TW200804551A - Binder for electrochemical cell electrode - Google Patents

Abstract

Disclosed is a binder for electrochemical cell electrodes which is composed of an emulsion composition wherein resin particles each composed of an olefin polymer (A) and an acrylic polymer (B) having an internally crosslinked structure are dispersed in water. The binder for electrochemical cell electrodes exhibits sufficient adhesion to a metal collector, a positive electrode active material and a negative electrode active material, and enables to improve high-rate discharge characteristics and cycle characteristics.

Description

200804551 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to an electrochemical unit electrode adhesive comprising an aqueous emulsified composition, which comprises an olefin polymer and a cesium bismuth hydride polymer. body. [Prior Art] An electrochemical cell such as a secondary battery or an electrochemical double layer capacitor is used in various fields. A secondary battery that can be reused by charging is used as a power source for a wireless electronic device such as a light-emitting telephone, a notebook computer, or a power tool, and is used as a power supply for a hybrid vehicle such as a hybrid automobile. In addition, it has been widely used, and a secondary battery (Ni-MH battery) obtained by using a hydrogen storage alloy, a non-aqueous liquid using a lithium compound, and a liquid secondary battery (lithium ion battery) have been put into practical use. In addition, the electric double-layer electric grid has been widely used as an electric power source for 1C, LSI memory, and actuators, and has been widely used in various fields such as the electronics industry, home appliances, and automobiles. In recent years, expectations for improvement in performance of electrochemical cells such as secondary batteries and electric double layer capacitors have been increasing.

In the positive and negative electrodes of a secondary battery such as a Ni-N battery or a lithium ion battery, the active materials for the positive and negative electrodes are bonded to the current collector by a binder. In the positive and negative electrodes of the electric double-layer capacitor, active carbon is used as the active material of the positive and negative electrodes, and the active material for the positive and negative electrodes is bonded to the metal current collector by the binder in the same manner as the secondary battery. And making. As the binder of the electrodes, various compositions of the resin 312 > / invention manual (supplement) / 96-08/96114780 5 200804551 have been used. Taking a lithium battery as an example, as a binder for the positive electrode, a solution in which polyvinylidene fluoride (PVDF) is dissolved in N-methyl-2-pyrrolidone (NMP) or polytetrafluoroethylene (PTFE) is used. As the aqueous dispersion, as the binder of the negative electrode, an aqueous dispersion of PVDF or ethylene-butadiene rubber (SBR) is used (Patent Document 1). The PVDF PTFE-specific fluorine-based resin has low adhesion to an active material or a metal current collector. Therefore, it is necessary to add a large amount of a binder, and there is a problem that the surface of the active material is covered to lower the characteristics of the battery. Further, since the adhesion of the fluorine-based resin to the active material or the metal current collector is low, the charge and discharge of the secondary battery and the capacitor are repeated, and the active material is detached from the metal current collector to reduce the battery capacity. Further, since the SBR has a double bond in the main chain, when the secondary battery and the capacitor are charged and discharged, the double bond is used when the positive electrode is used. The oxidative degradation of IM causes the active material to fall off from the metal current collector to reduce the capacity of the J battery or the capacitor. Further, in the case of using the negative electrode, since the swelling property with respect to the electrolytic solution is high, there is a problem that the contact with the active material or the current collector is lost, resulting in a decrease in high-rate discharge characteristics or cycle characteristics. In order to solve such a problem, an olefin-based polymer which is electrochemically stable and has a small degree of swelling of an electrolytic solution is used as a binder (Patent Document 2), but the adhesion to an active material or a metal collector is carried out. Still not enough. As a means for improving the adhesion, a method of copolymerizing an olefin monomer with an acrylate or a mercapto acrylate monomer (Patent Document 3) or a method of adding an acrylic resin to an olefin is disclosed (Patent Document 4) However, since the acrylic resin portion swells against the electrolyte solution, the 312XP/invention specification (supplement)/96-08/96114780 6 200804551 has a problem of loss of contact with the active material or the current collector, resulting in a decrease in the battery or the capacitor. 'Or in the latter, a large amount of surfactant must be added due to the agglomeration of the adhesive used in the electrode used to make the electrode, so that the free surfactant present in the paste = large battery causes the battery characteristics to be lowered. . Due to the adhesion of the active material or the metal current collector and the horse speed discharge characteristics or cycle characteristics of the two or the electric double layer capacitor

Capacity or internal resistance is still insufficient. I

(Patent Document 1) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent (4) 2__327{) No. 64 of the invention] ^ (Problem to be solved by the invention) The purpose of the present invention is to provide an electrochemical unit agent which is known for metal smashing, for bonding, and right and right v-pole The active material and the negative electrode active material have a dense adhesion, which can improve the cycle characteristics of 1 lb., static and sturdy, and the characteristics of the discharge between the early and the late, and the internal resistance can be reduced. (Means for Solving the Problem) When the inventors of the present invention have dealt with the problem of the above-mentioned technique, it was found that the electrode can be solved by the binder of 仃/朱入入极, and the electrochemical composition of the object Unit unit is compared to the items described below. #即,本发(1) A kind of electrochemical unit electrode with a binder particle dispersed in water, and the sputum is a sacred composition containing a tree, which is made up of a smog system. Bile Invention Specification (Supplement) / 96 Te 6114· ? 200804551 The polymer (A) is formed with an acrylic polymer (β) having an internal crosslinked structure. (2) The electrode for an electrochemical cell electrode according to (1), wherein the acrylic polymer (B) having an internal crosslinked structure is produced from a monomer having the following components: an acrylic monofunctional monomer (b-i), polyfunctional monomer (b-2) 〇 (3) The electrode for electrochemical cell electrodes of (1), wherein the acrylic polymer (B) having an internal crosslinked structure is Manufactured from a conjugated compound of the following composition: an acrylic monofunctional monomer (b-1-2) having a reactive group, and two or more acrylic monomers (b) Compound (c) based on the reactive group reaction. (4) The electrode for an electrochemical cell electrode according to (3), wherein the reactive group of the reactive monofunctional acrylic monomer (b-U) is a rebel group and/or a group, The group reactive with the reactive group of the acrylic monomer (b-1-2) in the compound (c) is an epoxy group. 10. The binder for an electrochemical cell electrode according to (1), wherein the acrylic polymer (B) having an internal crosslinked structure is made of a monomer containing a component having a reactive group (1). An acrylic monofunctional monomer (b~1-2) and an acrylic monofunctional monomer capable of reacting with a reactive group (〇-reactive reactive group (2). (6) Such as (1) to (5) The binder for an electrochemical cell electrode according to any one of the invention, wherein the olefin-based polymer (A) contains a copolymer of an olefin-based monomer. (7) Electrochemical unit electrode bonding according to any one of (1) to (6) 3 UXP / invention specification (supplement) / 96-08/96114780 200804551 agent 'where 'olefin polymer (A) A copolymer of an olefin-based monomer (a") and another monomer (a_2) copolymerizable with the olefin-based monomer. (8) The binder for an electrochemical cell electrode according to (7), wherein a ratio of the olefin precursor (a-1) and another monomer "_2) copolymerizable with the olefin monomer is (a-1) And (b)) is 99.9 to 35·〇% by weight, and (a-2) is 〇1 to 65〇% by weight. (9) As in (1) to (8) Any of the binders for electrochemical cell electrodes of the above-mentioned item, wherein the olefin-based polymer (4) is 95 to 30% based on the total weight of the oxime-based polymer (4) shawl-based polymer (B) in the emulsion. %, the acrylic polymer (B) is % by weight. (10) An electrode comprising the adhesive of any one of (1) to (9). (11) An electrochemical unit, It is characterized by the use of positive and/or negative electrodes of (1)). (12) Electrochemical unit of the (11)--sub-cell. U3) Electrochemical double-layer capacitor of the electrochemical cell of (11). (Effect of the invention) In the above electrochemical unit, wherein the electrochemical unit is an adhesive for an electrochemical cell electrode obtained by the present invention, and the dragon is for a metal current collector and a positive electrode. The viscosity of the drug # and the bungee active material ^ knife is improved, and the high-rate discharge characteristics and cycle characteristics can be improved. [Embodiment] The present invention will be described in detail below. 312XP/Invention Manual (Supplement)/96-08/961147 ^0 200804551 [Olefin-based polymer (A)] The polyolefin-based polymerization system used in this month refers to a copolymer of an olefin-based monomer (a-1) ^ a homo-xa body and an olefinic monomer (a-1). The olefin-based precursor (al) is a copolymer of the other monomer (a2) which can be copolymerized. The olefin-based monomer (al) is not particularly limited, and examples thereof include ethylene propylene and 1-butene. Dilute, 1-pentene, 1-hexene, 4-methyl-mono;|monopentene, 3-methyl-4-pentene, heptene,}-hexene, i-decene, b-dodecene, etc. The α-olefin; butadiene, ethylene, decene, dicyclopentadiene, 'small fine, a fine, non-a total of diene, etc.. In addition, continue to use alone! It is used in combination of two or more kinds. The other monomer (a-2) which can be copolymerized with the olefin monomer (a-1) can be copolymerized as long as it can be copolymerized. The limitation includes styrene, acetophenone, methacrylate, ethyl acetate, ethylene glycol, and unsaturated acid such as succinic acid, propylene glycol, and methacrylic acid. In addition, these monomers may be used singly or in combination of two or more kinds. Among the oxime and the like, the monomer (& 〇 is preferably ethylene or propylene) from the viewpoint of electrochemical cycle characteristics. Monomer (a_2), odorant dibutyric acid, acrylic acid, methacrylic acid is preferred. As a homopolymer of the above olefinic (tetra) monomer (a)), alkene monomer (al) Specific examples thereof include low density polyethylene, still density polyethylene, polypropylene, polybutene, poly-3_mercapto+butene, poly+methyl+pentene, or copolymerization with ethylene and propylene. Complex, ethylene·butene copolymer, propylene·butene copolymer, propylene·bubutene·312XP/invention specification (supplement)/96-08/96114780 10 200804551 Ethylene copolymer is represented by ethylene and propylene埽,卜稀稀, a certain _Bu Ding, 4-methyl + pentene, 3-methyl- ene small Geng, Bu: ene, terpene, Bu twelve carbon Alpha-olefin polymer; ethylene/butylene dimer copolymer, ethylene/ethylene (tetra) polymerized diene copolymer, ethylene, propylene, butane-α婶/兀 copolymer, ethylene, propylene, and ethylene The basal-formed rice olefin is copolymerized with a mixture of human cockroaches, a mouth-opening body, an ethylene/acrylic comb, a 5-hexadiene ternary copolymer, and the like. Among the above-mentioned copolymers of olefins and dienes, among the characteristics of the electrochemical unit, ethylene-propylene copolymer, propylene, propylene, and ruthenium-butene copolymer are preferable. A specific example of the above-mentioned fluorene-based monomer (m (0 Λ ) and a copolymerizable other monomer (a-2), 丘 鹈 鹈 ^ ^.] cites ethylene vinyl acetate. #笪夕^ p π μ ι Ethylene/methacrylic acid co-kappa-4 ethylene/unsaturated phthalic acid anhydride copolymer. κ conjugate and propylene·cis butylene, among the electrochemical units a cyclic olefinic/methacrylic acid copolymer or the like is a copolymer of ethylene and propylene and maleic anhydride. The olefinic monomer of the koji body is a monomer of the copolymerization of the olefinic monomer "1). : the situation 'the ratio of the olefinic monomer (-Ο and the olefinic mono-', based on the total weight of (a-1) and (a-w, usually (a-n).π, cr, 7. a υ is 99.9 ～35.0 wt%, (a, 2) is 〇. 1~6 5 · 0 wt%, preferably 仫r) ((^1) is 99.9~50 wt%, (a 2) is 〇. ; 〜5〇重量%, . ^qqq^ 尺1 soil system (3-1) is 99.9~7〇重三胃Μ Instructions (supplement)/96·08/96Π4780 ^ 200804551 里 / ' U-2) .; [~3〇% by weight. If the second rate is in the above range, the characteristics of the dilute smoke can be expressed, and the electric properties are determined. The electrochemical cell characteristics are not reduced and the welding can be maintained. (1) Two types of propylene glycol-based polymer (Β) can be used alone or in combination with each other to have an internal structure of the acrylic polymer in the present invention.

As described above, the binder for an acrylic polymer electrolyte unit electrode having an internal crosslinked structure can suppress swelling of the solvent of the electrolyte solution and sufficiently reduce the adhesion to the metal current collector and the positive electrode active material. Babe has an acrylic polymer having an internal crosslinked structure (not particularly limited, and an acrylic polymer is produced from a monomer containing acryl (bi) and a polyfunctional monomer (b-2) ( The method of B) (hereinafter, the polymer obtained by the production method is also referred to as a propylene I-based polymer (β1 )); and the acrylic mono-monomer (b-1-2) containing a reactive group is A method of producing an acrylic polymer (B) by using a compound of the compound (c) having two or more reactive groups reactive with the acrylic monomer (b-1-2) (the following production method is also employed) The obtained polymer is referred to as an acrylic polymer (B2)); two or more reactive monovalent acrylic monofunctional monomers (b-1-2) are used to polymerize the monomers while allowing the monomers (B2) Bi-2) a reaction between reactive groups having a 'methym for producing an acrylic polymer (B) (hereinafter also referred to as 312XP/invention specification (supplement)/96·_611478〇12 200804551 by the production method The polymer is referred to as an acrylic polymer (B3). The acrylic polymer (B) of the present invention is composed of The monomer having at least the acrylic monofunctional monomer (b-1) is produced. The acrylic monofunctional monomer (b-1) can be classified into an acrylic monofunctional monomer having no reactive group (b) -1-1) an acrylic monofunctional monomer (b-1-2) having a reactive group. Further, in the acrylic polymer (B2), in the acrylic monofunctional monomer (b-1) The reactive group is a group which reacts with a group (for example, an epoxy group) of the compound (c) to be described later. Further, in the acrylic polymer (B3), two or more kinds of the above-mentioned acrylic monofunctional monomer are used. (b-i), the two kinds of monomers are not particularly limited as long as they can react with each other. For example, when the i monomers (b-1) have an epoxy group, As another monomer, a monomer having a carboxyl group can be used. Examples of the acrylic monofunctional monomer (b-1 to 1) having no reactive group include methyl acrylate, ethyl acrylate, and n-butyl acrylate. , isopropyl isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, mercapto propylene Ethyl ester, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, etc.; alkyl acrylate, methacrylic acid An alkyl-substituted (mercapto) acrylamide such as guanamine, N,N-dimethylpropenylamine, n,N-diethyl acrylamide or N-isopropyl acrylamide. (b-1-1) may be used alone or in combination of two or more. The acrylic monofunctional monomer (b-1-2) having a reactive group may have a reaction with the compound (c) described later. The acrylic single 312XP/invention specification (supplement)/96-08/96114780 13 200804551 can be a monomer, and is not particularly limited. For example, when the compound (C) is a compound having an epoxy group, a carboxyl group-containing acrylic monofunctional monomer such as acrylic acid or methacrylic acid; hydroxyethyl acrylate or hydroxypropyl acrylate; A hydroxyalkyl (meth) acrylate such as hydroxyethyl methacrylate or hydroxypropyl methacrylate is an acrylic monofunctional body represented by a hydroxyl group. Further, when producing the acrylic polymer (B3), a carboxyl group-containing acrylic monofunctional monomer such as acrylic acid or methacrylic acid is used as the reactive group-based acrylic monofunctional monomer (b-U). In the case of sputum: an epoxy-based acrylic monofunctional monomer such as epoxy propyl acrylate or epoxy propyl methacrylate may be used as another monofunctional monomer (bl-2). The above monomers (b-1-2) may be used alone or in combination of two or more. In the production of the acrylic polymer (B1), in addition to the acrylic monofunctional monomer (b-1), the polyfunctional monomer (b-2) is further used (that is, two or more of them are used). Vinyl monomer). Specific examples of the monomer having two or more vinyl groups include ethylene glycol dimethacrylate, propylene glycol dimercaptopropene ruthenium, diethylene glycol diacrylate, and tetraethylbenzene. I, diethylene glycol dipropylene glycol diacrylate, diethylene The above-mentioned monomer (b-2) may be used alone or in combination of two or more. In the production of the acrylic polymer (B2), in addition to the above-mentioned reactive group-containing acrylic monofunctional monomer (b-1-2), the invention specification (supplement)/96-08/ 96114780 14 200804551 The reactive group of (bl-2) is a compound (c) having two or more groups reactive with an acrylic monomer. Substrate: 匕Acrylic monomer (5)—2) The group in which the reaction is carried out. When the reactive group of the monohydrazine sq is, for example, (iv) or a slow group, it may be a group, a carbodiimide group or an oxazoline group. Among these, from the viewpoint of the reaction rate, an epoxy group is preferred.

The above compound (c) having two or more octyloxy groups may, for example, be a glycidyl ether compound such as a double-type epoxy resin or a (four) varnish-type epoxy resin; a base ester compound; a sulfonium propylamine compound or the like. This is equal. In view of the reaction rate, a epoxidized propyl ether compound such as a bisphenol-A type epoxy resin is preferably used as a commercial product of the above-mentioned epoxy propyl ether compound, and Ep〇Mic (Ep〇Mic ( Mitsui Chemicals Co., Ltd.). The above compound (C) may be used alone or in combination of two or more. By using such a compound, acrylic polymers (B1) and (B2) can be produced. Further, in the production of the acrylic polymer (B2), it is necessary to use a reactive monovalent acrylic monofunctional monomer (b-1-2) and a compound (c), and it is also possible to further use a non-reactive group as needed. The acrylic monofunctional monomer (b-1-1) and the polyfunctional monomer (b-2). Further, in the production of the acrylic polymer (B3), two or more kinds of acrylic monofunctional monomers (b-1 - 2 ) having a reactive group are used. Further, the acrylic polymer (B3) can be obtained by polymerizing the monomers (b-1-2) while allowing the reactive groups of the monomers (b-1-2) to enter the 312XP/invention specification ( Supplement) /96-〇8/96114780 15 200804551 Manufactured by reaction. Therefore, in the production of the acrylic polymer (B3), it is necessary to use a reactive group (one monomer (b-1-2) of the oxime and a reactive group reactive with the reactive group (1). (i) another monomer (bl-2). For example, a carboxyl group-containing acrylic monofunctional monomer such as acrylic acid or mercaptoacrylic acid is used as the acrylic monofunctional group having a reactive group (1). In the case of the monomer (b-1-2), an epoxy-based acrylic monofunctional monomer such as epoxypropyl acrylate or glycidyl methacrylate may be used as the reactive group (2). Monofunctional monoterpene (b-Ι-2). For the production of the acrylic polymer (B3), as described above, it is necessary to use an acrylic monofunctional monomer (bU) having a reactive group (1). a monomer having another monomer (b+2) having a reactive group (2), or a non-reactive group of a non-reactive group (b-1-l) may be further used as needed. Acrylic monofunctional (b-1-2) and polyfunctional monomer (b-2) having other reactive groups. In addition, acrylic monofunctional with other reactive groups The reactive group (3) of the singly may be a group reactive with both the reactive group (1) and the reactive group (1), or may be either one or the other In addition, the non-acrylic monomer (b_3) which can be used as the usable acrylic polymer (β can be used with propylene (tetra) or monofunctional monomer (bi): two° When the reaction is such that the compound (C) is used as the above-mentioned precursor (b-3), and the acid or the compound is exemplified, there are several groups such as croton-re-butanic acid and cis-butanic acid. 312XP/Invention Manual (Repair) Grab 08/96114780 16 200804551 For example, in the case of producing an acrylic polymer (B2) using an epoxy group-containing compound (C), by further combining the above monomers (b- 3), the internal cross-linking structure can be controlled step by step. For example, in the manufacture of propylene _ small, "muscle, 兀 广 广 widely use acrylic monofunctional monoterpene having an epoxy group as a reactive group (Bu 1-2 In the case of producing the acrylic polymer (B3), the above monomer (b-3) can be used in combination with the above step. The internal monomer (b-3) may be used alone or in combination of two or more. In the case of producing the acrylic polymer (B), it may be further used in combination with acrylic. The other monomer (b-4) is a monomer (b-4). The above monomer (b_4) can be exemplified by a polar group-containing monomer such as acrylonitrile or methacrylic acid; styrene and α. Aromaticity of methicillin et al [etc.: However, the above monomer (b-4) excludes ethylene, propylene, and olefin oxime monomers. The homing body (H) may be used alone or in combination. Two or more types are used. (b丨: polymer (β1) +, acrylic monofunctional monomer (Bu 3) and ^ used to be an early body (Bu) is called (a) weight ~:: Feng' two from Generally, the amount of weight used is %, and (") is 〇~6〇) in the range of 曰^^, and the resulting binder is ". If the amount of use in the above electrolyte is reduced, it becomes pure, and the battery characteristics of the battery of the agent are reduced less and the adhesive is used 312XP/invention specification (supplement)/96-08/96114780 200804551 In the acid-based polymer (B2), a reactive group of a bupropion-based monofunctional monomer (b+2) and a compound (C) are used as needed, and a reactive group is used. The total weight of the acid monofunctional monomer (bab), the polyfunctional monomer (b-2), the monomers u_3), and (b_4) is based on the total amount of each (b-^2). For the Bu 7〇 weight% 八卜卜玉) 2 98· 5 Reset %, (b-2) is 0~5〇% by weight, (b-3) is 0~50 Tongue: 乂, (卜4) 0 to 50% by weight, and the compound (c) is 0.5 to 30% by weight. When the amount of money is within the above range, the obtained binder can maintain the tendency to be "sticky" and at the same time, the tendency to lower the swelling property of the electrolyte becomes: ,, and the battery characteristics of the battery using the adhesive are lowered. There is a tendency to be less. In the di-propionic acid-based polymer (B3), 'the reactive group of propyl cation == energy monomer (Bub 2) and the step-by-step need to use the anti-TIL 'acrylic monofunctional The total weight of the monomer (b-H), the polyfunctional monomer, the T body (b-3) and the (b_4), and the respective tongue denier 0/c 2) is 1 to 100% by weight. (bii) is 〇~99. (b-2) is 〇~50% by weight, and (b_3) is 〇~5. The weight % is G to 5 G weight%. If the amount used is within the above range, the obtained drill & agent can maintain the adhesiveness of the electrode. The tendency of the immersion property of the electrolyte to be low is more remarkable, and the characteristics are lowered. Less tendency. The battery of the battery of the binder: The acid-based polymer (1) is used in the polymerization of η. As an example of the initiator of the acrylic polymer, for example, as long as it is 312 ΧΡ / duck duck (supplement) / 96_G8 / 9611478g 18 200804551 two can be used in the emulsion polymerization . Examples of the emulsified poly=second generation initiator include persulfate or ammonium persulfate, stupid alpha ΓΑ 虱 虱 过氧化物 peroxide, t-butyl hydroperoxide L = = basal peroxide, and third butyl An azo compound such as an organic peroxyl-ethyl hexanoic acid vinegar, a hydrazinyl benzoic acid, a lauryl hydrazine peroxide, or the like; a bisazo compound such as a diisobutyronitrile; or the persulfuric acid : Reduction of the combination of a metal halide such as a ruthenium compound or an azo compound with iron ions, a heart stone: sodium hydride, formaldehyde, sodium metabisulfite, sodium hydrogen sulfite, L_ascorbic acid, I2, ngalite) Oxidation of the mouth agent special. These starters can be used alone! Use 2 types or more. : 'Can use third - dodecyl thiol, n-dodecyl thiol 4 butyl thiol; allyl tarnish, methallyl tartaric acid, and such sodium salts, etc. An allylic compound or the like as a molecular weight modifier. The emulsified composition of the present invention is obtained by dispersing the olefin-based polymer (A) and the resin particles formed of the (iv) acid-based polymer (8) having an internal cross-linking structure in water. In the present invention, the emulsified composition which is composed of resin particles containing both the olefin polymer (A) and the acrylic polymer (1) in the resin particles may be a resin composed of the olefin polymer (4). The emulsified composition of the resin particles of the acrylic polymer (1). The resin particles which are constituent components of the emulsified composition may be composed of a single type of polymer, or may be a mixture of two or more kinds of polymers. In the emulsified composition of the present invention, the emulsified composition containing the olefin-based polymer (A) and the acrylic polymer (8) in the same particle is described in the specification of the invention (supplement)/96·〇8/96114780 19 200804551 The particles of the olefin-based polymer (4) are dispersed in the presence of an emulsion of a water-based product, and the above-mentioned initiator is used to polymerize the acrylic-based polymer (8) from the monomer and the compound. In the resin particles containing the olefin-based polymer (4), a compound (B) is produced. The emulsified composition of the present invention relates to a resin granule composed of an olefin-based polymer. The composition of the resin particles composed of the acrylic polymer (B) is an emulsion of an acrylic polymer from the above initiator, monomer and compound by a general emulsion polymerization method. An emulsifier obtained by dispersing an emulsion of the obtained acrylic polymer (β) and an emulsion of the vodonic polymer (U) dispersed in water is produced. The olefin system is obtained by dispersing particles of an olefin polymer (water) in water. The method for producing the emulsion is not particularly limited, and examples thereof include a method of forcibly agitating by mixing a resin in a molten form in water, or adding water to a resin kneaded by a melter. The method and the like are disclosed in, for example, 曰本 Φ Patent 4 inch Gongzhao 42_〇〇〇275, Special Fair 7_〇〇8933, etc. Polymerized acrylic polymer in the presence of an emulsifier of the olefin polymer (4) ( B) In the case of producing an emulsion of the acrylic polymer (8) alone, in order to enhance the stability of the particles, a surfactant used in a general emulsion polymerization method may be used. Specific examples of the surfactant include, for example, a surfactant. Anionic system A surfactant, a nonionic surfactant, a cationic surfactant, another reactive surfactant, etc. These surfactants may be used alone or in combination of two or more. Specific examples of the nonionic surfactant For example, polyoxyethylene 312XP / invention specification (supplement) / 96-08/96114780 〇〇 200804551 olefinic hexyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene ethyl phenyl phenyl bond, Polyoxyethylene decyl phenyl, Oxygen, Oxygen, and propylene propylene, trioctylphenoxyethylpolyethoxyethanol, nonylphenoxyethylpolyethylethanol, etc. as an anionic interface Specific examples of the active agent include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyl diphenyl ether sulfonate, sodium alkyl sulphate, sodium dialkyl sulfosuccinate, Sodium stearate, potassium oleate, sodium dioctylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sodium dialkyl sulfosuccinate, tert-butyl Phenoxyethoxypolyethoxyethyl sulfate salt, and the like. Specific examples of the cationic surfactant include lauryl triammonium chloride and stearyl triammonium chloride. The amount of the surfactant to be used is not particularly limited, and when the emulsified composition of the olefin polymer (A) and the acrylic polymer (B) is contained in the same particle, if the amount of the surfactant is used, Particles composed only of the propienoic acid-based polymer (B) are produced. Further, in the case where the amount of the surfactant is large, the amount of free interface active agent in the obtained binder is relatively increased, which results in a decrease in the characteristics of the electrochemical cell. Therefore, in the case where the acrylic polymer (B) is polymerized in the presence of the anthraquinone polymer (A) emulsion, and the acrylic polymer (B) is polymerized alone, the amount of the surfactant used is Preferably, based on the total weight of the monomers (b1), (b-2), (b-3), (b-4), and compound (c) used in the acrylic polymer (Β), It is 〇~5 wt%. For the production of an emulsified composition containing the olefin-based polymer (A) and the acrylic 312XP/invention specification (supplement)/96-08/96114780 21 200804551 in the same particle, and the production of the olefin-containing & In the case of the emulsified composition of the resin particles composed of the body (A) and the resin particles composed of the acrylic polymer (b), the above various monomers and compounds may be added at once, or separately, or continuously added dropwise. . The acrylic polymer (B) is in the presence of the above-mentioned initiator, and ▲ is in the range of 0 to 1 (10). C, preferably 30 to 90. Temperature polymerization. The form of the resin particles constituting the emulsified composition is not particularly limited. For example, an emulsion of the olefin-based polymer (A) and the acrylic polymer (β) is contained in the same particle, and examples of the form of the particles include a core/shell structure, a composite structure, a localized structure, a tumbler-like structure, and Raspberry structure and so on. In the present invention, the weight average particle diameter (Microtrac UPA: measured by Honneyweli Co., Ltd.) of the resin particles constituting the emulsified composition is preferably 10 nm to 10 #m, more preferably 10 nm to 2 #m. If the particle size exceeds the adhesion to the active material or the metal current collector, the electrochemical unit is degraded. The weight ratio of the olefin polymer (A) to the acrylic polymer (B) in the emulsified composition is preferably based on the total weight of the olefin polymer (A) and the acrylic polymer (β). (A) is 95 to 30% by weight, (B) is 5 to 70% by weight, more preferably (A) is 95 to 5 % by weight, and (B) is 5 to 50% by weight. If the weight ratio of (a) to (B) is within the above range, it is preferable from the viewpoint of electrochemical stability and adhesion. The constituent material other than the binder used for the electrode for an electrochemical cell is not particularly limited. For example, in the case of secondary battery and electric double layer electricity 3 i2xp / invention manual (supplement) / 96-08/96114780 22 200804551 The use of the active material 盥W s

From the binder as a constituent material, the negative electrode uses the R material and the binder as the furnace to use the negative active carbon black, and the amorphous surface is required; however, other materials such as a negative electrode active material for the battery may be added. It can be used with metal clocks, clocks, de-doped and de-doped carbon materials, and can be doped with lithium ions: di-n=tin, antimony oxide, antimony oxide, and (4) sub-dosing The doping and dedoping of the bell ions can be carried out by lithium-deposited transition metal lithium nitride ion doping and dedoping. Amorphous carbon,: two: this: carbon material can be stone natural graphite. ..., a mesocarbon microbead, and a binder for an electrochemical cell electrode of the present invention may further contain a tackifier such as carboxymethylcellulose or sodium polyacrylate. Further, examples of the positive electrode active material for a primary battery include transition metal oxides and transition metal sulfides such as &, TiS2, Mn〇2, and V2〇5;

a composite oxide composed of a transition metal of a bellfish such as LlC〇〇2, LiMn〇4, LiMn2〇4, Li Yin, (4) heart, and the like; polyaniline, polythiophene, polypyrrole: polyacetylene, polyacene (p导电 lyacene), a conductive polymer material such as a dimercapto thiadiazolidine aniline complex. Among these, a composite compound composed of a bell and a transition metal is preferred. In the case where the negative electrode is a lithium metal or a lithium alloy, a carbon material may be used as the positive electrode. Further, as the positive electrode, a mixture of a composite oxide of lithium and a transition metal and a carbon material may be used. 312XP/Invention Manual (Supplement)/96-08/96114780 23 200804551 Carbon is used as a positive and negative active material for electric double layer capacitors, and various active materials can be used. The above can be used to correspond to the use form of the battery. , the male piece (seperat〇r) is made into a cylindrical type, a hard 瞥 type, a pole and a wound shape of any type 'in a battery bottle', and the above positive electrode and the negative electrode can be used as a medium overlapping liquid, thereby making two Secondary battery. i is sealed in the non-aqueous electrolyte 所 type =, in order to correspond to the use form of the battery, it can be made into any shape, such as ^ type, hard (four), etc. 1 battery bottle electrode is centered on the spacer and recrystallized J This liquid is used to prepare an electric double layer capacitor = /, and both sides are sealed with electrolysis to obtain a separator. For example, a porous film may be used as the separator, and porous fluorinated fluorine is preferably used. The material of the Γ film can be exemplified by a polythene hydrocarbon, a polythene plate, a water-biased mouse, a vinegar, etc. The porosity is preferably a porous polyolefin film, and the second/two, bridge The soil hires ^ π /, body and § can be exemplified by porous poly-B:,,,,,,,,,, a film or a porous propylene multilayer film. In addition, the other resin which is excellent in water and heat stability can be used as a separator for the surface, except for the secondary battery. In addition to the sputum sheet, a porous membrane or the like can be used. The inorganic ceramsite powder is used as an electrolyte for a secondary battery, and examples thereof include UPF6, 3l2xp/invention specification (supplement)/96. -08/96114780 24 200804551 ^lF^UC1〇i, UAsFi, _Li, (CF coffee) N/Li, etc. The 2 = mass can be used alone or in combination of two or more. These electrolytes are dissolved, non-aqueous electrolytes. It is used in an electrolyte solution (organic solvent), etc. /乍^ The electrolyte used for the electric double layer capacitor, for example, tetraethyl sulfonium tetrafluoride, triethylmonomethylammonium tetrafluoro ruthenium hydride This type of beta can be used alone or in combination of two types. These electrolytes are used by dissolving in an electrolyte solution. In an electric double layer capacitor, any electrolyte capable of exhibiting its performance can be used, but the electrolyte is not water-based. The electrolyte is better. As a secondary battery and electric double layer Examples of the non-aqueous electrolysis used in the apparatus include propyl carbonate, ethyl hexyl carbonate, dimethyl sulfite, dimethyl carbonate, ethyl methyl carbonate, and diethyl ether. An organic solvent such as a hydroxycarbonate, a U-dimethoxyethane, a u-diethoxyethane or a tetrahydrofuran. These non-aqueous electrolyte solutions may be used singly or in combination of two or more. Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples. <Preparation of emulsified composition> [Example 1] Ethylene was charged in the same autoclave • 263 parts of methacrylic acid copolymer (NUCREL N2〇6〇, thioglycolic acid 20-injury by Mitsui DuPont Polymer Chemical Co., Ltd.), 25 parts of sodium hydroxide, 712 parts of deionized water, and stirred at 15 °C. After an hour, it was cooled to obtain a particle size of 2 〇 nm, a nonvolatile 31 ZKP / invention specification (supplement) / 96 〇 8 / 96114780 25 200804551 parts of a 27% olefin emulsion. The sulphate was added to the reaction vessel, and the mixture was heated to a temperature of 8 Torr. In addition, 0.3 parts of sodium dodecylbenzenesulfonate was used in 56 parts of deionized water to make 32 parts of 2-ethylhexyl acrylate, '63 parts of styrene, 42 parts of hydroxyethyl methacrylate, and ethylene glycol. An emulsified mixture obtained by emulsification of 3 parts of dimercapto acrylate was dropped into the reaction vessel over 3 hours, and then further maintained at this temperature for 2 hours to complete the polymerization. The obtained emulsion had a nonvolatile content of 27%, and the weight average particle diameter measured by light scattering at pH 9.5 was 6 〇 nm. [Example 2] 735 parts of the olefin emulsion obtained in Example 1 and 198 parts of deionized water were placed in a reaction vessel, and the temperature was raised to 8 (rc, 0.4 parts of ammonium persulfate was added under a nitrogen stream. Further, it was produced in deionized water. 34 parts using sodium dodecylbenzene sulfonate 0. 2 wounds made 2-ethylhexyl acrylate vinegar 19. 4 parts, styrene ylide 38.3 parts, hydroxyethyl methacrylate 25.5 parts, ethylene glycol two Ethyl acrylate-ester 1 · 8 parts of an emulsified mixture, the emulsion mixture was dropped into the reaction valley for 2 hours, and then further maintained at this temperature for 2 hours to form a polymer. The weight average particle diameter of the non-volatile fraction was 5 以ηιη. [Example 3] 519 parts of the diluted hydrocarbon emulsion obtained in Example 1 and 3 25 parts of deionized water were charged. In the reaction vessel, the temperature was raised to 8 Torr in a nitrogen stream, and 0. 7 parts of ammonium persulfate was added. In addition, in the deionized water, sodium dodecyl benzoate was used to make 2-ethylhexyl acrylate. 4 parts of ester, 曱312 甲基/invention specification (supplement)/96-08/96114780 26 200804551 酉曰9 0 parts An emulsified mixture obtained by emulsifying 1 part of diethyl benzene, the emulsified mixture was dropped into the reaction vessel over 3 hours, and then further maintained at the temperature for 2 hours to complete the polymerization. The obtained emulsion was nonvolatile. The weight average particle diameter measured by light scattering at 27% 'pH 9.5 was 120 nm. [Example 4] 519 parts of the olefin emulsion obtained in Example 1 and 325 parts of deionized water were placed in a reaction vessel. The temperature was raised to 8 Torr under a nitrogen stream. 〇, 0.7 parts of ammonium persulfate was added. Further, in 56 parts of deionized water, 49 parts of sodium dodecylbenzenesulfonate was used to make 49 parts of 2-ethylhexyl acrylate. 81 parts of styrene, 7 parts of methacrylic acid, and emulsified mixture of 3 parts of epoxy methacrylate emulsified' The emulsified mixture was dropped into the reaction vessel over 3 hours, and then further maintained at this temperature 2 The polymerization was completed in an hour. The obtained emulsion had a nonvolatile content of 27%, and the weight average particle diameter measured by light scattering at ρΗ9·5 was 6 〇 nm. • [Example 5] 83 parts of deionized water , sodium dodecylbenzenesulfonate 2. 2 parts charged into the reaction volume The temperature was raised to 80 ° C under a nitrogen stream. After the temperature was raised, 0.5 parts of potassium persulfate was added to the reaction vessel, and 40 parts of deionized water was used to prepare sodium sulfonate. Emulsified mixture of 3 parts of acrylic acid, EPOMIKR140 (manufactured by Mitsui Chemicals Co., Ltd., diepoxypropyl etherate), 1 part by weight, 47 parts of styrene, and 40 parts of 2-ethylhexyl acrylate. The mixture was dropped into the reaction vessel over 4 hours, and then further maintained at this temperature for 3 hours to complete the polymerization. The polymerization of the acrylic acid 312XP/invention specification (supplement)/96-08/96114780 27 200804551 ΐ emulsion was carried out. The solution was adjusted to pH 8 with Noroxygen. The non-volatile content of the =C-acid emulsion was 鄕, and the weight average particle diameter measured by light scattering was 100 nm. The propionate-based emulsion prepared as described above is added in an amount of not less than the volatile matter, and the olefin emulsion prepared in the first embodiment is added in an amount of 7 parts in terms of non-volatile matter, and then added, and then added, steamed, adjusted, fgj 25% of the emulsified composition. [Example 6] • CHEMIPEARLS650 (a sodium hydroxide neutralized product of an ethylene-unsaturated carboxylic acid copolymer) having a non-volatile content of 27% by weight of a olefin-based emulsion in a reaction vessel under a nitrogen stream, Mitsui Chemicals Co., Ltd. 346 parts by weight and 93 parts by weight of deionized water, the reactor was heated to 8 Torr. Further, 2 parts by weight of ammonium persulfate was added to the reactor raised to 80 °C. Further, 16 parts by weight of 2-ethylhexyl acrylate, 1 part by weight of hydroxyethyl methacrylate, 11 parts by weight of styrene 10, and 3 parts by weight of divinylbenzene were added to 16 parts by weight of deionized water. An emulsified mixture was prepared by making 0.2 part by weight of sodium dodecyl sulfonate as an emulsifier. The emulsified mixture was dropped into the above reaction vessel maintained at 80 ° C for 3 hours, and then further maintained at this temperature for 2 hours to complete the polymerization. The obtained emulsified composition had a nonvolatile content of 27%, and the weight average particle diameter measured by light scattering at ρ Η 9.5 was 10 〇 nm. [Example 7] 70 parts by weight of CHEMIPEARL S650 belonging to a polyolefin-based emulsion was added to 30 parts by weight of the acrylic emulsion prepared in Example 5, and 312XP/invention specification (supplement)/96-08/96114780 was added. 28 200804551 Thereafter, distilled water was further added to prepare an emulsified composition of 25% by weight of the solid content. [Comparative Example 1] 519 parts of an olefin emulsion prepared in Example and 325 parts of deionized water were placed in a reaction container, and the temperature was raised to 8 (rc, and ammonium persulfate was added to 0.7 parts under a nitrogen stream. An emulsified mixed 10 of emulsified 32 parts of 2-ethylhexyl acrylate, 32 parts of styrene 63 and hydroxyethyl methacrylate by using 0.3 parts of sodium dodecyl sulfonate in 56 parts of water, The emulsified mixture was dropped into the reaction vessel over 3 hours, and then further maintained at this temperature for 2 hours to complete the polymerization. The obtained emulsion was a nonvolatile matter of 27%, and the weight obtained by light scattering was measured at ΡΗ9.5. The average grain size was 60 nm. [Comparative Example 2] 83 parts of deionized water and 2 parts of sodium dodecyl benzoate were added to the reaction state, and the temperature was raised to 80 in a nitrogen stream. 5 parts of potassium persulfate was added to the reaction vessel, and 4 parts of sodium dodecyl sulfonate was used in 4 parts of deionized water to make EPOMIK R140 (made by Mitsui Chemicals Co., Ltd.) Propyl etherate) 10 parts, 50 parts of styrene, 2-ethylhexyl acrylate 4〇 The emulsified mixture was emulsified, and the emulsified mixture was dropped into the reaction vessel over 4 hours, and then further maintained at the temperature for 3 hours to complete the polymerization. The polymerization liquid composed of the acrylic emulsion was 5%. The sodium hydroxide was adjusted to pH 8. The obtained emulsion was 45% nonvolatile, and the weight average particle diameter determined by light scattering was 312XP/invention specification (supplement)/96·〇8/96114780 29 200804551 = The prepared acrylic emulsion was converted to 3 parts by weight in terms of nonvolatile matter, and the olefin emulsion prepared in Example 1 was converted into 7 parts by weight in terms of nonvolatile matter. After adding and stirring, distilled water was added thereto to prepare an emulsion of 25% solid content. 2重量%的固形 形成 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固 固The emulsified composition prepared in Example 1 was mixed in an amount of 2 parts by weight in terms of solid content, after converting into 1 part by weight of a tackifier-based thiol cellulose solution (such as CMC Daicel 1160 of (4) Co., Ltd.) After adding further The plugged water was prepared to prepare a negative electrode mixture paste having a solid content concentration of 50% by weight. The negative electrode mixture paste was applied to a negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 m, and then dried. And compression-molding to prepare a negative electrode having a thickness of 7 〇 #m. [Example B] In the same example, except that the emulsified composition was changed to the emulsion prepared in Example 2, the same operation was carried out. Negative electrode 0 having a thickness of 7 〇 &quot; m [Example C] In Example A, except that the emulsified composition was changed to the emulsion prepared in Example 3, the same operation was carried out to prepare a thickness of 7 〇 #m Negative electrode 〇 [Example D] 312XP / invention specification (supplement) / 96-08/96114780 30 200804551 In Example A, except that the emulsified composition was changed to the emulsion prepared in Example 4, the same was carried out. Operation, making thickness #m negative, though. [Example E] In the case of the addition of the emulsified composition to the emulsion prepared in Example 5, the same operation was carried out to prepare a negative electrode 0 having a thickness of 70 μm [Example F] In A, except that the emulsified composition was changed to the emulsion prepared in Example 6, the same operation was carried out to prepare a negative electrode 0 having a thickness of 70/zm [Example G] in Bega addition A, except that the emulsified composition was The material was changed to the emulsion prepared in Example 7, and the same operation was carried out to prepare a thickness of 0 Φ [Comparative Example A] In Example A, except that the emulsified composition was changed to Comparative Example 1. In the same manner as the emulsion, the same operation was carried out to produce a negative thickness of 70//111. [0] [Comparative Example B] In the example A, except that the emulsified composition was changed to the emulsion prepared in Comparative Example 2. Outside the 'do the same operation, make the negative electrode 0 with a thickness of 7〇# m [Comparative Example C] 312XP/Invention Manual (Supplement)/96-08/96114780 200804551 In Natural Graphite (made by Yueyue Graphite Industry Co., Ltd.) LF18A) 98 heavy wounds, adding 8% by weight of pVj)jr (polydifluoroethylene) NMP (N-methyl-2-pyrrolidone) solution of olefin) (KF polymer #112〇 manufactured by Wu Yu Chemical Industry Co., Ltd.) 25 parts by weight, further mixed viscosity adjustment with Li P, and preparation of negative electrode mixture Paste. Then, the negative electrode mixture paste was applied to a negative electrode current collector made of a strip-shaped copper foil having a thickness of 18/im, and then subjected to dry pressing and compression molding to prepare a negative electrode having a thickness of 7 Å #m. [Comparative Example D] The same procedure as in Example A was carried out except that the emulsified composition was changed to an aqueous dispersion of SBR having a nonvolatile content of 48% by weight (SR143 manufactured by A&L Co., Ltd.). 7〇# m's negative electrode. <Preparation of positive electrode of secondary battery> [Example H] Addition of LiCo 2 (HLC-22 manufactured by FMC Energy Systems Co., Ltd.) 85.5 parts by weight, 8 parts by weight of graphite, 3 parts by weight of acetylene black, and carboxyl group _ The base cellulose (Daicel Chemical Co., Ltd., 116 〇) was converted into a solid content of 1.5 parts by weight, and the emulsified composition prepared in Example 1 was converted into 2 parts in terms of solid content to prepare a LiCo 2 mixture paste, and the uc was prepared. The mash 2 mixture paste was applied to an aluminum foil having a thickness of 20 /zm, and dried and compression-molded to prepare a positive electrode having a thickness of 70/m. [Example I] In the case of the shellfish, except that the emulsified composition was changed to the emulsion prepared in Example 2, the same operation was carried out to prepare a thickness of 70/zm, although the 312XP/invention specification ( Supplement) /96-08/96114780 32 200804551 [Example j] In the example, except that the emulsified composition was changed to the emulsion prepared in Example 3, the same operation was carried out to prepare a positive electrode having a thickness of 70 0 [Example K] In the Example, except that the emulsified composition was changed to the emulsion prepared in Example 4, the same operation was carried out to prepare a thickness of 70 // m. L] In the example, except that the emulsified composition was changed to the emulsion prepared in Example 5, the same operation was carried out to prepare a positive electrode having a thickness of 70 // m [Example Μ] in Example Η Except that the emulsified composition was changed to the emulsion prepared in Example 6, the same operation was carried out to prepare a positive electrode having a thickness of 7 〇 from m. [Example N] In the Example, except that the emulsified composition was changed to the emulsion prepared in Example 7, the same operation was carried out to prepare a thickness of 7 〇//ln, although [Comparative Example] In the example, except that the emulsified composition was changed to the emulsion prepared in Comparative Example 1, the same operation was carried out to prepare a thickness of 7 〇 / ζ π1, although 〇 ΧΡ 发明 / invention description (supplement) / 96-08/96114780 33 200804551 [Comparative Example F] In the example, except that the emulsified composition was changed to the emulsion prepared in Comparative Example 2, the same operation was carried out to prepare the thickness #m. 0 [Comparative Example G] This LiCo 2 (HLC-22 manufactured by FMC Energy Systems Co., Ltd.) 87 parts by weight, 8 parts by weight of graphite, 3 parts by weight of acetylene black, and PVDF of 8 parts by weight of nonvolatile matter. NMP solution (KF polymer #112〇, manufactured by Kureha Chemical Industries Co., Ltd.) After 25 parts by weight, NMP for viscosity adjustment was further mixed to prepare a LiCo 2 mixture paste. The Lic〇〇2 mixture paste was applied to an aluminum foil having a thickness of 2 〇 // m, and dried and compression-molded to prepare a positive electrode having a thickness of 70 μm. <Evaluation of adhesion of secondary battery> The electrodes prepared in Examples A to G and Comparative Examples A to G were cut out and attached to a glass article by an instant carrier to be used as a sample for evaluation. The sample for Lu will be evaluated as a film peeling strength measuring device SAICAS DN2〇 (made by Dai Brown Inteix Co., Ltd.), and the interface between the composite layer and the current collector will be cut at a horizontal speed of 2 // m/sec. 'The peel strength of the interface between the composite layer and the current collector is measured by the horizontal direction force necessary for cutting. The average of the three peel strengths was taken to evaluate the adhesion. The results are shown in Table 1. (Table 1) Negative electrode_Pressure sample used composition peel strength (kN/m) Sample peel strength + (kN/nO Example A Example 1 0. 23 Example 实施 Example 1 〇. 25 Implementation Example B Example 2 0.25 Example I Example 2 0. 25 Example C Example 3 0. 25 Example J Example 3 0. 25 312 ΧΡ / invention specification (supplement) / 96-08/96114780 34 200804551

Preparation of secondary battery non-aqueous electrolyte > As a non-aqueous solvent, the mixture is made of ethylene carbonate (EC) and ethyl sulfite vinegar (EMC) in a ratio of EC: EMC = 4: 6 (weight ratio).

Then, the electrolyte UpF6 was dissolved to make the electrolyte concentration ι·〇 mol/liter, and a non-aqueous electrolyte was prepared. <Production of Coin-Type Secondary Battery> The negative electrode made of Examples A, b, d, C, and E and Comparative Examples A and B was punched into a disk shape having a diameter of 14 mm. A coin-shaped negative electrode weighing 2〇mg/14mm0. For the positive electrode for the hard t-type battery, the positive electrode prepared in Examples F, g, Η, I, J and Comparative Examples C and D was punched into a disk shape having a diameter of 13 5 mm to obtain a weight of 101 42 mg / l 3 · 5 mm 0 The coin-shaped positive electrode. The coin-shaped negative electrode, the positive electrode, and the porous polypropylene film made of a porous polypropylene film having a thickness of 25/zm and a diameter of 16 are placed in a negative electrode bottle of a stainless steel 2032-size battery bottle, and the negative electrode is isolated. The sheets and the positive electrodes are laminated in sequence. Thereafter, 4 ml of the above nonaqueous electrolyte 〇.〇 was injected into the separator, and then an aluminum plate (thickness: 1.2 mm, diameter: 16 Å) and a spring were superposed on the laminate. Finally, a polypropylene-made gasket was used to cover the positive electrode bottle of the battery, and the bottle cap was closed to maintain the airtightness in the battery, and a coin-type battery having a diameter of 2 inches and a height of 3.2 mm was produced. For the condition of The current is 0. 05 mA until the current is 0. 05 mA. The current value is 0. 05 mA until the constant current of 1 mA, 3. 0V constant voltage conditions, discharge to 3. 0V constant voltage when the current value is 0. 05mA. This cycle was repeated 200 times, and the capacity % relative to the initial battery capacity after 200 cycles was evaluated. The evaluation results of the batteries using the respective electrodes are shown in Table 2. (Table 2) Battery No. Positive electrode negative electrode 200 cycle capacity (%) Sample Composition 1 used for the sample of the composition used Example Η Example A Example 1 95 2 Example 实施 Example 1 Example B Example 2 95 3 Example Η Example 1 Example C Implementation Example 3 95 4 Example 实施 Example 1 Example D Example 4 94 5 Example 实施 Example 1 Example E Example 5 94 6 Example Η Example 1 Example F Example 6 95 7 Example 实施 Implementation Example 1 Example G Example 7 95 8 Example Η Example 1 Comparative Example A Comparative Example 1 80 9 Example 实施 Example 1 Comparative Example B Comparative Example 2 80 10 Example 实施 Example 1 Comparative Example C PVDF 70 11 Example 实施 Example 1 Comparative Example D SBR 70 12 Implementation EXAMPLE I Example 2 Example A Example 1 94 13 Example J Example 3 Example A Example 1 95 14 Example Κ Example 4 Example A Example 1 95 15 Example L Example 5 Example 1 95 16 Example 实施 Example 6 Example A Example 1 95 17 Example Ν Example 7 Example A Example 1 95 18 Example Ε Comparative Example 1 Example A Example 1 75 19 Example F Comparative Example 2 Example A Example 1 79 20 Example G PVDF Example A Example 1 70

<Preparation of Electrode Double-Capacitor Electrode> [Example 0] In activated carbon (Kuraray Co., Ltd. RP-20) 100 parts by weight, 312XP/invention specification (supplement)/96-08/96114780 36 200804551,., ( Electric Chemical Co., Ltd. Denka Black) 3 parts by weight,

Ketjen black Uetjen Black International Company's face-to-face) 2 parts by weight of 2 parts and 15 parts by weight of solids are adjusted as &quot;Heavy U-tackifier thiol-methylcellulose (Daicel Division CMC1160), in i In the middle of the 々 々, from #. Λ, ^, , and f were mixed in two parts in a solid form, and the composition of the mixture of Example j, f was added, and steamed water was added in a stepwise manner to prepare a mixture paste having a solid concentration of 50% by weight. Next, the negative electrode mixture paste was applied to a thickness of 2G&quot; (4), and dried and compression-molded to prepare an electrode having a thickness of 70 μm. [Example P] In Example 0, except that the emulsified composition was changed to the emulsion prepared in Example 2, the same operation was carried out to prepare a thickness of 70 &quot;m. [Example Q] In the same manner as in the case of changing the emulsified composition to the emulsion prepared in Example 3, the same operation was carried out to prepare an electrode having a thickness of 70 cm [Example R] in Example 0, except The emulsified composition was changed to the emulsion prepared in Example 4, and the same operation was carried out to prepare an electrode having a thickness of 7 μm. [Example S] In Example 0, except that the emulsified composition was changed to Example 5 In the same manner as the prepared emulsion, the same operation was carried out to prepare a battery having a thickness of 70 μm/inventive specification (supplement)/96-08/96114780 37 200804551 pole 0 [Example τ] In Example 0, except that the emulsion was emulsified The composition was changed to the emulsion prepared in Example 6, and the same operation was carried out to prepare an electrode having a thickness of 7 Å/zm. [Example U] In Example 0, except that the emulsified composition was changed to Example 7. Made

In the same manner as the emulsion, the same procedure was carried out to prepare a thickness of 7 〇 #m [Comparative Example] In Example 0, except that the emulsified composition was changed to the emulsion prepared in Comparative Example 1. The same operation was carried out to prepare an electrode having a thickness of 70/zm [Comparative Example I] In Example 0, except that the emulsified composition was changed to the emulsion prepared in Comparative Example 2, the same operation was carried out. Thickness core = [Comparative Example J], Example 0 t, except that the emulsified composition was changed to a glaze (Daikin Industries Co., Ltd. (4)) = operation, an electrode having a thickness of 70/^ was produced. Appropriate questioning <Evaluation of adhesion of electric double-layer capacitors> Sub-electrode Electrodes made in Examples 0 to T and Comparative Examples H to J were subjected to the same method as the evaluation of the fish pond adhesion evaluation /, ,,, The fruit is not shown in Table 3 312XP/Invention Manual (Supplement)/96_08/9611478() 38 200804551 (Table 3) Sample use composition peel strength (kN/m) Example 0 Example 1 0. 36 Example P Implementation Example 2 0. 35 Example Q Example 3 0. 35 Example R Example 4 0. 35 Example S Example 5 0. 36 Example T Example 6 0. 35 Example U Example 7 0. 35 Comparative Example Η Comparative Example 1 0.30 Comparative Example I Comparative Example 2 0. 28 Comparative Example J PTFE 0. 08 馨 <Preparation of Electrolytic Double Layer Capacitor Electrolyte> Dissolving Electrolyte Tetraethyl Carbon Tetrafluoroborate 22 in Propylene Carbon The electrolyte concentration was adjusted to 1.5 mol/liter. <Preparation of coin-type electric double layer capacitor> The electrodes prepared in Examples 0 to U and Comparative Examples H to j were punched into a disk shape having a diameter of 14 mm to obtain a coin electrode having a weight of 2 Torr/14. The coin-shaped electrode and the separator made of a propylene film formed by a thickness of a core m and a diameter of 16 angstroms are placed in a negative electrode bottle of a stainless steel snap-in battery bottle, using electrodes, separators, electrodes The order is laminated. Thereafter, after injecting the above electrolyte solution 〇. 4 ml into the separator, the plate (thickness h 2 face, diameter 16 ship) and the sapphire were re-applied to the laminate. Finally, a coin-type electric double-layer capacitor having a diameter of 2 inches and a height of 3 2 mm was produced by covering a battery bottle with a polypropylene film, closing the bottle cap, and keeping the airtightness inside the battery. <Evaluation of characteristics of electric double-layer capacitors> Use a hard-type electric double-layer capacitor fabricated as described above, with 〇 〇 α 312XP / invention manual (supplement) / 96 with 9611478 〇 200804551 constant current charging ί ο to 2 After the v, the current is discharged by the constant current of lmA, and the charge and discharge characteristics are obtained, and the electrostatic capacity is determined. The internal resistance is charged and discharged by each characteristic 'according to the specification RC specified by the corporate electronic information technology industry association. Calculated by the calculation method of -2377. The evaluation results of the cereals using each electrode are shown in Table 4. (Table 4)

Electrode use composition static capacitance F(F/g) internal resistance (Ω F) Example 0 Example 1 45 __ 4. 0 Example P Example 2 44 __— 4. 0 Example Q Example 3 1 45 3.9 EXAMPLE R Example 4 44 _ 4. 0 Example S Example 5 45 _ 4. 0 Example T Example 6 45 4. 0 Example U Example 7 44 __ 4. 0 Comparative Example Η Comparative Example 1 32 __ 4. 4 Comparative Example I Comparative Example 2 30 4. 6 Comparative Example J Comparative Example 3 32 __ 4. 4

312XP/Invention Manual (supplement)/96-08/96114780 40

Claims (1)

200804551 X. Application for Patent Park: 1·-An electrochemical cell electrode binder, characterized in that it comprises a resin composition in a water, and the resin particle is a thin smoke-based polymer (A) It is formed with an acrylic polymer (1) having an internal crosslinked structure. The bonding agent for an electrochemical cell electrode according to the first aspect of the invention, wherein the acrylic acid-based polymer (B) having an internal cross-linking structure is produced from a monomer having the following components: an acrylic monofunctional Sexual monomer (b-1), polyfunctional monomer (2). 3· &gt; Patent Application 帛 1 type electrochemical cell electrode binder, wherein the acrylic polymer (B) having an internal crosslinked structure is produced from a compound containing a reactive group of acrylic acid The monofunctional monomer (b-1-2) and the compound (c) having two or more groups reactive with the reactive group of the acrylic monomer (b_1-2). 4. The adhesive agent for an electrochemical cell electrode according to the third aspect of the invention, wherein the reactive group of the reactive acrylic group monofunctional monomer (b-1-2) is a carboxyl group and/or The base of the above compound ((a) • which can react with the reactive group of the acrylic monomer (b-Ι-2) is a ring: an oxy group. 5. The electrochemical unit electrode of the first aspect of the patent application is A binder in which an acrylic polymer (B) having an internal crosslinked structure is produced from a monomer containing a component: an acrylic monofunctional monomer having a reactive group (1) (b-1- 2) an acrylic monofunctional monomer having a reactive group (2) reactive with a reactive group (i). 312XP/Invention Manual (Supplement)/96-08/96114780 41 200804551 6. Patent application The range of the first electrode binder, wherein the electrochemical unit of any one of the items U-1) is a copolymer. ～合合体(1) contains a hydrocarbon-derived unit. 7. As claimed in the patent scope, the #hydrocarbon-based polymerization & electrode electrochemical cell electrode is bonded and can be copolymerized with a dilute hydrocarbon monomer. The monomer is a monomer, wherein the ratio of the olefinic monomer, the electrochemical unit electrode to the other monomer U-2, can be copolymerized with the olefin monomer. The amount of L is 99.9. ~35.0% by weight, ((9) is 9. :: Please note the electric agent of the scope of the patent, wherein the weight of the adhesive polymer (B) in the emulsion is "poly" and "into A" with acrylic acid 9595^30 #-〇/ * w is a base # 'ene olefin polymer (4) is 5% by weight, and the propylene I polymer (B) is 5 to 70% by weight. An adhesive consisting of any one of the patents from item 9 to item 9. 11. An electrochemical unit characterized in that the electrode of the first aspect of the patent application is used as a positive and/or negative electrode. The electrochemical unit of the third aspect of the invention, wherein the electrochemical unit is a secondary battery. 13·Electrification as claimed in claim 11 The above-mentioned electrochemical unit is an electric double layer capacitor. 〃 312XP/invention specification (supplement)/96-08/96114780 42 200804551 VII. Designated representative figure (1) The designated representative figure of the case is: none ( b) A brief description of the symbol of the representative figure: None 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 312XP/Invention Manual (supplement)/96-08/96114780 4