TW201140924A - Mixture for non-aqueous electrolyte secondary battery, electrode for same, and non-aqueous electrolyte secondary battery - Google Patents

Abstract

An object of the present invention is to provide a mixture layer and mixture for a non-aqueous electrolyte secondary battery with excellent peeling strength from a power collector, that is highly productive in manufacturing a non-aqueous secondary battery electrode and a non-aqueous secondary battery, and suppresses mal-distribution of a binding agent in the mixture layer when manufacturing the electrode. The non-aqueous secondary battery mixture contains at least one type of unsaturated carboxylic acid polymer (A) selected from a polyacrylic acid and polymethacrylic acid, vinylidene fluoride polymer containing carboxyl (B), an electrode active material, and a weight-average molecular weight of 1,000 - 150,000 of polyethylene oxide conversion measured by GPC of the unsaturated carboxylic acid polymer (A).

Description

[Technical Field] The present invention relates to a mixture for a nonaqueous electrolyte secondary battery, an electrode for a nonaqueous electrolyte secondary battery, and a nonaqueous electrolyte secondary battery. [First-hand technology] In recent years, the development of electronic technology has been remarkable, and various machines have been reduced in size and weight. With the miniaturization and weight reduction of the above-mentioned electronic equipment, it is required to reduce the size and weight of the battery to be used as a power source. As a battery that can obtain a large amount of energy with a small volume and weight, a non-aqueous electrolyte secondary battery using lithium is mainly used as a small electronic device used in a home such as a mobile phone, a personal computer, or a video camera. power supply. The electrode of the nonaqueous electrolyte secondary battery mainly uses polyvinylidene fluoride (PVDF ' Polyvinylidene flU0ride) as a binder (adhesive resin). PVDF has excellent electrochemical stability, mechanical properties and slurry properties. However, the adhesion of PVDF to the metal foil as a current collector is weak. Therefore, there has been proposed a method of introducing a functional group such as a carboxyl group into PVDF to improve the adhesion to metalloid (see, for example, Patent Documents 丨 to 5). However, in the case of using an active material having a large specific surface area, a case where the amount of the binder added is small, and a case where an electrode is produced by rapid drying, PVDF is liable to be unevenly distributed on the surface of the electrode. As a result of uneven surface distribution, the amount of bonding near the current collector is reduced, and the adhesion to the current collector is lowered. Further, if the PVDF is unevenly distributed on the surface, the adhesive force of the active materials decreases when the amount of pvdf is small. Therefore, in the case where the distribution of the adhesive is uneven, even if pVDF having a functional group such as a carboxyl group introduced therein is used, 154705.doc 201140924 also obtains an electrode having a low peel strength. = Various methods have been proposed to suppress the uneven distribution of the binder. There has been proposed a method for suppressing the unevenness of surface distribution by suppressing the movement of the binder to the surface by stabilizing the drying conditions (for example, referring to the patent core, & lack, the method is required to stabilize the drying conditions, so the mixture is dried. The speed decreases. The productivity of the electrode decreases. The method is as follows: The following method: _ the mixture of different binders is prepared. The closer the binder is to the substrate (collector), the more the binder is: In the meantime, the multilayer coating is applied at the same time to produce an electrode having a uniform distribution of the binder (for example, refer to Patent Document 8). However, in this method, it is necessary to prepare a plurality of kinds of the mixture, which leads to an increase in the number of steps in the electrode production, and the productivity is lowered. A special device is required for coating. The following method is proposed: after the electrode is formed, an organic solvent capable of dissolving the binder is injected into the electrode group, and heat treatment is performed under pressure bonding, so that the binder is dissolved again in the electrode. Thereby, the uneven distribution of the binder is suppressed (for example, refer to Patent Documents 9, 1). However, the method is also added to manufacture a battery. In addition, it is known that when the PVDF and the polyacrylic acid are used together as a binder, the adhesion to the current collector is improved (for example, refer to the patent document 丨丨). However, even if PVDF and polyacrylic acid are used in combination, In the case of a binder, the uneven distribution of the binder on the surface of the electrode is not suppressed, so that the adhesion to the current collector is insufficient. On the other hand, it is known that only the acrylic acid is used for the electrode of the binder ( For example, refer to Patent Documents 12 and 13). It is known that when only polyacrylic acid is used as the binder, the higher the molecular weight, the greater the adhesion, and if polyacrylic acid having a weight average molecular weight of 154,705.doc 201140924 is used, it is 300,000 or more. The cycle durability of the battery is improved. However, when only polyacrylic acid is used as the binder, the electrode becomes hard, and in the manufacturing step of the battery, there is a case where the electrode is broken when the electrode is wound, and the yield of the battery is deteriorated. It is known that if a functional group-containing PVDF and a carbonyl-containing polar polymer are used as a binder, the safety of the internal short circuit of the battery is improved (for example, Refer to Patent Document 14). In Example 2 of Patent Document 14, it is described that PVDF containing a carboxyl group and polyacrylic acid are used in combination as a binder. However, in this embodiment, the polyacrylic acid is a crosslinked type having a very large molecular weight. The peeling strength of the obtained electrode of the acrylic acid is insufficient. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1 Patent Application Patent Publication No. JP-A No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. [Patent Document 7] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. Patent Document No. 2004-95538 Patent Document 11: Japanese Patent Laid-Open No. Hei. (9) No. Patent Document 12: Japanese Patent Laid-Open No. 2〇〇5·2165〇2 No. 154705.doc 201140924 Patent Document 13: Japanese Patent Laid-Open No. 2007-35434 Patent Document 14: International Publication No. 2004/〇49475. SUMMARY OF INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the problems of the prior art described above. The purpose of the invention is to provide a non-aqueous electrolyte secondary battery mixture, which is excellent in productivity, and which is capable of producing an electrode for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery. The uneven distribution of the binder in the mixture layer can be suppressed, and the separation strength of the mixture layer and the current collector is excellent. In addition, an object of the present invention is to provide an electrode for a nonaqueous electrolyte secondary battery obtained by coating the mixture on a current collector and drying the same, and a nonaqueous electrolyte secondary battery having the electrode. Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above problems, and have found that a specific unsaturated carboxylic acid polymer and a carboxyl group-containing vinylidene fluoride polymer (B) are used as a binder. The mixture for a nonaqueous electrolyte secondary battery can solve the above problems, and the present invention has been completed. That is, the mixture for a nonaqueous electrolyte secondary battery of the present invention contains at least one unsaturated carboxylic acid polymer (A) selected from polyacrylic acid and polymethacrylic acid, and a vinylidene fluoride polymer containing a carboxyl group (B). The electrode active material and the organic a agent 'the above-mentioned unsaturated acid polymer (4) has a weight average molecular weight of 1,000 to 150,000 in terms of polyethylene oxide as measured by gel permeation chromatography (GPC).不g夂 Polymer (4) is determined by gel permeation chromatography (GPC). J54705.doc 201140924 The weight average molecular weight in terms of polyoxyethylene is preferably 1,000 to 1 Torr, 〇〇〇〇 The unsaturated carboxylic acid polymer (A) is preferably from 0.5 to 15 per 100 parts by weight of the total of the unsaturated carboxylic acid polymer (A) and the carboxyl group-containing vinylidene fluoride polymer (B). The weight is ❶/❶, more preferably 88 to 6% by weight. The specific surface area of the above electrode active material is preferably 丨~(7) m2/g, more preferably 2 to 6 m2/g. The carboxyl group-containing vinylidene fluoride polymer (B) is preferably at least one selected from the group consisting of an unsaturated dibasic acid, an unsaturated dibasic acid monoester, acrylic acid, and methacrylic acid, and a carboxyl group-containing monomer. a copolymer of vinyl fluoride. The electrode for a nonaqueous electrolyte secondary battery of the present invention is obtained by applying the above-mentioned nonaqueous electrolyte secondary battery mixture to a current collector and drying it. The electrode for a nonaqueous electrolyte secondary battery preferably has a mixture layer having a thickness of 2 Torr to 15 pm formed of the above mixture for a nonaqueous electrolyte secondary battery. The nonaqueous electrolyte secondary battery of the present invention has the above electrode for a nonaqueous electrolyte secondary battery. Advantageous Effects of Invention The non-aqueous electrolyte secondary electric (four) mixture of the present invention can produce an electrode for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery with high productivity, and can be used for producing an electrode for a non-aqueous electrolyte secondary battery. The distribution unevenness of the spotting agent in the mixture layer is suppressed, and the peel strength of the mixture layer and the current collector is excellent. Further, the non-aqueous electrolysis f: secondary battery electrode and the non-aqueous electrolyte secondary battery of the present invention are produced by using the non-aqueous electrolytic f secondary battery mixture 154705.doc 201140924, and thus can be produced with high productivity. [Embodiment] Next, the present invention will be specifically described. The mixture for a nonaqueous electrolyte secondary battery of the present invention comprises at least one unsaturated carboxylic acid polymer (A) selected from the group consisting of polyacrylic acid and polyacrylic acid, and a vinylidene-based polymer (B) containing a rebel group. The electrode active material and the organic solvent, the weight average molecular weight of the unsaturated carboxylic acid polymer (A) measured by gel permeation chromatography (Gpc) in terms of polyethylene oxide is 1, 〇〇〇 150,000. The mixture of the present invention is generally used as a mixture for a negative electrode, that is, a negative electrode mixture. [Unsaturated carboxylic acid polymer (A)] The mixture for a nonaqueous electrolyte secondary battery of the present invention contains at least one unsaturated carboxylic acid polymer selected from the group consisting of polyacrylic acid and polyacrylic acid. As the unsaturated carboxylic acid polymer (A), a polymer having a weight average molecular weight of 1,000 to 150,000 in terms of polyethylene oxide as measured by gel permeation chromatography (GPC) can be used. The unsaturated acid-initiating polymer (A) contained in the nonaqueous electrolyte primary battery of the present invention may be polyacrylic acid, or may be polyacrylic acid, or a mixture of polyacrylic acid and polyacrylic acid. The unsaturated carboxylic acid polymer (A) used in the present invention may be used singly or in combination of two or more. As the unsaturated carboxylic acid polymer (A), from the viewpoint of easiness of obtaining, polyacrylic acid is preferred. The polyacrylic acid' can be exemplified by a homopolymer of acrylic acid or a copolymer of acrylic acid and another monomer. As polyacrylic acid, it can be used for polymer 1% by weight 154705.doc

S 201140924 contains a polymer derived from a structural unit derived from acrylic acid in an amount of usually 6 g by weight or more, preferably 75% by weight or more, more preferably 90% by weight or more. As the polyacrylic acid, a homopolymer of acrylic acid is preferred. As the monomer other than the acrylic acid, a monomer copolymerizable with acrylic acid can be used. Specific examples of the other monomer include methacrylic acid; an α-olefin such as ethylene, propylene or 1-butene; an alkyl acrylate such as methyl acrylate or ethyl acrylate; and methyl methacrylate and methyl methacrylate. A methacrylic acid-based vinegar such as ethyl acrylate; an ethylene vinegar such as acetic acid; an aromatic vinyl compound such as styrene or the like. Examples of the polymethacrylic acid include a homopolymer of methacrylic acid and a copolymer of methacrylic acid and another monomer. The polyacrylic acid is a polymer containing a thioglycol-derived structural unit in an amount of usually 60% by weight or more, preferably 75% by weight or more, and more preferably 90% by weight or more based on 100% by weight of the polymer. . As the polyacrylic acid, a homopolymer of mercaptoacrylic acid is preferred. As the monomer other than methacrylic acid, a monomer copolymerizable with mercaptopropionic acid can be used. Specifically, 'as another monomer, an acrylic acid; an α-olefin such as ethylene, propylene or 1-butene; an alkyl acrylate such as decyl acrylate or ethyl acrylate; methyl methacrylate or methyl amide; Acrylic acid. Alkyl methacrylate such as ethyl vinegar; vinyl acetate; aromatic styrene compound such as styrene. The unsaturated carboxylic acid polymer (A) used in the present invention preferably contains 8 χ 10·3 to 1.4 x 1 (T2 mol/g of a carboxyl group. The unsaturated carboxylic acid polymer (A) used in the present invention, as above The 154705.doc 201140924 uses a polyethylene oxide-equivalent polymer having a weight average molecular weight of 1, 〇〇〇 15 〇〇〇〇 as measured by gel permeation chromatography (GPC). The weight average molecular weight of the substance (A) is preferably 〖, 〇〇〇~!〇〇〇〇〇. The electrolyte resistance of the unsaturated carboxylic acid polymer (A) when the weight average molecular weight is less than 1000 On the other hand, if the molecular weight exceeds 15 Å (), the compatibility of the unsaturated carboxylic acid polymer (A) with the vinylidene fluoride-containing polymer (B) having a carboxyl group is inferior, so that no peeling is observed. In the unsaturated carboxylic acid polymer (A) used in the present invention, a part of the carboxyl group may be neutralized. As the unsaturated carboxylic acid polymer (A) used in the present invention, a commercially available product may be used. [Polyvinylidene fluoride-based polymer (B) having a carboxyl group] The mixture for a water-electrolyte secondary battery includes a vinylidene fluoride-based polymer (B) having a carboxyl group and the above-mentioned unsaturated carboxylic acid polymer as a binder resin (adhesive). In the present invention, a carboxyl group-containing partial bond is used. The difluoroethylene-based polymer (b) is a polymer obtained by containing a carboxyl group in a polymer and using at least vinylidene fluoride as a monomer. Further, a vinylidene fluoride-based polymer (B) having a carboxyl group is usually The polymer obtained by using a vinylidene fluoride and a monomer having a carboxyl group may further use another monomer. Further, the carboxyl group-containing vinylidene fluoride polymer (B) used in the present invention may be used alone. Further, two or more kinds of the vinylidene fluoride-based polymer (B) having a carboxyl group are contained in an amount of usually 80 parts by weight or more, preferably 85 parts by weight or more, per liter by weight of the polymer. Doc

S -10- 201140924 A polymer derived from a structural unit of vinylidene fluoride. The carboxyl group-containing vinylidene fluoride-based polymer (B) used in the present invention is usually produced by any one of the following methods: (1) a vinylidene fluoride and a carboxyl group-containing monomer, if necessary, other monomers a method of copolymerization (hereinafter also referred to as (i)), and (2) a vinylidene fluoride-based polymer obtained by polymerizing vinylidene fluoride or copolymerizing vinylidene fluoride with another monomer And a method of grafting a polymer containing a carboxyl group onto a vinylidene fluoride-based polymer by polymerizing a carboxyl group-containing polymer obtained by polymerizing a monomer having a rebel group or copolymerizing a monomer having a carboxyl group with another monomer; (hereinafter also referred to as the method of (2)); (3) by polymerizing vinylidene fluoride or copolymerizing vinylidene fluoride with another monomer to obtain a vinylidene fluoride-based polymer, and then using a carboxyl group such as acrylic acid. A method of graft-polymerizing the vinylidene fluoride-based polymer by a monomer (hereinafter also referred to as a method of (3)). The vinylidene fluoride-based polymer containing a carboxyl group used in the present invention has a carboxyl group and has better adhesion to a current collector than a polyvinylidene fluoride having no carboxyl group. Further, the (tetra)-containing red fluoroethylene system and the polymer (B) have the same electrolyte resistance as the polyvinylidene fluoride having no carboxyl group. In the method for producing the vinylidene fluoride-based polymer (B), the method of the above (1) to (3) is preferably carried out by the method of (1) in terms of the number of steps and the production cost. Namely, the second group containing the (tetra) group: the olefin polymer (8) is preferably a fluoroethylene group and a silk polymer. In the case of a cat, the vinylidene fluoride polymer having a thiol group having a thiol group used in the present invention is usually 80 to 99.9 parts by weight, more preferably 1 to 99.7 parts by weight, more preferably 95 to 99.7 parts by weight. Difluoroethylene 154705.doc • II - 201140924 Alkene and usually a G.1 to 2G parts by weight, preferably 3 to 5 parts by weight of a monomer having a plurality of groups (wherein a vinylidene fluoride and a carboxyl group-containing monomer) The total amount of the particles is a part by weight of a vinylidene fluoride-based polymer obtained by copolymerization. Further, the vinylidene fluoride-based polymer (8) as the above-mentioned money-containing group may be a polymer obtained by arbitrarily combining other monomers in addition to the above-mentioned meta-ethylene and a monomer having a carboxyl group. Further, in the case where another monomer is used, the total amount of the vinylidene fluoride and the monomer containing the prefecture is set to be a part by weight, and usually, other monomers are used in an amount of 〜 2 to 2 parts by weight. The above-mentioned silk-containing monomer is preferably a residual mono-acid, an unsaturated dicarboxylic acid, a monoester of an unsaturated dibasic acid or the like. As the feed saturated-acid, (4) (tetra) acid, methacrylic acid and the like. As the above unsaturated dibasic acid, cis-butane diacid and methyl cis-butyl $=4 are listed. Further, the mono-I as the unsaturated dibasic acid is preferably carbon: two or more, and examples thereof include maleic acid monomethyl vinegar and cis-butane dicarboxylic acid:酉曰, methyl cis-butane dicarboxylic acid monomethyl vinegar, methyl cis-butane dicarboxylic acid, single-branched succinimide, m-based monomer, preferably selected from unsaturated dibasic acid: saturated dibasic acid At least one of vinegar, acrylic acid and methacrylic acid is better for cis-but

"Maleic acid, maleic acid I: diterpene dibutyric acid monomethyl vinegar, acrylic acid, methyl propyl. He single:::=Secondary ethylene and thiol-containing monomer The other monomer of the copolymerization refers to the removal of the difluoroethylene as the other monomer, for example, it can be exemplified by the deviation === 154705.doc

S -12· 201140924 A fluorine-based monomer which is a combination of fluoroethylene, trifluoroethylene, tetrafluoroethylene, and fluorene fluorene, which is represented by perfluoromethylacetate. Further, the above-mentioned other monomers may be used alone or in combination of two or more. Further, as the method (1), methods such as suspension polymerization, emulsion polymerization, and solution polymerization may be employed, and the ease of subsequent treatment may be used. It is preferably aqueous suspension polymerization or emulsion polymerization, and particularly preferably aqueous suspension polymerization. In the suspension polymerization from water as a dispersion medium, the weight ratio of the whole body (the monomer of the second ethylene and the monomer containing the can, if necessary, the monomer) ιοο is 〇oow 〇 by weight, preferably for reading ~" in parts by weight, adding thiol cellulose, bismuth oxide yttrium cellulose, propoxy phthalocyanine, auxin, ethyl cellulose, propyl cellulose, poly It is used as a suspending agent such as ethylene glycol, polyethylene oxide or gelatin. As the polymerization initiator, diisopropyl vinegar peroxydicarbonate, peroxidation: di-n-propyl acrylate, di-n-heptafluoropropane acetonate, isopropyl hydrazine peroxide, isobutyl pentoxide can be used. , two (gas-fired base) peroxide, - (perfluorononyl) peroxide and the like. If all of the monomers used for copolymerization (metaethylene and a monomer containing a rebel group, if necessary, other monomers) are again (10) parts by weight ', the amount used is G.1-5 parts by weight. Preferably, it is 3 to 2 parts by weight. Bu can also be added with ethyl acetate, methyl acetate, diethyl carbonate, copper, copper, SI, n-propanol, acetic acid, propionic acid, ethyl acetate, carbon tetrachloride and other chain transfer agents to adjust the resulting silk containing The tetra-I-vinyl polymer () will be used for the copolymerization of all the monomers at 45 ° right (vinylidene fluoride and 154705.doc -13- 201140924 repulsive monomers, if necessary, other copolymerization The monomer is used in an amount of 1 part by weight, and the amount of the chain transfer agent is usually 0.5 part by weight, preferably 5 to 3 parts by weight. In addition, the total amount of all monomers (vinylidene fluoride and a monomer having a carboxyl group, and other monomers copolymerized as needed) for copolymerization is usually in the total weight of monomers: water by weight.丨··^, preferably 1:2~^, the polymerization temperature is 10 to 80 t, the polymerization time is 10 to 100 hours, and the pressure at the time of polymerization is usually carried out under pressure, preferably 2 〇 to 8 〇. MPa-G. By carrying out the aqueous suspension polymerization under the above conditions, the vinylidene fluoride and the (tetra) group-containing monomer and the other monomers which are optionally polymerized can be easily copolymerized to obtain the second-order containing county used in the present invention. Ethylene polymer CB). In the case where the carboxyl group-containing vinylidene fluoride-based polymer (8) is produced by the method of the above (7), for example, it can be carried out by the following method. In the case of producing a partial ethylene-containing ethylene-based polymer (8) by the method of (7), first, a second partial gas is obtained by polymerizing a vinylidene or copolymerizing with a vinylidene gas and other precursors. Ethylene polymer. The polymerization or the polymerization is usually carried out by suspension polymerization or emulsion polymerization. In addition, by dissociating the two vinylidene-based polymers, the monomers of the fluorenyl group are polymerized or copolymerized with other monomers of a single limb of the county (4) to obtain a polymer containing a (tetra) group: a polymer containing a plurality of groups It is usually paid by emulsion polymerization or suspension polymerization. Further, by using the above-mentioned second-half ethylene-based polymer and containing a rebel-like polymer, a graft containing a few substances on the vinylidene-based ethylene polymer can obtain a vinylidene-containing difluoroethylene complex. The grafting of the graft I54705.doc 201140924 can be carried out using a peroxide or by radiation, preferably by a mixture of a vinylidene fluoride polymer and a polymer containing a peroxide in the presence of a peroxide. It is carried out by heat treatment. The carboxyl group-containing ethylene-containing polymer (8) used in the present invention has an intrinsic viscosity (a solution obtained by dissolving 4 g of the resin in i kN, N-dimethylamine) at a logarithmic viscosity of 3 (hereinafter, TC). The same) is preferably a value in the range of 〇5 to 5 〇cn/g, more preferably in the range of ii to 4·0 dl/g. As long as the viscosity within the above range is 'applicable to non-aqueous Mixture for electrolyte secondary battery. Calculation of intrinsic viscosity 1 80 mg of a vinylidene-containing polymer (B) containing a carboxyl group can be dissolved in 20 ml of ketone dimethylamine at 3 (rc) The U-type viscometer is used in the constant temperature bath and is carried out by the following formula: ηί=(1/€)·1η(η/η〇) Here, η is the viscosity of the polymer solution, and η〇 is the solvent of the ice. Methylformamide alone has a viscosity of C of 0.4 g/dl. Further, the vinylidene fluoride-containing polymer (B) having a carboxyl group is determined by Gpc (Gel Permeation Chr〇matography). The weight average molecular weight in terms of polystyrene is usually in the range of 50,000 to 2,000,000, preferably in the range of 200,000 to 1,500,000. When the infrared absorption spectrum of the ethylene-based polymer (B) is measured, the absorbance ratio (Ir) represented by the following formula (1) is preferably in the range of 0.1 to 5.0, more preferably 〇3 to 2.5. In the case of ruthenium, there is a case where the adhesion to the current collector is insufficient. On the other hand, if Ir exceeds 5.0 Å, the electrolyte resistance of the obtained polymer tends to decrease. Further 154705.doc. is. 201140924 Received spectrum. "The infrared absorption spectrum of the sputum is determined by the method of measuring the film produced by hot pressing the polymer as follows:

The absorbance of the carbonyl group detected in the range of 1650~1 800 cm-1 in the range of 1丨65〇-18〇〇 in the gas (1), and the WW is detected in the range of 3000~3100 cm-丨The absorbance derived from the CH structure is a measure indicating the amount of the carbonyl group present in the vinylidene fluoride-based polymer (B) containing a slow group, and is a measure indicating the amount of the carboxyl group present. [Electrode Active Material] The mixed composition for a nonaqueous electrolyte secondary battery of the present invention contains an electrode active material. The electrode active material is not particularly limited, and a conventionally known electrode active material for a negative electrode can be used. Specific examples thereof include a carbon material, a metal alloy material, a metal oxide, and the like. Among them, a carbon material is preferable. As the carbon material, artificial graphite, natural graphite, non-graphitizable carbon, easily graphitizable carbon or the like can be used. Further, the above-mentioned carbon materials may be used singly or in combination of two or more. If such a carbon material is used, the energy density of the battery can be increased. The artificial graphite can be obtained, for example, by carbonizing an organic material, heat-treating it at a temperature, and pulverizing and classifying the organic graphite. As the artificial graphite, MAG series (manufactured by Hitachi Chemical Co., Ltd.), MCMB (manufactured by Osaka Gas Co., Ltd.), etc. can be used. The specific surface area of the electrode active material is preferably 1 〇 m 2 /g, more preferably 2 to 6 m /g. When the specific surface area is less than 1 m2/g, even when the first 154705.doc • 16 - 201140924 point & agent is used, it is difficult to cause uneven distribution of the binder, so the effect of the present invention is small. When the specific surface area exceeds 10 m2/g, the amount of the electrolytic solution is increased, and the initial irreversible capacity is increased, which is preferable. Furthermore, the specific surface area of the electrode living material can be determined by a nitrogen adsorption method. [Organic solvent] The mixture for a nonaqueous electrolyte secondary battery of the present invention contains an organic solvent. As the organic solvent, those having a function of dissolving the above unsaturated carboxylic acid polymer (A) and a carboxyl group-containing vinylidene fluoride polymer (B) are preferably used, and a solvent having polarity is preferably used. Specific examples of the organic solvent include methylpyrrolidone, N,N-didecylguanamine, N,N-dimercaptoacetamide, dimercaptoarylene, hexamethylene-based triamine, and Nisaki, tetrachloromethane, tetramethylurea, triethylphosphate, trimethylphosphate, etc., preferably N-methyl such as ketone, N, N• dimercaptoamine, n, n-dimercaptoacetamide, dimercaptosulfoxide. Further, the organic solvent may be used alone or in combination of two or more. The mixture for a nonaqueous electrolyte secondary battery of the present invention comprises the above unsaturated ortho-acid polymer (Α), a carboxyl group-containing vinylidene fluoride polymer (8), an electrode active material, and an organic solvent. The mixture for a nonaqueous electrolyte secondary battery of the present invention comprises an unsaturated tetrandic acid t-based compound and a mercapto group-containing ditungethylene ethylene polymer (β), and an unsaturated acid-saturated polymer (4) and The unsaturated citric acid polymer (4) is preferably 〇5 to 15% by weight, more preferably 0.8 to 6% by weight, per 100 parts by weight of the carboxyl group-containing vinylidene fluoride polymer (8). In addition, in the total weight fraction of the binder resin (unsaturated: (4) polymer (Α) and the partial ethylene-containing ethylene polymer (10) and the electric 154705.doc 201140924 polar active substance, the binder The resin is preferably 〇5 to i5 parts by weight, more preferably 〜10 parts by weight, and the active material is preferably 85 to 99 parts by weight, more preferably 9 Å to "parts by weight. Further, if the binder resin is used (The total amount of the unsaturated tauric polymer (A) and the vinylidene fluoride-based polymer (10) and the electrode active material is 100 parts by weight, and the organic solvent is preferably 20 to 300 parts by weight, more preferably 50. ～2〇〇重量份. When the components are contained in the above range, the nonaqueous electrolyte secondary battery electrode can be produced by using the mixture for a nonaqueous electrolyte secondary battery of the present invention to produce a nonaqueous electrolyte secondary electrode. In the case of the electrode for a secondary battery, the uneven distribution of the binder in the mixture layer can be sufficiently suppressed, and the peeling strength of the mixed county and the current collector is excellent. Further, the mixture for a nonaqueous electrolyte secondary battery of the present invention may contain In addition to the age of the material m × compound (4), containing The other components other than the trifluoroethylene polymer (8), the electrode active material, and the organic solvent may be included as a conductive component such as carbon black or a pigment dispersant such as a polyethylene material. Further, it may include, in addition to the above-mentioned unsaturated tick acid polymer (A) and a silk-containing vinylidene fluoride polymer (8). As the other polymer, for example, polypyrene gas may be mentioned. Ethylene, partial ethylene, ethylene dilute - six stupid, method 4 + take ^, /, chaotic propylene copolymer, vinylidene fluoride · trifluoroethylene copolymer, vinylidene fluoride _ perfluoromethyl b a second-half ethylene-based polymer such as a copolymer. When the other polymer is contained in the mixture for a non-aqueous electrolyte secondary battery of the present invention, it is usually based on the above-mentioned unsaturated carboxylic acid polymer (VIII) and contains a rebel group. The other polymer is contained in an amount of 25 parts by weight or less based on 100 parts by weight or less of the total of the ethylene-based ethylene-based polymer (β).

154705.doc,. -18 - S 201140924 The use of the mixture for a non-aqueous electrolyte secondary battery of the present invention has an E-type viscosity of from 2,000 to 50,000 mPa.s, preferably at a shear rate of 2 s·1 at 25 C. For 5〇〇〇~mpa.s. In the method for producing a mixture for a nonaqueous electrolyte secondary battery of the present invention, the unsaturated carboxylic acid polymer (A) and the carboxyl group-containing vinylidene fluoride polymer are added so as to be a uniform slurry. The electrode active material and the organic solvent may be mixed, and the order of mixing is not particularly limited. For example, the unsaturated carboxylic acid polymer (a) and the carboxyl group-containing vinylidene fluoride polymer (B) are dissolved. a part of the organic solvent to obtain a binder 'liquid mixture, adding an electrode active ^ ^ ^ ^ ^ ^ solvent to the binder solution, and collecting and mixing, thereby obtaining a non-aqueous electrolyte secondary battery, and the above The saturated acid polymer (4) and the vinylidene-containing di-f-vinyl polymer (B) are respectively dissolved in one part of the organic solvent to obtain two kinds of binder solutions, and the two binder solutions are mixed and mixed. The electrode active material and the remaining organic solvent are added to the binder solution: and the mixture is blended to obtain a non-aqueous electrolyte f: a secondary battery mixture. [Electrode for non-aqueous electrolyte secondary battery] The non-aqueous electrolyte of the present invention: the electrode for a secondary battery is obtained by applying the above-mentioned nonaqueous electrolyte secondary battery mixture to a current collector and drying it, and has A current collector and a layer formed of a mixture for a nonaqueous electrolyte secondary battery. The nonaqueous electrolyte of the present invention - an electrode for an electric fresh-human battery is generally used as a negative electrode. Further, in the present invention, a non-aqueous electrolyte secondary battery mixture is applied to a current collector, and a non-aqueous electrolyte secondary battery is also used. The layer formed by the agent is referred to as a mixture layer. I54705.doc • 19-201140924 The current collector made of the present invention is, for example, copper, and examples of the shape thereof include a metal foil or a metal mesh. As the current collector, copper foil is preferred. The thickness of a current collector is usually 5 to 10 Å μηι, preferably 5 to 20 μηι. The thickness of the mixed alpha agent layer is usually from 20 to 250 μm, preferably from 2 to 5 μm. When the electrode for a nonaqueous electrolyte secondary battery of the present invention is produced, it is preferred to apply the above-mentioned nonaqueous electrolyte secondary battery mixture to at least one of the current collectors. The method at the time of coating is not particularly limited, and examples thereof include a bar coater, a slit press coater, and a knife coater. Further, the drying after coating is usually carried out at a temperature of 50 Torr 5 Torr for 1 to _ minutes. Further, the pressure at the time of drying is not particularly limited and is usually carried out under atmospheric pressure or under reduced pressure. Further, heat treatment may be performed after drying. In the case of heat treatment, 'normally at the temperature τ of _ rhyme t! ~ then minutes. Further, the degree of heat treatment is the same as the above drying temperature. The steps may be carried out separately or may be carried out continuously. Further, it is also possible to carry out a pressing treatment. In the case of performing the pressing treatment, it is usually carried out under the MP_G. If the (4) process is carried out, the electrode density can be increased, so that it is preferable. The electrode for a nonaqueous electrolyte secondary battery of the present invention can be produced by the above method. In addition, as a layer structure of an electrode for a nonaqueous electrolyte secondary battery, a mixture for a nonaqueous electrolyte secondary battery is applied to one side of a current collector 154705.doc

S 20-201140924 In the case of a double layer of a mixture layer/current collector, when a mixture of a nonaqueous electrolyte secondary battery is applied to both sides of a current collector, it is a mixture layer/set The electrical/mixer layer is composed of three layers. In the non-aqueous electrolyte of the present invention, the electrode for a secondary battery is excellent in peeling strength of the fruit electric material and the mixture layer by using the above-mentioned non-aqueous electrolyte primary battery mixture, and therefore, steps such as pressing, cutting, and winding are performed. Among them, the electrode is less likely to be cracked or peeled, which contributes to an improvement in productivity, and is therefore preferred. The second electrode of the non-aqueous electrolyte of the present invention also has excellent peeling strength of the current collector and the mixture layer as described above, and has a peeling strength of the current collector and the mixture layer in accordance with Jis. When K6854 is measured by the 180 peel test, it is usually 〇5~2〇gf/_, preferably l10gf/mm. The non-aqueous electrolyte secondary battery of the present invention has a mixture layer of a non-aqueous electrolyte secondary battery having a mixture of the non-aqueous electrolyte secondary battery, and the mixture layer suppresses the adhesive. uneven distribution. Therefore, the peel strength of the collector and the mixture layer is excellent. [Non-aqueous electrolyte secondary battery] The non-aqueous electrolyte secondary battery of the present invention has the above-mentioned electrode for a non-aqueous electrolyte secondary battery. As the nonaqueous electrolyte secondary battery of the present invention, the above nonaqueous power A is not limited to (4). The non-aqueous electrolyte primary battery usually has the above-described non-aqueous electrolyte crucible, and the electrode for the de-solvent-sub-battery is used as a portion other than the negative electrode 'negative electrode, for example, a known one. j. For example, a positive electrode, a separator, or the like can be used. The present invention will be described in more detail by the following examples, but the invention is not limited thereto. [Manufacturing Example 1] (Manufacture of a vinylidene fluoride-based polymer (1) containing a carboxyl group) Adding ion exchanged water 丨〇 4〇g, methyl cellulose 0.8 g, diisopropyl dicarbonate 3 〇g, vinylidene fluoride 396 g and cis-butyl to an autoclave with a volume of 2 L The monodecyl succinimide yttrium g was suspended for 45 hours at 28 ° C. The maximum pressure during the period reached 4.1 MPa. After the end of the polymerization, the polymer slurry was dehydrated and washed with water. Thereafter, at 8 The mixture was dried for 2 hours to obtain a powdery vinylidene fluoride-based polymer (1) (polymer (1)). The weight average molecular weight of the polymer (1) was 50,000. Viscosity is 1.7 dl/g, IR(=i165|)_18Q()/l3__3i() ()) (Further, the absorbance derived from the carbonyl group was observed to be 1750 cm·1, and the absorbance derived from the CH structure was observed to be 3025 cm-1) was 0.5. [Manufacturing Example 2] (Manufacture of polyvinylidene fluoride) Add 1075 g of ion-exchanged water, 0.4 g of methylcellulose, 2 g of di-n-propyl peroxydicarbonate, 5 g of ethyl acetate, and 420 g of vinylidene fluoride in a high-pressure dad with a volume of 2 L. The suspension polymerization was carried out at 25 ° C for 14 hours, during which the maximum pressure reached 4.0 MPa ^ After the end of the polymerization, the polymer was dehydrated and washed with water, and then at 80 ° (2: 2 hours) Drying to obtain powdery polyvinylidene fluoride (PVDF). The weight average molecular weight of PVDF is 50,000 Å, and the inherent viscosity is 1.7 dl/g. [Polyvinylidene fluoride polymer (1) containing carboxyl group and polydisperse Determination of the weight average molecular weight of vinyl fluoride] 3 has a base of vinylidene fluoride polymer (1) and polyvinylidene fluoride. • 22· 154705.doc

S 201140924 The weight average molecular weight in terms of polystyrene is determined by gel permeation chromatography (GPC). The measurement was performed on a separation column using Shodex KD-806M (manufactured by Showa Denko Co., Ltd.), the detector using RI-930 (refractive index detector) manufactured by JASCO Corporation, and a flow rate of the elution solution of 1 mL/min. The column temperature was 40 ° C. Further, in the measurement, a LiBr-NMP solution having a concentration of 10 mM was used as a dissolving solution, and TSK standard POLY (STYRENE) (manufactured by Tosoh Co., Ltd.) was used as a standard polymer for a calibration curve. [Measurement of Weight Average Molecular Weight of Polyacrylic Acid] The weight average molecular weight of the polyacrylic acid used in the examples and the comparative examples in terms of polyoxyethylene oxime was measured by gel permeation chromatography (GPC). The measurement was performed on a separation column using Shodex Asahipak GF-7M HQ (manufactured by Showa Denko Co., Ltd.), and the detector used RID-6A (refractive index detector) manufactured by Shimadzu Corporation, and the flow rate of the solution was 0.6 mL/ Min, the column temperature is 40 ° C. Further, in the measurement, Na2HP04/CH3CN=90/10 (weight ratio) was used as the elution liquid, and TSK standard POLY (ETHYLENE OXIDE) (manufactured by Tosoh Co., Ltd.) was used as a standard for the calibration curve. polymer. [Measurement of Specific Surface Area of Active Material] The specific surface area of the active material was measured by a nitrogen adsorption method. An approximation induced by the BET (Brunauer-Emmett-Tellern) formula is used: Vm = l / (v (lx)) and by using nitrogen adsorption at liquid nitrogen temperature 154705.doc -23- 201140924 The point method (relative pressure x = 〇. 3) was used to determine Vm, and the specific surface area of the sample (active material) was calculated by the following formula. Specific surface area [m2/g]=4.35xVm where 'Vm is the amount of adsorption necessary for forming a monolayer on the surface of the sample (cm3/g) 'v is the measured adsorption amount (cm3/g), and X is the relative pressure . Specifically, the amount of nitrogen adsorbed on the active material at a liquid nitrogen temperature (v) was measured by using "Flow Sorb 112300" manufactured by MICROMETRITICS. The active material was filled in a test tube, and the test tube was cooled to 丨96丨c while flowing a helium gas containing nitrogen gas at a concentration of 2 Torr, and nitrogen was adsorbed to the active material. The tube is then returned to room temperature. At this time, the amount of nitrogen detached from the sample was measured by a thermal conductivity detector and set as the adsorption amount (v). [Example 1] (Preparation of a mixture for a nonaqueous electrolyte secondary battery) 3.9 g of a vinylidene fluoride-based polymer (1) and a polyacrylic acid having a weight average molecular weight of 5,000 (Wako Pure Chemical Industries, Ltd.) Manufactured by the company, carboxy 虿.1.4X102 m〇i/g) 〇"g was dissolved in N_mercapto-2-pyrrolidone 9 〇 Lu and received 10 weight. /. Adhesive solution (1). The obtained binder solution (1) 8 g, artificial graphite (manufactured by Hitachi Chemical Co., Ltd., mag, average particle diameter of 20 μπι, specific surface area of 4 2 m 2 /g) 9 2 Lu and mixture viscosity adjustment N_methyl Each of the H-burning ketones was mixed and mixed to obtain a non-aqueous electrolyte secondary battery. Agent (1). The viscosity of the non-aqueous electrolyte secondary battery mixture (1) is 12000 mPa·s 〇 (Production of the electrode). The weight per unit area after drying is 15 〇 2, which will be used 154705.doc

S • 24· 201140924 Non-aqueous electrolyte secondary battery obtained by a spacer and a bar coater The mixture (1) is applied to a steel foil having a thickness of 1 μm as a current collector. After drying at 110 ° C in a nitrogen atmosphere, heat treatment was carried out at 13 (rCT), followed by pressing at 40 MPa to obtain a bulk density of a mixture layer formed of the mixture (1) for a nonaqueous electrolyte secondary battery. It is an electrode (1) for a nonaqueous electrolyte secondary battery of 6 g/cm 3 , and the thickness of the mixture layer is calculated by subtracting the thickness of the current collector from the thickness of the electrode. [Comparative Example 1] The second ethylene ethylene polymer (1) 10. g is dissolved in 90 g of N.methyl-2-pyrrolidone to obtain a binder solution (cl) of 1% by weight. In addition to using the binder solution (cl) In the same manner as in the first embodiment, the non-aqueous electrolyte secondary battery mixture (c 1) and the non-aqueous electrolyte secondary battery electrode (cl) are obtained. The non-aqueous electrolyte secondary battery mixture (cl) The viscosity is 1 2000 mPa·s 实施 [Example 2] 9.75 g of a vinylidene fluoride-based polymer (1) containing a carboxyl group and polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Co., Ltd., carboxyl group) Amount: 1.4xl0·2 mol/g) 0.25 g dissolved in N-methyl-2-pyrrolidone 90 g to obtain 10 weights In the same manner as in Example 1, except that the binder solution (2) was used, the non-aqueous electrolyte secondary battery mixture (2) and the non-aqueous electrolyte secondary battery electrode were obtained. (2) The viscosity of the mixture (2) for a nonaqueous electrolyte secondary battery was 11800 mPa·s. [Example 3] A vinylidene fluoride polymer (1) containing a carboxyl group (1) and a weight average of 154,705. Doc -25- 201140924 Polyacrylic acid with a molecular weight of 5,000 (manufactured by Wako Pure Chemical Co., Ltd., carboxyl group: 1.4xl0·2 mol/g) 〇.5 g dissolved in N-mercapto-2-0 10% by weight of a binder solution (3) was obtained in 90 g of the ketone, and the mixture (3) for a nonaqueous electrolyte secondary battery was obtained in the same manner as in Example 1 except that the binder solution (3) was used. The electrode (3) for a nonaqueous electrolyte secondary battery. The viscosity of the mixture (3) for a nonaqueous electrolyte secondary battery is 11 500 mPa·s. [Example 4] A vinylidene fluoride polymer containing a carboxyl group ( 1) 9·〇g and polyacrylic acid with a weight average molecular weight of 5,000 (made by Wako Pure Chemical Co., Ltd., slow basis weight) 1.4xl0·2 mol/g) l.〇g is dissolved in 90 g of N-mercapto-2-pyrrolidone to obtain 10% by weight of a binder solution (4), except that the binder solution (4) is used. In the same manner as in the first embodiment, the non-aqueous electrolyte secondary battery mixture (4) and the non-aqueous electrolyte secondary battery electrode (4) were obtained. The non-aqueous electrolyte secondary battery mixture (4) had a viscosity of 11 500. mPa*s. [Example 5] 8.7 g of a vinylidene fluoride-based polymer (1) containing a carboxyl group and polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Industries, Ltd., slow basis: 1.4) <10· 2 mol/g) 1.3 g was dissolved in 90 g of N-mercapto-2-pyrrolidone to obtain 10% by weight of a binder solution (5). A non-aqueous electrolyte secondary battery mixture (5) and a non-aqueous electrolyte secondary battery electrode (5) were obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive solution (5) was used. The viscosity of the non-aqueous electrolyte secondary battery mixture (5) was 11 〇〇〇 mPa.s. [Comparative Example 2] 10.0 g of PVDF was dissolved in 90 g of N-methyl-2-pyrrolidone to obtain a binder solution (C2) of 154705.doc • 26-201140924 1% by weight. The non-aqueous electrolyte secondary battery mixture (c2) and the non-aqueous electrolyte secondary battery electrode (C2) were obtained in the same manner as in Example 1 except that the binder solution (C2) was used. The viscosity of the non-aqueous electrolyte secondary battery mixture (c2) was 12,500 mPa·s. [Comparative Example 3] PVDF 9.9 g and polyacrylic acid (manufactured by Wako Pure Chemical Co., Ltd., ruthenium: 1.4χ1〇-2 mol/g) 0.1 g of a weight average molecular weight of 5,000 were dissolved in N-mercapto-2 - 1% by weight of a binder solution (c3) in a pyrrolidone 90 g. The non-aqueous electrolyte secondary battery mixture (c3) and the non-aqueous electrolyte secondary battery electrode (c3) were obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive solution (c3) was used. The viscosity of the non-aqueous electrolyte secondary battery mixture (c3) was 12,500 mPa·s. [Comparative Example 4] PVDF 9.75 g and polyacrylic acid having a weight average molecular weight of 5, yttrium (manufactured by Wako Pure Chemical Co., Ltd., 'carboxyl group: 14 x l 〇 -2 m 〇 i / g) 〇. 25 g dissolved in N - mercapto-2-pyrrolidone 90 g to obtain 1% by weight of a binder solution (c4). A non-aqueous electrolyte secondary battery mixture (c sentence and non-aqueous electrolyte secondary battery electrode (c4) was obtained in the same manner as in Example 1 except that the binder solution (c4) was used. The non-aqueous electrolyte was twice. The viscosity of the battery mixture (c4) was 12,000 mPa·s. [Comparative Example 5] PVDF 9.5 g and polyacrylic acid having a weight average molecular weight of 5 Å (manufactured by Wako Pure Chemical Co., Ltd., carboxyl group: 14 χ 1 〇) _2 m〇1/g) 〇5 g / combined with N-mercapto-2-pyrrolidone 90 g to obtain 1 〇 weight 0 / 〇 binder 154705.doc • 27- 201140924 solution (c5). A non-aqueous electrolyte secondary battery mixture (c5) and a non-aqueous electrolyte secondary battery electrode (C5) were obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive solution (c5) was used. Non-aqueous electrolyte secondary battery The viscosity of the mixture (c5) was 11800 mPa·s. [Comparative Example 6] PVDF 9.0 g and polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Co., Ltd., carboxyl group: 1.4×l〇-2) Moi/gw 〇g is dissolved in N-mercapto-2-pyrrolidone 90 g to obtain a binder weight of 1 〇 The solution (c6) was obtained in the same manner as in Example 1 except that the binder solution (c6) was used, and a non-aqueous electrolyte secondary battery mixture (c6) and a non-aqueous electrolyte secondary battery electrode (c6) were obtained. The viscosity of the mixture (c6) for a nonaqueous electrolyte secondary battery was 11500 mPa·s. [Comparative Example 7] 9.75 g of a vinylidene fluoride-based polymer (1) containing a slow group and a crosslinked polyacrylic acid (commercial product) Named "AQUPEC HV-501", manufactured by Sumitomo Seika Co., Ltd., carboxyl group amount: 1.3><10-2111〇1/1) 0.25§ dissolved in 1^-methyl-2-'> pyrrolidone A binder solution (C7) of 1% by weight was obtained in 90 g, and a mixture for a nonaqueous electrolyte secondary battery (c7) was obtained in the same manner as in Example 1 except that the binder solution (c 7) was used. And a non-aqueous electrolyte secondary battery electrode (c7). The viscosity of the non-aqueous electrolyte secondary battery mixture (C7) is 丨3〇〇〇mPa.s. [Comparative Example 8] Ethylene polymer (]) 95 g and cross-linked polyglycolic acid (commercial ασ named "AQUPEC HV-501", manufactured by Sumitomo Seika Co., Ltd., carboxyl group: 1.3x 0_2 mol/g) 0.5 g is dissolved in Ν_methyl-2-pyrrolidone 9〇g 154705.doc -28· 201140924 to obtain ίο% by weight of the binder solution (c8), except for the use of the binder solution (c8) In the same manner as in the first embodiment, a non-aqueous electrolyte secondary battery mixture (c8) and a non-aqueous electrolyte secondary battery electrode (c8) were obtained. The viscosity of the non-aqueous electrolyte secondary battery mixture (c8) was 13,500 mPa·s. [Comparative Example 9] 9.2 g of a vinylidene-containing polymer containing a rebel group (1) and a cross-linked polyacrylic acid (trade name "AQUPEC HV-501", manufactured by Sumitomo Seika Co., Ltd., carboxyl group amount: 1.3X10 2 mol/g) 0.8 g was dissolved in 9 〇g of N-mercapto-2-pyrrolidone to obtain a 10% by weight binder solution (C9). The non-aqueous electrolyte secondary battery mixture (c9) and the non-aqueous electrolyte secondary battery electrode (c9) were obtained in the same manner as in Example 1 except that the binder solution (c9) was used. The viscosity of the mixture for nonaqueous electrolyte secondary battery (c9) was 14,000 mPa·s » [Example 6] 9.5 g of a vinylidene fluoride-based polymer (1) containing a carboxyl group and polyacrylic acid having a weight average molecular weight of 15,000 (The product name is "jurymer AC-10P", manufactured by Sakamoto Pure Chemical Co., Ltd., slow basis: ι 4χΐ〇-2 mol/g) 0.5 g dissolved in N-mercapto-2-pyrrolidone 90 g A 1% by weight of a binder solution (6) was obtained. The non-aqueous electrolyte secondary battery mixture (6) and the non-aqueous electrolyte secondary battery electrode (6) were obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive solution (6) was used. The viscosity of the non-aqueous electrolyte secondary battery (6) was 12,000 mPa·s. [Example 7] 9.5 g of a vinylidene fluoride-based polymer (1) containing a carboxyl group and polyacrylic acid having a weight average molecular weight of 25,000 (manufactured by Wako Pure Chemical Industries, Ltd., 154705.doc -29-201140924 :1·4χ10·2 m〇l/g)〇5 g was dissolved in 9〇g of N_mercapto-2-pyrrolidone to obtain 10% by weight of a binder solution (7). The non-aqueous electrolyte secondary battery mixture (7) and the non-aqueous electrolyte secondary battery electrode (7) were obtained in the same manner as in Example 1 except that the binder solution (7) was used. The viscosity of the non-aqueous electrolyte secondary battery mixture (7) is 丨23〇〇 mPa.s. [Example 8] 9 5 g of a vinylidene fluoride-based polymer (1) containing a carboxyl group and polyacrylic acid having a weight average molecular weight of 73,000 (trade name "jurymer ac-iolp", manufactured by Sakamoto Pure Chemical Co., Ltd. The amount of the carboxyl group: 丄4χΐ〇_2 mol/g) 5.5 g was dissolved in 〇-methyl-2-pyrrolidone 9 〇g to obtain a 〇% by weight of the binder solution (8). A non-aqueous electrolyte secondary battery mixture (8) and a non-aqueous electrolyte secondary battery electrode (8) were obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive solution (8) was used. The viscosity of the non-aqueous electrolyte secondary battery (8) was 12,500 mPa·s. [Comparative Example 1 0] 95 g of a vinylidene fluoride-based polymer having a carboxyl group and polyacrylic acid having a weight average knife amount of 250,000 (manufactured by Wako Pure Chemical Co., Ltd., carboxyl group amount: 1.4×l0·2) M〇i/g) 05 g was dissolved in N_methyl-2-pyrrolidine^90 g to obtain 10% by weight of a binder solution (ci〇). A non-aqueous electrolyte secondary battery mixture (cl0) and a non-aqueous electrolyte secondary battery electrode (do) and a non-aqueous electrolyte secondary were obtained in the same manner as in Example 丨 except that the binder solution (clO) was used. The viscosity of the battery mixture (Cl0) was 13 〇〇〇mPa*s 〇 [Comparative Example 11] 154705.doc 201140924 The vinylidene fluoride polymer (丨) having a carboxyl group (9.5 g) and a weight average molecular weight of 800,000 Polyacrylic acid (trade name: r aquaLIC), manufactured by Nippon Shokubai Co., Ltd., 'carboxyl number: 1.4·2 m〇l/g) 〇.5 g dissolved in N-methyl-2-pyrrolidone 90 g The binder solution (c 11) in % by weight was obtained. The non-aqueous electrolyte secondary battery mixture (c 11) and the non-aqueous electrolyte secondary battery electrode (c 11) were obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive solution (c 11) was used. The viscosity of the mixture for nonaqueous electrolyte secondary batteries (ell) is 13,000 rnPa.s. [Comparative Example 12] Polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Co., Ltd., 'Essential amount: 1·4 χ 1 〇·2 m〇l/g) i〇.〇g dissolved in n_曱10% by weight of a binder solution (cl2) was obtained in 90-2-g of pyranone. A non-aqueous electrolyte secondary battery mixture (cl2) was obtained in the same manner as in Example 1 except that the binder solution (cl2) was used and the N-methyl-2-pyrrolidone for the viscosity adjustment of the mixture was changed to 3 g. And an electrode (cl2) for a nonaqueous electrolyte secondary battery. The viscosity of the non-aqueous electrolyte secondary battery mixture (cl2) was 8500 mPa·s 比较 [Comparative Example 13] 10.0 g of a vinylidene fluoride-based polymer (1) containing a carboxyl group was dissolved in N-methyl-2- A 1% by weight of a binder solution (ci3) was obtained in 9 〇g of pyrrolidone. The obtained binder solution (cl3) 4 g, artificial graphite (manufactured by Osaka Gas, MCMB, average particle diameter 6.5 μηη, specific surface area 2'9 m2/g) 9.6 g and N-methyl group for viscosity adjustment of the mixture -2-pyrrolidone 7.0 g was stirred and mixed to obtain a mixture (cl3) for a nonaqueous electrolyte secondary battery. 153705.doc 31 201140924 An electrode (cl3) for a nonaqueous electrolyte secondary battery was obtained in the same manner as in Example 1 except that the mixture (c丨3) for a nonaqueous electrolyte secondary battery was used. The viscosity of the non-aqueous electrolyte primary battery mixture (ci3) is 135 〇〇 mPa «s 〇 [Example 9] 9.5 g of a vinylidene fluoride polymer (丨) containing a slow base and a weight average amount 10 wt% of a binder solution was prepared by dissolving 0.5 g of N-methyl-2-pyrrolidinone 90 g in a polyacrylic acid (manufactured by Wako Pure Chemical Co., Ltd., carboxyl group. 1.4 x 10 mol/g). . The obtained binder solution (9) 4 g, human 4 graphite (manufactured by Osaka Gas Co., Ltd., average particle diameter 6.5 μηη, specific surface area: 29 m 2 /g) 96 g and mixture viscosity adjustment N-曱The base-2-pyrrolidone 7.0 g was stirred and mixed to obtain a mixture (9) for a nonaqueous electrolyte secondary battery. Non-aqueous electrolyte secondary battery obtained in the same manner as in Example 1 except that the non-aqueous electrolyte secondary battery mixture (9) has a viscosity of 13,000 niPa*s. Use electrode (9). [Comparative Example 14] A 3-carboxyl group of a vinylidene fluoride-based polymer g was dissolved in N?-methyl-2-pyrrolidone 9? g to obtain a 1% by weight of a binder solution (ci4). The obtained binder solution (4) 4) 8 g, spherical natural graphite (produced in China, average particle size 24 μηι, specific surface area of 5.4 m 2 / g) 92 g and mixture viscosity adjusted by 1 N-methyl-2 The ketone was mixed with 5 8 g to obtain a non-aqueous electrolyte-human battery mixture (cl4). The viscosity of the non-aqueous electrolyte secondary battery mixture (cl4) was 13 〇〇〇 mPa.s. 154705.doc

In the same manner as in Example 1, except that the non-aqueous electrolyte secondary battery mixture (cl4) was used, an electrode (c丨4) for a non-aqueous electrolyte secondary battery was obtained. [Example 10] 95 g of a vinylidene fluoride-containing polymer (1) and a polyacrylic acid having a weight average molecular weight of 5,000 (manufactured by Wako Pure Chemical Industries, Ltd., carboxyl group: 1.4 x 10 mol/g) 55 g was dissolved in 90 g of ν·methyl·2-pyrrolidone to obtain 10% by weight of a binder solution (1 〇). The obtained binder solution (10) 8 g, spherical natural graphite (produced in China, average particle size of 24 μηη, specific surface area of 5.4 m 2 /g) 9.2 g and mixture viscosity adjustment for Ν-mercapto-2-pyrrolidone 5.8 g was mixed and mixed to obtain a non-aqueous electrolyte secondary battery mixture (1 〇). The viscosity of the non-aqueous electrolyte secondary battery mixture (1 〇) was 13 〇〇〇 mPa·s. An electrode for a nonaqueous electrolyte secondary battery (obtained) was obtained in the same manner as in Example 1 except that the mixture for a nonaqueous electrolyte secondary battery was used. <Evaluation of Electrodes> [Peel Strength] The electrodes obtained in the examples and the comparative examples were used as samples, and were used according to JIS K6854 and by 180. The peeling test measures the peeling strength of the mixture layer and the current collector. [Fluority] (Fluority of the electrode surface) The electrode obtained in the examples and the comparative examples was cut into a 40 mm square, and a fluorescent X-ray measuring apparatus (manufactured by Shimadzu, a fluorescent X-ray apparatus, XRF-1700) was used. The fluorine strength of the electrode surface on the side of the mixture layer was measured under conditions of 40 kV, 60 mA, and an irradiation diameter of 30 mm. 154705.doc •33· 201140924 (Fluority of the peeling surface of the mixture layer and the peeling surface of the current collector) The electrode obtained in the examples and the comparative examples was cut into 40 mm square, and the surface of the electrode on the side of the mixture layer was attached. Attached to DANPRON (registered trademark) tape (N03 75) (manufactured by Jidong Electric CS System). The gauge pressure was set to 7 MPa, and the electrode to which the DANPRON tape was attached was pressed for 2 seconds, and then the mixture layer was peeled off from the current collector. The gas strength was measured by the same method as the fluorine strength of the electrode surface described above, and the peeling surface of the current collector separated from the current collector and the peeling surface of the current collector separated from the mixture layer of the current collector. In addition, the peeling surface of the mixture layer of the current collector and the current collector is also referred to as "the peeling surface of the mixture layer", and the peeling surface of the current collector of the mixture layer and the mixture layer is also peeled off. It is described as "the peeling surface of the current collector". The composition of the binder solution used in the examples and the comparative examples and the composition of the nonaqueous electrolyte secondary battery mixture, the thickness of the obtained mixture layer of the electrode, and the evaluation results of the electrodes are shown in Tables 1 and 2. 154705.doc

S •34· 201140924 [I Phosphorus] The active substance mass of the non-aqueous secondary battery mixture [wt parts f Ο^^\〇\〇\〇\〇\〇\〇\〇\〇\〇\〇\〇\ 〇\〇\〇\〇\〇^〇^〇^〇^〇^〇^^ Adhesive dose [wt parts Γ OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO 比 inch 〇〇〇〇 active material specific surface area [m2/g] (NCNCNCNCNCNCNCNCsjCNCNiNCNCNCNtNCNCNCNiN^ON'^i -^r 4 inch inch*·^ Inch binder solution polymer (A) ratio [% by weight]" 〇 - ... ... 〇 ... Polymer (B) Polymer (1) Polymer (1) Polymerization (1) Polymer (1) Polymer (1) Polymer (1) PVDF PVDF PVDF PVDF PVDF Polymer (1) Polymer (1) Polymer (1) Polymer (1) Polymer (1) Polymerization (1) Polymer (1) Polymer (1) Polymer-free (1) Polymer (1) Polymer (1) Polymer (1) Weight average molecular weight of (A) [χΙΟ4] 〇〇〇〇〇 〇〇〇〇—(N 卜~°°0 0 0 Polymer (A) No PAA PAA PAA PAA PAA No PAA PAA PAA PAA HV-501 HV-501 HV-501 PAA PAA PAA PAA PAA PAA No PAA No PAA Comparison Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Example 6 Example 7 Example 8 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Example 9 Comparative Example 14 Example 10 Take # 辋ool^^+l-^wae^^^'^cs^^i^ii^irg^^lii-^fr:^ %φιΟΟΙΟΟΙ^^^φνβ) #φ^β(ν)#<(η^ΛΓ:Γ •35- 154705.doc 201140924

[ίι——I-electrode evaluation of fluorine strength [kcps] The peeling surface of the current collector 0.76 1.55 1.59 1.44 1.23 1.14 0.64 0.65 0.63 0.61 0.67 0.65 0.61 0.58 1.52 1.52 1.56 0.73 0.77 0.35 0.79 0.73 1.52 Stripping surface of the mixture 0.91 1.06 1.09 1.05 0.95 0.98 0.80 0.76 0.79 0.77 0.80 0.78 0.73 0.65 1.02 1.02 1.07 0.83 0.87 0.43 0.48 0.91 1.08 Electrode surface 1.04 1.04 1.03 1.03 0.98 0.94 1.14 1.12 1.15 1.09 0.94 1.12 1.09 0.92 1.06 1.04 1.07 1.15 1.12 0.51 0.50 1.09 1.02 Peel strength [gf/ Mm] oooO'^foor-^ovqrnOvOOOOOOO^Dvoi^oo^o-^ONrou^vq — — csir^ — — — — — The thickness of the electrode mixture layer [μτη] —— Ό^ΟΟΓΛΓΛ inch 〇 00 < N ( NV0^f^n〇口ΟΟΟΟΌ OOOOOOOOONOOOOOOOOOOOOOsOOONOOOOOOOOON^ONOOONOO Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Example 6 Example 7 Example 8 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Example 9 Comparative Example 14 Example 10 154705.doc • 36-

Claims (1)

201140924 VII. Patent application scope: 1 · A non-aqueous electrolyte secondary battery mixture comprising at least one unsaturated carboxylic acid polymer (A) selected from polyacrylic acid and polyacrylic acid, and having a thiol group a difluoroethylene-based polymer (B), an electrode active material, and an organic solvent, and the weight average molecular weight of the unsaturated carboxylic acid polymer (A) measured by gel permeation chromatography (Gpc) in terms of polyethylene oxide is Hey, (9) '丨5〇〇〇〇. 2. The non-aqueous electrolyte secondary battery mixture according to claim 1, wherein the unsaturated acid-lowering polymer (A) has a weight average molecular weight in terms of polyethylene oxide by gel permeation chromatography (Gp〇 measurement) </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> A mixture of non-aqueous electrolyte secondary batteries according to claim 1 or 2, wherein the unsaturated tert-acid polymer (A) and the carboxyl group-containing difluoro The unsaturated carboxylic acid polymer (A) is 0.5 to 15% by weight per 100% by weight of the total of the ethylene-based polymer (B). 4. The non-aqueous electrolyte secondary battery mixture according to claim 1 or 2, The unsaturated carboxylic acid polymer is 0.8 to 6% by weight per 1% by weight of the total of the unsaturated acid polymer (A) and the carboxyl group-containing vinylidene fluoride polymer (B). The mixture for a non-aqueous electrolyte secondary battery according to claim 2, wherein the electrode active material has a specific surface area of biO m 2 /g. 6. The nonaqueous electrolyte secondary battery mixture according to claim 2, wherein the electrode The specific surface area of the active material is 2 to 6 m 2 /g. 7. Non-aqueous electrolysis according to claim 2 A secondary battery mixture, wherein the above-mentioned carboxyl group-containing vinylidene fluoride polymer (B) is selected from the group consisting of unsaturated monobasic acid, S 154705.doc 201140924 unsaturated dibasic acid monoester, acrylic acid and mercaptoacrylic acid. a copolymer of at least one carboxyl group-containing monomer and vinylidene fluoride. 8. 9. 10. An electrode for a nonaqueous electrolyte secondary battery, which comprises the nonaqueous solution according to any one of claims 1 to 7. The electrode for a non-aqueous electrolyte secondary battery according to claim 8 has a thickness of a mixture of the above-mentioned nonaqueous electrolyte secondary battery. A mixture of 2 〇 丨 丨 。. A nonaqueous electrolyte secondary battery having the electrode for a nonaqueous electrolyte secondary battery according to claim 8 or 9. 154705.doc -2- 201140924 IV. Designated representative map: (1) The representative representative picture of this case is: (none) (2) The symbol of the symbol of this representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) 154705.doc S