JP2015041502A - Coating material composition for nonaqueous storage devices, and nonaqueous storage device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition which enables the formation of a coat layer including alumina having the effect of increasing the rate characteristic of a nonaqueous storage device.SOLUTION: A coating material composition for nonaqueous storage devices comprises: alumina including 5-2000 ppm of iron and/or magnesium; a binding agent; and a solvent. An electrode for nonaqueous storage devices and a separator for nonaqueous storage devices each have, on its surface, a coat layer formed by the coating material composition. A nonaqueous storage device comprises the electrode and/or the separator.

Description

  The present invention provides a coating agent composition for a non-aqueous storage element using alumina containing 5 ppm to 2000 ppm of iron and / or magnesium, and an electrode for a non-aqueous storage element having a coating layer obtained using the coating composition. The present invention relates to a separator for a non-aqueous storage element, and a non-aqueous storage element including the electrode or the separator.

  A non-aqueous power storage element can extract a higher voltage than a water-based power storage element, and thus can store energy at a high energy density and has high utility value as a power source for mobile devices and automobiles. For example, lithium ion primary batteries and secondary batteries are widely used as power sources for portable electronic devices such as mobile phones and laptop computers, and electric double layer capacitors are used as power sources for power tools and energy regeneration devices for heavy machinery. Has been. Furthermore, calcium ion primary batteries and secondary batteries, magnesium ion primary potentials and secondary batteries, sodium ion primary batteries and secondary batteries, and the like are also promising as power storage elements having both high voltage and high energy density. However, since these non-aqueous storage elements use a flammable substance as an electrolyte, there is a risk of fire and explosion due to heat generated by short-circuiting the positive electrode and the negative electrode, and ensuring safety is important. It has become a challenge.

  As a means for ensuring safety at present, there is a shutdown function in which the pores of the polyolefin separator are closed when the electricity storage element generates heat, thereby blocking ionic conduction. When an abnormality such as a short circuit between the positive and negative electrodes occurs in the battery, the shutdown function works to suppress heat generation and prevent thermal runaway.

  However, the melting point of the polyolefin separator is 200 ° C. or less, and if the heat is intense, the separator shrinks, causing a direct contact between the positive and negative electrodes, leading to a risk of thermal runaway. In addition, since the polyolefin separator is softer than the active material and metal foreign matter and is very thin with a thickness of about 10 to 30 μm, if the active material falls off or metal foreign matter is mixed in the manufacturing process of the storage element, the separator is removed. There is a risk of breaking through and causing electrical contact between the positive and negative electrodes. Thus, the safety of the non-aqueous power storage element is not sufficient, and further improvement in safety is required.

  As an improvement measure for the above problem, a method has been devised in which a porous film made of alumina powder or silica powder is formed on the active material coating layer applied to the current collector to prevent the active material from falling off the electrode. (Patent Document 1). Since this porous membrane has an inorganic filler as a skeleton, even when a separator with a low melting point melts and shrinks due to a temperature rise at the time of a short circuit, it can prevent contact between positive and negative electrodes and suppress thermal runaway. There is an effect as a coat layer having. Moreover, even if an active material or a metal foreign substance is mixed, the piercing strength of the rigid inorganic filler film is high, and there is an effect of preventing the hole from being broken through the separator.

  In addition, such a coating layer functions as a layer that suppresses the generation of dendrites and retains the electrolytic solution. In addition, the coating layer is buffered to accelerate local degradation due to concentration of electrode reactions due to electrode surface non-uniformity, which also has the effect of preventing degradation of the active material layer when used for a long period of time. .

  Furthermore, a method has been devised in which the separator having such a coating layer contains a trace amount of different elements such as Na and Ca to improve the characteristics of the electricity storage device. In Patent Document 2, the inorganic filler hydroxide forming the heat-resistant porous film contains a small amount of water-soluble Na, so that the SEI film at the negative electrode interface in the lithium ion battery is kept in a good state and the battery life is extended. A method has been proposed. Patent Document 3 proposes a method in which the separator contains a small amount of Ca, so that hydrogen fluoride generated during battery operation is supplemented and gas expansion of the lithium ion battery is suppressed. In Patent Document 4, a heat-resistant layer is provided. A method of improving the output characteristics of a lithium ion battery by supplementing water molecules and hydrogen fluoride in an electrolytic solution by containing Na, S, Ca, and Si at a ratio of 1000 ppm or less has been devised.

  By the way, when a coat layer is introduced into a power storage element, the distance between the electrodes increases, so that the internal resistance increases in principle and the output characteristics deteriorate. In Patent Document 4, dissimilar elements such as Na capture water molecules and hydrogen fluoride in the electrolyte, thereby suppressing a decrease in the conductivity of the electrolyte, resulting in a decrease in internal resistance. No consideration is given to the resistance increase by introducing layers. In addition, ions having high solubility in an electrolytic solution such as Na are present in a state of being released from the separator in the electrolytic solution, and are highly likely to cause a side reaction on the electrode surface during a long-term operation of the power storage device. From the viewpoint of ensuring reliability, it is desirable to remove impurity ions having high solubility such as Na as much as possible.

Japanese Patent Laid-Open No. 7-220759 JP 2011-28947 A JP 2011-216318 A JP 2012-252969 A

  The objective of this invention is providing the composition which can form the coating layer containing an alumina which improves the rate characteristic of a non-aqueous storage element.

  The present inventor has intensively studied to solve the above-mentioned problems of the prior art, and as a filler contained in the coating composition, by using alumina containing iron and / or magnesium at a ratio of 5 ppm to 2000 ppm, It has been found that an electricity storage device including a coating layer formed using a coating agent composition exhibits good rate characteristics.

That is, the present invention comprises the following.
(1) A coating composition for a non-aqueous storage element, comprising alumina containing 5 ppm to 2000 ppm of iron and / or magnesium, a binder, and a solvent.
(2) The coating agent composition for nonaqueous power storage elements according to (2), wherein the alumina contains 50 ppm or more and less than 200 ppm of iron.
(3) The coating agent composition for non-aqueous power storage elements according to (1) or (2), wherein the alumina contains magnesium at 200 ppm or more and less than 500 ppm.
(4) A nonaqueous storage element electrode having a coating layer formed using the coating composition for a nonaqueous storage element according to any one of (1) to (3).
(5) A separator for a nonaqueous storage element having a coat layer formed using the coating composition for a nonaqueous storage element according to any one of (1) to (3).
(6) A non-aqueous storage element comprising the non-aqueous storage element electrode according to (4) and / or the non-aqueous storage element separator according to (5).

  According to the present invention, there is provided a composition capable of forming a coating layer containing alumina, which improves the rate characteristics of a non-aqueous storage element.

FIG. 1 is a cross-sectional view of an electrode having a coating layer of the present invention. FIG. 2 is a cross-sectional view of a separator having a coating layer of the present invention.

  The coating agent composition of the present invention comprises (1) alumina containing 5 ppm to 2000 ppm of iron and / or magnesium, (2) a binder, and (3) a solvent.

A coating layer having high heat resistance and high cation conductivity can be obtained by coating the electrode and / or separator with the coating composition for a nonaqueous electricity storage device of the present invention and evaporating the solvent. By using an electrode and / or separator having this coating layer for an electricity storage element, the melting of the separator due to accidental collapse of the non-aqueous electricity storage element due to an accident, mixing of conductive foreign matter, thermal runaway, etc., without deteriorating rate characteristics It is possible to prevent a short circuit between the electrodes due to the above.
According to the present invention, the nonaqueous storage element coating agent composition containing alumina, binder component, and solvent containing 5 ppm to 2000 ppm of iron and / or magnesium is applied to the nonaqueous storage element and dried. In the coating layer obtained in the above, iron and / or magnesium present on the alumina surface serves as a Lewis acid site. Therefore, since iron and / or magnesium are positively charged on the alumina surface, there is an effect of capturing an electrolyte anion having a negative charge. As a result, only cations involved in the electricity storage reaction can be efficiently electrophoresed, and an increase in internal resistance of the electricity storage device can be suppressed. Moreover, in a preferable aspect, since iron and magnesium are bonded to the alumina particles, the rate of dissolution into the electrolytic solution is small, and the internal resistance can be further reduced. Therefore, the non-aqueous energy storage device provided with the coating layer of the present invention has high heat resistance, low internal resistance, and can improve safety without deteriorating rate characteristics.

[alumina]
(1) Alumina containing 5 ppm to 2000 ppm of iron and / or magnesium (hereinafter sometimes referred to as “alumina of the present invention”) will be described. In addition, when the alumina of this invention contains both iron and magnesium, said content is the sum total of content of iron and magnesium.

  When the content of iron and / or magnesium is less than 5 ppm, the Lewis acid sites on the alumina surface are too few, so that the anion scavenging ability is not sufficient, and the cation transport number cannot be increased. In addition, when the content of iron and magnesium exceeds 2000 ppm, the amount of iron ions and magnesium ions that dissolves in the electrolyte increases, which impedes the transport of electrolyte ions and deteriorates charge / discharge characteristics and cycle characteristics. Let From the viewpoint of improving the rate characteristics, the iron content is preferably 50 to less than 200 ppm. Similarly, from the viewpoint of improving rate characteristics, the magnesium content is preferably less than 200 to 500 ppm. Therefore, in this invention, it is preferable that content of iron and / or magnesium is 5 ppm-2000 ppm, It is more preferable that it is 10 ppm-1000 ppm, It is further more preferable that it is less than 250-700 ppm.

  The alumina of the present invention may contain additional elements such as sodium, silicon, and calcium. However, from the viewpoint of ensuring long-term reliability of the nonaqueous storage element, it is preferable to reduce the amount of highly soluble impurity ions such as sodium. From such a viewpoint, the alumina of the present invention preferably has a total content of sodium, silicon and calcium of 2000 ppm or less. Further, the alumina of the present invention preferably has a sodium content of 2000 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less.

  The contents of iron, magnesium, sodium, silicon, and calcium contained in the alumina of the present invention can be quantified by inductively coupled plasma mass spectrometry.

  The average particle diameter of the alumina of the present invention is preferably in the range of 0.001 to 100 μm, and more preferably in the range of 0.005 to 10 μm. The average particle size and particle size distribution can be measured by, for example, a laser diffraction / scattering particle size distribution measuring apparatus, and specifically LA-920 manufactured by Horiba, Ltd. can be used.

  Although the manufacturing method of the alumina of this invention is not specifically limited, For example, it is possible to manufacture by the alkoxide method or the Bayer method.

  The alkoxide method is a method for producing alumina by hydrolyzing aluminum alkoxide. In the case of producing by the alkoxide method, the aluminum alkoxide is mixed with the iron salt and / or magnesium salt in the stage before the hydrolysis reaction or before the alumina hydrate is calcined, so that 5 ppm to 2000 ppm. Alumina containing iron and / or magnesium can be produced. Since iron and / or magnesium are preferably combined with alumina, that is, alumina and iron and / or magnesium are preferably combined, the raw aluminum alkoxide is mixed with iron salt and / or magnesium salt before hydrolysis. It is preferable to perform a process.

The aluminum alkoxide that can be used when producing alumina by the alkoxide method is represented by the formula (1):
Al (OR ¹ ) (OR ² ) (OR ³ ) (1)
[Wherein R ¹ , R ² and R ³ each independently represents an alkyl group]
It is a compound shown by these.

  The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, and tert-butyl group. Can be mentioned. Therefore, the aluminum alkoxide represented by the general formula (1) is preferably aluminum isopropoxide, aluminum ethoxide, aluminum sec-butoxide, aluminum tert-butoxide, or the like. Aluminum alkoxides may be used alone or in combination.

As iron salts, ferrous chloride (FeCl ₂ ), ferric chloride (FeCl ₃ ), ferrous bromide (FeBr ₂ ), ferric bromide (FeBr ₃ ), ferrous iodide (FeI ₂₎ ), ferrous tetrahydrate chloride _{(FeCl 2 · 4H 2 O)} , ferric hexahydrate chloride _{(FeCl 3 · 6H 2 O)} , ferric nitrate nonahydrate _{(Fe (NO 3) 3 ·} 9H ₂ O), ferrous oxalate dihydrate (FeC ₂ O ₄ .2H ₂ O), ferric sulfate (Fe ₂ (SO ₄ ) ₃ ), ferrous sulfate heptahydrate (FeSO ₄ .7H ₂₎ O), ferric sulfate n-hydrate (Fe ₂ (SO ₄ ) ₃ .nH ₂ O), and the like.

As magnesium salts, magnesium chloride hexahydrate (MgCl ₂ · 6H ₂ O), magnesium bromide (MgBr ₂ ), magnesium iodide octahydrate (MgI ₂ · 8H ₂ O), magnesium nitrate hexahydrate (Mg (NO _{3) 3 · 6H 2 O)} , magnesium oxalate dihydrate _{(MgC 2 O 4 · 2H 2} O), magnesium sulfate (MgSO _4), and magnesium sulfate heptahydrate _(MgSO 4 · _7H 2 O) and the like .

  When manufacturing by the buyer method, the raw material bauxite is treated with a hot solution of sodium hydroxide, and the sodium aluminate solution obtained by removing the precipitate is hydrolyzed and cooled, so that iron and / or impurities are introduced. Alternatively, aluminum hydroxide containing magnesium is obtained. The obtained aluminum hydroxide is calcined at a temperature of 1000 ° C. or higher, and if necessary, calcined under vacuum, whereby alumina containing 5 ppm to 2000 ppm of iron and / or magnesium can be obtained. The alumina thus obtained contains iron and magnesium on the inner and outer surfaces of the alumina, and has a strong bond with the alumina due to the high-temperature baking treatment of aluminum hydroxide. Here, when the content of iron and / or magnesium is not 5 ppm to 2000 ppm, the amount of iron and / or magnesium is reduced by baking under vacuum, or baking is performed by adding a salt of iron and / or magnesium. By doing so, the ratio in which iron and / or magnesium are contained can be made into 5 ppm-2000 ppm by increasing the quantity of iron and / or magnesium. Such iron salts and magnesium salts are as described above.

  Alumina produced by the Bayer method contains not only iron and / or magnesium but also elements such as sodium, silicon, and calcium. If the total of these contents exceeds 2000 ppm, the charge / discharge characteristics are affected. It is desirable to remove it because it is highly likely to affect. These elements can be removed by washing with water or baking at 1000 ° C. or higher under vacuum.

  The content of the alumina of the present invention is preferably 0.1 to 99.9% by weight or more of the components contained in the coating composition excluding the solvent, and is 0.5 to 99.5% by weight. More preferably, it is 1.0 to 99.0% by weight. If it is such a range, it will adhere | attach with an electrode or a separator with sufficient adhesive force, and can form into a film, without peeling off. In addition, the solvent for the binder mentioned later is contained in a solvent.

[Binder]
The (2) binder of the present invention will be described. The coating agent composition of the present invention contains a binder. Examples of the binder include a solid (for example, particulate) binder or a liquid binder. The binder can be in a state dispersed in a solvent, a state dissolved in a solvent, a state dispersed in a solvent, and a state dissolved in a solvent.

[Solid binder]
Various known solid binders can be used as the solid binder. Examples of the solid binder include thermoplastic organic particles, organic crystals, and organic particles that crosslink during heat fusion. The average particle diameter of the solid binder is not particularly limited, and can be 0.01 to 500 μm.

  The thermoplastic organic particles are not particularly limited as long as they can be bonded by hot-melting the particles with a hot melt, and include thermoplastic polymer particles.

  Examples of thermoplastic polymers include polyethylene, polypropylene, polystyrene, polycarbonate, polyacetal, polyphenylene sulfide, liquid crystal polymer, polyvinyl chloride, celluloid, polyvinyl alcohol, polyester, polyvinyl acetate, polyethylene glycol, polymers having a polyethylene glycol structure, and carbonate groups. High polymer, polyvinylidene fluoride, polytetrafluoroethylene, styrene / butadiene rubber, polyisoprene, chloroprene rubber, acrylic rubber, polymer having cyano group, urethane rubber, ethylene propylene rubber, epichlorohydrin rubber, butadiene rubber, fluoro rubber, Ethylene-vinyl alcohol copolymer, acrylic-vinyl alcohol copolymer, epoxy resin, oxetane resin, urethane resin, acrylic resin Polysaccharides, polyimide, polyamide-imide, silicone, polymers and copolymers of these with a β- diketone structure, a prepolymer, is alloy or derivatives thereof.

As the polymer derivative having a cyano group, specifically, cyanoethylated vinyl alcohol, cyanoethylated carboxymethylcellulose, cyanoethylated pullulan, cyanoethylated cellulose, cyanoethylated starch, cyanoethylated esterified starch, cyanoethylated dextrin, cyanoethylated collagen, And nitrile rubber. Specific examples of the polymer derivative having a polyethylene glycol structure include polyethylene glycol acrylic acid amide styrene copolymer, polyethylene glycol polylactic acid copolymer, polyvinyl alcohol pendant with a polyethylene glycol chain, and the like. Specifically, as a polymer having a β-diketone structure, specifically, a polyacryl having a β-diketone structure that can be prepared by radical copolymerization of a vinyl compound having a β-diketone structure such as allyl acetoacetate and an acrylate ester. Examples thereof include ester copolymers and polyvinyl alcohol copolymerized with vinyl acetate. Specific examples of the polymer having a carbonate group include polycarbonate, CO ₂ -philic Co-polymer (CO ₂ amphiphilic copolymer), and the like.

  These thermoplastic organic particles may be used alone or in combination of two or more. As thermoplastic organic particles, it is easy to interact with ions, and from the viewpoint of ion conduction, particles of polymer derivatives having a cyano group, particles of polymer derivatives having a polyethylene glycol structure, polymers having a β-diketone structure And polymer particles having a carbonate group are preferred, polymer derivative particles having a cyano group, polymer particles having a polyethylene glycol structure, and polymer particles having a carbonate group are more preferred.

  The thermoplastic organic particles can be adjusted in molecular weight and crosslinking density to such an extent that they have a melting point and a softening point in the range of -40 to 300 ° C.

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

[Organic crystals]
Examples of organic crystals include hydrazide crystals, acid anhydride crystals, amine crystals, imidazole crystals, triazine crystals, and mixed crystals thereof. The melting point of the organic crystals is preferably 40 ° C. or higher, more preferably 50 to 300 ° C.

  As hydrazide crystals, adipic acid dihydrazide (melting point: 177 to 180 ° C.), 1,3-bis (hydrazinecarbonoethyl) -5-isopropylhydantoin (melting point: 120 ° C.), 7,11-octadecadien-1,18-di And carbohydrazide (melting point: 160 ° C.). 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 ° C.) and dicyandiamide (melting point: 208 ° C.). Examples of the imidazole crystal include 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. Examples of the triazine crystal include 2,4-diamino-6-vinyl-S-triazine (melting point 240 ° C.), 2,4-diamino-6-methacryloyloxyethyl-S-triazine (melting point 170 ° C.), and the like. Organic crystals can be used in the form of a solid solution by mixing two or more kinds for the purpose of adjusting the melting point and the softening point.

[Organic particles that crosslink during thermal fusion]
The organic particles that are crosslinked at the time of heat fusion are various known latent curable solid resin particles. Examples of latent curable solid resins include epoxy resins, mixtures of epoxy resins and oxirane compounds, (meth) acrylic acid esters, and prepolymers having active hydrogen groups. Therefore, as a particle of an organic substance that crosslinks at the time of heat fusion, a particle in which a latent thermal initiator is blended with a solid epoxy resin; a particle in which a latent thermal initiator is blended in a mixture of a solid epoxy resin and an oxirane compound Particles that are a system containing a solid (meth) acrylic acid ester and a curing agent or an initiator; and particles that are a combination of a prepolymer having an active hydrogen group and a crosslinking agent. In the present invention, (meth) acrylic acid ester refers to acrylic acid ester and methacrylic acid ester.

  As a solid epoxy resin, manufactured by DIC Corporation; EPICLON 1050 (bisphenol A type epoxy resin having a softening point of 64 to 74 ° C.), manufactured by DIC Corporation; EPICLON N-660 (cresol novolac type epoxy having a softening point of 62 to 70 ° C. Resin), manufactured by DIC Corporation; EPICLON N-770 (phenol novolac type epoxy resin having a softening point of 65 to 75 ° C.), manufactured by DIC Corporation; HP-7200HH (dicyclopentadiene type epoxy resin having a softening point of 88 to 98 ° C.) Manufactured by DIC Corporation; EPICLON HP-4700 (naphthalene type epoxy resin having a softening point of 85 to 95 ° C.), manufactured by Nagase ChemteX Corporation; EX-721 (monofunctional solid epoxy phthalimide skeleton having a melting point of 94 to 96 ° C.), Nagase Chemtex Co., Ltd .; EX-17 (Melting point 40 ° C. of lauryl alcohol (EO) 15 glycidyl ether).

  Examples of the oxirane compound include oxetane compounds. Specific examples of the oxirane compounds include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-Ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ) Ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) Ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclo Pentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl ( 3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, Roxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl- 3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa- Nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) Methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmeth) Xyl) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl- 3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl- 3-Oxetanylmethoxy) hexane, pen Erythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexas ( 3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylo Rupropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3-ethyl-3) -Oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3 -Ethyl-3-oxetanylmethyl) ether, oxetanylsilsesquioxane and the like.

  Potential thermal initiators for epoxy resins and oxirane compounds are catalysts for cationic polymerization, such as diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluoro). Phenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) ) Borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluo Phosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium / tetrakis (pentafluorophenyl) borate, 4-methoxydiphenyliodonium / hexafluorophosphate, bis (4-methylphenyl) iodonium / hexafluorophosphate, bis (4-t-butylphenyl) iodonium Hexafluorophosphate, bis (dodecylphenyl) iodonium, iodonium salts such as tricumyl iodonium hexafluorophosphate; triarylsulfonium hexafluoroa Sulfonium salts such as timonate; phosphonium salts such as triphenylpyrenylmethylphosphonium salt; (η6-benzene) (η5-cyclopentadienyl) iron (II) hexafluoroantimonate; o-nitrobenzylsilyl ether and aluminum acetylacetate Combinations with narate; combinations of silsesquioxane and aluminum acetylacetonate; and the like.

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

  Solid epoxy resin blended with latent thermal initiator, and solid epoxy resin and oxirane compound blended with latent thermal initiator, carboxylic acid, carboxylic anhydride, amine , And hardener particles such as hydrazide. Thereby, a crosslinking reaction can also be advanced at the time of heat fusion. By blending the curing agent particles, the cross-linking reaction can proceed simultaneously with the heat fusion, so that a mutually cross-linked and cross-linked structure can be obtained. The compounding amount of the curing agent is preferably 1 to 500 parts by weight, and more preferably 2 to 200 parts by weight with respect to 100 parts by weight of the solid prepolymer particles.

  Particles that are blended with a latent heat initiator in a solid epoxy resin, or particles that are blended with a latent heat initiator in a mixture of a solid epoxy resin and an oxirane compound are the solid epoxy resin. Producing solid prepolymer particles by mixing a resin or a mixture of the solid epoxy resin and oxirane compound, a latent thermal initiator, and optionally a curing agent, and then grinding. Can do. Alternatively, solid epoxy resin particles or particles of a mixture of the solid epoxy resin and the oxirane compound, initiator particles, and curing agent particles may be mixed to obtain solid prepolymer particles.

  As a system containing a solid (meth) acrylic acid ester and a curing agent or an initiator, a mixture of a methacrylic acid ester and a thermal initiator (EBECRYL 767 (manufactured by Daicel Cytec Corporation): Perhexa HC (manufactured by NOF Corporation) = 100: 5 mixture), and as a photocurable system, a mixture of a methacrylic acid ester and a photoinitiator (EBECRYL 740-40TP (manufactured by Daicel Cytec Co., Ltd.)): 1 -Hydroxy-cyclohexyl-phenyl-ketone = 100: 5) and the like.

  Examples of the crosslinking agent in the combination of the prepolymer having an active hydrogen group and the crosslinking agent include carboxylic acid, carboxylic anhydride, and metal chelate. Examples of the combination of the prepolymer having an active hydrogen group and the crosslinking agent include a mixture of polyvinyl alcohol and polycarboxylic acid and derivatives thereof, a mixture of polyvinyl alcohol and derivatives thereof with metal chelates and alkoxides, and the like. Examples of polycarboxylic acids include citric acid, butanetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, hexahydrophthalic acid, 1,3,3a, 4,5,9b-hexahydro-5 (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione (anhydride), glycerin bisanhydro trimellitate monoacetate (anhydride), 3 , 3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, ethylene glycol bisanhydrotrimellitate (anhydride), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, ethylene glycol bisanhydro Trimellitate, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, bicyclo [2.2.1] heptane-2,3-di Carboxylic acid, aspartic acid, pyromellitic acid, mellitic acid, phosphorus-containing ester group tetracarboxylic acid, phenyl ethynyl phthalic acid, oxydiphthalic acid, polyacrylic acid, polymethacrylic acid, and derivatives thereof. Among them, aromatic carboxylic acids are preferable from the viewpoint of reactivity, and those in which three or more carboxylic acids are substituted in one molecule are more preferable from the viewpoint of reactivity and crosslink density. Moreover, the acid anhydride of the above-mentioned polycarboxylic acid can also be used. Examples of metal chelates include titanium tetraisopropoxide, titanium tetranormal butoxide, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium lactate ammonium salt, titanium diisopropoxybis (triethanolaminate), etc. Titanium chelate and titanium alkoxide, zirconium tetranormal propoxide, zirconium tetraacetylacetonate, zirconium dibutoxybis (ethylacetoacetate), zirconium tributoxy monostearate, etc. zirconium chelate, alkoxide, aluminum isopropoxide, etc. Known metal compounds such as Moreover, the combination of the prepolymer which has an active hydrogen group, and a crosslinking agent may contain the said hardening | curing agent and thermal initiator depending on the case. Particles that are a combination of a prepolymer having active hydrogen groups and a crosslinker will not react with heat when mixing the prepolymer having active hydrogen groups, the crosslinker, and any hardeners and initiators present. In addition, these are mixed in a good solvent, casted thinly and dried at room temperature, and can be produced by grinding while cooling and used as an organic particle type binder that crosslinks during thermal fusion. Can do.

  The coating composition containing organic particles that are crosslinked during heat fusion as a binder is coated with the composition, and then the solvent is evaporated to simultaneously fuse the composition with the electrode or separator and / or. After fusing, crosslinking can be advanced by heating or irradiation with energy rays. Thereby, a protective film having excellent mechanical strength and high heat resistance can be obtained.

[Liquid binder]
A liquid binder can be used as the binder of the present invention.

  Various known liquid binders can be used as the liquid binder. Specific examples of the liquid binder include a mixture of a liquid prepolymer and an initiator; a solid polymer substance dissolved in a solvent; a solid inorganic substance by a sol-gel reaction; and water glass It is done.

(Mixture of liquid prepolymer and initiator)
As a mixture of a liquid prepolymer and an initiator, a combination of a photo radical initiator or a thermal radical generator and a compound having a (meth) acryl group, an allyl group, a vinyl group, a maleimide group, etc .; a photo cation initiator or A combination of a thermal cation initiator and a compound having an epoxy group, an oxirane ring such as an oxetane ring, a vinyl ether, a cyclic acetal, etc .; and a photoanion initiator, a compound having an epoxy group and / or a compound having a cyanoacrylate group And combinations thereof. The (meth) acryl group includes an acryl group and a methacryl group.

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

  As photo radical initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-Isopropylfeinyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2 Acetophenone series such as -hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1; Benzoin, benzoin methyl ether, benzoin ethyl ether Benzoins such as benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide Benzophenone series such as 3,3′-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4- Thioxanthone systems such as diethylthioxanthone and 2,4-diisopropylthioxanthone; 1-phenyl-1,2-propanedione-2 ( -Ethoxycarbonyl) oxime, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 "-diethyl Isophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 1- [4- (3-mercaptopropylthio) phenyl] -2-methyl-2-morpholine-4- Yl-propan-1-one, 1- [4- (10-mercaptodecanylthio) phenyl] -2-methyl-2-morpholin-4-yl-propan-1-one, 1- (4- {2- [2- (2-Mercapto-ethoxy) ethoxy] ethylthio} phenyl) -2-methyl-2-morpholy -4-yl-propan-1-one, 1- [3- (mercaptopropylthio) phenyl] -2-dimethylamino-2-benzyl-propan-1-one, 1- [4- (3-mercaptopropyl) Amino) phenyl] -2-dimethylamino-2-benzyl-propan-1-one, 1- [4- (3-mercapto-propoxy) phenyl] -2-methyl-2-morpholin-4-yl-propane-1 -One, bis (η5-2,4-cyclopentadien-1-yl) bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium, α-allylbenzoin, α-allylbenzoin Aryl ether, 1,2-octanedione, 1-4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Tylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and 1,3-bis (p-dimethylamino) Benzylidene) acetone and the like. Among photoradical initiators, electron donors (hydrogen donors) for intermolecular hydrogen abstraction type photoinitiators such as benzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, camphorquinone, and isobutylthioxanthone Can be added as an initiation aid. Such electron donors include aliphatic amines and aromatic amines having active hydrogen. Specific examples of the aliphatic amine include triethanolamine, methyldiethanolamine, and triisopropanolamine. Specific examples of the aromatic amine include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, and ethyl 4-dimethylaminobenzoate.

  Thermal radical generators include 4-azidoaniline hydrochloride and azides such as 4,4′-dithiobis (1-azidobenzene); 4,4′-diethyl-1,2-dithiolane, tetramethylthiuram disulfide, And disulfides such as tetraethylthiuram disulfide; octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluyl peroxide Diacyl peroxides such as di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, and di- (2-ethoxyethyl) per Peroxydicarbonates such as xydicarbonate; t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyoctanoate, octylperoxyoctanoate, t-butylperoxy-3,5,5 Peroxyesters such as trimethylhexanoate, t-butylperoxyneodecanoate, octylperoxyneodecanoate, t-butylperoxylaurate, and t-butylperoxybenzoate; di-t-butylperoxide, t- Such as butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 2,5-dimethyl-2,5-di (t-butyl) hexyne-3 Dialkyl peroxide; 2,2-bis (t-butyl Ruperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, and n-butyl-4,4-bis (t -Peroxyketals such as butylperoxy) valerate; ketone peroxides such as methyl ethyl ketone peroxide; peroxides such as p-menthane hydroperoxide and cumene hydroperoxide; 2,2'-azobis (4-methoxy-2,4-dimethylvalero) Nitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutylnitrile), 1, 1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1- Methylethyl) azo] formamide, and azonitriles such as 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2, 2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [N- (4-hydroxyphenyl) -2-methylpropionamidine] dihydrochloride, 2,2 '-Azobis [2-methyl-N- (4-phenylmethyl) propionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2' Azobis (2-methylpropionamidine) dihydrochloride, 2,2′-a Bis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2 '-Azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] and the like Azoamides; 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- (hydroxymethy ) Propionate] and the like; bipyridine; initiators with transition metals (eg, copper (I) chloride and copper (II) chloride); methyl 2-bromopropionate, ethyl 2-bromopropionate, ethyl 2 -Halogen compounds such as bromoisobutyrate;

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

  As thiourea derivatives, N, N′-dimethylthiourea, tetramethylthiourea, N, N′-diethylthiourea, N, N′-dibutylthiourea, benzoylthiourea, acetylthiourea, ethylenethiourea, N, N′-diethylenethio Examples include urea, N, N′-diphenylthiourea, and N, N′-dilaurylthiourea, with tetramethylthiourea or benzoylthiourea being preferred. Examples of the organometallic complex include cobalt naphthenate, vanadium naphthenate, copper naphthenate, iron naphthenate, manganese naphthenate, cobalt stearate, vanadium stearate, copper stearate, iron stearate, and manganese stearate. As an amine compound, an alkyl group or an alkylene group having 1 to 18 carbon atoms having 1 to 18 carbon atoms or an alkylene diamine, diethanolamine, triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethyl Phenol, 1,8-diazabicyclo (5,4,0) undecene-7, 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) -nonene-5 6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7, 2-methylimidazole, 2-ethyl-4-methylimidazole and the like. Examples of the phosphate compound include methacrylic phosphate, dimethacrylic phosphate, monoalkyl acid phosphate, dialkyl phosphate, trialkyl phosphate, dialkyl phosphate, and trialkyl phosphate. Examples of toluidine derivatives include N, N-dimethyl-p-toluidine and N, N-diethyl-p-toluidine. Examples of aniline derivatives include N, N-dimethylaniline and N, N-diethylaniline.

  A compound having a (meth) acryl group, an allyl group, a vinyl group, or a maleimide group is a liquid prepolymer. As the compound having a (meth) acryl group, butanediol mono (meth) acrylate, t-butylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) Acrylate, 2-ethoxyethyl (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxypropyl (meth) acrylate 2-methoxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, pyriethylene glycol 400 di (meth) acrylate, propylene glycol mono (meth) acrylate, polyethylene glycol Cole mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acryloxyethyl phthalate, N- (meth) acryloxy-N-carboxypiperidine, N- (meth) acryloxy-N, N-dicarboxymethyl -P-phenylenediamine, hydroxynaphthoxypropyl (meth) acrylate, (meth) acryloxyethyl phosphorisphenyl, 4- (meth) acryloxyethyl trimellitic acid, (meth) acryloxyethyl phosphate, long chain aliphatic ( (Meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butanediol mono (meth) acrylate, butoxytriethylene glycol (meth) acrylate, ECH-modified butyl ( ) Acrylate, t-butylaminoethyl (meth) acrylate, caprolactone (meth) acrylate, 3-chloro-2-hydroxypromyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclo Pentanyl (meth) acrylate, cycloaliphatic modified neopentyl glycol (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N , N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-ethyl Xyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, 2-hydroxy -3- (meth) acryloxypropyltrimethylammonium chloride, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, γ- (meta ) Acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethyleneglycol (Meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol 1000 (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, morpholine (meth) acrylate, nonylphenoxy Preethylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, octyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) ) Acrylate, phenoxyhexaethylene glycol (meth) acrylate, EO (EO = Ethylene oxide) modified phenoxylated phosphoric 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, PO ( PO = propylene oxide) modified phthalic acid (meth) acrylate, polyethylene glycol 90 (meth) acrylate, polyethylene glycol 200 (meth) acrylate, polyethylene glycol 400 (meth) acrylate, polypropylene glycol (meth) acrylate, polypropylene glycol 500 (meth) Acrylate, polypropylene glycol 800 (meth) acrylate, polyethylene glycol / polypropylene glycol (meth) acrylate, stearyl (meth) acrylate Relate, EO modified succinic acid (meth) acrylate, sodium ethoxy (meth) acrylate sulfonate, tetrafluoropropyl (meth) acrylate, tetrahydrofurfuryl (meth) EO modified bisphenol A di (meth) acrylate, acrylate, caprolactone modified tetrahydrofur Furyl (meth) acrylate, trifluoroethyl (meth) acrylate, allylated cyclohexyl di (meth) acrylate, (meth) acrylated isocyanurate, bis (acryloxyneopentylglycol) adipate, EO-modified bisphenol A di (meth) acrylate , EO modified bisphenol S di (meth) acrylate, bisphenol F di (meth) acrylate, EO modified bisphenol AD di (meth) acrylate, EO modified Bisphenol AF di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, diethylene glycol di (meth) acrylate, ECH-modified diethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, silsesquioxane (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipenta Erythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene glycol di (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, methoxy Cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol diacrylate, caprolactone-modified hydroxypivalate neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, EO modified phosphoric acid di (meta Acrylate, EO-modified tri (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triethylene glycol (meth) acrylate, triglycerol Di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate , Zinc di (meth) acrylate, isocyanate ethyl methacrylate, chlorendic acid di (meth) acrylate, methoxy ether (meth) acrylate, and 2- (methacryloyloxy) ethyltrimethylaminium bis (trifluoromethylsulfonyl) amine anion Etc.

  Examples of the compound having a vinyl group include vinyl acetate, chloroethylene, vinyltrimethoxysilane, 1-vinyl-3,4-epoxycyclohexane, vinyl acetate and the like. Examples of the compound having an allyl group include allyl alcohol, 3-aminopropene, allyl bromide, allyl chloride, diallyl ether, diallyl sulfide, allicin, allyl disulfide, and allyl isothiocyanate. As a compound having a maleimide group, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 4,4′-diphenylmethanemaleimide, m-phenylenemaleimide, bisphenol A diphenylether bismaleimide, 3,3′-dimethyl-5,5′- Examples include diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, and 1,6′-bismaleimide- (2,2,4-trimethyl) hexane. Of the compounds having a (meth) acryl group, an allyl group, a vinyl group, a maleimide group, etc., a compound having a (meth) acryl group and a compound having a vinyl group are preferred. These compounds can be cured with an electron beam even in the absence of a photoradical initiator.

  Two or more photoradical initiators and thermal radical generators can be used in combination. The content of the photo radical initiator and the thermal radical generator is 0.01 to 100 parts by weight with respect to 100 parts by weight of the compound having a (meth) acryl group, an allyl group, a vinyl group, or a maleimide group, which is a liquid prepolymer. The amount is preferably 50 parts by weight, more preferably 0.1 to 20 parts by weight, and still more preferably 1.0 to 10 parts by weight. When the photoradical initiator and the thermal radical generator are used in combination, the above content is the total content of the photoradical initiator and the thermal radical generator. Moreover, it is preferable that content of an electron donor is 10-500 weight part with respect to 100 weight part of photoradical initiators. The content of the decomposition accelerator is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the thermal radical generator.

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

  Examples of the photocationic initiator include compounds other than the combination of silsesquioxane and aluminum acetylacetonate in the latent thermal initiator for the epoxy resin and oxirane compound described above.

  A sensitizer can be used in combination with the photocationic initiator. As such sensitizers, 9,10-butoxyanthracene, acridine orange, acridine yellow, benzoflavin, cetoflavin T, perylene, pyrene, anthracene, phenothiazine, 1,2-benzacetracene, coronene, thioxanthone, fluorenone, benzophenone , And anthraquinone.

  Examples of the thermal cation initiator include latent thermal initiators for the above-described epoxy resins and oxirane compounds.

  Examples of the photoanion initiator include a 2-nitrobenzyl carbamate compound obtained by blocking a bifunctional or higher isocyanate with an o-nitrobenzyl alcohol compound, and a combination of a quinonediazide sulfonate compound and an N-alkylaziridine compound. The photoanion initiator is used for polymerizing a compound having an epoxy group and a compound having a cyanoacrylate group.

  A compound having an epoxy group, a cyanoacrylate group, an episulfide, an oxetane ring, a spiro ortho carbonate, or a vinyl ether group is a liquid prepolymer and is crosslinked with a photocationic initiator, a thermal cationic initiator, and / or a photoanionic initiator. It is a compound having a reactive substituent.

  Compounds having an epoxy group are (3 ', 4'-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate, 4-vinylcyclohexene oxide, 1-methyl-4- (2-methyloxiranyl) -7- 1 of oxabicyclo [4.1.0] heptane, epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified epsilon-caprolactone, epoxidized polybutadiene, 2,2-bis (hydroxymethyl) -1-butanol , 2-epoxy-4- (2-oxiranyl) cyclohexane adduct, 1,2-epoxy-4- (2-oxiranyl) cyclosoxane adduct of 2,2-bis (hydroxymethyl) -1-butanol, 3, 4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclo Xene carboxylate, 3,4-epoxycyclohexylmethyl methacrylate, α-olefin epoxide, epoxidized product of styrene-butadiene block copolymer, epoxidized product of styrene-butadiene block copolymer, bisphenol A type epoxy resin, bisphenol AD type Epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, α-naphthol novolak type epoxy resin, bisphenol A novolac type epoxy resin, tetrabromobisphenol A type epoxy resin, Tetraglycidyldiaminodiphenylmethane, dihydroxynaphthalene / diglycidyl ether, biphenyl type epoxy resin, silsesquioxy Type epoxy resin, isoprene type epoxy resin, isobonyl skeleton, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, epoxy modified silicone, and epoxy modified silsesqui Oxane and the like.

  Examples of the compound having a cyanoacrylate group include methyl cyanoacrylate and ethyl cyanoacrylate.

  The compound having an episulfide is a compound in which the oxygen atom of the above-mentioned compound having an epoxy group is substituted with a sulfur atom, ethylene sulfide, propylene sulfide, 1-butene sulfide, 2-butene sulfide, isobutylene sulfide, 1-pentene sulfide. 2-pentene sulfide, 1-hexene sulfide, 1-octene sulfide, 1-dodecene sulfide, cyclopentene sulfide, cyclohexene sulfide, styrene sulfide, vinylcyclohexene sulfide, 3-phenylpropylene sulfide, 3, 3, 3 -Trifluoropropylene sulfide, 3-naphthylpropylene sulfide, 3-phenoxypropylene sulfide, 3-naphthoxypropylene sulfide, butadiene monosulfide, and 3-tri Etc. chill silyl oxypropylene sulfide and the like.

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

  Examples of the compound having spiro ortho carbonate include spiro glycol diallyl ether and bicycloorthoester.

  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, allyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether. 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethano Distearate ether, triethylene glycol divinyl ether, trimethyl propane trivinyl ether, and pentaerythritol tetra vinyl ether.

  Among the compounds having an epoxy group, a cyanoacrylate group, an episulfide, an oxetane ring, a spiro ortho carbonate, or a vinyl ether group, a compound having an oxetane ring is preferable.

  Two or more photocationic initiators, thermal cationic initiators and photoanionic initiators can be used in combination. The addition amount of these photocation initiator, thermal cation initiator and photoanion initiator is 100 weight of a compound having an epoxy group, a cyanoacrylate group, an episulfide, an oxetane ring, a spiro ortho carbonate, or a vinyl ether group which is a liquid prepolymer. The amount is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, and still more preferably 1.0 to 10 parts by weight with respect to parts. When a photocationic initiator, a thermal cation initiator, and a photoanion initiator are used in combination, the above content is the total content of the photocationic initiator, the thermal cation initiator, and the photoanion initiator. Moreover, it is preferable that content of a sensitizer is 5-500 weight part with respect to 100 weight part of photocation initiators.

(Liquid binder with solid polymer dissolved in solvent)
Examples of the liquid binder obtained by dissolving a solid polymer substance in a solvent include those obtained by dissolving the aforementioned polymer particles in a solvent and those suspended in a solvent. As a solvent, it can select suitably from the solvent which can melt | dissolve a solid polymer, and can mix and use 2 or more.

  As a solid polymer substance, completely saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray Poval PVA-124, Nippon Vinegar Poval Co., Ltd .; JC-25, etc.), partially saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray Poval PVA-235, manufactured by Nihon Vinegar Pover Co., Ltd .; JP-33, etc.) Modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; Kuraray K Polymer KL-118, Kuraray C Polymer CM-318, Kuraray R Polymer R-1130, Kuraray LM Polymer LM-10HD, manufactured by NIPPON BI POVAL Co., Ltd .; D polymer DF-20, anion-modified PVA AF-17, alkyl-modified PVA ZF-15, carboxymethyl cellulose (manufactured by Daicel Industries, Ltd .; H-CMC, DN -100L, 1120, 2200, Nippon Paper Industries Mical Co., Ltd .; MAC200HC, etc.), Hydroxyethylcellulose (Daicel Industrial Co., Ltd .; SP-400, etc.), Polyacrylamide (MT Aqua Polymer Co., Ltd .; Acoflock A-102), Polyoxyethylene (Meisei Chemical Industries, Ltd.) ; Alcox E-30), epoxy resin (manufactured by Nagase ChemteX Corporation; EX-614, manufactured by Japan Chemtech Co., Ltd .; Epicoat 5003-W55, etc.), polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd .; Epomin P-1000) , Polyacrylic acid ester (manufactured by MT Aquapolymer Co., Ltd .; Acofloc C-502, etc.), and saccharides and derivatives thereof (Wako Pure Chemical Industries, Ltd .; Chitosan 5, manufactured by Nissho Chemical Co., Ltd .; esterified starch lacta, glyco Made by Co., Ltd .; cluster dextrin, poly Chirensuruhon acid (Tosoh Organic Chemical Co., Ltd .; Bolinas PS-100, etc.) a water-soluble polymer such as may be used in a state dissolved in water.

  As solid polymer substances, acrylic ester polymerization emulsions (manufactured by Showa Denko KK; Polysol F-361, F-417, S-65, SH-502), and ethylene / vinyl acetate copolymer emulsion (manufactured by Kuraray Co., Ltd.) An emulsion such as Panflex OM-4000NT, OM-4200NT, OM-28NT, OM-5010NT) can be used in a state suspended in water. Further, as a solid polymer substance, polyvinylidene fluoride (manufactured by Kureha Co., Ltd .; Kureha KF Polymer # 1120), modified polyvinyl alcohol (manufactured by Shin-Etsu Chemical Co., Ltd .; cyanoresin CR-V), modified pullulan (Shin-Etsu Chemical Co., Ltd.) A polymer such as Cyanoresin CR-S) can be used in a state dissolved in N-methylpyrrolidone.

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

  A liquid binder obtained by dissolving a solid polymer substance in a solvent can be solidified by removing the solvent by heating and / or reducing the pressure. Such a binder can also improve the ionic conductivity of the coating film by impregnating the electrolytic solution in the coating film to form a gel electrolytic layer.

(Liquid binder that becomes solid inorganic substance by sol-gel reaction)
Liquid binders that become solid inorganic substances by sol-gel reaction include triethoxysilane, trimethoxysilane, aluminum isopropoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxy. Titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethylacetoacetate), titanium diisopropoxybis (triethanol) Aminates), titanium lactate, polyhydroxytitanium stearate, zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetraacetylacetonate , Zirconium tributoxy monoacetylacetonate, zirconium monobutoxy acetylacetonate bis (ethylacetoacetate), zirconium dibutoxy bis (ethylacetoacetate), zirconium tetra acetylacetonate, zirconium tributoxy monostearate and the like. Moreover, the catalyst for sol-gel reaction can be added to these. The catalyst for the sol-gel reaction is not particularly limited as long as it is a catalyst for a reaction in which an inorganic component is hydrolyzed and polycondensed. Examples of such catalysts include acids such as hydrochloric acid; alkalis such as sodium hydroxide; amines; or dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin dimalate, dioctyltin dilaurate, dioctyltin dimaleate, octyl Organotin compounds such as tin oxide; Organotitanate compounds such as isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraalkyl titanate; tetrabutyl zirconate, tetrakis (acetyl Acetonato) zirconium, tetraisobutylzirconate, butoxytris (acetylacetonato) zirconium, zirconium naphthenate Organozirconium compounds such as; tris (ethylacetoacetate) aluminum, tris (acetylacetonate) organoaluminum compounds such as aluminum; zinc naphthenate, cobalt naphthenate, organic metal catalysts such as cobalt octylate, and the like. Among these, a dibutyltin compound (SCAT-24 manufactured by Sansha Machinery Chemical Co., Ltd.) is mentioned as a commercial product. These compounds can be used alone or in combination of two or more.

(Water glass)
In addition to the liquid binder that becomes a solid inorganic substance by the sol-gel reaction, water glass is mentioned as a liquid binder from which a solid inorganic substance is obtained. Specifically, No. 1 water glass, No. 2, water glass, No. 3 water glass of JIS standard table K1408, 1 type of sodium metasilicate, 2 types of sodium metasilicate, 1 type of potassium silicate, 2 type of potassium silicate, and Lithium silicate or the like can be used.

  The content of the binder is preferably a practically sufficient addition amount without filling the voids generated between the particles. In the coating agent composition of the present invention, the content of the binder is preferably 0.01 to 49 parts by weight with respect to 100 parts by weight of the total inorganic particles including the alumina of the present invention and the further inorganic filler. 5 to 30 parts by weight is more preferable, and 1 to 20 parts by weight is even more preferable.

[solvent]
The (3) solvent of the present invention will be described. The coating composition of the present invention has a solvent for generating voids accompanying transpiration and adjusting fluidity. The solvent can be evaporated by heat drying, vacuum drying, freeze drying, or a combination thereof. Moreover, the electrolyte solution solvent used for an electrical storage element can be added previously, and the impregnation of electrolyte can also be assisted. Solvents include hydrocarbons (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, amylbenzene, turpentine oil, pinene, etc.), halogenated hydrocarbons (chlorinated) Methyl, chloroform, carbon tetrachloride, ethylene chloride, methyl bromide, ethyl bromide, chlorobenzene, chlorobromomethane, bromobenzene, fluorodichloromethane, dichlorodifluoromethane, difluorochloroethane, etc.), alcohol (methanol, ethanol, n-propanol, (Isopropanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, n-heptanol, 2-octanol, n-dodecanol, nonanol, cyclohexanol, glycidol, etc.) Ether, acetal (ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, ethyl benzyl ether, furan, furfural, 2-methyl furan, cineol, methylal), ketone (acetone, methyl ethyl ketone, Methyl-n-propyl ketone, methyl-n-amyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone, acetophenone, etc.), ester (methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, acetic acid-n- Amyl, methyl cyclohexyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl stearate, propylene carbonate, diethyl carbonate, ethylene carbonate, vinylene car , Etc.), polyhydric alcohols and derivatives thereof (ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, propylene glycol, propylene Glycol monoethyl ether), fatty acids and phenols (formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, isovaleric acid, phenol, cresol, o-cresol, xylenol, etc.), nitrogen compounds (nitromethane, nitroethane, 1-nitropropane, nitrobenzene, monomethylamine, dimethylamine, trimethylamine, monoethylamine Min, diamylamine, aniline, monomethylaniline, o-toluidine, o-chloroaniline, dicyclohexylamine, dicyclohexylamine, monoethanolamine, formamide, N, N-dimethylformamide, acetamide, acetonitrile, pyridine, α-picoline, 2, 4-lutidine, quinoline, morpholine, etc.), sulfur, phosphorus, other compounds (carbon disulfide, dimethyl sulfoxide, 4,4-diethyl-1,2-dithiolane, dimethyl sulfide, dimethyl disulfide, methanethiol, propane sultone, phosphoric acid Liquids such as triethyl, tophenyl phosphate, diethyl carbonate, ethylene carbonate, amyl borate), inorganic solvents (liquid ammonia, silicone oil, etc.) and water.

  In the coating agent composition of the present invention, a solvent can be added at an arbitrary ratio in order to adjust the viscosity in accordance with the coating apparatus. The coating agent composition of the present invention preferably has a viscosity of 1 to 10,000 mPa · s, more preferably 2 to 5000 mPa · s, and even more preferably 3 to 1,000 mPa · s from the viewpoint of coating properties. preferable. The kind and content of the solvent for obtaining such a viscosity can be determined as appropriate. In the present invention, the viscosity is a value obtained with a cone plate type rotational viscometer.

  The coating agent composition of the present invention includes other particles, a core-shell type foaming agent, a salt, an ionic liquid, a coupling agent, a stabilizer, an antiseptic, and a surface activity, as long as the object of the present invention is not impaired. An agent can be included.

[Other particles]
The coating agent composition of the present invention can further contain one or more particles selected from the group consisting of further inorganic fillers, organic fillers, and carbon-based fillers as other particles.

[Further inorganic filler]
As further inorganic fillers, powders of metal oxides such as alumina, silica, zirconia, beryllia, magnesium oxide, titania and iron oxide; sols such as colloidal silica, titania sol and alumina sol, clays such as talc, kaolinite and smectite Minerals; 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; Examples include hydroxides such as aluminum, magnesium hydroxide, and iron hydroxide; barium titanate, strontium carbonate, magnesium silicate, lithium silicate, sodium silicate, potassium silicate, and glass. Further, examples of the inorganic filler that can be added to such an extent that the insulating property is not impaired include lithium cobaltate and olivine type lithium iron phosphate. In the present invention, alumina containing iron and / or magnesium is not included in the further inorganic filler.

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

  The further inorganic filler may be used in the form of powder, or in the form of a water-dispersed colloid such as silica sol or aluminum sol or in a state dispersed in an organic solvent such as organosol.

  The size of the further inorganic filler particles is preferably in the range of 0.001 to 100 μm, more preferably in the range of 0.005 to 10 μm.

  The content of the further inorganic filler is preferably 0.1 to 49.9% by weight, and preferably 0.5 to 49.5% by weight, based on the total of the alumina of the present invention and the further inorganic filler. Is more preferably 1 to 49% by weight. If it is such a range, the internal resistance reduction effect by the alumina containing iron and / or magnesium will further improve.

  Examples of the organic filler include polymers that are three-dimensionally cross-linked among polymers such as acrylic resin, epoxy resin, and polyimide and that do not substantially plastically deform, cellulose particles, fibers, and flakes. An organic filler can be used 1 type or in combination of 2 or more types.

  Examples of the carbon filler include graphite, acetylene black, and carbon nanotube. A carbon type filler can be used combining 1 type or 2 types or more. The carbon-based filler is a particle that can be added to such an extent that the insulating property is not impaired.

  The size of the organic filler and / or carbon-based filler particles is as described above for the further inorganic filler including preferable ones. Content of an organic filler and a carbonaceous filler is 0.1-49. With respect to the sum total of the alumina which contains 5 ppm-2000 ppm of iron and / or magnesium, the further inorganic filler, and an organic filler and / or a carbonaceous filler. It is preferably 9% by weight, more preferably 0.5 to 49.5% by weight, and even more preferably 1 to 49% by weight. In addition, when an organic filler and a carbonaceous filler are included, said content is the sum total of an organic filler and a carbonaceous filler.

[Core-shell type foaming agent]
The coating agent composition of the present invention can contain a core-shell type foaming agent. As such a foaming agent, EXPANCEL (made by Nippon Philite Co., Ltd.) etc. can be used. Since the shell is organic, long-term reliability with respect to the electrolyte is poor. Therefore, what coat | covered this core shell type foaming agent with the inorganic substance further can also be used. Examples of such inorganic substances include metal oxides such as alumina, silica, zirconia, beryllia, magnesium oxide, titania and iron oxide; sols such as colloidal silica, titania sol and alumina sol; gels such as silica gel and activated alumina; mullite and the like Complex oxides; hydroxides such as aluminum hydroxide, magnesium hydroxide, and iron hydroxide: and barium titanate.

By using a core-shell type foaming agent that combines a shell that softens at a certain temperature and a core made of a material whose volume expands due to evaporation due to heating, etc., the foaming agent foams when the battery runs out of heat. In addition, the distance between the electrodes can be increased, and thereby the shutdown function can be exhibited. Furthermore, since the shell portion expands greatly, the distance between the electrodes can be increased, thereby preventing a short circuit or the like. Further, since the expanded shell portion maintains its shape even after the heat generation has subsided, it is possible to prevent the electrodes from being narrowed again and short-circuiting again. In addition, by coating the core-shell type foaming agent with an inorganic substance, the influence of electrolysis during charging and discharging can be reduced, and further, the active hydrogen group on the inorganic substance surface becomes a counter ion when conducting ions, thereby improving the ionic conductivity. It can also be increased efficiently.
The content of the core-shell type foaming agent is preferably 1 to 99 parts by weight, more preferably 10 to 98 parts by weight, based on 100 parts by weight of the total of the alumina and the binder of the present invention. More preferred is -97 parts by weight.

[salt]
The coating agent composition of the present invention can contain salts that serve as various ion sources. Thereby, ion conductivity can be improved. It is also possible to add the electrolyte of the battery used. In the case of a lithium ion battery, as an electrolyte, lithium hydroxide, lithium silicate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (pentafluoro) Ethanesulfonyl) imide, lithium trifluoromethanesulfonate, and the like. In the case of a sodium ion battery, sodium hydroxide, sodium perchlorate, and the like are included. 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, examples of the electrolyte include magnesium perchlorate. In the case of an electric double layer capacitor, examples of the electrolyte include tetraethylammonium tetrafluoroborate, triethylmethylammonium bis (trifluoromethanesulfonyl) imide, and tetraethylammonium bis (trifluoromethanesulfonyl) imide.

  The content of the salt is preferably 0.1 to 300 parts by weight, more preferably 0.5 to 200 parts by weight, with respect to 100 parts by weight of the total of the alumina and the binder of the present invention. More preferably, it is 1 to 100 parts by weight. The salt may be added as a powder, made porous, or dissolved in a compounding component.

[Ionic liquid]
The coating agent composition of this invention can contain the liquid which has ionicity. The ionic liquid may be a solution in which the salt is dissolved in a solvent or an ionic liquid. Examples of the solution in which the salt is dissolved in a solvent include a solution in which a salt such as lithium hexafluorophosphate or tetraethylammonium borofluoride is dissolved in a solvent such as dimethyl carbonate.

  Examples of ionic liquids include imidazo such as 1,3-dimethylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide, 1-ethyl-3-methylimidazolium bromide and the like. Pyridinium salt derivatives such as 3-methyl-1-propylpyridinium bis (trifluoromethylsulfonyl) imide and 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide; tetrabutylammonium heptadeca Alkylammonium derivatives such as fluorooctane sulfonate and tetraphenylammonium methanesulfonate; phosphonium salt derivatives such as tetrabutylphosphonium methanesulfonate; polyalkylene glycol and lithium perchlorate Composite conductivity imparting agent of the complex, such as the arm and the like.

  The content of the ionic liquid is preferably 0.01 to 40 parts by weight, and 0.1 to 30 parts by weight with respect to 100 parts by weight of alumina containing iron and / or magnesium at a ratio of 5 ppm to 2000 ppm. More preferably, it is 0.5 to 5 parts by weight.

[Stabilizer]
The coating agent composition of the present invention can contain a stabilizer. Specific examples of such stabilizers include 2,6-di-tert-butyl-phenol, 2,4-di-tert-butyl-phenol, 2,6-di-tert-butyl-4-ethyl- Phenolic antioxidants such as phenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butyl-anilino) -1,3,5-triazine; alkyl Aromatics such as diphenylamine, N, N′-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-N′-isopropyl-p-phenylenediamine Amine-based antioxidants; dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, bis [2-methyl-4- {3-n-al Kilthiopropionyloxy} -5-tert-butyl-phenyl] sulfide, sulfide hydroperoxide decomposer such as 2-mercapto-5-methyl-benzimidazole; tris (isodecyl) phosphite, phenyldiisooctylphosphite, diphenyl Phosphorous such as isooctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate diethyl ester, sodium bis (4-tert-butylphenyl) phosphate Hydroperoxide decomposition agents; salicylate light stabilizers such as phenyl salicylate and 4-tert-octylphenyl salicylate; 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzo Benzophenone light stabilizers such as enone-5-sulfonic acid; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetra Benzotriazole light stabilizers such as methylbutyl) -6- (2N-benzotriazol-2-yl) phenol]; phenyl-4-piperidinyl carbonate, bis- [2,2,6,6-sebacate] Hindered amine light stabilizers such as tetramethyl-4-piperidinyl]; Ni light such as [2,2′-thio-bis (4-t-octylphenolate)]-2-ethylhexylamine-nickel- (II) Stabilizers; cyanoacrylate light stabilizers; oxalic anilide light stabilizers; fullerene light stabilizers such as fullerene, hydrogenated fullerene, and fullerene hydroxide That. These stabilizers can 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 5.0 parts by weight, with respect to 100 parts by weight of the alumina of the present invention. More preferably, it is -1.0 weight part.

[Preservative]
The coating composition of the present invention can further contain a preservative, whereby the storage stability of the composition can be adjusted.

  Examples of preservatives include acids such as benzoic acid, salicylic acid, dehydroacetic acid, and sorbic acid; salts such as sodium benzoate, sodium salicylate, sodium dehydroacetate, and potassium sorbate; 2-methyl-4-isothiazolin-3-one And isothiazoline preservatives such as 1,2-benzisothiazolin-3-one; alcohols such as methanol, ethanol, isopropyl alcohol, and ethylene glycol; parahydroxybenzoates, phenoxyethanol, benzalkonium chloride, chlorhexidine hydrochloride Etc.

  These preservatives can be used alone or in combination of two or more.

  The content of the preservative is preferably 0.0001 to 1.0 part by weight and more preferably 0.0005 to 0.5 part by weight with respect to 100 parts by weight of the alumina of the present invention.

[Surfactant]
The coating agent composition of the present invention can further contain a surfactant for the purpose of adjusting the wettability and antifoaming property of the composition. Moreover, the coating agent composition of this invention can contain an ionic surfactant for the purpose of improving an ionic conductivity further.

  Surfactants include anionic surfactants such as soap, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate (eg, dodecyl benzene sulfonate), polyoxyethylene alkyl ether phosphate, poly Oxyethylene alkyl phenyl ether phosphate, N-acyl amino acid salt, α-olefin sulfonate, alkyl sulfate ester salt, alkyl phenyl ether sulfate ester salt, methyl taurate, trifluoromethane sulfonate, pentafluoroethane sulfonate , Heptafluoropropane sulfonate, and nonafluorobutane sulfonate, and the counter cation includes sodium ion and lithium ion. In the lithium ion battery, a lithium ion type surfactant is more preferable, and in the sodium ion battery, a sodium ion type surfactant is more preferable.

  Examples of amphoteric surfactants include alkyldiaminoethylglycine hydrochloride, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amide propyl betaine, fatty acid alkyl betaine, sulfobetaine And amide oxide.

  Nonionic (nonionic) type surfactants include polyethylene glycol alkyl ester type compounds, alkyl ether type compounds such as triethylene glycol monobutyl ether, ester type compounds such as polyoxysorbitan ester, alkylphenol type compounds, fluorine type compounds, Examples include silicone type compounds.

  Surfactant can be used 1 type or in combination of 2 or more types.

  The content of the surfactant is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 20 parts by weight, with respect to 100 parts by weight of the alumina of the present invention. More preferably, it is 10 parts by weight.

  The coating agent composition of the present invention is used for forming a coating layer on a non-aqueous power storage element. Specifically, the coating agent composition of the present invention is a composition for a coating layer formed on at least the surface of a member of a non-aqueous storage element, for example, an electrode of a non-aqueous storage element or a separator of a non-aqueous storage element. Used. A part of the coating layer obtained by using the coating agent composition of the present invention may enter the inside of the electrode or the separator.

[Method for producing coating composition]
The coating agent composition of the present invention can be prepared by mixing and stirring the above components. In addition, you may mix the alumina of this invention in the state disperse | distributed to the solvent. Stirring can be performed using a stirring device such as a propeller mixer, a planetary mixer, a hybrid mixer, a kneader, an emulsifying homogenizer, and an ultrasonic homogenizer. Moreover, it can also stir, heating or cooling as needed.

[Manufacturing method of coat layer]
In the method for producing a coating layer obtained using the coating agent composition of the present invention, when the binder is dissolved in a solvent, at least one layer of the coating agent composition is formed on the electrode or separator surface. And a step of evaporating the solvent. In the case where the binder is a solid that does not dissolve in a solvent, a step of forming at least one layer of the coating composition on the electrode or separator surface, a step of evaporating the solvent, and a temperature condition for evaporating the solvent In the case where the solid binder is not heat-sealed, a step of heat-sealing the solid binder is included.

[Method of forming layer of coating agent composition]
Examples of the method for forming the layer of the coating agent composition include a gravure coater, a slit die coater, a spray coater, and dipping. The thickness of the coating agent composition layer can be adjusted according to the thickness of the coating layer obtained by drying the coating agent composition layer. In the present invention, from the viewpoint of electrical characteristics and adhesion, the thickness of the coat layer is preferably 0.01 to 100 μm, more preferably 0.05 to 50 μm. If the thickness of the coat layer is too thin, the insulation against electronic conduction is deteriorated and the risk of short-circuiting increases. If the thickness of the coat layer is too thick, the resistance increases in proportion to the thickness, so that the resistance to ionic conduction increases and the charge / discharge characteristics deteriorate.

[Method of transpiration of solvent]
The solvent can be evaporated by heating or vacuuming, and a heating method such as a hot stove, an infrared heater, a heat roll, etc. can be used, and vacuum drying is performed by applying a coating composition layer in the chamber. It can be dried by putting an electrode or a separator of the non-aqueous power storage element having a vacuum. Moreover, when using a solvent with sublimation property, a solvent can also be evaporated by freeze-drying. The heating temperature and heating time in the heating method are not particularly limited as long as the temperature and time at which the solvent evaporates, and can be, for example, 80 to 120 ° C. and 0.1 to 2 hours. By evaporating the solvent, the components excluding the solvent of the coating agent composition of the present invention are brought into close contact with the member of the nonaqueous power storage element, whereby the coating layer of the present invention is formed. When the binder is hot melt particles, the coating layer of the present invention is formed by heat-sealing after the solvent is evaporated.

[Heating method]
In the present invention, when the binder is used in the form of particles, the binder can be heat-sealed and solidified. In that case, the particles can be solidified by heat fusion at a temperature at which the particles are completely melted, or the surfaces of the organic particles can be melted and welded and cooled in a state of being in close contact with each other. It can also be solidified in a state where it is in close contact with a gap. According to the former heat fusion solidification, there are many portions in a continuous phase, and ion conductivity, mechanical strength, and heat resistance are high. According to the latter heat fusion solidification, since there are few portions in the continuous phase, the ion conductivity, mechanical strength and heat resistance through the fused organic particles are inferior. Impregnation can improve ion conductivity. Further, since the latter has a structure in which gaps are randomly opened, the effect of preventing a short circuit can be enhanced by preventing the linear growth when dentlite is generated. Examples of the heat fusion method at the time of hot melt include known methods such as hot air, hot plate, oven, infrared ray, ultrasonic fusion, and the like, and the density of the coating layer can be increased by pressing at the time of heating. In addition to natural cooling, cooling can be performed by a known method such as cooling gas or pressing on a heat sink. Moreover, when heating to the temperature which a binder melt | dissolves, it can heat for 0.1 to 1000 second at the temperature which a binder melt | dissolves.

[Magnetic field and / or electric field orientation]
In the production method of the present invention, the compounded material can be solidified in an oriented state using a magnetic field and / or an electric field. Thereby, the coating layer which has anisotropy in ion conductivity, mechanical strength, and heat resistance can be formed. In addition, an anisotropic filler can be used, and the ion conductivity can be improved by orienting the major axis so as to stand perpendicular to the electrode surface. The magnetic field and / or electric field may be a static magnetic field and / or electric field or a time-varying magnetic field and / or electric field such as a rotating magnetic field and / or electric field, and the magnetic field and electric field may be applied simultaneously.

  By the manufacturing method of the present invention including the above steps, a member of a non-aqueous power storage element having a coat layer on the surface thereof is obtained. Note that at least a part of the coat layer may be formed so as to enter the inside of the member of the non-aqueous power storage element. The porosity of the coat layer is 40% or more, preferably 40 to 90%, and more preferably 40 to 80%.

[Electrodes and / or separators]
Examples of the electrode include a known nonaqueous battery and a positive electrode and / or a negative electrode of an electric double layer capacitor, and at least one surface thereof can be coated or impregnated with the coating agent composition of the present invention. Examples of the separator include a porous material made of polypropylene or polyethylene, a nonwoven fabric made of cellulose, polypropylene, polyethylene, or polyester, and a non-woven fabric and a film made of polypropylene, and the coating agent composition of the present invention is applied or impregnated on both sides or one side. You can. The coating layer of the present invention can be used in close contact with the opposing separator or electrode, and the separator and electrode are in close contact before the solvent evaporates and then dried or hot pressed after battery assembly. Thus, these members can be brought into close contact with each other.

[Non-aqueous storage element]
The present invention relates to a non-aqueous electricity storage device including an electrode and / or a separator having a coat layer formed on the surface thereof using the coating agent composition of the present invention. Non-aqueous storage elements include various known non-aqueous systems such as lithium ion primary batteries and secondary batteries, calcium ion primary batteries and secondary batteries, magnesium ion primary potentials and secondary batteries, and sodium ion primary batteries and secondary batteries. A battery and an electric double layer type capacitor are mentioned. These non-aqueous power storage elements can be manufactured by a known method. In addition, the non-aqueous storage element can be impregnated with an electrolytic solution in a coating layer to impart ionic conductivity, or the coating layer itself can have ionic conductivity and can be incorporated into a battery as a solid electrolyte membrane.

  EXAMPLES The present invention will be specifically described below using examples, but the present invention is not limited to these.

[Test Example 1]
About the alumina tried by the Example and comparative example which are mentioned later, content of iron, magnesium, and a sodium element was evaluated with the following method. The evaluation results are shown in Tables 1 and 3.

(Measurement of metal element content in alumina)
Put 0.3g of alumina in a Teflon pressure decomposition vessel (HU-25, manufactured by Sanai Kagaku) with an internal volume of 25ml, add 10ml of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd .; for measuring harmful metals), and heat at 230 ° C for 24 hours. The alumina was decomposed under pressure. The solution after pressure decomposition was introduced into an inductively coupled plasma mass spectrometer (ICPM-8500, manufactured by Shimadzu Corporation), and the metal element content was quantified. The content ratio of the metal element was calculated by dividing the content (mass) of the metal element by the mass of the whole substance, and the unit was expressed in ppm. For example, in the case of iron, calculation was performed by dividing the mass of Fe contained in the alumina of the sample by the mass of the sample.

[Test Example 2]
(Porosity)
The porosity was measured about the coating layer manufactured by the Example and comparative example which are mentioned later. The constituent materials of the coat layer are A, B, C,..., N, the respective weights are W _A , W _B , W _C ,..., W _n , and the respective true densities are D _A , D _B , D _C ,. , D _n and the coating layer thickness t, the porosity of the coating layer can be calculated from the following formula.

Porosity = (1− (W _A / D _A + W _B / D _B + W _C / D _C +... + W _n / D _n ) / t) × 100

The measurement results are shown in Tables 1 and 3.

[Test Example 3]
(Transport rate of lithium)
About the coat layer formed in the surface of the separator manufactured by the Example and comparative example which are mentioned later, the transport number of lithium was measured with the following method. Note that the coating layer formed on the surface of the electrode is not measured because it cannot be measured by being sandwiched between metallic lithium electrodes.

(Electrochemical cell for lithium transport number measurement)
An electrochemical cell for lithium transport number measurement was assembled as follows. A separator having a separator or a coating layer formed on the surface was punched out to a diameter of 24 mm to prepare a test piece. The test piece was introduced into a dry glove box, sandwiched between coin-type metallic lithium with a diameter of 16 mm, and placed on the bottom of a stainless steel beaker-type container with an inner diameter of 24 mm. Electrolytic lithium hexafluorophosphate / EC: DEC = 1: 1 1M electrolytic solution (manufactured by Kishida Chemical Co., Ltd .; LBG-96533) is impregnated into a separator or a separator having a coating layer formed on its surface, and a metallic lithium electrode A stainless steel current collector having a diameter of 16 mm was placed from above. A spring for adhering the metallic lithium electrode and the separator was placed on the stainless steel current collector, and the stainless steel lid was closed from above. A PTFE O-ring was inserted between the lid and the beaker container so that the metal lithium electrodes on both sides of the separator were not short-circuited. A bipolar cell using a lid and a beaker type container as an external terminal was used. EC is ethylene carbonate, DEC is diethyl carbonate, and PTFE is polytetrafluoroethylene.

(Transportation measurement of lithium)
Using the lithium transport number measurement cell, an AC voltage was applied to the metal lithium electrodes on both sides of the separator having a separator or a coating layer formed on the surface thereof, and AC impedance measurement was performed. Next, a DC voltage of 10 mV was applied between the metal lithium electrodes, and the change with time of the DC current was measured. After applying a DC voltage for 2 hours, AC impedance was measured with the DC voltage applied, and from these results, the lithium transport number was determined based on the following known Evans equation.

t ⁺ = I _s (ΔV−I ₀ R ₀ ) / (I ₀ (ΔV−I _s R _s ))

Wherein, t ⁺ is a lithium transference number, I _s is the DC current in the steady state, [Delta] V is the applied voltage, I ₀ is the initial current, R ₀ is the initial interfacial resistance, R _s is the surface resistance at steady state . A steady state was obtained after 2 hours from the application of DC voltage. Further, the current after one second was I _s by applying a voltage. The measurement results are shown in Tables 1 and 3.

[Test Example 4]
The following characteristics were measured for the lithium ion secondary batteries manufactured in Examples and Comparative Examples described later.

(Initial capacity measurement)
To obtain the initial capacity, the battery was charged at a constant current of 0.005 mA until the voltage reached 4.2 V, and then charged at a constant voltage of 4.2 V for 2 hours. Thereafter, the battery was discharged at a constant current of 0.005 mA until the voltage reached 3.5V. This was repeated three times, and the third discharge capacity was set as the initial capacity.

(Capacity maintenance rate)
The discharge rate was obtained from the initial capacity, and the discharge capacity for each discharge rate was measured. The charge was increased to 4.2 V with a constant current over 10 hours each time, and then charged with a 4.2 V constant voltage for 2 hours. Thereafter, the battery was discharged at a constant current to 3.5 V over 10 hours, and the discharge capacity at this time was set to a discharge capacity of 0.1 C. Next, the battery was fully charged at a current value of 0.1 C, discharged at a current value at which discharge was completed in 12 minutes, and the discharge capacity at that time was determined to be the discharge capacity at 5 C. The capacity retention rate at the 5C rate when the discharge capacity at 0.1C was 100% was calculated. The calculated capacity retention rate is shown in Table 1.

(Cycle life)
A charge and discharge test was performed in which the battery was charged to 4.2 V at 1 C, charged at a constant voltage of 4.2 V for 2 hours, and then discharged to 3.5 V at 1 C. At this time, it was calculated what percentage the discharge capacity was with respect to the first discharge, and the number of times of charging and discharging when the capacity was less than 80% was defined as the lifetime. Tables 2 and 4 show the number of times of charging and discharging that are measured lifetimes.

(Heat resistance insulation test)
Charge to 4.2V at 1C, charge for 2 hours at a constant voltage of 4.2V and fully charged, then raise the temperature from 25 ° C to 260 ° C in 10 ° C increments per hour, then increase to approximately 25 ° C in 1 hour The test which cools 20 degreeC at a time was implemented, and the alternating current impedance after an endurance test was measured. The evaluation criteria were as follows.
The impedance of 1 kHz is ◎; 10 MΩ or more × less than 1 kΩ Evaluation results are shown in Tables 2 and 4.

(Check heat resistant appearance)
The test method was the same as the heat-resistant insulation test described above, and the battery after the test was disassembled to confirm the internal state. The evaluation criteria were as follows.
A: There was no direct touch between the positive electrode and the negative electrode, and the insulation state was maintained, and the battery electrode protective layer was in close contact with the electrode and / or the separator. It is shown in Table 4.

[Example 1]
In Example 1, a coating obtained by coating a separator with a coating agent composition containing a solvent, a binder, and an alumina containing a specific amount of iron produced by an alkoxide method, and evaporating the solvent. A method of manufacturing a separator having a layer and manufacturing a lithium ion secondary battery using the separator will be described.

(Manufacture of coating agent composition)
(Manufacture of alumina particles)
In a glass reaction vessel having a capacity of 5000 cc, 2000 g of 2-propanol (Wako Pure Chemical Industries, Ltd., code: 163-04841), ferric chloride (Wako Pure Chemical Industries, Ltd., code: 093-01672) 1.45 g And 1000 g of aluminum isopropoxide (Alfa Aesar, code: 014007) were added and stirred for 5 hours. Hydrolysis was performed by adding 2400 g of ion-exchanged water little by little while stirring. After reacting for 1 week, the solvent was evaporated by heating to 100 ° C. to obtain a dry powder of alumina hydrate. The obtained alumina hydrate was put in an electric furnace and fired at 1300 ° C. to obtain α-alumina. α-alumina was placed in a polyethylene container having a capacity of 1 L, 1000 g of zirconia balls having a diameter of 15 mm were placed, and pulverized at 100 rpm for 3 days to produce alumina particles.

(Production of alumina slurry)
In a 500 mL polypropylene container, 250 mL of ion exchange water and 250 g of alumina particles were added and stirred for 12 hours to prepare a 50% dispersion. The dispersion was filtered with a nylon mesh having an opening of 20 μm, and water removed in the process was added to prepare a dispersion containing 50% alumina particles.

(Composition of composition)
200 g of water was added to 500 g of the dispersion, and 5 g of polyoxyethylene (manufactured by Meisei Chemical Industry Co., Ltd .; Alcox E-30) was added and dissolved by stirring for 6 hours to obtain a coating composition. In the coating composition, the alumina content in the components excluding the solvent was 98% by weight.

(Manufacture of a separator having a coating layer)
The above composition was applied to a polyolefin micro-multilayer separator (Celgard Corp .; # 2400, film thickness 25 μm) using a gravure coater so that the dry thickness was 5 μm, and heated at 60 ° C. for 60 seconds to obtain a thickness. A separator having a 5 μm coat layer on its surface was produced.

(Manufacture of positive electrode)
To a 10 L planetary mixer with a cooling jacket, 520 parts of 15% NMP solution of PVdF (manufactured by Kureha; Kureha KF Polymer # 1120), lithium cobaltate (abbreviation: LCO) (manufactured by Nippon Chemical Industry Co., Ltd .; Cellseed C- 5H) 1140 parts, 120 parts of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd .; Denka Black HS-100) and 5400 parts of NMP were added and stirred until the liquid temperature did not exceed 30 ° C. until uniform. This was coated on a rolled aluminum current collector (manufactured by Nippon Foil Co., Ltd .; width 300 mm, thickness 20 μm) with a width of 180 mm and a thickness of 200 μm, and dried in a 130 ° C. hot air oven 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 μm.

(Manufacture of negative electrode)
In a 10 L planetary mixer with a cooling jacket, 530 parts of 15% NMP solution of PVdF (polyvinylidene fluoride) (manufactured by Kureha Co., Ltd .; Kureha KF Polymer # 9130), 1180 parts of graphite (manufactured by Nippon Graphite Co., Ltd .; GR-15), 4100 parts of NMP was added and stirred until it became uniform while cooling so that the liquid temperature did not exceed 30 ° C. This was coated on a rolled copper foil current collector (manufactured by Nippon Foil Co., Ltd .; width 300 mm, thickness 20 μm) with a width of 180 mm and a thickness of 200 μm, and dried in a 100 ° C. hot air oven 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 μm.

(Manufacture of lithium ion secondary batteries)
Cut the positive electrode and negative electrode to 40 mm x 50 mm so that the short side is 10 mm wide and the active material layer is not coated on both ends, and the positive electrode has aluminum tabs on the exposed metal parts. A nickel tab was joined to the negative electrode by resistance welding. A separator having a coat layer is cut to a width of 45 mm and a length of 120 mm, folded back into three and sandwiched so that the positive electrode and the negative electrode face each other, and this is an aluminum laminate cell with a width of 50 mm and a length of 100 mm. The sealant was sandwiched between the portions where the tabs hit, and the sealant portion and the side perpendicular to the sealant were heat laminated to form a bag. This was placed in a vacuum oven at 80 ° C. for 24 hours and dried in a vacuum oven, and then in a drive lobe box, lithium hexafluorophosphate / EC: DEC = 1: 1 1 M electrolyte (manufactured by Kishida Chemical Co., Ltd .; LBG-96533) Was injected and vacuum impregnated, and then the remaining electrolyte was handled and sealed with a vacuum sealer to produce a lithium ion secondary battery.

[Example 2]
A coating agent composition was produced in the same manner as in Example 1 except that the amount of ferric chloride was changed to 0.725 g. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 3]
A coating agent composition was produced in the same manner as in Example 1 except that the amount of ferric chloride was changed to 0.290 g. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 4]
A coating agent composition was produced in the same manner as in Example 1 except that the amount of ferric chloride was changed to 0.072 g. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 5]
A coating agent composition was produced in the same manner as in Example 1 except that the amount of ferric chloride was changed to 0.022 g. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 6]
A coating agent composition was produced in the same manner as in Example 1 except that the amount of ferric chloride was 0.0036 g. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 7]
A coating composition was produced in the same manner as in Example 1 except that 4.175 g of magnesium chloride hexahydrate was added instead of ferric chloride. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 8]
A coating agent composition was produced in the same manner as in Example 1 except that 2.087 g of magnesium chloride hexahydrate was added instead of ferric chloride. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 9]
A coating agent composition was produced in the same manner as in Example 1 except that 0.835 g of magnesium chloride hexahydrate was added instead of ferric chloride. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 10]
A coating composition was produced in the same manner as in Example 1 except that 0.209 g of magnesium chloride hexahydrate was added instead of ferric chloride. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 11]
A coating composition was produced in the same manner as in Example 1 except that 0.063 g of magnesium chloride hexahydrate was added instead of ferric chloride. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 12]
A coating agent composition was produced in the same manner as in Example 1 except that 0.0104 g of magnesium chloride hexahydrate was added instead of ferric chloride. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 13]
A coating agent composition was produced in the same manner as in Example 1, except that the amount of ferric chloride was 0.072 g, and 0.835 g of magnesium chloride hexahydrate was further added. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 14]
A coating composition was prepared in the same manner as in Example 1 except that the amount of ferric chloride was 0.072 g, and further 0.835 g of magnesium chloride hexahydrate and 0.317 g of sodium chloride were added. did. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Example 15]
In Example 15, a positive electrode having a coating layer obtained by coating a positive electrode with a coating composition composed of alumina containing a solvent, a binder, and iron and magnesium and evaporating the solvent, A method for producing a lithium ion secondary battery using a battery will be described.

(Manufacture of coating agent composition)
Manufactured in the same manner as in Example 1 except that the amount of ferric chloride was 0.072 g and 0.835 g of magnesium chloride hexahydrate was added.

(Manufacture of positive electrode)
Manufactured by the method of Example 1.

(Manufacture of negative electrode)
Manufactured by the method of Example 1.

(Manufacture of positive electrode with coat layer)
The said coating agent composition was applied to the said positive electrode using the gravure coater so that the dry thickness might be set to 5 micrometers, and it heated at 60 degreeC * 60 second, and manufactured the positive electrode which has a coating layer of thickness 5 micrometers on the surface.

(Manufacture of lithium ion secondary batteries)
It was produced in the same manner as in Example 1 except that a positive electrode having a coat layer was used and a separator having no coat layer was used.

[Example 16]
A coating composition was prepared in the same manner as in Example 1 except that the amount of ferric chloride was 0.072 g, and further 0.835 g of magnesium chloride hexahydrate and 0.317 g of sodium chloride were added. did. The electrodes and the lithium ion battery were produced in the same manner as in Example 15.

[Comparative Example 1]
A coating agent composition was produced in the same manner as in Example 1 except that ferric chloride was not added. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Comparative Example 2]
A coating agent composition was produced in the same manner as in Example 1 except that the amount of ferric chloride was 7.250 g, and further 20.874 g of magnesium chloride hexahydrate was added. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Comparative Example 3]
A coating agent composition was produced in the same manner as in Example 1 except that 0.317 g of sodium chloride was added instead of ferric chloride. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 1.

[Comparative Example 4]
A coating agent composition was produced in the same manner as in Example 15 except that ferric chloride and magnesium chloride hexahydrate were not added. Further, the electrodes and the lithium ion battery were produced in the same manner as in Example 15.

[Comparative Example 5]
A lithium ion secondary battery was produced in the same manner as in Example 1 except that an electrode having no coating layer and a separator were used.

[Example 17]
In Example 17, the separator is coated with a coating agent composition containing a solvent, a binder, and alumina containing a specific amount of iron and magnesium produced by the Bayer method, and the solvent is evaporated. A method for producing a separator having a coating layer and producing a lithium ion secondary battery using the separator will be described.

(Manufacture of coating agent composition)
(Production of aluminum hydroxide by the buyer method)
3 L of a sodium hydroxide aqueous solution (350 g / L) was placed in a PTFE container having a capacity of 5 L, and 600 g of bauxite (manufactured by Excel Industries) was added. While stirring, the mixture was heated to 170 ° C. with a heater to dissolve the alumina component in the bauxite. Next, insoluble materials such as iron oxide, silica, and titanium oxide were filtered off. 1 L of water was added to 1 L of the filtrate, and then allowed to cool to precipitate aluminum hydroxide. The precipitate was collected and washed with water according to the following procedure. After adding 1 L of water to 100 g of the precipitate and stirring for 1 hour, the mixture was allowed to stand for 5 hours to precipitate aluminum hydroxide. The supernatant was discarded, and the aluminum hydroxide remaining in the container was collected by filtration. The water washing performed in the above procedure was repeated 10 times, and then dried at 80 ° C. for 24 hours to obtain a dry powder of aluminum hydroxide.

(Production of α-alumina using aluminum hydroxide synthesized by the Bayer method)
500 g of dry powder of aluminum hydroxide was placed in an electric furnace and calcined at 1300 ° C. for 2 hours to obtain α-alumina. α-Alumina was placed in a polyethylene container having a capacity of 1 L, 1000 g of zirconia balls having a diameter of 15 mm were placed, and the mixture was pulverized for 3 days at 100 rpm. 8 L of water was put into a polyethylene container having a capacity of 10 L, the pulverized alumina particles were added, stirred for 20 minutes, and left for 24 hours to recover the precipitated alumina particles, which was then washed with water. The alumina particles after washing with water were dried at 150 ° C. to produce powdery alumina particles.

(Production of alumina slurry)
A slurry was produced in the same manner as in Example 1 except that alumina particles produced by the Bayer method were used.

(Composition of composition)
The composition was blended in the same manner as in Example 1 except that an alumina slurry produced from alumina particles produced by the Bayer method was used. In the composition, the content of alumina among the components excluding the solvent was 98% by weight.

(Manufacture of a separator having a coating layer)
A separator having a coating layer was produced in the same manner as in Example 1.

(Manufacture of positive electrode)
A positive electrode was produced in the same manner as in Example 1.

(Manufacture of negative electrode)
A negative electrode was produced in the same manner as in Example 1.

(Manufacture of positive electrode, negative electrode and lithium ion secondary battery)
A positive electrode, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 1.

[Example 18]
A coating agent composition was produced in the same manner as in Example 17 except that the α-alumina was washed with water five times. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 17.

[Comparative Example 6]
A coating agent composition was produced in the same manner as in Example 17 except that the aluminum hydroxide was washed once with water. The separator, electrode, and lithium ion battery were also produced in the same manner as in Example 17.

  As is clear from the results in Table 1, for Examples 1 to 6, since the iron content in alumina is in the range of 5 ppm to 2000 ppm, Comparative Example 2 in which the iron content is greater than 2000 ppm, and Compared with Comparative Examples 1 and 3 in which the iron content is less than 5 ppm, the cation transport number is high and the capacity retention rate is high. Moreover, about Examples 7-12, since the content of magnesium in alumina is in the range of 5 ppm to 2000 ppm, Comparative Example 2 in which the magnesium content is more than 2000 ppm, and the magnesium content is more than 5 ppm. Compared with few Comparative Examples 1 and 3, the cation transport number is high and the capacity retention rate is high. Further, Examples 13 and 14 used alumina containing 100 ppm of iron and 400 ppm of magnesium, had a high cation transport number, and the capacity retention rate was comparable to the value of Comparative Example 5 where no coat layer was used. From the results of Examples 15 and 16, it is clear that a high capacity retention ratio can be obtained even if the coat layer is formed on the electrode. By comparing Examples 13 and 15 using alumina containing iron and magnesium with Examples 14 and 16 using alumina containing iron in addition to iron and magnesium, the capacity retention rate is clearly due to the presence of sodium. It turns out that it falls.

  As is clear from the results in Table 2, Examples 1 to 16 and Comparative Examples 1 to 4 in which lithium ion batteries having separators or electrodes having a coating layer containing alumina or the alumina of the present invention as a filler were produced, In the heat resistance insulation test and the heat resistance appearance confirmation, excellent effects are obtained. Moreover, it turns out that the cycling characteristics of Examples 1-16 using the separator or electrode which has a coating layer show favorable cycling characteristics compared with the comparative example 5 which does not use a coating layer.

  As is apparent from the results in Table 3, in the case of Example 17 using a separator having a coating layer containing alumina containing a specific amount of iron and magnesium produced by the Bayer method, the cation transport number is high and the capacity is maintained. The rate is high. Further, Example 18 in which the sodium content was reduced by repeating the water washing shows a further excellent capacity retention rate. Moreover, also in the heat-resistant insulation test and heat-resistant external appearance confirmation, both Example 17 and Example 18 had excellent effects, and the cycle characteristics were also good. On the other hand, Comparative Example 6 using a separator having a coating layer containing alumina other than the present invention, which is manufactured by the Bayer method, has a low cation transport number and a low capacity retention rate. .

  Since the coating layer formed using the coating composition of the present invention has a high cation transport number, it has a low internal resistance and maintains a cycle life and capacity retention rate, while maintaining a high heat resistance non-aqueous storage element. Can be provided.

[Explanation of symbols]
1 Coat layer 2 Active material layer 3 Current collector 4 Separator

Claims (6)

  A coating composition for a non-aqueous storage element, comprising alumina containing 5 ppm to 2000 ppm of iron and / or magnesium, a binder, and a solvent.   The coating agent composition for non-aqueous power storage elements according to claim 1, wherein the alumina contains 50 ppm or more and less than 200 ppm of iron.   The coating agent composition for non-aqueous power storage elements according to claim 1 or 2, wherein the alumina contains 200 ppm or more and less than 500 ppm of magnesium.   The electrode for non-aqueous storage elements which has a coating layer formed using the coating agent composition for non-aqueous storage elements of any one of Claims 1-3.   The separator for non-aqueous energy storage elements which has a coating layer formed using the coating agent composition for non-aqueous energy storage elements of any one of Claims 1-3.   A non-aqueous storage element comprising the non-aqueous storage element electrode according to claim 4 and / or the non-aqueous storage element separator according to claim 5.