-vinyl-S-triazine (melting point 240 캜), 2,4-diamino-6-methacryloyloxyethyl-S-triazine (having a melting point of 170 캜 ), And the like. For the purpose of adjusting the melting point or the softening point, the organic substance crystals may be used as a solid solution by mixing two or more kinds thereof.

[Particles of organic material crosslinked at the time of heat fusion]

The particles of the organic material which are crosslinked at the time of heat fusion are various known latent curable solid resin particles. Examples of the latent curable solid resin include an epoxy resin, a mixture of an epoxy resin and an oxirane compound, a prepolymer having a (meth) acrylate ester and an active hydrogen group. Therefore, as particles of an organic material which is crosslinked at the time of thermal fusion bonding, particles obtained by blending a solid thermal initiator 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; A core particle containing a solid (meth) acrylic acid ester and a curing agent or an initiator; And particles which are a combination of a prepolymer having an active hydrogen group and a crosslinking agent. In the present invention, (meth) acrylic acid esters refer to acrylic acid esters and methacrylic acid esters.

As the solid epoxy resin, DIC manufactured by K.K. EPICLON 1050 (bisphenol A type epoxy resin having a softening point of 64 to 74 캜), manufactured by DIC Corporation; EPICLON N-660 (cresol novolak type epoxy resin having a softening point of 62 to 70 캜), manufactured by DIC Corporation; EPICLON N-770 (phenol novolak type epoxy resin having a softening point of 65 to 75 캜), manufactured by DIC Corporation; HP-7200HH (dicyclopentadiene type epoxy resin having a softening point of 88 to 98 占 폚), manufactured by DIC Corporation; EPICLON HP-4700 (naphthalene type epoxy resin having a softening point of 85 to 95 캜), manufactured by Nagase ChemteX Kabushiki Kaisha; EX-721 (monofunctional solid epoxy phthalimide skeleton having a melting point of 94 to 96 캜), manufactured by Nagase ChemteX Kabushiki Kaisha; EX-171 (lauryl alcohol (EO) 15 glycidyl ether having a melting point of 40 占 폚), and the like. In the present specification, "EO" refers to ethylene oxide, and "PO" refers to propylene oxide.

As oxirane compounds, oxetane compounds can be mentioned. Specific examples of the oxirane compound include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1 - (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl Ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, isobornyl 3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl Ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl 3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl 3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) Ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl 3-oxetanylmethyl) ether, boron (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1 - (2-methylethyl) propanediylbis , 3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol mono (3- Ethyl-3-oxetanylmethyl) ether, di Triethyleneglycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycol bis (3-ethyl-3-oxetanylmethyl) Ethyl-3-oxetanylmethyl) ether, tricyclodecanediyl dimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris Ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexas Methyl-3-oxetanylmethyl) ether, dipentaerythritol pentaquis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis Lithol hexas (3- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentaquis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis Ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis 3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F Ether, oxetanyl silsesquioxane, and the like.

Potential thermal initiators for epoxy resins and oxirane compounds are catalysts for cationic polymerization and include diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium tetra (Dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (Dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- Iodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl- Tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium te (4-methylphenyl) iodonium hexafluorophosphate, bis (4-t-butylphenyl) borate, tetrakis (pentafluorophenyl) Iodonium salts such as lithium hexafluorophosphate, bis (dodecylphenyl) iodonium, tolyl cumyl iodonium hexafluorophosphate and the like;

Sulfonium salts such as triallylsulfonium hexafluoroantimonate and the like;

Phosphonium salts such as triphenylpyrenylmethylphosphonium salt and the like;

(? 6-benzene) (? 5-cyclopentadienyl) iron (II) hexafluoroantimonate;

a combination of o-nitrobenzyl silyl ether and aluminum acetylacetonate;

The combination of silsesquioxane and aluminum acetylacetonate

And the like.

The blending amount of the thermal initiator is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 20 parts by weight, and more preferably 0.1 to 10 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 preferable.

The combination of a latent thermal initiator with a solid epoxy resin and a latent thermal initiator with a mixture of a solid epoxy resin and an oxirane compound is a method in which a hardening agent particle such as a carboxylic acid, May be further contained. Thereby, the crosslinking reaction can be promoted at the time of heat fusion. By blending the hardener particles, the crosslinking reaction can proceed simultaneously with the heat fusion, and the crosslinked structure can be obtained which is continuous with each other. 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 the solid prepolymer particles to be described later.

Particles obtained by blending a solid thermal initiator with a solid epoxy resin or a mixture of a solid epoxy resin and an oxirane compound with a latent thermal initiator can be obtained by mixing the solid epoxy resin or the solid epoxy resin with the oxy Can be prepared as solid prepolymer particles by mixing a mixture with a silane compound, a latent thermal initiator, and optionally a curing agent, and subsequently pulverizing. In addition, solid prepolymer particles may be obtained by mixing particles of a solid epoxy resin particle or a mixture of the solid epoxy resin and an oxirane compound, an initiator particle and a curing agent particle.

As a system containing a solid (meth) acrylate ester and a curing agent or an initiator, a mixture of a methacrylate ester and a thermal initiator (EBECRYL 767 (manufactured by Daicel-Cotech Kabushiki Kaisha): Perhexa HC A mixture of a methacrylic acid ester and a photoinitiator (EBECRYL 740-40TP (manufactured by Daicel-Cytec Kagaku K.K.): < RTI ID = 0.0 > 1- Hydroxy-cyclohexyl-phenyl-ketone = 100: 5).

As the crosslinking agent in combination of the prepolymer having an active hydrogen group and the crosslinking agent, a carboxylic acid, a carboxylic acid anhydride, a metal chelate and the like can be exemplified. Examples of the combination of a prepolymer having an active hydrogen group and a crosslinking agent include a mixture of polyvinyl alcohol and a polycarboxylic acid or a derivative thereof, or a mixture of a polyvinyl alcohol or a derivative thereof and a metal chelate or alkoxide . Examples of the polycarboxylic acid include citric acid, butanetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, hexahydrophthalic acid, 1,3,3a, 4,5,9b-hexa (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione (acid anhydride), glycerin bisanhydrotrimellitate monoacetate Acid anhydride), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, ethylene glycol bisanhydrotrimellitate (acid anhydride), 3,3', 4,4'-diphenylsulfone tetracarboxylic acid Heptane-2,3-dicarboxylic acid, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, asparaginic acid, ethyleneglycol bisanhydrotrimellitate, methylbicyclo [2.2.1] heptane- , Pyromellitic acid, melitic acid, phosphorus-containing ester group, tetracarboxylic acid, phenylethynylphthalic acid, oxydiphthalic acid, polyacrylic acid, polymethacrylic acid and derivatives thereof. Among them, an aromatic carboxylic acid is preferred from the viewpoint of reactivity, and it is preferable to have three or more carboxyl groups in one molecule from the viewpoints of reactivity and crosslinking density. Among the exemplified polycarboxylic acids, those corresponding to the acid anhydrides can also be used. Examples of the metal chelate include titanium tetraisopropoxide, titanium tetra n-butoxide, titanium diisopropoxy bis (acetylacetonate), titanium tetraacetylacetonate, titanium lactate ammonium salt, titanium diisopropoxy bis (triethanolamine ), Zirconium chelates such as zirconium tetraacetylacetonate, zirconium dibutoxybis (ethylacetoacetate), zirconium tributoxymonostearate, and alkoxides such as zirconium tetra n-propoxide, zirconium tetra-n-propoxide, And an aluminum chelate such as a wide seed. In addition, the combination of the prepolymer having an active hydrogen group and the crosslinking agent may optionally contain the above-mentioned curing agent and a thermal initiator. The particles in combination with the prepolymer having an active hydrogen group and the crosslinking agent are prepared by mixing the prepolymer having an active hydrogen group, the crosslinking agent, and optionally the curing agent and the initiator, which are present, , Casting it thinly, and drying the solvent at room temperature, followed by cooling and grinding, and can be used as an organic particle type binder to be crosslinked at the time of heat fusion.

An electrode cell or a separator coating film composition containing organic particles bridging at the time of thermal fusion bonding as a binder can be obtained by heating and evaporating a solvent after coating the composition so that the composition is fused with a battery electrode or a separator, The crosslinking can be carried out by irradiation of the energy ray. Thereby, a protective film excellent in mechanical strength and high in heat resistance can be obtained.

[Liquid binding agent]

A liquid binder may be used as the binder of the present invention.

As the liquid binder, various known binder agents may be used. As the liquid binder, specifically, a mixture of a liquid prepolymer and an initiator; A solid polymer material dissolved in a solvent; Becoming a solid inorganic substance by the sol-gel reaction; And water glass.

(A mixture of liquid prepolymer and initiator)

As the mixture of the liquid prepolymer and the initiator, a combination of a photo radical initiator or a heat radical generator and a compound having a (meth) acryl group, an ally group, a vinyl group, a maleimide group, or the like; A combination of a photo cationic initiator or a thermal cationic initiator and a compound having an oxirane ring, a vinyl ether, a cyclic acetal, etc., such as an epoxy group, an oxetane ring and the like; And a combination of a photoanion initiator and a compound having an epoxy group and / or a cyanoacrylate group. Further, the (meth) acrylic group includes an acryl group and a methacryl group.

A combination of a photo radical initiator or a thermal radical generator with a compound having a (meth) acryl group, an allyl group, a vinyl group, a maleimide group and the like will be described.

As photo radical initiators there may be mentioned 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2- 2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl Propane) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methyl (2-hydroxyphenyl) Thio) phenyl] -2-morpholinopropane-1; Benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal,? -Allylbenzoin and? -Allylbenzoin aryl ether; Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl- Benzophenone type such as phenone; Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4- Thioxanthone systems such as santone and 2,4-diisopropylthioxanthone; 1-phenyl-1,2-propanedione-2 (O-ethoxycarbonyl) oxime, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, 9,10- Benzoquinone, camphorquinone, dibenzosuberone, 2-ethyl anthraquinone, 4 ', 4 "-diethylisophthalophenone, 3,3', 4,4'-tetra (t- butylperoxycarbonyl) benzophenone, 1- [4- (3-mercaptopropylthio) phenyl] -2-methyl-2-morpholin- Methyl-2-morpholin-4-yl-propan-1-one, 1- (4- {2- [2- Propan-1-one, 1- [3- (mercaptopropylthio) phenyl] -2-dimethylamino-2-benzyl- Methoxy-propyl) -2-methyl-isobutyramide, 1- [4- (3-mercaptopropyl) (Η5-2,4-cyclopentadien-1-yl) bis [2,6-difluoro-3- (1H-pyrrol- Yl) phenyl] tita , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbaldehyde, 3-yl] -, 1- (O-acetyloxime), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 1,3-bis (p- dimethylaminobenzylidene) Among the photo radical initiators, for the photoinitiator of the intermolecular hydrogen drawing type such as benzophenone, Michler's ketone, dibenzosuberone, 2-ethyl anthraquinone, camphorquinone, isobutyl thioxanthone, As the electron donor, aliphatic amines having an active hydrogen and aromatic amines can be mentioned. As the aliphatic amines, concretely, triethanolamine, methyldiethanolamine, triisopropanol Specific examples of the aromatic amine include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2- There may be mentioned dimethylamino benzoate and 4-dimethylamino benzoate.

As thermal radical generators, azides such as 4-azidaniline hydrochloride and 4,4'-dithiobis (1-azidobenzene); Disulfide such as 4,4'-diethyl-1,2-dithiolane, tetramethylthiuram disulfide and tetraethylthiuram disulfide; Octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m- Diacyl peroxide such as seed; Di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and per- (2-ethoxyethyl) peroxydicarbonate. Dicarbonate; t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxy octanoate, octylperoxy octanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t Peroxy esters such as butyl peroxyneododecanoate, octylperoxy neododecanoate, t-butyl peroxy laurate and t-butyl peroxy benzoate; Di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5- Dialkyl peroxides such as di (t-butyl) hexyne-3; Bis (t-butylperoxy) -3,3,5-trimethylcyclohexylcarbodiimide, 1,1-bis (t-butylperoxy) Peroxyketals such as hexane and n-butyl-4, 4-bis (t-butylperoxy) valerate; Ketone peroxides such as methyl ethyl ketone peroxide; peroxides such as p-menthydroperoxide and cumene hydroperoxide; Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (Methylpropionitrile), 2,2'-azobis (2-methylbutylnitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) Methylethyl) azo] formamide and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride Azobis [N- (4-hydroxyphenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2-methyl- Propionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'- ) Dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'- 2-yl] propane] dihydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin- Azoamides such as chloride and 2,2'-azobis [2- (2-imidazolin-2-yl) propane]; Alkyl azo compounds such as 2,2'-azobis (2,4,4-trimethylpentane) and 2,2'-azobis (2-methylpropane); And other dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (4-cyanovaleric acid) and 2,2'-azobis [2- Methyl) propionate]; Bipyridine; Initiators with transition metals (e.g., copper (I) chloride and copper (II) chloride); And halogen compounds such as methyl 2-bromopropionate, ethyl 2-bromopropionate and ethyl 2-bromoisobutyrate.

A decomposition accelerator may be used in combination with the thermal radical generator described above. As the decomposition accelerator, thiourea derivatives, organometallic complexes, amine compounds, phosphate compounds, toluidine derivatives, and aniline derivatives can be exemplified.

Examples of the thiourea derivative include N, N'-dimethyl thiourea, tetramethyl thiourea, N, N'-diethyl thiourea, N, N'- dibutyl thiourea, benzoyl thiourea, acetyl thiourea, , N, N'-diethylene thiourea, N, N'-diphenyl thiourea and N, N'-dilauryl thiourea, preferably tetramethyl thiourea or benzoyl thiourea. Examples of the organometallic complexes include cobalt naphthenate, vanadium naphthenate, copper naphthenate, iron naphthenate, manganese naphthenate, cobalt stearate, vanadium stearate, copper stearate, iron stearate and manganese stearate . As the amine compound, an alkyl group or a primary to tertiary alkylamine or an alkylene diamine represented by an integer of 1 to 18 in the alkylene group, diethanolamine, triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, tris Diazabicyclo (5,4,0) undecene-7, 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo Cyclo (4,3,0) -nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7,2-methylimidazole and 2- 4-methylimidazole, and the like. As the phosphate compound, methacrylate, dimethacrylate, monoalkyl acid phosphate, dialkyl phosphate, trialkyl phosphate, dialkyl phosphite and trialkyl phosphite can be exemplified. As the toluidine derivative, N, N-dimethyl-p-toluidine and N, N-diethyl-p-toluidine can be exemplified. As the aniline derivative, N, N-dimethylaniline and N, N-diethylaniline can be exemplified.

The compound having a (meth) acryl group, an allyl group, a vinyl group, or a maleimide group is a liquid prepolymer. (Meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, (Meth) acrylate, N (meth) acryloxy-N-carboxypiperidine, N (meth) acryloyloxyethylcarboxypiperidine, - (meth) Acrylate, (meth) acryloxyethyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, (Meth) acrylate, butanediol mono (meth) acrylate, butoxymethyl (meth) acrylate, butoxymethyl (meth) acrylate, (Meth) acrylate, ethylene glycol (meth) acrylate, ECH modified butyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, caprolactone (Meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, alicyclic modified neopentyl glycol (meth) acrylate, 2,3-dibromopropyl (Meth) acrylate (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, caprolactone modified 2-hydroxyethyl (Meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, (Meth) acryloxypropyltrimethoxy (Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxyethyleneglycol (Meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, morpholine (meth) acrylate, nonylphenoxypolyethylene glycol (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, (Meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, EO-modified phenoxyphosphoric acid (meth) acrylate, phenoxy (Meth) acrylate, EO modified phosphoric acid (meth) acrylate, EO modified phosphoric acid (meth) acrylate, EO modified phthalic acid (meth) acrylate, EO modified phthalic acid (Meth) acrylate, polypropylene glycol 800 (meth) acrylate, polypropylene glycol 800 (meth) acrylate, polyethylene glycol 400 (meth) (Meth) acrylate, stearyl (meth) acrylate, EO modified succinic acid (meth) acrylate, sodium sulfonate ethoxy (meth) acrylate, tetrafluoropropyl (meth) acrylate, tetra (Meth) EO-modified bisphenol A di (meth) acrylate, acrylate, caprolactone modified te (Meth) acrylate isocyanurate, bis (acryloxy neopentyl glycol) adipate (meth) acrylate, isophthalate (meth) acrylate, , EO-modified bisphenol A di (meth) acrylate, EO-modified bisphenol S di (meth) acrylate, bisphenol F di (meth) acrylate, EO- Acrylate, 1,3-butylene di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, diethyleneglycol di (meth) acrylate, ECH (epichlorohydrin) Glycol di (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, silsesquioxane (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) (Meth) acrylate, glycerol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, (Meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol diacrylate, caprolactone-modified hydroxypivalic acid Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) (Meth) acrylate, EO modified di (meth) acrylate, EO modified phosphoric tri (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, tetraethylene glycol di , Tetrabromobisphenol A di (meth) acrylate, triethylene glycol (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone modified tris (acryloxyethyl) isocyanurate, acrylonitrile, (Methacryloxyethyl) isocyanurate, zinc di (meth) acrylate, isocyanatoethyl methacrylate (Meth) acrylate, 2- (methacryloyloxy) ethyl trimethylammonium bis (trifluoromethylsulfonyl) amine anion, and the like .

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, allysine, allyl disulfide, allyl isothiocyanate and the like. Examples of the compound having a maleimide group include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 4,4'-diphenylmethane maleimide, m-phenylene maleimide, bisphenol A diphenylether bismaleimide, Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide and 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, and the like. Among these compounds, compounds having a (meth) acryl group and a vinyl group are preferable. These compounds can be cured by electron beam even when the photo radical initiator is not present.

The photo radical initiator and the thermal radical generator may be used in combination of two or more. These photo radical initiators and thermal radical generators are preferably added in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the compound having a (meth) acrylic group, an allyl group, a vinyl group or a maleimide group, which is a liquid prepolymer, Preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight. When the photo radical initiator and the thermal radical generator are used together, the content is the total content of the photo radical initiator and the heat radical generator. The content of the electron donor is preferably 10 to 500 parts by weight based on 100 parts by weight of the photo-radical initiator. The content of the decomposition promoting agent is preferably 1 to 500 parts by weight based on 100 parts by weight of the thermal radical generator.

A combination of a photo cationic initiator, a thermal cationic initiator or a photoanion initiator, and a compound having an oxirane ring, vinyl ether, cyclic acetal, etc., such as an epoxy group, an oxetane ring, etc. will be described.

As the photo cationic initiator, a compound other than the combination of silsesquioxane and aluminum acetylacetonate in the latent thermal initiator for the epoxy resin or oxirane compound described above may be mentioned.

A sensitizer may be used in combination with the photo cationic initiator. Examples of such sensitizers include 9,10-butoxyanthracene, acridine orange, acridine yellow, benzoflavin, cetoflavin T, perylene, pyrene, anthracene, phenothiazine, 1,2- , Coronene, thioxanthone, fluorenone, benzophenone, and anthraquinone.

As the thermal cationic initiator, there may be mentioned a latent thermal initiator for the above-mentioned epoxy resin or oxirane compound.

Examples of the photoanion initiator include a 2-nitrobenzyl carbamate compound in which an isocyanate having two or more functional groups is blocked with an o-nitrobenzyl alcohol compound, and a combination of a quinone diazide sulfonic acid ester compound and an N-alkyl aziridine compound have. The photoanion initiator is used for polymerizing a compound having an epoxy group, a compound having a cyanoacrylate group.

The compound having an epoxy group, cyanoacrylate group, episulfide, oxetane ring, spiroorthocarbonate, or vinyl ether group is a prepolymer in liquid state and is a prepolymer in the form of a liquid, which is crosslinked with a photo cationic initiator, a thermal cationic initiator and / A compound having a reactive substituent.

Examples of the compound having an epoxy group include (3 ', 4'-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate, 4-vinylcyclohexene oxide, 1-methyl- -7-oxabicyclo [4.1.0] heptane, epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) -glycone-caprolactone, epoxidized polybutadiene, 2,2- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, 1,2-epoxy- Cyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, 3,4-epoxycyclohexylmethyl methacrylate,? -Olefin epoxide , Epoxides of styrene-butadiene block copolymers, epoxides of styrene-butadiene block copolymers, bisphenol A type epoxy resins, bisphenol AD type epoxy resins, bisphenol F type epoxides Cresol novolak type epoxy resin,? -Naphthol novolak type epoxy resin, bisphenol A novolak type epoxy resin, tetrabromo bisphenol A type epoxy resin, tetraglycidyl ether type epoxy resin, Bisphenol S epoxy resin, hydrogen siloxane type epoxy resin, isoprene type epoxy resin, isobornyl skeleton, bisphenol S type epoxy resin, hydrogenated dicyclopentadiene, A bisphenol A type epoxy resin, a propylene oxide-added bisphenol A type epoxy resin, a resorcinol type epoxy resin, an epoxy-modified silicone, and an epoxy-modified silsesquioxane.

Compounds having a cyanoacrylate group can be exemplified by methyl cyanoacrylate and ethyl cyanoacrylate.

The compound having episulfide is a compound in which the oxygen atom of the above-mentioned epoxy group-containing compound is substituted with a sulfur atom, and examples thereof include ethylene sulfide, propylene sulfide, 1-butene sulfide, 2-butene sulfide, But are not limited to, cyclopentene sulfide, cyclopentene sulfide, cyclopentene sulfide, cyclohexene sulfide, styrene sulfide, vinylcyclohexene sulfide, 3-phenylpropylene sulfide, 3,3-trifluoropropylene sulfide, 3-naphthylpropylene sulfide, 3-phenoxypropylene sulfide, 3-naphthoxypropylene sulfide, butadiene monosulfide, and 3 -Trimethylsilyloxypropylene sulfide, and the like.

Examples of the compound having an oxetane ring include the oxetane compounds described above.

Examples of the compound having spiroorthocarbonate include spiroglycol diallyl ether and bicycloorthoester.

Examples of the compound 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, 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, cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, trimethylpropane trivinyl ether and pentaerythritol tetravinyl ether And the like.

The compound having an epoxy group, cyanoacrylate group, episulfide, oxetane ring, spiroorthocarbonate, or vinyl ether group is preferably a compound having an oxetane ring.

The photo cationic initiator, the thermal cationic initiator and the photoanionic initiator may be used in combination of two or more. These photo cationic initiators, thermal cationic initiators and photoanion initiators are used in amounts of 100 parts by weight per 100 parts by weight of a compound having an epoxy group, cyanoacrylate group, episulfide, oxetane ring, spiroorthocarbonate or vinyl ether group, It is preferably added in an amount of 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. When the photo cationic initiator, the thermal cationic initiator and the photoanionic initiator are used together, the content is the total content of the photo cationic initiator, the thermal cationic initiator, and the photoanion initiator. The content of the sensitizer is preferably 5 to 500 parts by weight based on 100 parts by weight of the photo cationic initiator.

(A liquid binder in which a solid polymer material is dissolved in a solvent)

As a liquid binder in which a solid polymer material is dissolved in a solvent, the above polymer particles are dissolved in a solvent and suspended in a solvent. The solvent may be appropriately selected from a solvent capable of dissolving the solid polymer, or a mixture of two or more solvents may be used.

As the solid polymeric substance, there can be used a completely saponified polyvinyl alcohol (Kuraray Pure PVA-124 manufactured by Kabushiki Kaisha Co., Ltd., JC-25 manufactured by Nihon Sakai Poval Kagaku K.K.), partially saponified polyvinyl alcohol Denatured polyvinyl alcohol (Kuraray K Polymer KL-118, Kuraray C Polymer CM-318 (trade name, manufactured by Kasei Kogyo Co., Ltd.) D-polymer DF-20, anion-modified PVA AF-17, alkyl modified PVA ZF-15, carboxymethylcellulose (trade name) manufactured by Nihon Sakeru Co., (Manufactured by Daicel Chemical Industries, Ltd., H-CMC, DN-100L, 1120, 2200, manufactured by Nippon Kasei Kikai Kabushiki Kaisha; MAC200HC, etc.), hydroxyethylcellulose (manufactured by Daicel Kogyo Kabushiki Kaisha; ), Polyacrylamide (MT Aquapoly Epoxy resin (EX-614 manufactured by Nagase ChemteX Kabushiki Kaisha), polypropylene (manufactured by Nippon Kayaku Kogyo Co., Ltd., (Manufactured by Nippon Shokai Kabushiki Kaisha; Epomin P-1000), polyacrylic acid ester (MT manufactured by Aqua Polymer Kabushiki Kaisha, trade name: Akkoprok C- 502, etc.), and saccharides and derivatives thereof (manufactured by Wako Pure Chemical Industries, Ltd., chitosan 5, manufactured by Nitten Chemical Industries, Ltd., esterified starch emulsification, manufactured by Glyco Kabushiki Kaisha; cluster dextrin, polystyrenesulfonic acid Manufactured by KABUSHIKI KAISHA; POLYNAS PS-100, etc.) can be used in a state dissolved in water.

(Polyol F-361, F-417, S-65, SH-502, manufactured by Showa Denko K.K.) and an ethylene-vinyl acetate copolymer emulsion (Kuraray Co., Ltd., Emulsions such as Panflex OM-4000NT, OM-4200NT, OM-28NT and OM-5010NT can be used in a suspended state in water. As a solid polymer material, polyvinylidene fluoride (Kureha KF Polymer # 1120, Kureha KF Polymer # 9130, manufactured by Kureha Kabushiki Kaisha), modified polyvinyl alcohol (manufactured by Shinetsu Chemical Industry Co., CR-V) and modified pullulan (manufactured by Shin-Etsu Chemical Co., Ltd .; cyanorein CR-S) can be used in a state of being dissolved in N-methylpyrrolidone.

As the liquid binder in which the solid polymeric material is dissolved in a solvent, a binder in which a water-soluble polymer is dissolved in water and a binder in which an emulsion is suspended in water are preferable.

The liquid binder in which the solid polymeric material is dissolved in the solvent can be solidified by removing the solvent by heating and / or reducing the pressure. Such a binder may impregnate an electrolytic solution in a coating film to form a gel electrolyte layer, thereby enhancing ion conductivity of the coating film.

(A liquid binder that becomes a solid inorganic material by the sol-gel reaction)

Examples of the liquid binder which becomes a solid inorganic material by the sol-gel reaction include triethoxysilane, trimethoxysilane, aluminum isopropoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium butoxide dimer, Titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethylacetoacetate), titanium (Triethanolamine), titanium lactate, polyhydroxy titanium stearate, zirconium tetranormalpropoxide, zirconium tetra-n-butoxide, zirconium tetraacetylacetonate, zirconium tributoximo monoacetylacetonate, zirconium Monobutoxyacetylacetonate bis (ethyl < RTI ID = 0.0 > Sat acetate), zirconium dibutoxy bis (ethylacetoacetate), and the like can be given zirconium tetra acetylacetonate, zirconium tree butoxy monostearate, various coupling agents. In addition, they may be added with a catalyst for sol-gel reaction. As the catalyst for the sol-gel reaction, there is no particular limitation as long as it is a catalyst for a reaction of hydrolyzing and polycondensation of an inorganic component. As such a catalyst, an acid such as hydrochloric acid; Alkalis such as sodium hydroxide; Amine; Or organotin compounds such as dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, and octyltin tin; Organic titanate compounds such as isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, and tetraalkyl titanate; Organic zirconium compounds such as tetrabutyl zirconate, tetrakis (acetylacetonate) zirconium, tetraisobutyl zirconate, butoxytris (acetylacetonate) zirconium, and zirconium naphthenate; Organoaluminum compounds such as tris (ethyl acetoacetate) aluminum and tris (acetylacetonate) aluminum; And organic metal catalysts such as zinc naphthenate, cobalt naphthenate, cobalt octylate, and the like. Among them, a dibutyltin compound (SCAT-24, manufactured by Sankyo Yuki Kagaku Co., Ltd.) is specifically exemplified as a commercially available product. These compounds may be used alone or in combination of two or more.

When the cell electrode or the separator coating film composition contains a surfactant described later, the surfactant may form micelles. In this case, the solid inorganic material can be made into an inorganic porous material using the micelle as a template. As the surfactant for forming the inorganic porous body, a quaternary ammonium salt is preferable, and butyl trimethyl ammonium chloride, hexyl trimethyl ammonium chloride, dibutyl dimethyl ammonium chloride, and dihexyl dimethyl ammonium chloride are specifically exemplified.

(water glass)

As a liquid binder in which a solid inorganic material can be obtained, besides a liquid binder which becomes a solid inorganic material by the sol-gel reaction, water glass can be exemplified. Specific examples thereof include water glass No. 1, water glass No. 2, water glass No. 3, sodium metasilicate, two kinds of sodium metasilicate, potassium silicate, potassium silicate and lithium silicate of JIS standard table K1408 .

The degree of the elastic deforming property of the binder and the degree of the plastic deformation property can be expressed by the elastic modulus (h3) and the plastic strain (h6) as in the case of the viscoelastic particles. In the present invention, h3 of the binder is preferably 0.95 or less, more preferably 0.9 or less. The h3 of the binder is not particularly limited, but may be 0.5 or more, and preferably 0.6 or more. In the present invention, h6 of the binder is preferably 0.90 or less, more preferably 0.85 or less. Further, h6 is not particularly limited, but is preferably 0.5 or more, more preferably 0.6 or more. When h3 and h6 of the binder are below the upper limit, the stress relaxation ability is excellent, and the adhesive strength when the base material is bent is excellent. If h3 and h6 of the binder are above the lower limit value, the mechanical strength and heat resistance are further improved.

In the present invention, it is preferable that the viscoelastic particles have a viscoelasticity lower than that of the binder. In the present invention, "viscoelastic particles have a viscoelasticity lower than the viscoelasticity of the binder" means that h3 and h6 of the viscoelastic particles are smaller than h3 and h6 of the binder. When the modulus of viscoelasticity of the viscoelastic particles is lower than the modulus of viscoelasticity of the binder, the strength of the binder at the time of heat and the viscosity of the viscoelastic particles of the curl can be relaxed. As a result, a coating film having higher heat resistance and further suppressing the generation of curl can be obtained. The difference (h3 = h3 _binder- h3 _{viscoelastic particle} ) between h3 of the viscoelastic particles and the binder is preferably 0.01 to 0.3, more preferably 0.05 to 0.2. When the difference between h3 of the viscoelastic particles and the binder is not less than 0.01, improvement of heat resistance and suppression of curling can be efficiently achieved. When the difference is not more than 0.3, heat resistance is further improved and generation of curl is further suppressed. The difference (h6 = h6 _binder- h6 _{viscoelastic particle} ) between h6 of the viscoelastic particles and the binder is preferably 0.01 to 0.3, more preferably 0.05 to 0.2. When the difference between the viscoelastic particles and the h6 of the binder is not less than 0.01, the improvement of the heat resistance and the suppression of the curling can be efficiently achieved. If the difference is not more than 0.3, the heat resistance is further improved. Further, with respect to suppressing the generation of curl,? H6 representing plastic deformation amount is more dominant.

H3 and h6 of the binder can be measured similarly to those of the viscoelastic particles. That is, after solidifying into a film having a thickness of 50 mu m under the condition of using a binder, the binder particles can be obtained by pulverization using a mill (IKA; M20 universal mill) after cooling with liquid nitrogen. The binder particles can be used as the particles to be tested in the step (1) of [measurement method 1] and [measurement method 2]. Thus, h3 and h6 of the binder can be obtained.

It is preferable that the content of the binder does not fill the voids generated between the particles and is a sufficient amount in a practically sufficient amount. In the composition of the present invention, the content of the binder is preferably from 0.01 to 49 parts by weight, more preferably from 0.5 to 30 parts by weight, and still more preferably from 1 to 20 parts by weight, based on 100 parts by weight of the viscoelastic particles.

[menstruum]

(3) The solvent of the present invention will be explained. The battery electrode or separator coating film composition of the present invention has a solvent for generating pores accompanying the vaporization and also for adjusting the flowability. The evaporation of the solvent can be performed by heat drying, vacuum drying, freeze drying, or a combination thereof. In the case of a resin in which the binder is cured with light or an electron beam, the resin can be lyophilized and then cured with light or an electron beam to make a porous structure using the conformational shape. In addition, an electrolyte solvent used in the battery may be added in advance to help impregnate the electrolyte. Examples of the solvent include hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, amylbenzene, Chlorobenzene, chlorobenzene, bromobenzene, fluorodichloromethane, dichlorodifluoromethane, difluorochloroethane, etc.), alcohols (such as methylene chloride, chloroform, N-hexanol, n-heptanol, 2-octanol, n-dodecanol, nonanol, cyclohexanol, glycidol, and the like) , Ethers, acetals (ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, diisobutyl ether, methyl phenyl ether, ethyl benzyl ether, furan, furfural, 2-methylfuran, cineol, , Ketones (acetone, methyl ethyl ketone, methyl ether (such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, acetic acid, and the like) such as methyl acetate, ethyl acetate, n-propyl ketone, methyl n-amyl ketone, diisobutyl ketone, Propyl carbonate, diethyl carbonate, ethylenecarbonate, vinylene carbonate, etc.), polyhydric alcohols (such as methylene chloride, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, (Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, methoxymethoxy ethanol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, propylene glycol, Propylene glycol monoethyl ether, etc.), fatty acids and phenols (formic acid, acetic acid, Cresol, o-cresol, xylenol, etc.), nitrogen compounds (nitromethane, nitroethane, 1-nitropropane, nitrobenzene, monomethylamine, dimethyl The organic solvent is selected from the group consisting of amine, trimethylamine, monoethylamine, diamylamine, aniline, monomethylaniline, o-toluidine, o-chloroaniline, dicyclohexylamine, dicyclohexylamine, monoethanolamine, Phosphorus, other compounds (carbon disulfide, dimethylsulfoxide, 4,4-diethyl (meth) acrylate, Organic solvents such as liquid ammonia, silicone oil (such as methylene chloride, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, Etc.), liquids such as water, etc. .

In the battery electrode or the separator coating film composition, it is possible to add a solvent at an arbitrary ratio for adjusting the viscosity in accordance with the coating apparatus. The cell electrode or separator coating film composition preferably has a viscosity of 1 to 10,000 mPa · s, more preferably 2 to 5000 mPa · s, further preferably 3 to 1,000 mPa · s, from the viewpoint of coatability, The viscosity is preferably in the range of 1 < E < 3 when the viscosity at the speed of 20 sec ^-1 is C and the viscosity at the shearing speed of 200 sec ^-1 is D and C / D = E. The solvent type and content for achieving such a viscosity can be appropriately determined. In the present invention, the viscosity is a value obtained by a cone plate type rotational viscometer.

The battery electrode or the separator coating film composition may contain other particles, a core shell type foaming agent, a salt, an ionic liquid, a coupling agent, a stabilizer, an antiseptic and a surfactant to the extent that the object of the present invention is not impaired.

[Other Particles]

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. Other particles do not contain particles which are irreversibly plastically deformed against stress and particles having reversibly elastic deformability (i.e., viscoelastic particles).

Specific examples of the organic filler include polymer particles such as acrylic resin, epoxy resin, and polyimide that are three-dimensionally crosslinked and do not substantially undergo plastic deformation, particles of cellulose, silicon particles, or polyolefin particles, And the like. The organic fillers may be used alone or in combination of two or more.

Specific examples of the carbon-based filler include graphite, acetylene black and carbon nanotubes. The carbon-based filler may be used singly or in combination of two or more. The carbon-based filler is a particle that can be added to such an extent that the insulation property is not impaired.

Specific examples of the inorganic filler include powders of metal oxides such as alumina, silica, zirconia, beryllium, magnesium oxide, titania and iron oxide; Clay minerals such as colloidal silica, titania sol, alumina sol and the like, talc, kaolinite and smectite; Carbides 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; Hydroxides such as aluminum hydroxide, magnesium hydroxide and iron hydroxide; Barium titanate, strontium carbonate, magnesium silicate, lithium silicate, sodium silicate, potassium silicate and glass. Examples of the inorganic filler that can be added to such an extent that the insulation property is not impaired include lithium cobalt oxide and olivine type lithium iron phosphate. The inorganic fillers may be used singly or in combination of two or more.

It is preferable that the inorganic filler is dried at a high temperature of about 200 캜 for about 1 hour in order to activate active hydrogen groups on the surface. By activating the active hydrogen group, the adhesion to the organic particles is improved, the mechanical strength and the heat resistance are improved, and the ionic conductivity in the electrolyte is improved by stabilizing the ions in the electrolyte.

The inorganic filler may be used in the form of a powder, or may be dispersed in an organic solvent such as an aqueous dispersion colloid type such as silica sol or alumina sol, or an organosol. These may be contained in the heat-welded organic particles or in a state of being in close contact with the surface of the heat-welded organic particles, or may be added independently of the heat-welded organic particles.

The size of the other particles is preferably in the range of 0.001 to 100 mu m, more preferably in the range of 0.005 to 10 mu m. It is also preferable to use porous bodies of other particles from the viewpoint of increasing the porosity. Specifically, inorganic fillers such as silica gel, porous alumina and various zeolites may be used as other particles.

The surface of the other particles can be modified with various coupling agents. As the coupling agent, there can be mentioned a silane coupling agent and a titanium coupling agent.

As the silane-based coupling agent, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane as the fluorine-based silane coupling agent and (2-bromo- -Methyl) propionyloxypropyltriethoxysilane, an oxetane-modified silane coupling agent, a coupling agent (trade name: TESOX) manufactured by Toagosei Co., Ltd., or a vinyltrimethoxysilane, vinyltriethoxysilane, Propyl trimethoxysilane,? -Aminopropyltriethoxysilane, N- (? -Aminoethyl) -? - aminopropyltrimethoxysilane, N- (? -Aminoethyl) -? - aminopropylmethyldimethoxysilane , and? -glycidoxypropyltrimethoxysilane (commercially available as KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)),? -glycidoxypropylmethyldimethoxysilane,? -methacryloxypropyl Trimethoxysilane,? -Methacryloxypropylmethyldimethoxysilane,? -Mercapto Silane coupling agents such as propyltrimethoxysilane, cyanohydrin silyl ether and the like.

Examples of the titanium-based coupling agent include triethanolamine titanate, titanium acetylacetonate, titanium ethylacetoacetate, titanium lactate, titanium lactate ammonium salt, tetrastearyl titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N- Aminoethyl-aminoethyl) titanate, dicumylphenyloxyacetate titanate, isopropyltrioctanol titanate, isopropyldimethacrylisostearoyl titanate, titanium lactate ethyl ester, octylene glycol titanate, Isopropyl isostearoyl titanate, isopropyl triisostearoyl titanate, triisostearoyl isopropyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, tetra (2-ethylhexyl) titanate, butyl titanate dimer, isopropyl iso Stearoyl diacrylate titanate, isopropyl tri (dioctylphosphate (Dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2- Bis (di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, tetra- Propyl titanate, tetra-n-butyl titanate, diisostearoyl ethylene titanate, and the like.

As the coupling agent, a titanium coupling agent and a silane coupling agent such as vinyltrimethoxysilane, vinyltriethoxysilane,? -Chloropropyltrimethoxysilane,? -Aminopropyltriethoxysilane, N- (? -Aminoethyl) -γ- Aminopropyltrimethoxysilane, N- (? -Aminoethyl) -? - aminopropylmethyldimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Meta Methacryloxypropylmethyldimethoxysilane, gamma -mercaptopropyltrimethoxysilane, and cyanohydrinylsilyl ether are preferable. [0031] The term &quot; alkoxysilyloxyalkylsilane &quot; The silane-based coupling agent and the titanium-based coupling agent may be used alone or in combination of two or more.

Such a coupling agent can interact with the cell electrode surface or the separator surface to improve the adhesion. In addition, by coating the surfaces of the other particles with these coupling agents, gaps can be created between the other particles by the effect of repelling by the coupling agent molecules, and ions can be conducted therebetween to improve ion conductivity. Further, since the surface of the inorganic filler, the silicon particles, the polyolefin particles and the like is coated with a coupling agent, these particles can be hydrophobized, so that the bubble resistance can be further improved. In addition, since the amount of surface adsorbed water can be reduced by substituting the active hydrogen on the surface of the other particles with the silane coupling agent, the amount of water causing the characteristic deterioration in the non-aqueous battery can be reduced. The other particles are preferably particles whose surfaces are coated with a polymer chain formed by graft polymerization. Examples of the polymer chain include those described above for the viscoelastic particles of the present invention.

The same effect can be obtained by blending a dendrimer. It is preferable to introduce a structure having a highly dielectric constant cyano group or a structure having a strong interaction with a ion such as a polyoxyethylene group. The titanium-based coupling agent can more suitably adapt to inorganic particles having an isoelectric point pH of 7 or more, and the silane coupling agent can more suitably adapt to inorganic particles having an isoelectric point pH of less than 7. The pH of the isoelectric point of the inorganic particles can be measured by the method measured by the method specified in JIS R1638 &quot; Method of measuring the isoelectric point of fine ceramics powder &quot;, and the silica (pH about 1.8), kaolin (PH of about 6.2), tin oxide (pH of about 6.9), boehmite (pH of about 7.7), gamma -alumina (pH about 7.9),? -alumina (pH about 9.1), Berylia (pH about 10.1), iron hydroxide; Fe (OH) ₂ (pH of about 12.0), manganese hydroxide (pH of about 12.0), and magnesium hydroxide (pH of about 12.4).

The battery electrode or separator coating film composition of the present invention can be added to the above other particles in a range that does not deteriorate continuity of porosity or voids, and preferably 0 to 90 parts by weight based on 100 parts by weight of viscoelastic particles And more preferably from 0 to 50 parts by weight. In the composition of the present invention, 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 preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the visco- More preferable.

Two or more kinds of other particles can be used. The combination of the inorganic filler having a large difference in pH of the isoelectric point is preferable because acid base interaction is apt to occur and the active hydrogen of one side is mixed with the active hydrogen to improve the activity of the other active hydrogen. Specifically, a combination of silica having a small pH at an isoelectric point and? -Alumina,? -Alumina, beryllium, iron hydroxide, manganese hydroxide and magnesium hydroxide, which are inorganic fillers having a large isoelectric point pH, Or a combination of silica and magnesium hydroxide is more preferable. In the case of a Li-ion battery, the amount of silica having a low pH at the isoelectric point is preferably in the range of 0.1 to 100 wt%, more preferably in the range of 1 to 10 wt% with respect to the inorganic filler having a high pH of the isoelectric point.

[Core-shell type foaming agent]

The cell electrode or separator coating film composition of the present invention may contain a core-shell type foaming agent. As such a blowing agent, EXPANCEL (manufactured by Nippon Pylon Co., Ltd.) or the like can be used. Since the shell is an organic material, the long-term reliability of the electrolyte is insufficient. Therefore, it is also possible to use one obtained by further coating the core-shell type foaming agent with an inorganic substance. As such inorganic substances, metal oxides such as alumina, silica, zirconia, beryllium, 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 such as mullite; Hydroxides such as aluminum hydroxide, magnesium hydroxide, and iron hydroxide; and barium titanate. These inorganic substances can be coated on the surface of the viscoelastic particles by sol-gel reaction or heating. Further, before the inorganic material is coated, the surface may be subjected to a surface treatment with a chromate treatment, a plasma treatment, a water-soluble polymer such as PVA, carboxymethyl cellulose and starch, and a polycarboxylic acid, have.

By using a core shell type foaming agent in which a shell that softens at a constant temperature and a core that includes a material that expands in volume by evaporation by heating or the like is used to expand the interelectrode distance by foaming the foaming agent when the battery is subjected to thermal runaway So that the shutdown function can be performed. In addition, the shell portion greatly expands, so that the distance between the electrodes can be extended, thereby preventing a short circuit or the like. In addition, even if the heat generation is relaxed, since the expanded shell portion maintains its shape, it is possible to prevent the electrode from becoming short again and short-circuiting again. In addition, by covering the core-shell type foaming agent with an inorganic substance, the influence of electrolysis at the time of charging and discharging can be reduced, and the active hydrogen at the surface of the inorganic material becomes a counter ion at ion conduction, thereby effectively increasing ion conductivity .

The battery electrode or separator coating film composition of the present invention preferably contains 1 to 99 parts by weight, more preferably 10 to 98 parts by weight, of the core-shell type foaming agent per 100 parts by weight of the total of the viscoelastic particles and the binder , And more preferably 20 to 97 parts by weight.

[salt]

The battery electrode or separator protective film composition of the present invention can be mixed with a salt as various ion sources. Thereby, ion conductivity can be improved. An electrolyte of the battery to be used may be added. In the case of a lithium ion battery, the electrolyte includes lithium hydroxide, lithium silicate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (pentafluoroethanesulfonyl ) Imide and lithium trifluoromethanesulfonate, and in the case of a sodium ion battery, sodium hydroxide, sodium perchlorate and the like can be exemplified. In the case of a calcium ion battery, examples of the electrolyte include calcium hydroxide and calcium perchlorate. In the case of a magnesium ion battery, magnesium perchlorate and the like can be exemplified as an electrolyte. In the case of the electric double-layer capacitor, 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, more preferably 0.5 to 200 parts by weight, of the salt relative to 100 parts by weight of the total amount of the viscoelastic particles and the binder, By weight to 100 parts by weight. The salt may be added as a powder, as a porous material, or dissolved in a blending component.

[Liquid Having Ionic Property]

The battery electrode or separator coating film composition of the present invention may contain a liquid having an ionic property. The ionic liquid may be a solution in which the salt is dissolved in a solvent or an ionic liquid. As a solution in which a salt is dissolved in a solvent, a solution in which a salt such as lithium hexafluorophosphate or tetraethyl ammonium borofluoride is dissolved in a solvent such as dimethyl carbonate can be exemplified.

Examples of ionic liquids include 1,3-dimethylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide, 1-ethyl-3-methylimidazolium Imidazolium salt derivatives such as bromide; Pyridinium salt derivatives such as 3-methyl-1-propylpyridinium bis (trifluoromethylsulfonyl) imide and 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide; Alkylammonium derivatives such as tetrabutylammonium heptadecafluorooctanesulfonate and tetraphenylammonium methanesulfonate; Phosphonium salt derivatives such as tetrabutylphosphonium methanesulfonate; A composite conductivity imparting agent such as a composite of polyalkylene glycol and lithium perchlorate, and the like.

The content of the ionic liquid is preferably 0.01 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, and still more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the viscoelastic particles.

[Coupling agent]

The battery electrode or separator coating film composition of the present invention may further contain a coupling agent. The coupling agent may be exemplified by the coupling agent exemplified above, including those preferred. The content of the coupling agent is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the viscoelastic particles.

[stabilizator]

The cell electrode or separator coating film composition of the present invention may contain a stabilizer. Specific examples of such stabilizers include 2,6-di-tert-butyl-phenol, 2,4-di-tert- butylphenol, 2,6- Phenolic antioxidants exemplified by bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butyl-anilino) -1,3,5-triazine and the like; N, N'-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl- aromatic amine-based antioxidants exemplified by p-phenylenediamine and the like; Diureidyl-3,3'-thiodipropionate, bis [2-methyl-4- {3-n-alkylthiopropionyloxy} -5 -tert-butyl-phenyl] sulfide, 2-mercapto-5-methyl-benzimidazole and the like; Butyrolactone diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphite, tris (isodecyl) phosphite, phenyldiisooctyl phosphite, diphenyl isooctyl phosphite, Phosphorus dihydroperoxide decomposition as exemplified by sodium diisopropylate, sodium bis (4-tert-butylphenyl) phosphate and the like; Salicylate-based light stabilizers exemplified by phenyl salicylate, 4-tert-octylphenyl salicylate and the like; Benzophenone-based light stabilizers exemplified by 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and the like; (2'-hydroxy-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- 2-yl) phenol] and the like; benzotriazole-based light stabilizers; Phenyl-4-piperidinyl carbonate, sebacic acid bis- [2,2,6,6-tetramethyl-4-piperidinyl] and the like; Ni-based light stabilizers exemplified by [2,2'-thio-bis (4-t-octylphenolate)] -2-ethylhexylamine-nickel (II); A cyanoacrylate light stabilizer; Anilide oxalate light stabilizer; Fullerene-based light stabilizers such as fullerene, hydrogenated fullerene, and hydroxylated fullerene. These stabilizers may be used alone or in combination of two or more.

The content of the stabilizer is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.1 to 1 part by weight based on 100 parts by weight of the viscoelastic particles.

[antiseptic]

The cell electrode or separator coating film composition of the present invention may further contain a preservative, whereby the storage stability of the composition can be controlled.

Preservatives include salts such as benzoic acid, salicylic acid, dehydroacetic acid, acids such as sorbic acid, sodium benzoate, sodium salicylate, sodium dehydroacetate and potassium sorbate, salts such as 2-methyl-4-isothiazolin- 2-benzoisothiazolin-3-one, alcohols such as methanol, ethanol, isopropyl alcohol and ethylene glycol, parahydroxybenzoic acid esters, phenoxyethanol, benzalkonium chloride, chlorhexidine hydrochloride And the like.

These preservatives may 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 based on 100 parts by weight of the viscoelastic particles.

[Surfactants]

The cell electrode or separator coating film composition of the present invention may further contain a surfactant for the purpose of controlling the wettability and defoaming property of the composition. The cell electrode or separator coating film composition of the present invention may further contain an ionic surfactant for the purpose of improving ion conductivity.

Examples of the surfactant include anionic surfactants such as soap, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate (e.g., dodecylbenzene sulfonate), polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether And examples thereof include salts of phosphoric acid, N-acyl amino acid salts,? -Olefin sulfonic acid salts, alkyl sulfuric acid ester salts, alkylphenyl ether sulfuric acid ester salts, methyl taurate salts, trifluoromethane sulfonic acid salts, pentafluoroethanesulfonic acid salts and heptafluoropropanesulfonic acid salts , Nonafluorobutane sulfonic acid salt, and the like. As the counter cation, sodium ion, lithium ion, or the like can be used. In the lithium ion battery, a lithium ion type surfactant is more preferable, and in a sodium ion battery, a sodium ion type surfactant is more preferable.

Examples of amphoteric surfactants include alkyldiaminoethylglycine hydrochloride, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryldimethylaminoacetic acid betaine, coconut fatty acid amidopropyl betaine, fatty acid Alkyl betaine, sulfobetaine, and amide oxide.

Examples of the nonionic surfactant include alkyl ester type compounds such as polyethylene glycol and acetylene glycol, alkyl ether type compounds such as triethylene glycol monobutyl ether, ester type compounds such as polyoxy sorbitan ester, alkylphenol type compounds, Compounds, and silicone-type compounds.

The surfactant may 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 even more preferably 0.1 to 10 parts by weight based on 100 parts by weight of the viscoelastic particles.

The battery electrode or separator coating film composition of the present invention is used for protecting the battery electrode or the 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 thereof may be drawn into the battery electrode or the separator.

[Preparation of battery electrode or separator coating film composition]

The battery electrode or separator coating film composition of the present invention can be produced by mixing and stirring the above components. The viscoelastic particles of the present invention may be mixed while being dispersed in a solvent. The stirring can be carried out using a stirring device such as a propeller type mixer, a planetary mixer, a hybrid mixer, a kneader, a homogenizer for emulsification, and an ultrasonic homogenizer. If necessary, stirring may be performed while heating or cooling.

In the present invention, a method for producing a viscoelastic particle having a surface coated with a polymer formed by graft polymerization includes the following steps: a step of obtaining a surface-modified viscoelastic particle by mixing a viscoelastic particle of the present invention and a coupling agent having a reactive substituent; And a step of mixing the surface-modified viscoelastic particles with a polymerizable compound reactive with a reactive substituent of the surface-modified viscoelastic particles to obtain viscoelastic particles coated with a polymer formed by graft polymerization by graft polymerization.

By the step of obtaining the surface-modified viscoelastic particles, 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 after the surface modification as a reaction starting point. The immobilization refers to a state of being chemically bonded to the surface of viscoelastic particles or a state of being physically adsorbed.

Examples of the coupling agent having a reactive substituent at one end include the above-mentioned silane coupling agent and titanium coupling agent, and a fluorine-based silane coupling agent and a bromine-based silane coupling agent are preferable, and (2-bromo- Methyl) propionyloxypropyltriethoxysilane is particularly preferable.

The amount of the coupling agent having a reactive substituent at one end is preferably 0.1 to 200 parts by weight, more preferably 1 to 150 parts by weight based on 100 parts by weight of the solid content of the viscoelastic particles.

In the present invention, after the step of obtaining the surface-modified viscoelastic particles, the step of cleaning the viscoelastic particles using the above-mentioned solvent may be included. As a result, reaction residues such as unreacted coupling agents and the like can be removed. 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 remove the surface-modified polymer, and the amount of the solvent to be used is not particularly limited as far as it can remove the reaction residue.

Examples of the polymerizable compound which reacts with the reactive substituent group of the surface-modified viscoelastic particles include the above-mentioned (meth) acrylic group, allyl group, vinyl group, compound having maleimide group, oxirane ring such as epoxy group, oxetane ring, Cyclic acetals, and the like, and it is possible to select to react with a reactive substituent possessed by the surface-modified viscoelastic particles. As such a combination, for example, when the reactive substituent is a (2-bromo-2-methyl) propionyloxy group, a compound having a (meth) acrylic group, an allyl group and a vinyl group as a polymerizable compound can be mentioned. The amount of the polymerizable compound is not particularly limited as long as it is an amount capable of obtaining viscoelastic particles coated with a desired polymer, and is preferably 100 to 300 parts by weight based on 100 parts by weight of the viscoelastic particles as the raw material.

The polymerization may be carried out in the presence of an initiator. The initiator can be used depending on the kind of the polymerizable compound. As such an initiator, there may be mentioned the above-mentioned latent thermal initiator, photo cationic initiator and thermal cationic initiator, and it may be used depending on the kind of the polymerizable compound used. These initiators may be used alone or in combination of two or more. The amount of the initiator to be used can be exemplified by the contents of the above-mentioned latent heat initiator, photo cation initiator and thermal cation initiator.

And a step of cleaning the viscoelastic particles coated with the polymer after the step of obtaining the viscoelastic particles coated with the polymer whose surface is formed by graft polymerization. The above-mentioned solvent may be used for washing.

[Protecting Method of Battery Electrode or Separator Surface]

The method of protecting a battery electrode or a separator according to the present invention includes a step of forming a coating film having a void by forming at least one layer of the battery electrode or the separator coating composition on the surface of a battery electrode or a separator, do. The surface of the battery electrode or the separator is protected by the battery electrode or the separator coating film of the present invention.

[Method for producing battery electrode or separator coating film]

The present invention also relates to a coating film obtained by using the battery electrode or the separator coating film composition of the present invention in the method for protecting the surface of a battery electrode or a separator. That is, when the binder is dissolved in a solvent, the coating layer of the battery electrode or separator coating composition is formed on the surface of the battery electrode or the separator by using at least one layer , And a step of evaporating the solvent. When the binder is a solid that does not dissolve in the solvent, it is preferable that a step of forming at least one coating layer of the battery electrode or the separator coating composition on the surface of the battery electrode or the separator, a step of evaporating the solvent, And a step of heating and fusing the binder in the solid when the binder is not heat-sealed under the temperature condition.

[Method of forming coating layer of coating film composition]

In the method for manufacturing a battery electrode or a separator coating film of the present invention, a coating layer of a coating film composition for a battery electrode or a separator may be formed by gravure coater, slit die coater, spray coater, dipping or the like. The thickness of the coating layer is preferably in the range of 0.01 to 100 탆, and more preferably in the range of 0.05 to 50 탆 from the viewpoint of electrical characteristics and adhesion. The battery electrode or the separator coating film composition of the present invention may have a structure in which at least a part of the battery electrode or the separator coating film composition is impregnated into the cell electrode or the separator. Since at least a part of the battery electrode or the separator coating film composition of the present invention is impregnated in the interior of the battery electrode or the separator, curling or deformation during the process or heat can be further suppressed. In the present invention, 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 mu m, more preferably in the range of 0.05 to 50 mu m. When the thickness of the coating film is 0.01 탆 or more, the insulating property against electron conduction is good, and the risk of short-circuiting is suppressed. If the thickness of the coating film is 100 mu m or less, the resistance rises in proportion to the thickness, so the resistance to ion conduction is low and the charge / discharge characteristics of the battery are improved.

When at least a part of the battery electrode or the separator coating film composition of the present invention is impregnated into the cell electrode or the separator, the amount of the composition to be impregnated is such that the pore structure of the electrode or the separator is not completely filled, Is preferably in an amount exceeding 0%, preferably in an amount such that the porosity of the electrode or separator is 50% or more, and more preferably, the porosity of the electrode or separator is 75% or more.

When the viscoelastic particles are particles having shape anisotropy, the particles having shape anisotropy in the coating direction can be oriented by the shearing force at the time of coating. For example, by coating the long axis direction of the fibrous particles in parallel with the long axis direction of the separator, the fibrous particles having the curl derived from the contraction at the time of opening the tension of the separator at the time of coating, The stress can be relaxed more efficiently than in the case where it is disorderly present.

[Method of increasing the solvent]

The solvent can be carried out by heat drying, vacuum drying, freeze drying, or a combination thereof. The heating and drying can be performed using a hot air furnace, an infrared heater, a heat roll, or the like. Vacuum drying can be performed by putting a coating film of a coating film composition into a chamber and evacuating. Freeze-drying can be employed when a sublimable solvent is used. The heating temperature and the heating time in the heating and drying are not particularly limited as long as the temperature and the time at which the solvent is vaporized, and can be set at, for example, 80 to 120 DEG C for 0.1 to 2 hours. By evaporating the solvent, the coating film of the present invention is formed by bringing the components except for the solvent of the battery electrode or the separator coating film composition into close contact with the battery electrode or the separator and, when the binder is a hot melt particle, by thermal fusion.

[Heating method]

In the case of using the binder in the form of particles in the method for producing a battery electrode or a separator coating film of the present invention, the binders can be thermally fused and solidified. In this case, the particles may be thermally fused at a temperature at which the particles are completely melted and solidified. Alternatively, only the surface of the organic particles may be thermally melted and fused to cohere with each other to cool the particles, . According to the heat fusion solidification of electrons, there are many portions in a continuous phase, and ion conductivity, mechanical strength and heat resistance are high. According to the latter, the ion conductivity, mechanical strength and heat resistance through the fused organic particles are reduced, but the ion conductivity can be improved by impregnating the gap between the particles with the electrolyte solution. In addition, the latter is a structure in which the gap is opened at random, and therefore, when dentrite occurs, the effect of preventing short-circuiting by preventing the linear growth thereof can be enhanced. The hot melt bonding method during hot melt can be carried out by various known methods such as hot air blowing, hot plate, oven, infrared ray, ultrasonic welding, etc., and the density of the protective layer can be increased by pressing at the time of heating. In addition to natural cooling, various known methods such as compression of cooling gas and heat sink can be used for cooling. When the binder is heated to a temperature at which it melts, it may be heated at a temperature at which the binder melts for 0.1 to 1000 seconds.

[Magnetic field and / or electric field orientation]

In the method for producing a battery electrode or a separator coating film of the present invention, the compounding material can be solidified by using a magnetic field and / or an electric field. As a result, a coating film having anisotropy in ion conductivity, mechanical strength and heat resistance can be formed. The viscoelastic particles can be fixed in a state in which the viscoelastic particles are oriented in a direction easy to relax the stress using a magnetic field and / or an electric field, thereby enhancing the stress relaxation ability. In the case of the polymer material described above, anisotropy can be imparted to the magnetic susceptibility and / or the permittivity by stretching, and thus it can be oriented to a magnetic field and / or an electric field. Anisotropic fibers such as cellulose may also be used. The ion conductivity can be improved by pulverizing the fibers or fibers produced by stretching such a polymer to form particles, and aligning the long axis direction to stand perpendicular to the electrode surface. With respect to organic crystals, those having crystal magnetic and / or dielectric anisotropy can be oriented in a magnetic field and / or an electric field, and the above-described effects can be exhibited. The magnetic field and / or the electric field may be a time-varying magnetic field and / or an electric field such as a rotating magnetic field and / or an electric field in a static magnetic field and / or an electric field.

By the method for producing a battery electrode or separator coating film of the present invention including the above process, a battery electrode or a separator having a coating film on its surface is obtained. Further, at least a part of the coating film may be formed by being drawn into the battery electrode or the separator. The porosity of the coating film is 40% or more, preferably 41 to 90%, more preferably 41 to 80%.

[Battery electrode and / or separator]

The present invention relates to a battery electrode and / or a separator which is protected by the above-described battery electrode or separator coating film or has a coating film produced by the above-mentioned method of manufacturing a battery electrode or a separator coating film.

The battery electrode or separator protected by the cell electrode or separator coating film of the present invention can be produced by coating the composition of the present invention on a battery electrode or a separator and subsequently evaporating the solvent. Examples of the battery electrode include positive electrodes and negative electrodes of various known batteries and electric double layer capacitors, and at least one of them can be coated or impregnated with a battery electrode or a separator coating film composition. As the separator, a porous material made of polypropylene or polyethylene, a cellulose material, a nonwoven fabric made of polypropylene, polyethylene or polyester can be exemplified, and they can be applied or impregnated on both sides or one side thereof. The battery electrode or the separator coating film composition of the present invention can be used in a state in which it is in close contact with an opposing separator or an electrode. The separator and the electrode are brought into close contact with each other while the solvent is not evaporated, The member may be brought into close contact with each other.

The electrode or the separator may have anisotropy in the modulus of elasticity, coefficient of linear expansion, and shrinkage amount upon heat depending on the coating direction of the electrode active material layer, the direction of drawing and winding of the separator, and the like. For example, when the monoaxially stretched polyethylene separator is heated, the stress at the time of stretching is relaxed, and the amount of shrinkage in the stretching direction is increased, and as a result, the stress between the coating film becomes anisotropic. In this case, the cell electrode or separator coating film composition of the present invention, in which 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 substrate of the battery electrode or the separator A battery electrode or a separator having a coating film obtained by use is preferable. Here, the longest axis of the viscoelastic particles means a line having the longest straight line connecting the ends of arbitrary two points of the viscoelastic particles at the shortest point. The term &quot; battery electrode &quot; or &quot; separator &quot; When the longest axis of the viscoelastic particles is oriented parallel to the shrinking direction of the substrate of the battery electrode or the separator, the amount of deformation of the viscoelastic particles in the coating film is oriented in the stretching direction. As a result, in a battery electrode or separator having a coating film, the stress relaxation ability between the coating film and the substrate of the battery electrode or the separator is increased, curling is further suppressed, and heat resistance is further improved. For example, it is possible to increase the stress relaxation capacity by aligning the orientation direction of the fibers and the stretching direction of the separator by shortly cutting the polyethylene fibers stretched viscoelastic particles, further suppressing the generation of curl, and further improving the heat resistance .

[battery]

The present invention relates to a battery electrode comprising the battery electrode or the separator coated with the separator coating composition of the present invention. The production of the battery can be carried out by a known method. Further, a battery can be manufactured by impregnating a coating film with an electrolytic solution and using a coating film imparted with ion conductivity. In addition, the coating film composition itself may have ion conductivity so as to be embedded in a battery as a solid electrolyte membrane. When the electrolyte solution is impregnated into the coating film, the amount of the binder to the viscoelastic particles is set to 20 wt% or less, and ion conductivity can be imparted by impregnating the voids formed by the particle volume eliminating effect with the electrolyte solution. In the case of a structure free from voids, ion conductivity can be imparted by swelling the electrolyte solution in the binder.

<Examples>

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. The indication of the addition amount is, unless otherwise stated, parts by weight or percent by weight.

[Test Example 1]

For the viscoelastic particles and binder used in Examples and Comparative Examples described later, the elastic modulus and plastic strain were evaluated by the following methods. Here, for the viscoelastic particles, the dispersion of the viscoelastic particles to be used was filtered and dried to obtain test particles. The binder was solidified in the form of a film having a thickness of 50 탆 under the condition of using a binder to be used, then cooled with liquid nitrogen and then pulverized using a mill (IKA; M20 universal mill) Sieved to obtain test particles.

(Measurement of elastic modulus)

An iron bar having an outer diameter of 10 mm and a length of 200 mm was press-fitted into an acrylic barrel having an inner diameter of 10 mm, an outer diameter of 110 mm and a height of 150 mm. The ratio h1 / h2 = h3 of the height h1 when press-fitting at 1 kgf and the height h2 at the time of press-fitting with 0.5 kgf was measured as the modulus of elasticity.

(Measurement of plastic strain)

In the above measurement, the height h4 when the load was returned to 0.5 kgf was determined after applying a load of 1 kgf, and the ratio h5 / h5 to the height h5 when the load was returned to 0.5 kgf after the iron rod was press- h4 = h6 was measured as a plastic strain.

[Test Example 2]

The following characteristics were measured for the lithium ion secondary battery produced in the following Examples and Comparative Examples.

(Initial capacity measurement)

The battery was charged at a constant current of 0.005 mA until the voltage became 4.2 V in order to obtain an initial capacity, and subsequently 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 became 3.5 V. This was repeated three times, and the third discharge capacity was taken as the initial capacity.

(Initial internal resistance)

The cell measuring the initial capacity was set to a potential of 4.2 V, and the potential was measured at an impedance of 1 kHz with a voltage change of ± 15 mV at the center.

(Rate characteristic)

The discharge rate was determined from the initial capacity, and the discharge capacity at each discharge rate was measured. Charging was carried out for 10 hours at a constant current of 4.2 V, and charged at 4.2 V constant voltage for 2 hours. Thereafter, discharge was performed until the voltage reached 3.5 V with a constant current over 10 hours, and the discharge capacity at this time was set to 0.1 C discharge capacity. Next, after the battery was similarly charged, the battery was discharged at a current value at which the discharge was completed within one 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 1C. Likewise, the discharge capacity at 3C, 10C, and 30C was determined, and the capacity retention rate when the discharge capacity at 0.1C was taken as 100% was calculated.

(Cycle life)

Charging and discharging tests were performed in which the battery was charged from 1 C to 4.2 V, charged at a constant voltage of 4.2 V for 2 hours, and discharged from 1 C to 3.5 V. At this time, it was calculated how many percent of the discharge capacity with respect to the first first discharge, and the number of times of charging and discharging when the capacity was less than 80% was taken as the service life.

(Heat insulation test)

Charged from 1 C to 4.2 V, charged at a constant voltage of 4.2 V for 2 hours, heated from 25 캜 to 260 캜 in an hour at a rate of 10 캜, and then heated to about 25 캜 in an hour at 20 캜 And the resistance after the endurance test was confirmed by the above (initial internal resistance) measuring method. The evaluation criteria were as follows.

Impedance of 1 kHz

◎; 10MΩ or more

?: 100 k? To less than 10 M?

?: 1 k? To less than 100 k?

×: Less than 1 kΩ

(Heat resistance appearance test)

The test method was the same as the above-described heat-resisting insulation test, and the inside of the battery after the test was disassembled was confirmed. The evaluation criteria were as follows.

⊚: There is no direct contact between the positive electrode and the negative electrode, the insulated state is maintained, and the cell electrode protection layer is in close contact with the electrode and / or the separator.

○: There is no direct contact between the positive electrode and the negative electrode, and the insulated state is maintained, but the cell electrode protection layer shows some floating, but not peeled off.

△: Tally is going on and part of the government pole is revealed

X: State in which the control electrode is in contact with and is short-circuited

[Test Example 3]

In the electrodes or separators prepared in Examples and Comparative Examples described later, the following characteristics were measured.

(Curl test)

An electrode or a separator having a coating film formed thereon was cut into 50 mm square, and the curl state was confirmed. The evaluation criteria were as follows.

◎: Not fully curled

○: The end is turned to a height of less than 1 mm

△: The end is turned to a height of 1 to 5 mm

X: Curling on the roll

[Example 1]

Embodiment 1 describes a method of manufacturing a lithium ion secondary battery using a negative electrode having a coating film obtained by coating a negative electrode with a battery electrode or a separator coating film composition containing a solvent, a binder and viscoelastic particles, and evaporating a solvent.

(Preparation of composition)

(Production of viscoelastic particle slurry 1)

10 L of ion-exchanged water and 50 kg of urethane particles (manufactured by Negami Kogyo Kabushiki Kaisha; a 60% water mixture of low modulus urethane urethane 2 μm particles; Art Pearl MM-120TW) were added to a 100 L polypropylene tank, To prepare a dispersion. The dispersion was filtered with a nylon mesh having a graduation of 20 占 퐉, the magnetic foreign matter was removed with a 2T electromagnet, and water missing in the process was added to prepare a dispersion containing 50% viscoelastic particles.

(Composition of composition)

20 kg of water was added to 50 kg of the dispersion, and 200 g of polyoxyethylene (Alcox E-30, manufactured by MESEGA KOGAKU KOGYO CO., LTD.) Was further added and dissolved by stirring for 6 hours to obtain a battery electrode or separator coating film composition. The content of the viscoelastic particles in the composition excluding the solvent was 99.2% by weight.

(Preparation of positive electrode)

520 parts of a 15% NMP (N-methylpyrrolidone) solution of PVdF (polyvinylidene fluoride) (Kureha KF Polymer # 1120, manufactured by Kabushiki Kaisha K.K.), 10 parts of lithium cobalt oxide , 1140 parts of polyvinyl alcohol (abbreviated to LCO) (CELSID C-5H, manufactured by Nippon Chemical Industry Co., Ltd.), 120 parts of acetylene black (Denka Black HS-100, manufactured by Denki Kagaku Kogyo K.K.) and 5400 parts of NMP Lt; 0 &gt; C until it became homogeneous. This was coated with a rolled aluminum current collector (manufactured by Nippon Seika Kogyo Kabushiki Kaisha; width 300 mm, thickness 20 탆) with a width of 180 mm and a thickness of 200 탆 and dried in a 130 캜 hot air furnace for 30 seconds. This was roll-pressed at a linear pressure of 530 kgf / cm. The thickness of the positive electrode active material layer after pressing was 22 占 퐉.

(Preparation of negative electrode)

530 parts of a 15% NMP solution of PVdF (Kureha KF Polymer # 9130, manufactured by Kureha Kabushiki Kaisha), 1180 parts of graphite (GR-15, manufactured by Nippon Gosei Kogyo Co., Ltd.) 4100 parts of NMP was added and the solution was cooled while the liquid temperature did not exceed 30 캜 and stirred until it became homogeneous. This was coated with a rolled copper foil current collector (manufactured by Nippon Seifuku Kabushiki Kaisha; width 300 mm, thickness 20 탆) with a width of 180 mm and a thickness of 200 탆 and dried in a 100 캜 hot air furnace for 2 minutes. This was roll-pressed at a linear pressure of 360 kgf / cm. The thickness of the negative electrode active material layer after pressing was 28 mu m.

(Preparation of negative electrode having a coating film)

The composition was coated on the negative electrode using a gravure coater so as to have a dry thickness of 5 占 퐉 (cylinder # 100, conveying speed 1 m / min, cylinder / conveying speed ratio = 1) And heated at 100 占 폚 for 60 seconds to prepare a negative electrode having a coating film having a cell electrode or a separator coating film having a thickness of 5 占 퐉.

(Production of lithium ion secondary battery)

 The negative electrode coated with the positive electrode and the coating film was cut into 40 mm × 50 mm so that the active material layer was not coated at both ends with a width of 10 mm on the short side. The positive electrode was made of aluminum tab, The tabs were joined by resistance welding. The aluminum laminate cell having a width of 50 mm and a length of 100 mm was sandwiched between two aluminum laminate cells having a width of 45 mm and a length of 120 mm and folded into three sides so that the positive electrode and the negative electrode faced each other. And a sealant was inserted into a portion where the tab was contacted. Then, the sealant portion and the side of the sealant portion were thermally laminated to form a bag shape. This was placed in a vacuum oven at 100 캜 for 24 hours and vacuum dried. Subsequently, lithium hexafluorophosphate / EC: DEC = 1: 1 1M electrolyte (LBG-96533, manufactured by Kishida Chemical Co., Ltd.) After vacuum impregnation, the remaining electrolyte was withdrawn and sealed with a vacuum sealer to produce a lithium ion secondary battery.

[Example 2]

In Example 2, a method of manufacturing a lithium ion secondary battery using a positive electrode having a coating film obtained by coating a positive electrode with a battery electrode or a separator coating film composition containing a solvent, a binder and viscoelastic particles and evaporating a solvent is described .

(Preparation of composition)

Was prepared in the same manner as in Example 1.

(Preparation of positive electrode)

. &Lt; / RTI &gt;

(Preparation of negative electrode)

. &Lt; / RTI &gt;

(Preparation of positive electrode having a coating film)

A positive electrode was prepared by the method of Example 1.

(Production of lithium ion secondary battery)

. &Lt; / RTI &gt;

[Example 3]

Example 3 describes a method for producing a lithium ion secondary battery using a separator having a coating film obtained by coating a separator with a battery electrode or separator coating film composition comprising a solvent, a binder and viscoelastic particles, and evaporating the solvent.

(Preparation of composition)

Was prepared in the same manner as in Example 1.

(Preparation of positive electrode)

. &Lt; / RTI &gt;

(Preparation of negative electrode)

. &Lt; / RTI &gt;

(Preparation of separator having coating film)

Was prepared in the same manner as in Example 1 for the separator.

(Production of lithium ion secondary battery)

. &Lt; / RTI &gt;

[Example 4]

Embodiment 4 describes a method of manufacturing a lithium ion secondary battery using a separator having a coating film obtained by coating a separator with a battery electrode or separator coating film composition comprising a solvent, a binder and a viscoelastic particle, and evaporating the solvent.

(Preparation of composition)

(Production of viscoelastic particle slurry 1)

10 L of ion-exchanged water and 50 kg of urethane particles (manufactured by Negami Kogyo Kabushiki Kaisha; a 60% water mixture of low modulus urethane urethane 2 μm particles; Art Pearl MM-120TW) were added to a 100 L polypropylene tank, To prepare a dispersion. The dispersion was filtered with a nylon mesh having a graduation of 20 占 퐉, the magnetic foreign matter was removed with a 2T electromagnet, and water missing from the process was added to prepare a dispersion (viscoelastic particle slurry 1) containing 50% viscoelastic particles.

(Composition of composition)

2 kg of water was added to 12 kg of the above dispersion, and 0.1 kg of an ethylene / vinyl acetate copolymer emulsion (PFAFLEX OM-4000NT, manufactured by Kabushiki Kaisha Kureha Co., Ltd.) was further added and dissolved for 6 hours. Subsequently, 55% 0.01 kg of an aqueous solution was added, and the mixture was further stirred for 2 hours to obtain a battery electrode or a separator coating film composition. In the composition, the content of the viscoelastic particles in the components other than the solvent was 99.2 wt%.

(Preparation of positive electrode)

. &Lt; / RTI &gt;

(Preparation of negative electrode)

. &Lt; / RTI &gt;

(Preparation of separator having coating film)

. &Lt; / RTI &gt;

(Production of lithium ion secondary battery)

. &Lt; / RTI &gt;

[Example 5]

In Example 5, a method of manufacturing a lithium ion secondary battery using a separator having a coating film obtained by coating a separator with a battery electrode or a separator coating film composition comprising a solvent, a binder and viscoelastic particles, and evaporating a solvent is described.

(Preparation of composition)

(Production of viscoelastic particle slurry 2)

10 L of ion-exchanged water and 50 kg of polyethylene particles (manufactured by Unitika Kogyo Co., Ltd., 60% water mixture of polyethylene particles: CD-1200) were added to a 100 L polypropylene tank and stirred for 12 hours to prepare a 50% dispersion. The dispersion was filtered with a nylon mesh having a graduation of 20 占 퐉, the magnetic foreign matter was removed with a 2T electromagnet, and water missing in the process was added to prepare a dispersion (viscoelastic particle slurry 2) containing 50% viscoelastic particles.

(Composition of composition)

2 kg of water was added to 12 kg of the above dispersion, and 0.1 kg of an ethylene / vinyl acetate copolymer emulsion (PFAFLEX OM-4000NT, manufactured by Kabushiki Kaisha Kureha Co., Ltd.) was further added and dissolved by stirring for 6 hours. Subsequently, 55% 0.01 kg of an aqueous solution was added, and the mixture was further stirred for 2 hours to obtain a battery electrode or a separator coating film composition. In the composition, the content of the viscoelastic particles in the components other than the solvent was 99.2 wt%.

(Preparation of positive electrode)

. &Lt; / RTI &gt;

(Preparation of negative electrode)

. &Lt; / RTI &gt;

(Preparation of separator having coating film)

. &Lt; / RTI &gt;

(Production of lithium ion secondary battery)

. &Lt; / RTI &gt;

[Example 6]

Example 6 describes a method for producing a lithium ion secondary battery using a separator having a coating film obtained by coating a separator with a battery electrode or a separator coating film composition comprising a solvent, a binder and a viscoelastic particle, and evaporating a solvent.

(Preparation of composition)

(Production of inorganic particle dispersion slurry)

50 L of ion-exchanged water and 100 kg of corundum (A-50-F, manufactured by Showa Denko K.K.) were added to a 100 L polypropylene tank and stirred for 12 hours to prepare a 67% dispersion. The mixture was circulated and pulverized for 1 week using a 20-liter bead mill (0.3 mm zirconia beads filled at 80% and a peripheral speed of 10 m / s) while cooling it to prepare a pulverized slurry. The fine pulverized slurry was filtered with a nylon mesh having a scale of 5 탆 and stored in a tank made of 100 L polypropylene and allowed to stand for two days. Then, the supernatant layer of 1/5 of the volume was removed by a pump, The mixture was collected by a pump and stored in a 100 L polypropylene tank, and the remaining 1/5 of the bottom of the container was removed as a sedimentation layer. The collected 3/5 was added with water to make 67%, then stored in a 50L polypropylene tank and allowed to stand still for 2 days, and then the supernatant layer and the sedimentation layer were similarly removed. The operation of collecting the intermediate layer was repeated three times by changing the capacity of the tank made of polypropylene to 20 L and then the magnetic foreign matters were removed from the final intermediate layer with the electromagnet of 2 T and ion- To prepare an inorganic particle dispersion slurry containing 67% of the inorganic particles.

(Composition of composition)

1 kg of water was added to 3 kg of the inorganic particle dispersion slurry, and 0.03 kg of polyoxyethylene (Alcox E-30 manufactured by MESEGA KOGAKU KOGYO CO., LTD.) Was further added and dissolved by stirring for 6 hours. 100 g of CD- Followed by further stirring for 2 hours to obtain a battery electrode or a separator coating film composition. In the composition, the content of the viscoelastic particles in the components other than the solvent was 2.9% by weight.

(Preparation of positive electrode)

. &Lt; / RTI &gt;

(Preparation of negative electrode)

. &Lt; / RTI &gt;

(Preparation of separator having coating film)

. &Lt; / RTI &gt;

(Production of lithium ion secondary battery)

. &Lt; / RTI &gt;

[Example 7]

Example 7 describes a method for producing a lithium ion secondary battery using a separator having a coating film obtained by coating a separator with a battery electrode or separator coating film composition comprising a solvent, a binder and viscoelastic particles, and evaporating a solvent.

(Production of fibrous elastic particles)

A polyethylene fishing line (YKG Yotsuamije; G-soul Pe 0.3) was cut into a width of 1 mm and then dispersed in 5 kg of water to give 50 g. While cooling it, a bead mill (0.3 mm zirconia beads 80% At a peripheral speed of 10 m / s) for 1 day to prepare a slurry. Thereafter, the slurry was heated and stirred at 80 캜 to remove moisture, and the concentration was increased to 60%.

(Preparation of composition)

A composition was prepared in the same manner as in Example 6 except that the slurry was used instead of the CD-1200 of Example 6.

(Preparation of positive electrode)

. &Lt; / RTI &gt;

(Preparation of negative electrode)

. &Lt; / RTI &gt;

(Preparation of separator having coating film)

. &Lt; / RTI &gt;

(Production of lithium ion secondary battery)

. &Lt; / RTI &gt;

[Example 8]

Example 8 describes a method for producing a lithium ion secondary battery using a separator having a coating film obtained by coating a separator with a battery electrode or a separator coating film composition comprising a solvent, a binder and viscoelastic particles, and evaporating a solvent.

(Preparation of separator having coating film)

The procedure of Example 3 was repeated except that the cylinder / conveying speed ratio was set to 2, the cylinder was doubled the conveying speed, and the fiber was oriented so as to be parallel to the conveying direction of the substrate by the shearing force between the cylinder and the substrate . The appearance of the fiber orientation was observed with an optical microscope.

(Production of lithium ion secondary battery)

. &Lt; / RTI &gt;

[Comparative Example 1]

A lithium ion secondary battery was produced in the same manner as in Example 1 except that an electrode and a separator having no battery electrode or separator coating film were used.

[Comparative Example 2]

A lithium ion secondary battery was produced in the same manner as in Example 6, except that the viscoelastic particles were not used.

The results are shown in Tables 1 to 3.

According to the battery electrode or separator coating film composition of the present invention, the generation of curling is suppressed in the electrode or separator of the substrate even when the coating film is coated, and the process is suitably excellent because of having high heat resistance and electrochemical Since there is no deterioration in durability, a battery having excellent long-term reliability can be provided.

1 Battery electrode or separator coating film
2 active material layer
3 Home
4 Separator
5 Transport direction of substrate

Claims (6)

A binder, a solvent, and viscoelastic particles. The battery electrode or separator coating film composition according to claim 1, wherein the viscoelastic particles have a viscoelasticity lower than a viscoelasticity of the binder. The cell electrode or separator coating film composition according to claim 1 or 2, wherein the viscoelastic particles have shape anisotropy. A battery electrode or separator having a coating film obtained by using the battery electrode or the separator coating film composition according to any one of claims 1 to 3. The battery electrode or separator according to claim 4, wherein the viscoelastic particles have shape anisotropy and the longest axis of the viscoelastic particles is oriented parallel to the shrinking direction of the base material of the battery electrode or the separator. A battery having the battery electrode and / or the separator according to claim 4 or 5.

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