TW201136008A - Composition for electrode of non-aqueous electrolyte secondary battery, electrode and battery - Google Patents

Abstract

In conventional compositions for the electrodes of non-aqueous electrolyte secondary batteries, the binder resin inside the electrode rises to the surface of the electrode and electrode peeling and cracking occur if the drying phase is carried out rapidly at high temperatures. Thus, there is a need to carry out drying by gradually increasing the temperature from a low temperature. Also, because of the necessity to complete drying in a restricted drying zone when continuously manufacturing electrodes, there is a difficulty whereby a long period of time is required for the drying phase, with manufacturing line speeds of even 10m/min. The use of the disclosed composition for the electrodes of non-aqueous electrolyte secondary batteries, which contains an electrode active material, a binder resin, a liquid material, and a polymer exhibiting cationic properties in the liquid material, enables: the reduction of time for the drying phase; the inhibition of the rising of the binder resin to the surface of the electrode even when rapidly drying at high temperatures; and the improvement of the productivity for electrodes due to the possibility to significantly increase the speed of the manufacturing line.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition, an electrode and a battery for a nonaqueous electrolyte battery electrode. [Previous Art] A composition for a non-aqueous electrolyte battery negative electrode comprising an electrode active material, a binder resin, and a liquid material, or an electrode active material, a binder, is disclosed in Japanese Laid-Open Patent Publication No. SHO-62-90863 A composition for a non-aqueous electrolyte battery positive electrode of a resin, a conductive carbon, and a liquid material. SUMMARY OF THE INVENTION The present invention provides: a non-aqueous electrolyte battery electrode composition comprising an electrode active material, a binder resin, a liquid material, and a polymer which is cationic in the liquid material; [2] An electrode obtained by applying a composition for a nonaqueous electrolyte battery electrode such as the above π] to a current collector, and removing the liquid material from the obtained coating material; [3] A non-aqueous electrolyte storage battery characterized by comprising an electrode as described above and a non-aqueous electrolyte. [Embodiment] The composition for non-hydrolyzed liquid battery electrode of the present invention comprises an electrode active material, a binder liquid, a liquid substance, and a polymer which is cationic in the liquid substance, and is simply referred to as a cationic polymer. ). As the electrode active material, it is suitable to occlude and release the active substance of the ion 152565.doc 201136008. The electrode active material includes a negative electrode active material and a positive electrode active material, and examples of the negative electrode active material include various carbonaceous materials and metal composite oxides, and the positive electrode active material may, for example, be a metal composite oxide, preferably containing lithium and optionally A metal composite oxide of a metal of more than one of iron, cobalt, nickel, and manganese. As the negative electrode active material, carbonaceous materials such as amorphous carbon, graphite, natural graphite, MCMB (Mesocarb® microbeads, mesocarbon microbeads), pitch-based carbon fibers, and polyacene are preferable; and AxMy〇 a composite metal oxide represented by p (wherein A represents Li, M represents at least one selected from the group consisting of c〇, Νι, Ab, Sn, and Μη, and 〇 represents an oxygen atom; X represents an insufficiency of 1.1〇2Χ2〇) · The number of 05, 丫 indicates that the number of 4 〇〇 ^ 2 〇 85 is satisfied ' Ρ indicates that 5·0 〇 2 ρ ^; 1.5 number). The positive electrode active material is exemplified by LixM〇2 (wherein, ^ represents one or more kinds of transition metals, preferably at least one of Co, Μη or Ni, and X represents a number of 1.10> χ > 0.05 ), &LixM2〇4 (wherein M represents one or more transition metals, preferably river 11, \ represents satisfies the number of i 1〇>χ>〇〇5), and specific examples thereof Lift: LiC〇〇2, LiNi〇2

LlxNlyC〇(丨-y)〇2 (wherein X is 1.00 gt; X > 0.05, y is 1 > y > 0), and LiMn204. The point compound resin may, for example, be a fluorinated polymer, a diene polymer, an olefin polymer, a styrene polymer, an acrylate polymer, a polyamine or a polyimide polymer, An ester polymer, a vinyl chloride polymer, a vinyl acetate polymer, and a cellulose polymer. The fluorinated polymer 'is exemplified by polyvinylidene fluoride. 152565.doc 201136008 As the diene polymer, polybutadiene, polyisoprene, isoprene-isobutylene copolymer, natural rubber, stupid ethylene-ruthenium, 3 butadiene copolymer, Styrene-isoprene copolymer, 1,3-butadiene-isoprene·acrylonitrile copolymer, styrene-1,3-butadiene-isoprene copolymer, 1,3-butyl Diene-acrylonitrile copolymer, stupid ethylene-acrylonitrile-oxime, 3-butadiene-methyl methacrylate copolymer, stupid ethylene-acrylonitrile 4,3-butadiene-itaconic acid copolymer, styrene -Acrylonitrile_1,3_Butadiene_Methyl methacrylate-fumaric acid copolymer, stupid ethylene_1,3-butadiene_itaconic acid_Methyl methacrylate-acrylonitrile copolymer , acrylonitrile-1,3-butadiene-mercaptoacrylic acid-methyl methacrylate copolymer, styrene-1,3-butadiene-itaconic acid_methyl methacrylate-acrylonitrile copolymer And a styrene-acrylonitrile-1,3-butadiene-methyl methacrylate-fumaric acid copolymer. Examples of the olefin-based polymer include an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, polystyrene, polyethylene, polypropylene, an ethylene-vinyl acetate copolymer, and an ethylene-based ionomer. Polyvinyl alcohol, vinyl acetate polymer, ethylene-vinyl alcohol copolymer, vaporized polyethylene, polyacrylonitrile, polyacrylic acid, polyacrylic acid, and gas sulfonated polyethylene. The styrene-based polymer may, for example, be a styrene-ethylene-butadiene copolymer, a styrene-butadiene-propylene copolymer, a styrene-isoprene copolymer or a styrene-n-butyl acrylate. - itaconic acid-methyl methacrylate-acrylonitrile copolymer, and styrene-n-butyl acrylate-itaconic acid-mercapto acrylate-acrylonitrile copolymer. The acrylate-based polymer may, for example, be polydecyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate or acryl 152565.doc 201136008 ester-acrylonitrile copolymer, and acrylic acid 2 - Ethylhexyl ester - methacrylate - glycerol - methoxy polyethylene glycol monodecyl acrylate. The polyamidamide-based or polyamidimide-based polymer may, for example, be a polyamine 6, a polyamine 66, a polyamine 11, a polyamine 12, an aromatic polyamine or a polyimine. The ester-based polymer may, for example, be polyethylene terephthalate or polybutylene terephthalate. The cellulose polymer 'may be carboxymethyl cellulose, stearyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, carboxyethyl methyl cellulose', etc. Record salt, metal salt and other salts. Further, examples of the binder resin include a styrene-butadiene block copolymer, a styrene-butadiene-styrene block copolymer, and a styrene-ethylene-butylene-styrene block copolymer. a block copolymer such as a styrene-isoprene block copolymer or a styrene ethylene-propylene-styrene block copolymer; an ethylene-gas-ethylene copolymer; a bake-ethylene acetate copolymer; Other methacrylate polymers. These polymers may be used singly or in combination of two or more. The binder resin is preferably a particle, and the particle size thereof is preferably 〇〇〇5~i〇〇, more preferably 〇. (Η~50哗' is particularly good for 〇.〇5~3 〇. Here, the so-called "The particle size of the binder tree g" is a measurement of the length of the binder resin particles obtained by drying the composition for a non-aqueous electrolyte battery electrode of the present invention by an electron microscope. The average value of the value. The term "liquid substance" as used in the month of the month refers to a substance which is liquid at normal temperature and normal pressure. The liquid substance may, for example, be a substance containing an oxygen-containing organic compound having water and/or atmospheric pressure of 152565.doc 201136008, and having an oxygen-containing organic compound of TC. By using an oxygen-containing organic compound having an atomic point of 50,350 C. The non-aqueous electrolyte battery electrode composition of the compound can be used to produce an electrode more operably, and the "more uniform electrode active material layer can be easily formed. It does not cause coating of the non-aqueous electrolyte battery electrode composition. The liquid substance may include a liquid organic substance other than an oxygen-containing organic compound as an oxygen-containing organic substance having a boiling point of 50 to 350 ° C under normal pressure, in the range of a decrease in the properties of the obtained battery or a decrease in the performance of the obtained battery. Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, pentanol, isoamyl alcohol 'methyl isobutyl methanol, 2-ethylbutanol, 2- Ethylhexanol, cyclohexanol, decyl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexanediol, glycerin, etc., containing an alcoholic base; dipropylene, diisopropyl hydrazine, dibutyl ether, diisobutyl ether , di-n-pentyl ether, diisoamyl ether, decyl butyl ether, fluorenyl dibutyl mystery, methyl a saturated aliphatic ether compound such as glutinous eclipse, sulfhydryl hydrazine, ethyl propyl ether, ethyl isopropyl sulfonate, ethyl butyl bond, ethyl isobutyl hydrazine, ethyl n-pentamidine, ethyl isopentyl bromide; An unsaturated aliphatic ether compound such as allyl ether or ethyl allyl ether; an aromatic ether compound such as phenyl ether, phenethyl ether, phenyl ether or benzyl ether; or a cyclic ether compound such as tetrahydrofuran, tetrahydropyran or dioxane. _; ethylene glycol monoterpene ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other glycol Ether compound; monocarboxylic acid compound such as formic acid, acetic acid, anhydrous acetic acid, acrylic acid, citric acid, propionic acid, butyric acid; butyl phthalate, amyl citrate, propyl acetate, isopropyl acetate, butyl acetate, acetic acid Second butyl ester, amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, butyl ring 152565.doc 201136008 Brewed, ethyl propionate, butyl propionate, propionic acid Amyl ester, butyl butyrate, diethylene carbonate, diethyl oxalate, methyl lactate, ethyl lactate, butyl lactate, diethyl sulphate Etoxacinate compound; acetone, acetonide, methyl ketone, acetobutyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetyl ketone, diacetone alcohol, cyclohexyl a ketone compound such as a ketone, a cyclopentanone, a methylcyclohexanone or a cycloheptanone; a dicarboxylic acid compound such as succinic acid, glutaric acid, adipic acid, undecanoic acid, propionic acid or trans-coconic acid; And N• decyl pyrrolidone, preferably N-methyl ub. _. As a liquid substance, it is preferably water and N•methylpyrrolidone. As a liquid substance, water and oxygenated organic compounds can also be used. The mixture, the amount of the oxygen-containing organic compound in the mixture is preferably 0.1 to 1 part by weight, and 1 to 20 parts by weight, more preferably 0.5 to 50 parts by weight, based on 1 part by weight of water. High scores of nitrogen atoms in the molecule

The value calculated by the software.

As a cationic polymer, a sub-compound. Cationic; I; A mPa.s~3000 mPa/s 〇

The cationic polymer may, for example, be a cationic polymer having a viscosity of usually a poly-resin such as a polyether resin such as a polyethylene polyamine or a polypropylene polyamine; Modified resin; polyamine polyurea resin; amine ester resin; melamine-formaldehyde resin, urea-formaldehyde resin, polyamine polyurea/furfural resin; containing secondary or tertiary amine group or four-stage a copolymer of an acrylic polymer and the above acrylamide; a dicyano cationic compound such as a polyvinylamine, a polyethylene hydrazine or a dicyandiamide-furaldehyde copolymer; a dicyandiamide-polyvinylamine copolymer or the like Polyamine-based cationic compound; epichlorohydrin-didecylamine copolymer; monopropyl propyl hydrazino-S〇2 polycondensation product; diallylamine salt-so2 polycondensation product; gasified diallyl Dimethylammonium polymer, vaporized diallyl dimercapto _ acrylamide copolymer; copolymer of allylamine salt; dialkylaminoethyl acrylate tetrabasic salt copolymer ; acrylamide-diallylamine copolymer; diammonium propyl propyl Amides polymer; 5 and a cationic resin having an amidine structure of the ring. Further, 'the polymer which is cationic in the liquid substance may, for example, be a polystyrene-epichlorohydrin resin (refer to International Publication No. 2008/024444, 152565.doc. 〇. 201136008) JP-A-2010-501670 and Japanese Patent Laid-Open No. Hei 2-170825); di-propylamine hydrochloride-acrylamide copolymer (refer to Japanese Patent Laid-Open No. Hei 6-184246); a product obtained by reacting a polyalkyleneamine with urea or a dicarboxylic acid, and reacting with an aldehyde compound, a cogand alcohol compound and/or an alcohol compound to obtain a water-soluble polymer (refer to Japanese Patent Publication No. Sho 44-11667) The product obtained by condensation reaction of a polyalkylene polyamine with urea is disclosed in Japanese Patent Publication No. Sho 61-42931, Japanese Patent Publication No. Sho 61-42931, and Japanese Patent Laid-Open No. SHO 62-101621. a water-soluble polymer obtained by reacting with an aldehyde compound, a surface-alcohol compound, and/or an α,γ-dental-β-alcohol compound (refer to Japanese Patent Laid-Open No. Hei 4_1〇〇997); Or polyamines and acrylic compounds a product obtained by a Michael additix reaction of a polarized α,β·unsaturated monomer such as a methacrylic acid compound, and further reacted with a polyamine, α,β_* saturated monomer, respectively. The highly branched polyamidoamine compound obtained (the so-called starburst dendrimer, refer to Japanese Patent Laid-Open Publication No. SHO-6-5295); A polyamine polyurea resin obtained by a reaction of a urea or a cyanic acid (refer to Japanese Laid-Open Patent Publication No. SHO 55-A No. 837); a diisocyanate compound or a polyisocyanate compound having a tertiary amino group and at least two hydroxyl groups in the molecule The water-soluble resin obtained by the reaction of the hydroxy compound (refer to Japanese Patent Laid-Open No. Hei 6-166993); 52565.doc -10- 201136008 The amine compound having a primary or secondary amine group has at least 2 rings in the molecule. The epoxy compound of the oxy group is reacted to obtain a modified product of the polyamine resin (refer to Japanese Patent Laid-Open Publication No. Hei 2 〇〇 181996); U) is selected from the group consisting of alkylenediamine and polyalkylene Polyamine At least one of the groups, (b) a urea compound, (c) is selected from at least one aromatic compound having a group consisting of a primary ring or a secondary amine compound and an aromatic epoxy compound, and (d) Selecting at least one compound selected from the group consisting of an aldehyde compound, a pronol compound, and an α,γ_: _-β-alcohol compound, and obtaining a water-reactive resin (refer to Japanese Patent Laid-Open Publication No.); (a) at least one selected from the group consisting of alkylenediamines and polyalkylene polyamines, (8) urea compounds, and (4) selected from the group consisting of aldehyde compounds, epihalohydrin compounds, and α'γ-dental A water-soluble resin obtained by reacting at least one compound of a group consisting of a β-alcohol compound (refer to Japanese Laid-Open Patent Publication No. Hei 7-57997). The composition for a nonaqueous electrolyte battery electrode of the present invention may contain two kinds of the above cationic polymers. As the cationic polymer, it is preferably a polystyrene amine gas, a diallylamine hydrochloride-propyleneamine copolymer, a polyamine resin modified product 2 polyamine polyurea resin, preferably It is a modification of polyamidoamine-epichlorohydrin resin, diene P-amine hydrochloride hydrochloride acrylamide copolymer and polyamine resin. The composition for a non-aqueous electrolyte battery electrode according to the present invention comprises an electrode monthly substance, a #合骑, a liquid substance, and a cationic polymer. The composition of the non-aqueous electrolyte battery electrode of the present invention can be further advanced as needed. I52565.doc 201136008 contains other additives. The other additives may, for example, be a viscosity adjusting agent dissolved or swollen in a liquid substance, a conductive agent such as graphite or B-black, or a conductive material such as a metal powder or a water-soluble polymer. In the case where the electrode active material is a negative electrode active material, the composition for a non-aqueous electrolyte battery electrode of the present invention is preferably a viscosity adjusting agent which is dissolved or filled in a liquid substance. In the case where the electrode active material is a positive electrode active material, the composition for a non-aqueous electrolyte battery electrode of the present invention preferably contains a lead 2h. When the liquid material is water, the nonaqueous electrolyte battery electrode composition of the present invention preferably contains a water-soluble polymer. The method for producing the nonaqueous electrolyte battery electrode composition of the present invention is not limited. Specific examples of the production method include a method in which an electrode active material is mixed with a binder resin or a cationic polymer, and a liquid material is added to the obtained compound; and the electrode active material and the liquid compound are cationic. Polymer mixing 'method of adding ▲, ruthenium to the obtained mixture; method of simultaneously mixing electrode active material, binder resin, and cationic liquid substance; and 'bonding resin', liquid substance, cation A method in which a polymer is mixed and an additive is added to the obtained mixture. The cationic polymer may be previously mixed with the electrode active material, may be mixed with the binder resin in advance, or may be mixed with the liquid substance in advance. The cationic polymer may also be mixed with an electrode active material, a mixture of gluten and a liquid substance. In particular, the cationicity is higher. Electrode active materials, binder resins and liquids are more efficient. The σ substance is mixed with the cationic substance in the composition for non-aqueous electrolyte battery electrode of the present invention. 152565.doc 12 201136008 The content of the molecule is not limited, and the cation is preferably 001 ln ^ by weight relative to the resin of the point compound. The reference is °01·10 to 10 times, more preferably 0.05 to 5 times, and particularly preferably G.1 to 1 times 'extra good for Q 2 to 〇 5 times. The non-aqueous electrolyte battery material of the present invention has no limitation on the electrode active material in the X-ray electrode composition, and the electrode is preferably used on a reset basis, and is preferably relative to the binder resin. For Bu ^ (8) times, 3 to 300 times, especially good for 5 to 200 times. . ... 2 50 (H. 'Youjia is: the content of the liquid substance in the composition for the non-aqueous electrolyte battery electrode of the invention is also not limited, and the liquid substance 皙 _ _ mass basis, relative to the adhesive reading It is preferably 2 to 5 (9) times, more preferably 3 to 3 times, and particularly preferably 5 to 200 times. By using an electrode active material and a binder resin, it is a cationic spit in a liquid substance. The composition for non-aqueous electrolyte battery electrode, which can be easily mixed with a molecule and a liquid substance, can be further mixed by using a disperser such as a ball mill or a sand mill, an ultrasonic disperser, a homogenizer or the like. Further, a non-aqueous electrolyte f battery electrode composition can be obtained. The electrode of the present invention is obtained by applying the composition for a non-aqueous electrolyte battery electrode of the present invention to a current collector. The coating material (the current collector in which the composition layer is formed) is dried and produced by removing the liquid material, and the electrode active material layer in which the electrode active material is fixed to the substrate formed on the surface of the current collector is formed on the current collector. If the collector contains conductive materials, then The limitation is preferably made of a metal such as iron, copper, aluminum, nickel or stainless steel, and the shape thereof is not limited to a sheet having a thickness of about 0.001 to 0.5 mm. The non-aqueous electrolyte battery electrode composition is applied to the current collection. Coating 152565.doc 13 201136008 The method is also not limited. For example, using the slit die coating method, the reverse roll coating method, the direct squeezing method, the knife knives, the dipping method, the smashing, the brushing, etc. The composition of the non-battery electrode on the non-under-expanded M-cavity method, the extrusion coating method, and the immersion collector is applied to the coating composition of the composition for the electrolyte battery electrode, which is also limited by the helmet to remove the liquid by drying. The material is also.,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, (hereinafter referred to as "drying step") There is no limitation on the method. For example, use ', 弘, π. * Let's use warm air, hot air 'low humidity' s dry; use (far) infrared or Drying of electron beam, etc. As for drying conditions, usually does not cause stress Concentration causes the electrode active material layer to be cracked, or the electrode active material layer is not peeled off from the current collector, and the drying speed is adjusted so that the binder resin does not rise. The drying temperature is not limited, and is preferably 6 〇~2〇〇t: It is more preferable to dry the surface of the surface of the C-150 c. The surface composition of the non-aqueous electrolyte battery electrode of the present invention does not have to be from a low temperature to a high temperature stage. Drying at a high temperature and performing high temperature (for example, 100 C to 150. Rapid drying under the nipple, since the adhesion of the binder resin to the surface of the electrode can also be suppressed, the composition for the non-aqueous electrolyte battery electrode is used. In comparison with the case, the productivity of the electrode is further improved. In the case of continuous electrode fabrication, the line speed of the line is also unlimited. When the composition for a non-aqueous electrolyte battery electrode of the present invention is used, it is dried at a linear velocity of, for example, 0.5 m/min to 100 m/min, preferably 2 〇m/min to 1 〇〇m/min, or Cracking of the electrode active material layer may occur, and the electrode active material layer may not be peeled off from the current collector. The nonaqueous electrolyte secondary battery of the present invention comprises an electrolytic solution and an electrode of the present invention. The electrolytic solution contains the electrolytic solution f and the electrolytic solution solvent, and can be selected to function as a battery depending on the type of the electrode active material. As the electrolyte, a known lithium salt can be used. Specific examples are: ucl〇4, LiBFe, LiPF6, LiCF3S〇3, LiCF3C〇2, LUsF6, ^,

LiB10Cl10, LiAICl4, UC1, 玢, LiB(c2HA CF3S〇3Li 'CH3S〇3Li, UCF3S〇3, uC4F9S〇3

Li(CF3S〇2)2N and the lower fatty acid lithium carboxylate e right electrolyte solvent are generally used in the field of nonaqueous electrolyte batteries. Specific examples thereof include a propylene carbonate solvent such as propylene carbonate, ethylene carbonate, butylene carbonate, dinonyl carbonate, diethyl carbonate or decyl carbonate; a lactone solvent such as γ-butyrolactone; Ether solvent such as decane, hydrazine, 2-dimethoxyethane 'diethyl ether, 2. ethoxyethane, tetrahydrofuran, 2 methyltetrahydrofuran; sulfoxide solvent such as dimercaptoarthene; hydrazine, 3_ Dioxolane, 4-mercapto-1,3-dioxolane and other oxolane solvents; nitrogen-containing solvents such as acetonitrile or nitromethane; methyl decanoate, methyl acetate, ethyl acetate, butyl acetate , an organic acid ester solvent such as methyl propionate or ethyl propionate; a mineral acid glutinous gluten-based granule such as a phosphate triester or a carbonic acid diester such as a carbonic acid, a monoethyl carbonate or a dipropylene vinegar; Ethylene glycol dimethyl solvate; triethylene glycol dimethyl solvate; sulfolane solvent; 3-methyl-2-oxazolidinone and other alpha oxazolidinone solvent; hydrazine, 3_ propane sultone, 1, A single or a mixture of two or more of a sultone solvent such as 4-butane sultone or naphthalene lactone. The non-aqueous electrolyte secondary battery of the present invention contains, in addition to the electrolytic solution and the electrode of the present invention, 152565.doc •15·201136008, and includes a separator and the like, and can be manufactured according to a usual method. For example, the positive electrode and the negative electrode are separated by a separator to form a laminated body, and the laminated body is formed into a battery container by being subjected to curling, folding, or the like to form a shape corresponding to the shape of the battery, and an electrolyte is injected into the container. After that, use a sealing plate or a safety valve seal (Expand Metal). In addition, as needed, the expanded metal fuse and PTC (Positive Temperature)

An overcurrent protection element such as a Coefficient ‘positive temperature coefficient element, a guide plate, etc. are placed in the battery case to increase the pressure inside the battery and prevent overcharge and discharge. The shape of the battery is not limited, and examples thereof include a coin type, a button type, a sheet type, a cylinder type, a square type, and a flat type. In the drying step, if the composition for the non-aqueous electrolyte battery electrode is rapidly heated at a high temperature (four), the adhesive suspension in the electrode will rise to the surface of the electrode, causing the electrode to peel or rupture, so it is necessary to lower the temperature. The temperature is gradually increased and dried. In addition, in the case of continuous electrode fabrication, the following problems exist. Since the drying must be completed in a limited drying area, the line speed of the production line is also about 1 (m/min). The drying step takes a long time, but by using the composition for a non-aqueous electrolyte battery electrode of the present invention, the drying step can be shortened, and even if it is rapidly dried at a high temperature (for example, 100 to 150 C), it can be suppressed. The adhesion of the binder resin to the surface of the electrode can also greatly increase the line speed, thereby improving the productivity of the electrode. ^ EXAMPLES Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the examples. 152565.doc 201136008 (pKa value of cationic polymer) The pKa value of the cationic polymer is calculated using the pKa value prediction software of ACD/Labs (manufactured by Fujitsu Co., Ltd.). (Kneading analysis) The kneading analysis was carried out by the following method. A petri dish containing 2% hydrazine aqueous solution and a negative electrode processed by a cross section polisher were placed in a desiccator. The desiccator was sealed, and the negative electrode was exposed to a 2% aqueous solution of hydrogen for 2 days and night for iron dyeing of the binder resin. The elemental color surface analysis of the negative electrode section after dyeing was carried out by using an electrolytic radiation type electron beam microanalyzer (trade name: JXA-8500F, manufactured by JEOL Ltd.), and the distribution state of the ruthenium in the negative electrode was confirmed. It is understood that the adhesion of the binder resin to the surface of the negative electrode is less (〇) in the case where the distribution state is good, and the adhesion of the binder resin to the surface of the negative electrode (X) occurs when the adhesion is not good. (Viscosity) The viscosity at 25 ° C of an aqueous solution (solid content concentration as shown in Table 1) of a polymer which is cationic in a liquid substance was measured using a Β-type viscometer. The results are shown in Table 1. [Table 1] Polymeric solid content concentration (% by weight) in a liquid substance. Viscosity (mPa.s) Polyamine amine-epichlorohydrin resin A1 25 30~300 Diallylamine hydrochloride - acrylamide copolymer A2 30 700~2000 Polyamine resin modification A3 45 3~15 Polyamide polyurea resin A4 30 5~30 5 152565.doc • 17- 201136008 Example 1 in LiCo02 (Benyi Chemical Manufactured by the company (Honjo Chemical Corporation); product name "HLC-22") 90 parts by weight, acetylene black (manufactured by Electric Chemical Co., Ltd.: HS-100) 5 parts by weight, 1 part by weight of polyamine resin, and polyvinylidene fluoride In a mixture of 4 parts by weight of ethylene, N-methylpyrrolidone was added as a solid content of 6 〇 0 / 〇. The obtained mixture was stirred using a planetary mixer to obtain a uniform slurry for the positive electrode. This positive electrode slurry was uniformly applied to a foil (thickness of 20 μηι) using a multi-purpose laboratory coater (Multi-Lab Coater), and dried at 12 ° using a dryer. The coating material obtained by drying under the crucible was taken to obtain a positive electrode for a nonaqueous electrolyte battery. Example 2 95 parts by weight of carbon (manufactured by TIMCAL Co., Ltd.: trade name "SFG44"), 3 parts by weight of styrene-1,3-butadiene copolymer, 1 part by weight of sodium salt of hydroxymethylcellulose, and a blend of In a mixture of 1 part by weight of the amine polyabsorbent, the solid content was 60 ° /. Add water in a way. The obtained mixture was stirred using a planetary mixer to obtain a uniform slurry for a negative electrode. The slurry for negative electrode was uniformly applied to a copper foil (thickness: 2 μm) using a multi-functional laboratory coater, and the obtained coating material was dried using a dryer m12〇〇c to obtain a nonaqueous electrolytic solution. A negative electrode for liquid batteries. Reference Example 1 In the first embodiment, a positive electrode for a lithium ion secondary battery was obtained in the same manner as in Example 1 except that the polyamine polyurea resin was not added, but the drying time was longer than that of the first embodiment. Reference Example 2 152565.doc 201136008 In Example 2, a negative electrode for a lithium ion secondary battery was obtained in the same manner as in Example 2 except that the polyamine polyurea resin was not added, but the time required for drying was shorter than that of Example 2. long. Example 3 Lithium citrate (manufactured by Baoquan Co., Ltd.; product name "HLB-0711216") 92 parts by weight, acetylene black (manufactured by Electric Chemical Co., Ltd.: HS-100), 5 weight loss, sodium by sulfhydryl cellulose 1 part by weight of a salt, 2 parts by weight of a resin (manufactured by Kynar Aquatec, PVDF: polyvinylidene fluoride), and a mixture of polyamidoamine-gas alcohol tree means Al (pKa value: 8.57) 0.3 parts by weight, Water was added in such a manner that the solid content was 55%. The resulting mixture was stirred using a film rotary high speed mixer (FILMIX) (manufactured by PRIMIX Co., Ltd.) to obtain a uniform slurry for a positive electrode. The obtained slurry for a positive electrode was uniformly applied onto an aluminum foil having a thickness of 2 μm using a multi-functional laboratory coater, and the obtained coating material was dried at 25 t to obtain a non-aqueous electrolyte f battery. positive electrode. The time required for drying is 45 minutes. The time required for drying was judged by visually observing the dry state of the surface of the positive electrode. Example 4 In Example 3, in addition to the use of di- propylamine hydrochloride acrylamide (pKa value of 1 () 49) () 3 parts by weight instead of polyamine amine gas alcohol The same procedure as in Example 3 was carried out to obtain a positive electrode for a nonaqueous electrolyte battery. The dry time is 45 minutes. The time required for drying is judged by visually observing the dry state of the surface of the positive electrode. Example 5; η in 'in addition to the polyamine resin modified A3 (modified polyamine 152565.doc -19·201136008 resin, pKa value · 8.98) 0.3 parts by weight instead of polyamine amine - epichlorohydrin The positive electrode for a nonaqueous electrolyte battery was obtained in the same manner as in Example 3 except for the resin A1. The time required for drying was 55 minutes. The time required for drying was judged by visually observing the dry state of the surface of the positive electrode. Example 6 In the same manner as in Example 3 except that the polyamine amine-urea resin A4 (pKa value: -0.99) was used in an amount of 0.3 part by weight instead of the polyamine amine-gas alcohol resin A1. The positive electrode for a non-aqueous electrolyte battery is obtained. The time required for drying is 60 minutes. The time required for drying was judged by visually observing the dry state of the surface of the positive electrode. Reference Example 3 In Example 3, the same procedure as in Example 3 was carried out except that 0.3 part by weight of polyvinylpyrrolidone (pKa value: -0.41) was used instead of the polyamine amine-gas alcohol resin A1. A positive electrode for a nonaqueous electrolyte battery was obtained. The time required for drying is 60 minutes. The time required for drying was judged by visually observing the dry state of the surface of the positive electrode. [Table 2] Polymer drying time in the liquid material (minutes) Example 3 Polyamine amine-gas alcohol resin A1 45 Example 4 Diallylamine hydrochloride-acrylamide copolymerization A2 45 Example 5 Modification of Polyamine Resin A3 55 Example 6 Polyamide Polyurea Resin A4 60 Reference Comparative Example 3 Polyvinylpyrrolidone 60 Example 7 152565.doc -20- 201136008 in Carbon (Sumitomo Metal Industry) Manufactured; trade name "swFi5p2j" as a part by weight, styrene-1,3-butadiene 丑 / 、, / 3 篁 、, hydroxyf-based cellulose nano-salt 1 part by weight & Amine-epichlorohydrin resin AI: 6.·57) In a mixture of 0.3 parts by weight, water is added as a solid content of 601⁄4. The resulting mixture was stirred by a Chad-type intermixer (FILMIX) to obtain a uniform g Μ, a slurry for the negative electrode. The obtained negative electrode was used for a multi-purpose laboratory coater; ^ + Λι A , The L ^ shellfish was uniformly coated on a copper drop having a thickness of 20 μm, and dried in the same manner as in Example 3. The obtained coating material was used to obtain a negative electrode for a non-aqueous electrolyte battery. The drying time determined by visual observation of (4) (4) 干燥 dry state is shown in Table 3. Example 8; Real 7 & Hydrochloride-acrylic acid amine copolymer A2 (pKa value: 1 G.49) G3 parts by weight was used in the same manner as in Example 7 except that the polyanisole A1. The negative electrode for electrolyte battery. The drying time determined by visually observing the dry state of the surface of the negative electrode is shown in Table 3. Example 9 ^ Example 7, except that modified product A3 of polyamine resin (modified polyamine) was used.树月曰' pKa value: 8.98) 〇 3 parts by weight instead of polyamine amine-epichlorohydrin resin A1 was carried out in the same manner as in Example 7 to obtain a negative electrode for a non-aqueous electrolyte battery. The drying time judged by visually observing the dry state of the surface of the negative electrode is shown in Table 3. Example 1 〇; In 彳7, except for the polyamine polyamine resin A4 (pKa value: _〇99) 152565.doc -21- 201136008 0.3 parts by weight in place of polyamine amine-epichlorohydrin resin A1 The same procedure as in Example 7 was carried out to obtain a negative electrode for a non-aqueous electrolyte battery. The drying time determined by visually observing the dry state of the surface of the negative electrode is shown in Table 3. Reference Example 4 In Example 7, The negative electrode for a non-aqueous electrolyte battery was obtained in the same manner as in Example 7 except that the polyamine amine-epichlorohydrin resin A1 was not used. The dry state of the surface of the negative electrode was visually observed. The drying time is shown in Table 3. [Table 3] Polymer drying time in a liquid substance (minutes) Example 7 Polyamine amine-gas alcohol resin Α1 48 Example 8 Diallylamine hydrochloride-acrylamide copolymerization Example 2 47 Example 9 Modification of Polyamine Resin A3 75 Example 10 Polyamide Polyurea Resin Α 4 58 Reference Comparative Example 4 - 80 Example 11 In Carbon (manufactured by Sumitomo Metal Industries; trade name "SWF15P2") 100 Parts by weight, 3 parts by weight of styrene-1,3-butadiene copolymer, 1 part by weight of sodium salt of hydroxymethylcellulose, and 0.3 parts by weight of polyamidoamine-epichlorohydrin resin Al (pKa value: 8.57) In the mixture, water was added so that the solid content was 60%. The resulting mixture was stirred using a film rotary type high speed mixer (FILMIX) to obtain a uniform slurry for a negative electrode. The obtained slurry for negative electrode was uniformly coated on a copper box of 152565.doc -22-201136008 having a thickness of 20 μm using a multi-purpose laboratory coater, and the obtained coating material was rapidly dried at 120 tons to obtain a non- A negative electrode for a water electrolyte battery. The drying time judged by visually observing the dry state of the surface of the negative electrode is shown in Table 4. The distribution state of the binder resin in the cross section of the negative electrode for the non-aqueous electrolyte battery was observed by EPMA surface analysis. The results will not be as shown in Table 4. Example 12 In Example 2, except that di-propylamine hydrochloride-acrylic acid copolymer A2 (pKa value: Η).49) (). 3 parts by weight was used instead of polyamine amine gas The resin was used in the same manner as in Example u except for the resin Am, and a negative electrode for a non-aqueous electrolyte battery was obtained. The dry day temples judged by visually observing the dry state of the surface of the negative electrode are shown in Table 4. The distribution state of the binder resin was observed by EpMA surface analysis. The results are shown in Table 4. Example 13 In the Example " except that the modified A3 (modified polyamine resin, loud value: 8.98) 〇·3 parts by weight of the polyamine resin was used instead of the polyaminamine-epichlorohydrin resin The same was carried out in the same manner as in the practice of mi to obtain a negative electrode for a nonaqueous electrolyte battery. The drying time judged by visually observing the dry state of the surface of the negative electrode is shown in Table 4. The distribution state of the binder resin was observed by epma surface analysis. The results are shown in Table 4. Example 14: -0.99) 3·3 parts by weight In place of the polyamine amine-epichlorohydrin resin M, the α 盥 Example U was carried out in the same manner to obtain a non-aqueous electrolyte battery: a negative electrode. The dryness of the surface of the negative electrode was visually observed to be dry. 152565.doc -23-201136008 The time is shown in Table 4. The distribution state of the binder resin was observed by kneading. The results are shown in Table 4. Reference Example 5 In the same manner as in Example 11 except that the polyamidoamine-epichlorohydrin resin Α1 was not used, the negative electrode for a nonaqueous electrolyte battery was obtained. The drying time judged by visually observing the dry state of the surface of the negative electrode is shown in Table 4. The distribution state of the binder resin was observed by kneading. The results are shown in Table 4. ['Table 4]

Polymer drying time in liquid substance (seconds) Distribution state Example 11 Polyamine amine-epichlorohydrin resin A1 20 〇 Example 12 Diallylamine hydrochloride-acrylamide copolymer A2 18 〇 Example 13 Modification of polyamine resin A3 50 〇 Example 14 Polyamide polyurea resin A4 45 〇 Reference Comparative Example 5 60 X <Battery evaluation> Examples 7 to 10 and reference were compared The negative electrode obtained in Example 4 was cut into a circular shape having a diameter of 15 mm to prepare a circular negative electrode. The prepared circular negative electrode and the lithium foil of the positive electrode are disposed in such a manner that the respective active material layers are opposed to each other, and a circular polypropylene having a diameter of 18 mm and a thickness of 25 μm is inserted between the negative electrode and the positive electrode. A separator of the porous film is formed to form a laminate. The laminated body was placed in a stainless steel coin-shaped packaging container (having a diameter of 20 mm, a height of 1.8 mm, and a stainless steel thickness of 0.25 mm) so that the positive electrode was in contact with the bottom surface of the container. Put the expansion gold on the copper pig of the negative pole 152565.doc • 24· 201136008 Genus. The electrolytic solution (LlPF6 concentration: 1 mol/liter) obtained by dissolving the electrolyte LiPF0 was used to fill the inside of the vessel in a mixed solvent obtained by mixing ethylene carbonate and diethyl carbonate in a volume ratio of 1:1. A polypropylene gasket was placed in the upper portion of the trough and sealed with a stainless steel lid having a thickness of 0.2 mm to make a coin-type battery with a direct control of 20 mm' thickness of 2 mm. The TOSCAT-3 1 〇〇 charge and discharge # valence device manufactured by Toyo Systems Co., Ltd. was used to measure the charge and discharge capacity of the produced coin type battery, and the battery was evaluated. The coin-type battery produced was subjected to constant current charging at a current density of 25 Torr: 6 mA/g until the voltage value reached 〇〇〇 5 v. Thereafter, constant voltage charging is performed at a voltage of 0.005 V. The charging was performed in such a manner that the total of the constant current charging time and the constant voltage charging time was 12 hours. The charging capacity (mAh/g) after the end of the constant voltage charging is measured (hereinafter referred to as the initial charging capacity). After constant voltage charging, a constant current discharge was performed at a current density of 60 mA/g until the voltage value reached 1 > 5 v. The charge capacity [mAh/g] after the end of the constant current discharge was measured (hereinafter referred to as the initial discharge capacity). The initial discharge capacity (mAh/g) was divided by the initial charge capacity (mAh/g), and the value obtained by multiplying the obtained value by 100 was used as the initial charge and discharge efficiency (%). The results are shown in Table 5. The coin-type battery in which the first charge and discharge were completed was repeated four times in the same manner as described above. The charge capacity (mAh/g) after the end of the fourth charge (the following is the charge capacity of the fifth cycle) and the discharge capacity after the end of the *th discharge (mAh/g) (hereinafter referred to as the discharge of the fifth cycle) capacity). 152565.doc -25- 201136008 The results are shown in Table 5. [Table 5] Initial charge capacity (mAh/g) Initial discharge capacity (mAh/g) Initial charge/discharge efficiency (%) Cycle charge capacity (mAh/g) Cycle discharge capacity (mAh/g) Example 7 372 352 95 349 347 Example 8 372 352 95 361 360 Example 9 381 359 94 351 349 Example 10 378 357 94 353 351 Reference Comparative Example 4 379 358 95 358 357 Industrial Applicability According to the present invention, it can be shortened The time of the drying step in the electrode manufacturing, thus improving the productivity of the electrode. 152565.doc -26-

Claims (1)

201136008 VII. Patent application scope: 1 . A non-aqueous electrolyte battery electrode composition comprising an electrode active material, a binder resin, a liquid substance, and a polymer having a cationic property in the liquid substance. 2. An electrode which is obtained by applying a composition for a non-aqueous electrolyte battery electrode according to claim 1 to a current collector and removing the liquid material from the obtained coating material. A nonaqueous electrolyte secondary battery comprising the electrode of claim 2 and a nonaqueous electrolyte. 152565.doc 201136008 IV. Designation of representative drawings: (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure·· 5. If there is a chemical formula in this case, please reveal the characteristics that best show the invention. Chemical formula: (none) 152565.doc