JPH10312791A - Electrode material for nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode material generating no hydrogen fluoride(HF) and having high heat resistance and a high volume density by containing carbon powder and a thermoplastic resin of at least one kind selected from a group of polyimide and polyamide and containing no fluorine with the glass transition temperature of a specific temperature or above, and setting the volume density to the specific % of the true specific gravity of the carbon powder. SOLUTION: Carbon powder and one or two or more kinds of resins selected from polyimide, polyamide, polysulfone, and polyether and containing no fluorine with the glass transition temperature of 50 deg.C or above are heated and compressed at the temperature higher than the glass transition temperature of the resin. The volume density is set to 80-90% of the true specific gravity of the carbon powder. No hydrogen fluoride(HF) is practically generated, the volume density can be improved, and the electric capacity can be increased.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an electrode material for a non-aqueous electrolyte secondary battery.

[0002]

2. Description of the Related Art Electrode materials for non-aqueous electrolyte secondary batteries are usually
The carbon powder is dispersed in a binder solution to form a slurry, and the slurry is applied on a current collector metal foil by a doctor dope method or the like, and then is adhered to the current collector metal foil by a drying method or the like. Being manufactured. As the binder solution, generally, PVDF (polyvinylidene fluoride) is NM
A solution dissolved in P (N-methyl-2-pyrrolidone) is used. However, in an electrode material using PVDF as a binder, when the battery temperature rises due to a short circuit or the like, PVDF is decomposed, and the generated HF (hydrogen fluoride) reacts vigorously with lithium, which may cause the battery to be damaged or ruptured. There was a safety problem. As a binder other than PVDF, SBR (styrene-butadiene rubber) is used. However, SBR has a low softening temperature,
The electrode material using the resin has a problem that the electrode material is peeled off from the current collector metal foil under a temperature condition of about 100 ° C. and the carbon powder is missing. A highly heat-resistant electrode material using a resin other than PVDF as a binder is disclosed in, for example,
JP-A-7-210568, JP-A-58-147965, JP-A-2-213052, JP-A-6-16
Nos. 3031, 6-203836, 6-275279 and 7-213052. However, since the electrode materials obtained by these methods have low volume density, they have a drawback of low electric capacity. Therefore, there is no fear of HF generation,
There has been a demand for an electrode material having high heat resistance and high volume density.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an HF
An object of the present invention is to provide an electrode material for a non-aqueous electrolyte secondary battery having a high heat resistance and a high volume density without a risk of occurrence.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that fluorine-free polyimides, polyamides, polysulfones, and polyethers having a glass transition temperature of 50 ° C. or more are used. Only the electrode material obtained by heating and compressing the selected resin or a resin obtained by mixing two or more kinds thereof and a carbon powder at a temperature equal to or higher than the glass transition temperature of the resin has a high heat resistance and a high volume density. The inventors have found and completed the present invention.
That is, the present invention relates to an electrode material for a non-aqueous electrolyte secondary battery having a high heat resistance and a high volume density without fear of HF generation. The present invention is specified by the following items [1] to [25].

[1] A resin composition containing a fluorine-free thermoplastic resin having a glass transition temperature of at least 50 ° C. and a carbon powder selected from the group consisting of polyimide, polyamide, polysulfone, and polyether An electrode material for a non-aqueous electrolyte secondary battery, comprising a material and having a volume density of 80 to 90% of the true specific gravity of the carbon powder.

[2] The resin composition is obtained by adding at least one kind of conductive agent powder selected from the group consisting of acetylene black, carbon black, graphite (graphite), glassy carbon, and metal conductive agent powder. The electrode material for a non-aqueous electrolyte secondary battery according to [1], which has improved conductivity as compared with the resin composition in the case where it is not added.

[3] The resin composition has a glass transition temperature lowered by adding a plasticizer, as compared with a resin composition not added. [1] or [2] 2. The electrode material for a non-aqueous electrolyte secondary battery described in 1. above.

[4] The crystallization rate of the resin composition is increased by adding a crystallization nucleating agent, as compared with the resin composition without the crystallization nucleating agent. 3] The electrode material for a non-aqueous electrolyte secondary battery according to any one of [1] to [3].

[5] The carbon powder is selected from the group consisting of carbide obtained by firing coke, carbide obtained by firing graphite, carbide obtained by firing resin, soft carbon, hard carbon, and glassy carbon. The electrode material for a secondary battery according to any one of [1] to [4], which is at least one kind.

[6] An electrode for a non-aqueous electrolyte secondary battery, wherein the material according to any one of [1] to [5] is adhered to a current collector metal foil.

[7] An electrode for a non-aqueous electrolyte secondary battery, wherein the material according to any one of [1] to [5] is pressure-bonded to a current collector metal foil.

[8] The current collector metal foil is made of Al, Cu, N
i, Ti, Pt, Fe, and at least one alloy layer made of an alloy containing at least one metal selected from the group consisting of Au.
The electrode for a secondary battery according to [6] or [7].

[9] A resin composition containing a fluorine-free thermoplastic resin having a glass transition temperature of at least 50 ° C. and a carbon powder selected from the group consisting of polyimide, polyamide, polysulfone and polyether. A method for producing a molded article used for an electrode for a non-aqueous electrolyte secondary battery, wherein the article is heated and compressed at a temperature equal to or higher than the glass transition temperature of the thermoplastic resin.

[10] By adding at least one kind of conductive agent powder selected from the group consisting of acetylene black, carbon black, graphite (graphite), glassy carbon, and metal conductive agent powder, The production method according to [9], wherein the conductivity is increased as compared with the resin composition in the case where no resin composition is added.

[11] By adding a plasticizer to the resin composition, compared to the resin composition without the plasticizer,
The production method according to [9] or [10], wherein the glass transition temperature is lowered.

[12] The resin composition has a crystallization rate increased by adding a crystallization nucleating agent as compared with the resin composition not added. [9] to [9] 11].

[13] The carbon powder is selected from the group consisting of carbide obtained by firing coke, carbide obtained by firing graphite, carbide obtained by firing a resin, soft carbon, hard carbon, and glassy carbon. The production method according to any one of [9] to [12], which is at least one.

[14] An electrode material for a secondary battery obtained by the production method according to any one of [9] to [13].

[15] A resin composition containing a fluorine-free thermoplastic resin having a glass transition temperature of at least 50 ° C. and a carbon powder selected from the group consisting of polyimide, polyamide, polysulfone and polyether. A method for producing an electrode for a non-aqueous electrolyte secondary battery, comprising heating and compressing a product together with a current collector metal foil at a temperature equal to or higher than the glass transition temperature of the thermoplastic resin.

[16] The resin composition is prepared by adding at least one kind of conductive agent powder selected from the group consisting of acetylene black, carbon black, graphite (graphite), glassy carbon, and metal conductive agent powder. The production method according to [15], wherein the conductivity is increased as compared to the resin composition in the case where no resin composition is added.

[17] By adding a plasticizer to the resin composition, compared to the resin composition without the plasticizer,
The production method according to [15] or [16], wherein the glass transition temperature is lowered.

[18] The resin composition has a crystallization rate increased by adding a crystallization nucleating agent as compared with the resin composition not added. [15] to [15] 17].

[19] The carbon powder is selected from the group consisting of carbide obtained by firing coke, carbide obtained by firing graphite, carbide obtained by firing resin, soft carbon, hard carbon, and glassy carbon. The production method according to any one of [15] to [18], which is at least one kind.

[20] An electrode for a secondary battery obtained by the production method according to any one of [15] to [19].

[21] An electrode for a non-aqueous electrolyte secondary battery, wherein the material described in [14] is adhered to a current collector metal foil.

[22] An electrode for a non-aqueous electrolyte secondary battery, wherein the material described in [14] is pressure-bonded to a current collector metal foil.

[23] The current collector metal foil is made of Al, Cu,
It has at least one alloy layer made of an alloy containing at least one metal selected from the group consisting of Ni, Ti, Pt, Fe, and Au. [2
0] to [22].

[24] A resin composition containing a fluorine-free thermoplastic resin having a glass transition temperature of at least 50 ° C. and a carbon powder selected from the group consisting of polyimide, polyamide, polysulfone, and polyether An electrode material for a non-aqueous electrolyte secondary battery, comprising a material and having a volume density of 75 to 90% of the true specific gravity of the carbon powder.

[25] A resin composition containing a fluorine-free thermoplastic resin having a glass transition temperature of at least 50 ° C. and a carbon powder selected from the group consisting of polyimide, polyamide, polysulfone and polyether. An electrode material for a non-aqueous electrolyte secondary battery, comprising a material and having a volume density of 85 to 90% of the true specific gravity of the carbon powder.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION A resin selected from polyimide, polyamide, polysulfone, and polyether in the present invention has a glass transition temperature of 50 ° C. or higher, does not contain fluorine, and exhibits thermoplasticity. There are no particular restrictions on the type, structure, etc., and any conventionally known ones can be used. The glass transition temperature of the resin used in the present invention is 50 ° C. or higher, preferably 100 ° C. or higher, more preferably 160 ° C. or higher and 400 ° C. or lower. The higher the glass transition temperature of the resin, the higher the heat resistance of the obtained electrode material, but the glass material has a glass transition temperature that can be heated and compressed at a temperature that does not cause a change in characteristics due to oxidation of the current collector metal foil used. It is preferred to select a resin. When the glass transition temperature of the resin used is higher than 400 ° C., the resin is decomposed at the time of heating and compression, and when the glass transition temperature is lower than 50 ° C., the obtained electrode material is separated from the current collector metal foil at a temperature lower than 100 ° C. It is not preferable because carbon powder is missing. Resins containing fluorine are not preferred because they may generate HF during use. In addition, it is not preferable to use a resin that does not exhibit thermoplasticity, because the volume density of the electrode material obtained by heat compression is low. The resin conventionally used as a binder is a crystalline resin, but in the present invention, the resin can be used regardless of its crystallinity or amorphousness, and can be used in a crystalline state or an amorphous state.

As the polyimide resin in the present invention,
Aliphatic polyimides, semi-aromatic polyimides, aromatic polyimides, polyamideimides, polyetherimides, and the like can be used arbitrarily. Here, the aliphatic polyimide refers to a polyimide resin having an aliphatic chain, the semi-aromatic polyimide refers to a polyimide resin partially having an aromatic chain, and the aromatic polyimide refers to a polyimide resin having an aromatic chain. Further, the polyimide resin in the present invention also includes an imide resin having a bonding mode other than the imide bond, such as polyamide imide and polyether imide. In the present invention, polyamic acid, which is a precursor of polyimide, can also be used. The polyimide resin used in the present invention can be obtained by polymerizing a diamine compound and a tetracarboxylic dianhydride by a conventionally known method, and the production method is not particularly limited.

Examples of the diamine compound include diaminohexane, diaminooctane, diaminodecane, diaminododecane, 1,2-bis (2-aminoethoxy) ethane, and diethylene glycol bis (3-aminopropyl).
Ether, 1,4-bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4
8,10-tetraoxaspiro [5,5] undecane,
4,4′-methylenebis (cyclohexylamine),
1,3-bis (aminomethyl) cyclohexane, 1,4
-Bis (aminomethyl) cyclohexane, norbornanediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3'-diaminobiphenyl, 4,4 ' -Diaminobiphenyl, 4,
4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis (3-aminophenyl) sulfide,
(3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4- Aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-
Aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3′-diaminobenzophenone,
3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, bis [4- (3
-Aminophenoxy) phenyl] methane, bis [4-
(4-aminophenoxy) phenyl] methane, 1,1-
Bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4
-(3-aminophenoxy) phenyl] propane, 2,
2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy)
Phenyl] butane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy)
Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene,
1,3-bis (4-aminobenzoyl) benzene, 1,
4-bis (3-aminobenzoyl) benzene, 1,4-
Bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene,
1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4-
(3-aminophenoxy) phenyl] ketone, bis [4
-(4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl Sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- ( 3
-Aminophenoxy) phenyl] ether, bis [4-
(4-aminophenoxy) phenyl] ether, 1,4
-Bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy)
Benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether,
4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4
-Amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-
α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-
Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy)-
α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene,
3,3′-diamino-4,4′-difluorobenzophenone and the like are used, and these are used alone or in combination of two or more.

The tetracarboxylic dianhydride component includes, for example, ethylene tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3, 3 ', 4, 4' -Benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4 '
-Biphenyltetracarboxylic dianhydride, 2,2 ',
3,3′-biphenyltetracarboxylic dianhydride, 2,
2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride , Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3
-Dicarboxyphenyl) ethane dianhydride, bis (2,
3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride,
1,3-bis [(3,4-dicarboxy) benzoyl]
Benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} propane Dianhydride, 2,2-bis {4- [3-
(1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4
-[3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-
Dicarboxy) phenoxy] biphenyl dianhydride, 4,
4'-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-
Dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4-
(1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1 , 2-Dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- (1,
2-dicarboxy) phenoxy] phenyl disulfide dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,2 5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6 , 7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more.

The combination of these monomers produces thermoplastic, ie, melt-flowable polyimide, and non-thermoplastic, ie, non-melt-flowable polyimide, but the polyimide used in the present invention is thermoplastic. Limited.

The polyamide resin used in the present invention can be obtained by polymerizing a diamine compound and a dicarboxylic acid or a derivative thereof by a conventionally known method.
The production method is not particularly limited.

As the diamine compound, the above-mentioned diamine compounds can be used. Further, as the dicarboxylic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dotecanedioic acid, phenylsuccinic acid, 1,4- Phenylenediacetic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfidedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid , 4,
4'-diphenylsulfonedicarboxylic acid, bis (4-phenyl carboxylate) methane, 2,2-bis (phenyl phenyl carboxylate) propane, 1,4-bis (4-phenoxycarboxylate) benzene, 1,4- Bis (4-carboxylate benzoyl) benzene, 1,4-bis (4-carboxylate-α, α-dimethylbenzyl) benzene, 2,2-bis (4-phenoxy) phenylpropane, biphenyldicarboxylic acid, or Derivatives such as anhydrides and halides thereof are exemplified. These may be used alone or as a mixture of two or more.

The polysulfone resin used in the present invention refers to a polymer having a sulfone group and an ether group, and the production method is not particularly limited. Representative examples of polysulfone resins include those obtained by polymerizing 4,4′-biphenyldisulfonyl chloride with diphenyl ether and / or biphenyl by a Friedel-Crafts electrophilic reaction, sodium salt of bisphenol A and 4,4′-dichlorodiphenyl Polymerized by desulfonation of sulfone, 4,4′-disulfonyl chloride diphenyl ether and 4-sulfonyl chloride diphenyl ether and / or biphenyl polymerized by Friedel-craft type electrophilic reaction, 4-chloro-4′- Examples thereof include those polymerized by a desalting reaction of a sodium or potassium salt of hydroxy-diphenyl sulfone.

In the present invention, in addition to the polysulfone resin obtained by the above production method, a polysulfone resin using another dihydroxy compound instead of bisphenol A can be used. Examples of the dihydroxy compound include ethylene glycol, polyethylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, and 1,4-dihydroxy-2. -Butene, 1,4-
Dihydroxybutyne, 2,2-dimethyl-1,3-propanediol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 2,5-
Hexanediol, 2,4-dihydroxy-2-methylpentane, 1,5-dihydroxy-3-methylpentane, 2,5-dihydroxy-3-hexane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1 , 4-cyclohexanediol, 3-methylpentane-2,4-diol, 1,7-heptanediol,
2,2-diethyl-1,3-propanediol, 1,8
-Octanediol, 1,4-cyclohexanedimethanol, 2-ethyl-1,3-hexanediol, 2,5
-Dimethyl-2,5-hexanediol, 2,2,4-
Trimethyl-1,3-pentanediol, 1,9-nonanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 1,10-decanediol, 3,6-
Dihydroxy-3,6-dimethyl-4-octane, 1,
2-dihydroxy-5,9-cyclododecadiene, 1,
2-dihydroxycyclododecane, 1,12-dodecanediol, 2,5-dibutylhydroquinoline, 2,6-
Dibutyl-4-hydroxymethylphenol, p, p '
-Dihydroxy-2,2-dicyclohexylpropane,
1,16-hexadecanediol, 1,1,2,2-tetraphenyl-1,2-ethanediol, bis (4-hydroxyphenyl) methane, 1,1-bis (4′-hydroxyphenyl) ethane, 2-bis (4'-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl)
Diphenylmethane, bis (4-hydroxyphenyl)-
1-naphthylmethane, 1,1-bis (4′-hydroxyphenyl) -1-phenylethane, 2,2-bis (4 ′
-Hydroxyphenyl) propane ["bisphenol A"], 2- (4'-hydroxyphenyl) -2-
(3′-hydroxyphenyl) propane, 2,2-bis (4′-hydroxyphenyl) butane, 1,1-bis (4′-hydroxyphenyl) isobutane, 2,2-bis (4′-hydroxyphenyl) octane , 2,2-bis (3'-methyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-ethyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-n- Propyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-isopropyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-sec-butyl-4'-
Hydroxyphenyl) propane, 2,2-bis (3′-
tert-butyl-4′-hydroxyphenyl) propane, 2,2-bis (3′-cyclohexyl-4′-hydroxyphenyl) propane, 2,2-bis (3′-allyl-4′-hydroxyphenyl) propane, 2,2-bis (3′-methoxy-4′-hydroxyphenyl) propane, 2,2-bis (3 ′, 5′-dimethyl-4′-hydroxyphenyl) propane, 2,2-bis (2 ′,
3 ', 5', 6'-tetramethyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-chloro-4 '
-Hydroxyphenyl) propane, 2,2-bis (3 ', 5'-dichloro-4'-hydroxyphenyl)
Propane, 2,2-bis (3'-bromo-4'-hydroxyphenyl) propane, 2,2-bis (3 ', 5'-
Dibromo-4′-hydroxyphenyl) propane, 2,
2-bis (2 ', 6'-dibromo-3', 5'-dimethyl-4'-hydroxyphenyl) propane, bis (4-
(Hydroxyphenyl) cyanomethane, 1-cyano-3,
3-bis (4'-hydroxyphenyl) butane, 2,2
Bis (hydroxyaryl) alkanes such as -bis (4'-hydroxyphenyl) hexafluoropropane,
1,1-bis (4′-hydroxyphenyl) cyclopentane, 1,1-bis (4′-hydroxyphenyl) cyclohexane, 1,1-bis (4′-hydroxyphenyl) -3,3,5-trimethylcyclohexane , 1,1
-Bis (4'-hydroxyphenyl) cycloheptane,
Bis (hydroxyaryl) cycloalkanes such as 2,2-bis (4′-hydroxyphenyl) adamantane,
4,4′-dihydroxydiphenyl ether, 4,
Dihydroxydiaryl ethers such as 4′-dihydroxy-3,3′-dimethyldiphenyl ether and ethylene glycol bis (4-hydroxyphenyl) ether, 4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide , Dihydroxydiarylsulfones such as 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3- Bis (hydroxyaryl) ketones such as methylphenyl) ketone, and 6,6 ′
-Dihydroxy-3,3,3 ', 3'-tetramethylspiro (bis) indane ["spirobiindanebisphenol"], trans-2,3-bis (4'-hydroxyphenyl) -2-butene, 9, 9-bis (4 '
-Hydroxyphenyl) fluorene, 3,3-bis (4'-hydroxyphenyl) -2-butanone,
6-bis (4'-hydroxyphenyl) -1,6-hexanedione, 1,1-dichloro-2,2-bis (4'-
(Hydroxyphenyl) ethylene, 1,1-dibromo-
2,2-bis (4′-hydroxyphenyl) ethylene,
1,1-dichloro-2,2-bis (5′-phenoxy-
4′-hydroxyphenyl) ethylene, α, α, α ′,
α'-tetramethyl-α, α'-bis (4-hydroxyphenyl) -p-xylene, α, α, α ', α'-tetramethyl-α, α'-bis (4-hydroxyphenyl)
-M-xylene, 4,4'-dihydroxybiphenyl and the like. These may be used alone or as a mixture of two or more.

The polyether resin used in the present invention refers to a polymer having a phenyl group and an ether group, and the production method is not particularly limited. Typical examples of the polyether resin include polyphenylene ether obtained by an oxidative coupling reaction of 2,6-xylenol. In the present invention, in addition to the above polyether resin, an alloy of the above polyether resin and another resin such as polystyrene can also be used. In the present invention, two or more of the above-mentioned polyimides, polyamides, polysulfones and polyethers can be used as a mixture.

In the present invention, a thermoplastic resin and / or a crystallization nucleating agent may be added to a thermoplastic resin to change the glass transition temperature and / or the crystallinity.
As the plasticizer and the crystallization nucleating agent, any known plasticizer and chemical nucleating agent can be used as long as they do not involve a chemical reaction during production and do not affect the performance of the battery. Examples of the plasticizer include phosphates such as tributyl phosphate, triphenyl phosphate and tricresyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and di-n-phthalate.
Phthalates such as octyl, octyldecyl phthalate, diisodecyl phthalate, and butylbenzyl phthalate; aliphatic-basic acid esters such as butyl oleate and chrysine monooleate; dibutyl adipate; di-adipate Aliphatic dibasic acid esters such as n-hexyl, alkyl adipate, dibutyl sebacate, di-2-ethylhexyl sebacate, diethylene glycol dibenzoate, triethylene glycol di-2
-Dihydric alcohol esters such as ethyl butyrate; oxyesters such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, butyl phthalyl butyl glycolate, and tributyl acetyl citrate; other chlorinated paraffins, chlorinated biphenyls; Nitrobiphenyl,
Dinonylnaphthalene, diphenylether, diphenylsulfone, terphenyl, N-benzenesulfonyl-n
-Butylamine, toluenesulfonethylamide, camphor, methyl abietate, alkyl trimellitate, tris-2-ethylhexyl trimellitate, polyester plasticizer, epoxy plasticizer, stearic plasticizer, paraffin, silicone Oils and the like. Examples of the crystallization nucleating agent include sodium 2,2′-methylenebis (4,4-di-t-butylphenyl) phosphate, sodium bis (4-t-butylphenyl) phosphate, and bis (p-allylbenzylidene) sorbitol. Is mentioned. In addition, a monomer or oligomer of the resin used can be used. These plasticizers and crystallization nucleating agents can be used alone or in combination of two or more.
By changing the glass transition temperature using a plasticizer, it is possible to change the temperature during heat compression. By crystallizing the resin using a crystallization nucleating agent, the heat resistance of the obtained electrode material can be increased.

In the present invention, a conductive agent powder can be added to impart conductivity to the thermoplastic resin.
The type and shape of the conductive agent powder are not particularly limited as long as they have conductivity and have a function of imparting improved conductivity to the resin composition. The type and shape of the conductive agent powder in the present invention are not particularly limited as long as they have electric conductivity, and any conventionally known powder can be used. Examples of the conductive agent powder include acetylene black, carbon black, graphite (graphite), metal, and the like, and these can be used alone or in combination of two or more. Here, the true specific gravity of acetylene black, carbon black, and graphite (graphite) is usually 1.3 to 1.5 g / cm ³ .

The carbon powder in the present invention is not particularly limited as long as it has a function of taking in Li ions.
The type, shape, and crystal structure of the carbon powder in the present invention are not particularly limited as long as the carbon powder can be used as an electrode material of a battery. The true specific gravity of the carbon powder in the present invention is usually preferably 2.3 g / cm ³ or less,
2.1 g / cm ³ or less is more preferable, and 2.0 g / cm ³
/ Cm ³ or less is more preferable. The true specific gravity of the carbon powder in the present invention is usually preferably 1.4 g / cm ³ or more, more preferably 1.6 g / cm ³ or more, and still more preferably 1.8 g / cm ³ or more.
Examples of carbon powder include coke, graphite, resin carbide,
Soft carbon, hard carbon, glassy carbon and the like can be mentioned, and these can be used alone or in combination of two or more. Any conventionally known carbon powder can be used as the carbon powder in the present invention. Examples of the carbon powder include coke, graphite, resin carbide, soft carbon, hard carbon, glassy carbon, and the like, and these may be used alone or as a mixture of two or more. Here, the graphite has a layer structure in which crystals are orderly, and examples thereof include natural graphite and artificial graphite. Soft carbon is carbon having a crystal layer structure developed to some extent, and can be easily converted to graphite by heat treatment at a high temperature, and is also called graphitizable carbon. This soft carbon can be used as it is, or it can be graphitized by heat treatment. Coke (pitch coke, needle coke, petroleum coke, etc.) is classified as soft carbon, and can be used as it is, or even if it has been graphitized by heat treatment. The resin carbide is obtained by firing resins such as celluloses, phenolic resins, furan resins, and polyimides at an appropriate temperature and carbonizing them, and any resin can be used regardless of the resins used.

The type, shape and manufacturing method of the current collector metal foil in the present invention are not particularly limited as long as it can be used as an electrode material of a battery, and any conventionally known metal foil can be used. As the current collector metal foil, for example, Al, C
Examples thereof include u, Ni, Ti, Pt, Fe, Au and alloys of these and other metals, and metal oxides such as SnO ₂ , Ti ₂ O _{3 and the} like, and these are produced by rolling, electrolysis and the like. The thickness of the current collector metal foil is generally about 1 to 100 μm, but any thickness of foil can be used in the present invention.
In the present invention, a collector metal foil subjected to a surface treatment can also be used.

In the present invention, the electrode material is obtained by mixing a carbon powder and, if necessary, a conductive agent powder with a solution or dispersion of a thermoplastic resin to form a slurry, drying the slurry, and compressing it by heating. . Here, the slurry may be dried on a bat, a metal or resin belt or film and then pulverized, or may be pulverized while being dried in a kneader such as a kneader, and then heated and compressed together with the current collector metal foil. Alternatively, the slurry may be dried and heated and compressed on a metal or resin belt or film, and then peeled off from the belt or film and pressed on a current collector metal foil. Alternatively, the slurry may be applied directly on the current collector metal foil, dried and then heated and compressed. Here, the solvent used for the solution or dispersion is not particularly specified, and examples thereof include hydrocarbon solvents such as hexane, cyclohexane, isooctane, octane, benzene, toluene, xylene, and mesitylene, methanol, ethanol, propanol, butanol, and pentanol. , Hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, alcoholic solvents such as ethylene glycol, triethylene glycol, propylene glycol, glycerol, ethyl acetate, propylene acetate, methyl lactate, ethyl lactate, propyl lactate, ethylene carbonate, propylene carbonate, etc. Solvent, chloroform, carbon tetrachloride, dichloroethane, trichloroethylene, 1,1,2-trichloro-trifluoroethane, chlorobenzene, bromobenzene, dibromo Benzene, Yo - Dobenzen, dichlorobenzene, 1,
Halogen-based solvents such as 1,2,2-tetrachloroethane, tetrachloroethylene and p-chlorotoluene; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3-hexanone, acetophenone and benzophenone; diisopropyl ether, tetrahydrofuran and tetrahydropyran; 1,4-dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, methyl carbitol, ethyl carbitol, dibutyl ether, anisole, phenetole, o-dimethoxybenzene, p-dimethoxybenzene, 3-methoxytoluene, Ether solvents such as benzyl ether, benzyl phenyl ether and methoxynaphthalene; thioether solvents such as phenyl sulfide and thioanisole; Ester solvents such as methyl, methyl phthalate and ethyl phthalate; diphenyl ethers; or alkyl-substituted diphenyl ethers such as 4-methylphenyl ether, 3-methylphenyl ether and 3-phenoxytoluene; or 4-bromophenyl ether; Halogen-substituted diphenyl ethers such as chlorophenyl ether, 4-bromodiphenyl ether and 4-methyl-4'-bromodiphenyl ether, or 4-methoxydiphenyl ether, 4-methoxyphenyl ether, 3-methoxyphenyl ether,
Alkoxy-substituted diphenyl ethers such as methyl-4'-methoxydiphenyl ether, or diphenyl ether solvents such as cyclic diphenyl ethers such as dibenzofuran and xanthene, and other acetonitrile, propionitrile, benzonitrile, pyridine, picoline, N,
N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-pyrrolidone,
1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dimethyl sulfone, sulfolane, water and the like,
One type or a mixture of two or more types can be used.

The method for applying the slurry is not particularly specified. For example, a known method using a roller brush, an air spray, an airless spray, a roller coater, a curtain flow coater, or the like can be used. The method of drying the applied slurry is not particularly specified, and can be arbitrarily selected as long as the temperature and atmosphere do not decompose or deteriorate the solvent, thermoplastic resin, carbon powder, conductive material, current collector metal foil, and the like.

In the present invention, the electrode material can also be obtained by mixing a carbon powder and, if necessary, a conductive agent powder with a thermoplastic resin and heating and compressing the mixture. Here, it may be heated and compressed together with the current collector metal foil, or may be heated and compressed and then pressed against the current collector. As a method for obtaining the electrode material, for simplicity of the process, a carbon powder and, if necessary, a conductive agent powder are mixed with a solution or dispersion of a thermoplastic resin to form a slurry, and this slurry is directly applied to the current collector metal foil. Apply,
A method of heating and compressing after drying, or a method of mixing carbon powder and, if necessary, a conductive agent powder with a thermoplastic resin and heating and compressing the mixture with a current collector metal foil is preferable.

In the present invention, the glass transition temperature is 50
Since a thermoplastic resin having a temperature of not less than ° C. is used, the volume density of the electrode material is improved only when heated and compressed. Here, the volume density (the dimension is [g / cm ³ ])
Refers to the weight of the carbon powder used per unit volume of the electrode material, the apparent density of the carbon powder in the electrode material,
The higher the density, the greater the amount of carbon powder in the same volume,
As a result, the electric capacity of the battery increases. The true specific gravity of the carbon powder in the present invention is usually preferably 1.2 g / cm ³ or more, more preferably 1.4 g / cm ³ or more, and still more preferably 1.6 g / cm ³ or more. Has been described above. In the present invention, the volume density is usually
It is 80 to 90% of the true specific gravity of the carbon powder used. In the present invention, a heating method and a compression method during heating and compression are not particularly specified, and a conventionally known method can be used. As the heat compression method, for example, a hot press using a hot press machine, a roll press using a hot roll, or the like can be used.

In the present invention, the temperature at the time of heat compression is at least the glass transition temperature of the thermoplastic resin used, preferably at least 30 ° C. higher than the glass transition temperature, more preferably at least 50 ° C. higher than the glass transition temperature, and Below the temperature at which the thermoplastic resin used melts and flows. The pressure during heating and compression is 1 MPa or more, preferably 10 MPa or more, more preferably 100 MPa or more, and
The pressure is lower than the pressure at which the crystalline state of the carbon powder changes, preferably lower than the pressure at which the shape of the carbon powder changes. When the temperature and / or the pressure during the heating and compression are low, not only is it not possible to obtain an electrode material having a high volume density, but also the obtained electrode material is cracked or carbon powder is missing, which is not preferable. If the temperature during the heat compression is higher than the temperature at which the resin melts and flows, the resin flows during the heat compression and separates from the carbon powder, which is not preferable.

The amount of the thermoplastic resin used in the present invention is 0.2 parts by weight or more, preferably 2 parts by weight or more, more preferably 5 parts by weight or more, and 50 parts by weight or less based on 100 parts by weight of the carbon powder. , Preferably 20 parts by weight or less, more preferably 10 parts by weight or less. If the amount of the thermoplastic resin used is small, the obtained electrode material is cracked or the carbon powder is missing. If the amount is large, the capacity of the battery is reduced, which is not preferable. The amount of the conductive agent powder used in the present invention is 0 to 50 parts by weight based on 100 parts by weight of the carbon powder, but is not particularly limited.

Since the electrode material obtained by the present invention has a high softening temperature of the thermoplastic resin as a binder, it can be used under conditions that are difficult with conventional electrode materials. The conditions that can be used vary depending on the thermoplastic resin used.
At 00 ° C., the electrode material using any resin does not change its shape or lose carbon powder.
Even at 200 ° C., and even at 200 ° C., no change in the shape or loss of the carbon powder occurs, so that it can be used under conditions that were not possible before.

The electrode material obtained by the present invention can be used for a conventionally known negative electrode for a non-aqueous electrolyte secondary battery,
There is no limitation on the structure of the battery and the electrolyte used. For example, the electrode material obtained by the present invention, dimethyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, dimethoxyethane, as an electrolyte
Dimethoxyethane, diethoxyethane, ethoxymethoxyethane, diethoxyethane, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyllactone, dioxolane, triethylphosphite, dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, dimethoxy Ethane, polyethylene glycol, sulfolane,
The present invention can be used for a secondary battery using one or a mixture of two or more organic solvents such as 1,3-dimethyl-2-imidazolidinone, dichloroethane, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, and nitrobenzene. Further, the electrode material obtained by the present invention can also be used for a polymer battery using a resin having high conductivity or a resin absorbing an electrolytic solution as an electrolyte.

The shape and manufacturing method of the secondary battery using the electrode material obtained by the present invention are not particularly limited. For example, a square type, a plate (gum) type, a button (coin) type, a film using a flat electrode are used. It can be used for (ribbon) type, cylindrical type for processing electrodes and the like in a spiral shape, square type, plate (gum) type, button (coin) type and the like.

[0053]

EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples, and the present invention can be carried out by appropriately changing the scope without changing the gist. It is possible. In addition, the glass transition temperature (Tg) of the resin was measured at a rate of 10 ° C./min from 30 ° C. to 300 ° C. by a penetration method using TMA (Shimadzu TMA-40). Logarithmic viscosity of resin
The resin was adjusted to a concentration of 0.5 g / 100 ml of resin, and measured at 35 ° C. using an Ubbelohde viscosity tube.

Example 1 1.0 g of polyimide having a Tg of 215 ° C. (“Ultem” manufactured by GE) was dissolved in NMP (N-methyl-pyrrolidone) to obtain coke-treated graphite powder (true specific gravity 2.0 g) as carbon powder. / Cm ³ ]), and the slurry liquid in which 9.0 g had been diffused was placed in an evaporating dish, dried by ventilation at 250 ° C. for 12 hours, and then pulverized by a sample mill. The obtained powder was sandwiched between polyimide films (“UPILEX” manufactured by Ube Industries, Ltd.) and heated and compressed at 250 ° C. and 200 MPa to prepare an electrode material. The volume density of the obtained electrode material was 1.
It was 66 g / cm ³ . As a heat resistance test, the electrode material and dimethyl carbonate were placed in a closed stainless steel container, and the entire container was heated in a 120 ° C. oven for 12 hours. After cooling, the inside of the container was checked, but no carbon powder was missing.

Examples 2 to 9 An electrode material was prepared and the volume density was measured in the same manner as in Example 1 except that the resin and the temperature during drying and heating and compression were appropriately changed. Since some resins did not dissolve in NMP, a freeze-ground powder was used in a slurry state in which the powder was dispersed in NMP. Table-Results
2 [Table 2]. Example 1 using these electrode materials
The same heat resistance test was performed, but none of the electrode materials had carbon powder missing.

[Comparative Examples 1 to 9] An electrode material was prepared and the volume density was measured in the same manner as in Examples 1 to 9 except that the temperature during compression was set to room temperature. The results are shown in Table 2 [Table 2]. When a heat resistance test similar to that of Example 1 was performed using these electrode materials, it was confirmed that all of the electrode materials were missing carbon powder.

[Reference Example 1] An electrode material was prepared in the same manner as in Example 1 except that PVDF ("KF polymer" manufactured by Kureha Chemical Co., Ltd.) was used as a resin, dried at 200 ° C, and compressed at room temperature. . The volume density of the obtained electrode material was 1.7.
It was 1 g / cm ³ . Using the obtained electrode material, the same heat resistance test as in Example 1 was performed, but no carbon powder was missing.

Reference Example 2 The procedure of Example 1 was repeated, except that SBR (“JSR SIS” manufactured by Nippon Synthetic Rubber Co., Ltd.) was used as the resin, dried at 200 ° C., and compressed at room temperature.
An electrode material was prepared. The volume density of the obtained electrode material was 1.61 g / cm ³ . Using the obtained electrode material, a heat resistance test was performed in the same manner as in Example 1, and it was confirmed that carbon powder was missing.

Example 10 A vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet was charged with 2,2-bis [4
-(3-aminophenoxy) phenyl] propane 41.
05 g (0.10 mol), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride 31.58 g (0.
098 mol) and 290 g of NMP, and heated to 150 ° C. while stirring under a nitrogen atmosphere. After performing the reaction for 3 hours while distilling off the condensed water, phthalic anhydride 0.89 was obtained.
g (6 × 10 ⁻³ mol) was charged, and the reaction was further performed for 2 hours. Thereafter, the mixture is cooled to room temperature, and the polymer concentration is 20% by weight.
Was obtained. In addition, a part of the polyimide solution was cast on a glass plate, and 200 ° C.
After drying for 12 hours, an aromatic polyimide cast film was obtained. Logarithmic viscosity of the obtained aromatic polyimide is 1.0
3 dl / g and Tg were 200 ° C. 9.5 g of natural graphite was added to 2.5 g of the polyimide solution, and diluted with NMP while stirring until the whole became homogeneous. The obtained slurry liquid was applied to a Cu foil by a doctor dope method,
It was air-dried for 2 hours to prepare an electrode material adhered to the Cu foil. The volume density of the obtained electrode material is 1.47 g / cm3.
Met. The electrode material was heated and compressed at 50 MPa while changing the temperature, and the volume density was measured. The results are shown in Table 3 [Table 3].

Example 11 A vessel equipped with a stirrer, a reflux condenser, a water separator and a nitrogen inlet was charged with 2,2-bis [4
-(3-aminophenoxy) phenyl] propane 41.
05 g (0.10 mol), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride 31.58 g (0.
098 mol) and NMP (290 g), and the mixture was reacted at room temperature for 3 hours with stirring under a nitrogen atmosphere. Then, 0.89 g (6 × 10 ⁻³ mol) of phthalic anhydride was charged and the mixture was heated at 60 ° C. for 2 hours. After reacting for an hour, an aromatic polyamic acid-NMP solution having a polymer concentration of 20% by weight was obtained. A part of the polyamic acid solution was cast on a glass plate and dried at 250 ° C. for 12 hours to obtain a cast film of an aromatic polyimide. The logarithmic viscosity of the obtained aromatic polyimide is 1.01 dl /
g and Tg were 200 ° C. 1. the polyamic acid solution
9.5 g of natural graphite was added to 5 g, and diluted with NMP with stirring until the whole became homogeneous. The obtained slurry liquid was applied to a Cu foil by a doctor dope method, heated at 250 ° C. for 12 hours, and subjected to thermal imidization and drying to prepare an electrode material adhered to the Cu foil. The volume density of the obtained electrode material was 1.43 g / cm ³ . The electrode material is
The temperature was changed, and the sample was heated and compressed at 50 MPa, and the volume density was measured. The results are shown in Table 3 [Table 3].

Table 1 [Table 1] shows the thermoplastic resins used in Examples 1 to 9, Comparative Examples 1 to 9, and Reference Examples 1 and 2. Table 2 [Table 2] shows Examples 1 to 9 and Comparative Examples 1 to
9, the evaluation results of Reference Examples 1 and 2 are shown. Table 3 [Table 3]
Shows the heating and compression temperatures of Examples 10 to 11.

[0062]

[Table 1]

[0063]

[Table 2] [Legend] () indicates catalog data.

[0064]

[Table 3]

[0065]

According to the present invention, since it reacts violently with lithium, there is a possibility that the battery may be damaged or rupture, HF (hydrogen fluoride) is not substantially generated, and the volume density is high and the electricity is high. An electrode material for a high heat-resistant non-aqueous electrolyte secondary battery having a high capacity can be provided.

Continued on the front page (72) Inventor Tomomi Okumura 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Yuichi Okawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals (72) Inventor Hideaki Oikawa 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd.

Claims (23)

[Claims] 1. A resin composition containing carbon powder and a fluorine-free thermoplastic resin having a glass transition temperature of at least 50 ° C. selected from the group consisting of polyimide, polyamide, polysulfone, and polyether. And the true specific gravity of the carbon powder is 80
An electrode material for a non-aqueous electrolyte secondary battery having a volume density of up to 90%. 2. The method according to claim 1, wherein the resin composition comprises at least one kind of conductive agent powder selected from the group consisting of acetylene black, carbon black, graphite (graphite), glassy carbon, and metal conductive agent powder. The electrode material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the electrode material has improved conductivity as compared with the resin composition in the case of addition. 3. The resin composition according to claim 1, wherein the resin composition has a glass transition temperature lowered by adding a plasticizer, as compared with the resin composition in the case of not adding the plasticizer. Electrode material for non-aqueous electrolyte secondary batteries. 4. The resin composition according to claim 1, wherein a crystallization nucleating agent is added to the resin composition to increase the crystallization rate as compared with a resin composition not added. The electrode material for a non-aqueous electrolyte secondary battery described in any one of the above. 5. The carbon powder is selected from the group consisting of carbide obtained by firing coke, carbide obtained by firing graphite, carbide obtained by firing a resin, soft carbon, hard carbon, and glassy carbon. The electrode material for a secondary battery according to claim 1, which is at least one kind. 6. An electrode for a non-aqueous electrolyte secondary battery, wherein the material according to claim 1 is adhered to a current collector metal foil. 7. An electrode for a non-aqueous electrolyte secondary battery, wherein the material according to claim 1 is pressure-bonded to a current collector metal foil. 8. The current collector metal foil is made of Al, Cu, Ni, T
The secondary battery according to claim 6, further comprising at least one alloy layer made of an alloy containing at least one metal selected from the group consisting of i, Pt, Fe, and Au. Electrodes. 9. A resin composition containing a fluorine-free thermoplastic resin having a glass transition temperature of at least 50 ° C. and a carbon powder selected from the group consisting of polyimide, polyamide, polysulfone, and polyether. Is heated and compressed at a temperature equal to or higher than the glass transition temperature of the thermoplastic resin to produce a molded product used for an electrode for a non-aqueous electrolyte secondary battery. 10. A resin composition comprising: acetylene black;
By adding at least one type of conductive agent powder selected from the group consisting of carbon black, graphite (graphite), glassy carbon, and metal conductive agent powder, the conductivity of the resin composition is higher than that of the resin composition without addition. The method according to claim 9, wherein the property is enhanced. 11. The resin composition according to claim 9, wherein the resin composition has a glass transition temperature lowered by adding a plasticizer, as compared with the resin composition in the case of not adding the plasticizer. Production method. 12. The resin composition according to claim 9, wherein the crystallization rate is increased by adding a crystallization nucleating agent to the resin composition as compared with the resin composition in the case where no nucleating agent is added. The production method described in any of the above. 13. The carbon powder is selected from the group consisting of carbide obtained by firing coke, carbide obtained by firing graphite, carbide obtained by firing a resin, soft carbon, hard carbon, and glassy carbon. The method according to claim 9, which is at least one kind. 14. An electrode material for a secondary battery obtained by the production method according to claim 9. 15. A resin composition containing carbon powder and a fluorine-free thermoplastic resin having a glass transition temperature of at least 50 ° C. selected from the group consisting of polyimide, polyamide, polysulfone, and polyether. Is heated and compressed together with a current collector metal foil at a temperature equal to or higher than the glass transition temperature of the thermoplastic resin, to produce a non-aqueous electrolyte secondary battery electrode. 16. A resin composition comprising: acetylene black;
By adding at least one type of conductive agent powder selected from the group consisting of carbon black, graphite (graphite), glassy carbon, and metal conductive agent powder, the conductivity of the resin composition is higher than that of the resin composition without addition. The method according to claim 15, wherein the property is enhanced. 17. The resin composition according to claim 15, wherein a glass transition temperature is lowered by adding a plasticizer, as compared with a resin composition in which no plasticizer is added.
Production method described in 1. 18. The resin composition according to claim 15, wherein the addition of a crystallization nucleating agent has a higher crystallization rate than that of the resin composition not added.
The manufacturing method described in any one of the above. 19. The carbon powder is selected from the group consisting of carbide obtained by firing coke, carbide obtained by firing graphite, carbide obtained by firing a resin, soft carbon, hard carbon, and glassy carbon. The method according to any one of claims 15 to 18, wherein the method is at least one. 20. An electrode for a secondary battery obtained by the manufacturing method according to claim 15. Description: 21. An electrode for a non-aqueous electrolyte secondary battery, wherein the material according to claim 14 is adhered to a current collector metal foil. 22. An electrode for a non-aqueous electrolyte secondary battery, wherein the material according to claim 14 is pressure-bonded to a current collector metal foil. 23. A current collector metal foil comprising Al, Cu, Ni,
21. It has at least one alloy layer made of an alloy containing at least one metal selected from the group consisting of Ti, Pt, Fe, and Au.
23. The electrode for a secondary battery according to any one of the above items.