JP3066682B2 - Chemical battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemical battery and, more particularly, to a chemical battery having improved charge / discharge cycle characteristics using an electrode in which the electrode active material is prevented from falling off by a binder.

[0002]

2. Description of the Related Art In aqueous electrolytes such as manganese dry batteries, alkaline dry batteries and nickel-cadmium secondary batteries, starch, polyvinyl alcohol, carboxymethyl cellulose (Japanese Unexamined Patent Publication Nos. 1-175171 and 1-105471) are used as binders for electrode active materials. JP-A-51-5538 and 50-2
6500), hydroxypropylcellulose (JP-A-63-245859 and JP-A-54-49541), regenerated cellulose (JP-A-61-91872), polyvinyl chloride, polyvinylpyrrolidone, and the like. As the electrolyte, Teflon or the like is generally used. ("Battery Handbook" published by Denki Shoin, 1980) Particularly, in a secondary battery, the positive electrode or the negative electrode repeatedly expands and contracts in volume during charging and discharging, so that active material particles and a conductive agent fall off, shortening the charging and discharging cycle life. However, it is important to select a binder as a means for preventing this. However, the above-mentioned binder was insufficient to prevent the falling off of the active material and the like. On the other hand, Japanese Patent Application Laid-Open No. 3-1082
No. 63 discloses a positive electrode binder that prevents the active material from falling off, and describes that the charge / discharge cycle life has been improved. However, the binder has an affinity for aqueous and non-aqueous electrolytes. Poor, low active material utilization, and insufficient charge / discharge cycle life. Further, there is a drawback that the internal resistance is significantly increased when the amount of addition is increased.

As described above, the charge / discharge cycle life and the utilization rate of the active material (that is, discharge capacity) are inconsistent performances, and a binder technology that balances them has been desired. Also, in the primary battery, the lithium battery adopts a spiral structure in which sheet electrodes are wound to reduce the internal resistance, and the shape of the current collector is changed to a sheet shape so as to cope with heavy load discharge. Some are made of metal foil. However,
If the adhesion of the coating of the active material applied on the current collector is weak, the active material may peel off or fall off during the assembly of the battery such as a coil, resulting in many defective products. As a factor for improving the adhesive strength between the active material and the current collector, there is a binder. JP-A-3-222258 discloses a binder for improving the adhesive strength, but its performance is still insufficient.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to prevent the electrode active material from falling off in a chemical battery and to achieve good charge / discharge characteristics.

[0005]

The object of the present invention is to provide a polymer battery having a functional group as a binder and a reaction with a functional group of the polymer in a chemical battery comprising a positive electrode active material, a negative electrode active material and an electrolyte having ionic conductivity. This was achieved by incorporating a compound having at least two functional groups in one molecule into a positive electrode mixture and / or a negative electrode mixture.

As the functional groups of the polymer and the compound, for example, there are functional groups as shown in Formula 1. The reaction of these polymers with a polyfunctional compound having two or more functional groups is generally known as a crosslinking reaction of the polymer, thereby forming a three-dimensional network of the polymer.

The polymer used in the present invention is preferably a polymer having a main chain structure represented by the following general formulas (1) to (6).・ General formula (1)

[0008]

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(Wherein R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms,
An aryl group, an aralkyl group or -OH, -COOH,
Formula 2, Formula 3, a residue containing <br/> functional groups consisting of at least one among _{^{-NH 2, R 1, R 2}} , R 3, R
One or two of ⁴ are -OH, -COOH, Formula 2,
Formula 3 is a residue having a functional group comprising at least one kind among -NH _2. ・ General formula (2)

[0010]

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(Where R ¹ , R ² , R ³ , R ⁴ , R
⁵ , R ⁶ , R ⁷ , and R ^{8 each} represent a hydrogen atom, a hydroxyl group,
6, a hydroxyalkyl group, an acyloxy group, an acyloxymethyl group, an alkyl group, an alkoxy group, a carboxyalkyl group or -OH, -COOH, Formula 2, Formula 3,-
It is a residue having a functional group of at least one of NH ₂ .・ General formula (3)

[0012]

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Wherein L ₁ represents an alkylene group having 1 to 12 carbon atoms, L ₂ represents an arylene group or an alkyl arylene group having 6 to 12 carbon atoms, and -OH, -C
OOH, wherein 2, Formula 3, at least one among -NH ₂
Having a functional group consisting of -General formula (4)-(NR ¹ -L ₁ -NR ¹ -CO-L ₂ -CO)-wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and L ₁ and L ₂ Represents an alkylene group having 2 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms or an alkylarylene group, -OH, -COOH, Formula 2, Formula 3,
—NH ₂ contains at least one kind of functional group. - Formula ^{(5) - (CONR 1 -L} 1 -NR 1 CO-O-L 2 -O) - where Shikichu R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, L _1, L ₂ represents an alkylene group having 2 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, or an alkylarylene group, wherein -OH, -COOH, Formula 2, Formula 3,
—NH ₂ contains at least one kind of functional group. -General formula (6)-(LO)-However, L is a C2-C6 alkylene group, C6 carbon.
It represents 12 arylene group or an alkyl arylene group, -OH, -COOH, Formula 2, Formula 3, in the -NH ₂
At least one functional group.

Among the above general formulas, a more preferable structure is the general formula (1) or (2). Examples of the polymer used in the present invention include natural or semi-synthetic resins such as cellulose having a hydroxyl group (-OH) and derivatives thereof, ie, cellulose acetate having a degree of substitution of less than 3, cellulose acetate butyrate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and ethyl cellulose. And a copolymer of hydroxyethyl methacrylate alone or with another monomer, and a synthetic polymer such as polyvinyl alcohol and polyvinyl butyral.

Examples of the polymer having a carboxyl group (—COOH) include carboxymethylcellulose, alginic acid, acrylic acid, methacrylic acid, maleic acid,
There are homopolymers such as itaconic acid and copolymers with other monomers. Examples of the polymer having an amino group (—NH ₂ ) include a homopolymer of gelatin, chitosan, allylamine, and acrylamide, and a copolymer with another monomer.

Other structural units of the polymer having a functional group are shown below. These may be copolymerized with other monomers, or may have two or more functional groups. The present invention is not limited to these.

[0017]

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[0018] In the above examples of the reactive functional group-containing monomer in combination with copolymerizable monomers include, for example, ethylene, propylene, scan styrene, acrylonitrile, ethylidene norbornene, methylation ether, N- vinylpyrrolidone, methyl methacrylate, butyl Examples include acrylate, vinyl acetate, vinyl chloride, vinylidene chloride, tetrafluoroethylene, and vinylidene fluoride.

The above-mentioned polymers are all polymers of ethylenically unsaturated compounds, but may be polymers containing other heteroatoms in the polymer main chain and having a reactive functional group in the side chain. For example, a polymer having at least one kind of main chain among polyester, polyamide, polyether, polyurethane, polyurea, polysulfone, polyimine and polysiloxane can be used. Also,
The preferred molecular weight of the polymer used in the present invention is 5,000
１，1,000,000.

Next, more preferred examples of the polymer in the present invention are shown, but the invention is not limited thereto.

[0021]

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[0022]

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In the present invention, the term "compound having at least two sites capable of reacting with the functional group of the polymer in one molecule" is generally called a crosslinking agent or a curing agent. To form a three-dimensional network structure.
Preferred reactions include those represented by the following formula.

[0024]

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Among these, particularly preferred reactions include:
,,and so on. Any combination of these reactive functional groups may be included in the polymer and compound of the present invention. Preferred examples of the compound (crosslinking agent) of the present invention are shown below.
It is not limited to these. 1) General formula (7)

[0026]

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In the formula, L is a divalent linking group, which may be substituted. Preferably, L is an alkylene group, an arylene group or these groups and -O-, -NR-, -CO-,-
COO-, -CON (R)-, -S-, -SO-, -S
O ₂ —, —SO ₃ —, —SO ₂ NR—, —NRCO—N
It is a divalent group formed by combining one or a plurality of bonds represented by R-, -NRCOO-, -OP (OR) (O) O-. R is a hydrogen atom, 1 to 1
Represents an alkyl group, an aryl group, or an aralkyl group having a pentavalent carbon atom.

Also, -NR-, -CONR-, -SO ₂ N
When two or more R- and -NRCOO- are contained,
May be the same or different, and may combine with each other to form a ring. L may have a substituent, and examples of the substituent include a hydroxy group, an alkoxy group, a carbamoyl group, an alphamoyl group, an alkyl group, an aryl group, and the like. The substituent is represented by the formula 2
May contain one or more groups. The following are typical examples of L.

[0029]

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In the formula, a represents an integer of 1 to 20,
6 is particularly preferred. b, e, f, h, i, j, k, l,
m represents an integer of 1 to 5, particularly preferably 1.
c represents an integer of 2 to 5, particularly preferably 2.
d and g are numbers from 0 to 100, preferably from 0 to 20.
Specific examples of the compound of the general formula (7) are shown below.

[0031]

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[0032]

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[0033]

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2) General formula (8)

[0035]

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In the formula, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
Preferably, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom is particularly preferred. R ³ and R ^{4 each} represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 6 to 1 carbon atoms.
0 is an aryl group, which may be substituted. As the substituent, a halogen atom, an alkoxy group, an aryloxy group and the like are preferable. R ³ and R ⁴ may combine to form a ring.

Specific examples of the compound represented by formula (8) are shown below.

[0038]

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3) General formula (9) X ¹ —SO ₂ —L—SO ₂ —X ^{2 In the} above general formula, X ¹ and X ² represent —CH ＝ CH ₂ or —
CH ₂ CH ₂ Y, and X ¹ and X ² may be the same or different. Y represents a group substituted with a nucleophilic group or capable of leaving in the form of HY by a base (for example, a halogen atom, sulfonyloxy, sulfate monoester, etc.). L is a divalent linking group, which may be substituted.

Specific examples of X ¹ and X ² include, for example, the following. _{-CH = CH 2, -CH 2 CH} 2 Cl, 2 divalent linking group L is an alkylene group, an arylene group, or a ^{group, -O -, - NR 1 -} , - CO -, - S-,
_{-SO -, - SO 2 -,} - SO 3 -, - SO 2 NR
^1- , -COO-, -CONR ^1- , -NR ¹ CONR
¹ -, - a divalent group formed by combining one or more of the bond represented by - NR ¹ CO _2.
R ¹ represents a hydrogen atom, or an alkyl group or aralkyl group having 1 to 15 carbon atoms, or an aryl group.
Or -NR ^1- , -SO ₂ NR ^1- , -CONR
_{^{1 -, - NR 1 CO 2}} - If the containing two or more, those of R ¹ each other may be the same or may be different.
Further, they may combine with each other to form a ring. Further, L may have a substituent, and examples of the substituent include a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group, and an aryl group. Further, the substituent may be further substituted by one or more groups represented by X ³ —SO ₂ —. X ³ has the same meaning as X ¹ and X ² described above.

The following are typical examples of L. However, a to x in the examples are integers of 1 to 10, and only d may be 0. y is an integer of 2 to 6.

[0042]

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Among them, d, k, l, p and u are 1 to 3
It is preferable that other than d, k, l, p and u of a to x are 1 or 2. Y is preferably 2. R ¹ is a hydrogen atom, or 1 to 6
Alkyl groups having two carbon atoms are preferred, with hydrogen, methyl and ethyl being particularly preferred. The vinyl sulfone compound represented by the general formula (9) is described in, for example, JP-B-47-24259 and JP-B-50-358.
07, JP-A-49-24435 and JP-A-53-4122.
Nos. 1 and 59-18944 have detailed descriptions.

Specific examples of the compound represented by formula (9) are shown below.

[0045]

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[0046]

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4) General formula (10)

[0048]

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In the formula, R ¹ represents a hydroxyl group, —OM (M group is a monovalent metal atom), an alkyl group, —N (R ² ) R ³ group (R ² and R ³ represent an alkyl group and an aryl group, respectively). ^{represented), -. NHCOR 4 (R} 4 represents a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group), or an alkoxy group.. The alkyl group represented by R ^{1 in} the general formula (10) is preferably, for example, a methyl group, an ethyl group, a butyl group or the like, and the alkoxy group is preferably a methoxy group, an ethoxy group, a butoxy group, or the like. Specific examples of —N (R ₂ ) R ₃ groups include —NH ₂ , —NHCH
_3, -NHC ₂ H ₅ and the like, -NHCOCH ₃ Specific examples of the ^four -NHCOR, -NHCOC ₆ H ₅
Etc. Further, M of the —OM group represented by R ¹ is particularly preferably, for example, a sodium atom, a potassium atom and the like.

The cyanuric chloride compound represented by the general formula (10) is described in JP-B-47-6151.
No. 47-33380, No. 54-25411,
JP-A-56-130740 has a detailed description. JP-B-53-27 having a structure similar to that of the compound of the general formula
No. 26, JP-A-50-61219, JP-A-56-2713
The compounds described in Nos. 5, 56-60430 and 57-40244 are also useful in the present invention.

Specific examples of the compound represented by formula (10) are shown below.

[0052]

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5) General formula (11)

[0054]

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In the formula, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom,
Represents an alkyl group, an aryl group, or an aralkyl group, which may be substituted. Preferably, R ¹ and R ² are hydrogen atoms,
An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, which may be substituted. As the substituent, a halogen atom, an alkoxy group, an aryloxy group and the like are preferable. R ¹ and R ² may combine to form a ring. R ³ and R ⁴ are hydrogen atoms,
An alkyl group having 1 to 5 carbon atoms is preferred, and a hydrogen atom is particularly preferred.

Specific examples of the compound represented by formula (10) are shown below.

[0057]

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6) General formula (12)

[0059]

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In the formula, R ¹ and R ² represent an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a 2-ethylhexyl group, etc.) and an aryl group having 6 to 15 carbon atoms (eg, a phenyl group, a naphthyl group) Or an aralkyl group having 7 to 15 carbon atoms (such as a benzyl group or a phenethyl group), which may be the same or different. It is also preferable that R ¹ and R ² be bonded to each other to form a heterocyclic ring together with a nitrogen atom. Examples of ring formation include pyrrolidines, piperazine rings, morpholine rings, and the like. R ³ is a hydrogen atom, a halogen atom, a carbamoyl group,
It represents a substituent such as a sulfo group, a ureido group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and a dialkyl-substituted amino group having 2 to 20 carbon atoms. R ³ is an alkoxy group, an alkyl group, a dialkylamino group, N-
When it is an alkylcarbamoyl group, those groups may be further substituted, and examples of the substituent include a halogen atom, a carbamoyl group, a sulfo group, a sulfoxy group, a sulfoamino group, and a ureido group. X ^- represents an anion, a counter ion of N- carbamoyl pyridinium salts. When the substituent of R ³ contains a sulfo group, a sulfooxy group or a sulfoamino group, an internal salt is formed and X ⁻ may not be present. Preferred examples of the anion include a carbamoyl ammonium salt-based crosslinking agent represented by the general formula (12) such as a halide ion, a sulfate ion, a sulfonate ion, ClO ₄ ⁻ , BF ₄ ⁻ , and PF ₆ ⁻ . Tokiko 56-1285
No. 3, No. 58-32699, JP-A-49-51945.
Nos. 51-59625 and 61-9641.

7) General formula (13)

[0062]

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[0063] R ^1, R ^2, R ³ and X ^- definition is exactly the same as defined in the general formula (12), these compounds are familiar to the Belgian Patent No. 825,726. 8) General formula (14)

[0064]

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R ¹ , R ² , R ³ and R ⁴ have 1 to 1 carbon atoms.
20 alkyl groups (for example, methyl group, ethyl group, butyl group, 2-ethylhexyl group, dodecyl group, etc.), aralkyl groups having 6 to 20 carbon atoms (for example, benzyl group, phenethyl group, 3-pyridylmethyl group, etc.), or 5 carbon atoms
And 20 aryl groups (for example, phenyl group, naphthyl group, pyridyl group, etc.), which may be the same or different. R ¹ , R ² , R ³ and R ⁴ may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy having 6 to 20 carbon atoms. And N, N-disubstituted carbamoyl groups.

It is also preferred that any two members out of R ¹ , R ² , R ³ and R ⁴ combine to form a ring. Examples of the case where R ¹ and R ² or R ³ and R ⁴ are bonded to form a ring together with a nitrogen atom include a case where a pyrrolidine ring, a piperazine ring, a perhydroazepine ring, a morpholine ring and the like are formed. Examples of the case where R ¹ and R ³ , or R ² and R ⁴ combine to form a ring with two nitrogen atoms and a carbon atom sandwiched between them are an imidazoline ring, a tetrahydropyrimidine ring, a tetrahydrodiazepine In some cases, a ring or the like is formed.

X represents a group capable of leaving when the compound represented by the general formula (14) reacts with a nucleophile, and preferred examples include a halogen atom, a sulfonyloxy group,
-A pyridinium group and the like. Y ⁻ represents an anion, and is preferably a halide ion, a sulfonate ion, a sulfate ion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ or the like. Y ^- is to represent a sulfonate ^{ion, X, R 1, R 2} , combined with R ³ or R ⁴ may form an intramolecular salt.

The amidinium salt-based crosslinking agent represented by the general formula (14) is described in detail in JP-A-60-225148. 9) General formula (15)

[0069]

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In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, 2-ethylhexyl group, etc.), a cycloalkyl group having 5 to 8 carbon atoms (eg, cyclohexyl group, etc.), 3 to 10 alkoxyalkyl groups (for example, methoxyethyl group, etc.) or 7 carbon atoms
To 15 aralkyl groups (for example, benzyl group, phenethyl group and the like). R ² is -R ³ (R ⁴⁾ in addition to representing a defined group ^{R 1 N (R 5) R} 6 + X - group represented by are preferred. R ³ represents an alkylene group having 2 to 4 carbon atoms (eg, an ethylene group, a propylene group, and a trimethylene group). R ⁴ and R ⁵ each represent an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, etc.) which may be the same or different. Also, R ⁴ , R ⁵
Are preferably combined with a nitrogen atom to form a heterocyclic ring (for example, a pyrrolidine ring, a piperazine ring, a morpholine ring, etc.). R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms (for example, a methyl group, an ethyl group, a butyl group, etc.), but is preferably substituted. Preferred examples of the substituent include a substituted or unsubstituted carbamoyl group and a sulfo group. X ^- represents an anion, halide ions,
Sulfonate ion, sulfate ion, ClO ₄ ⁻ , BF ₄
^- , PF _6- ^{and the} like are preferable. When R ⁶ is substituted with a sulfo group, an internal salt is formed, and X ⁻ may not be present.

These carbodiimide-based crosslinking agents are described in detail in JP-A-51-126125 and JP-A-52-48311. 10) General formula (16)

[0072]

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In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, butyl, etc.), an aryl group having 6 to 15 carbon atoms (eg, phenyl, naphthyl, etc.), or carbon Represents an aralkyl group represented by Formulas 7 to 15 (for example, a benzyl group, a phenethyl group, etc.) These groups may be substituted, and examples of the substituent include a carbamoyl group, a sulfamoyl group, and a sulfo group.
R ² and R ³ represent substitution of a hydrogen atom, a halogen atom, an acylamide group, a nitro group, a carbamoyl group, a ureido group, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. May be different. It is also preferred that R ² and R ³ combine to form a condensed ring together with the pyridinium ring skeleton.

X represents a group capable of leaving when the compound represented by the general formula (10) is reacted with a nucleophile, and preferred examples thereof include a halogen atom, a sulfonyloxy group and —OP (O) (OR ⁴ ) _2. A group represented by the formula (R ⁴
Represents an alkyl group or an aryl group. ). When X represents a sulfonyloxy group, X and R
It is also preferred that ¹ is attached.

[0075] Y ^- is represents an anion, halide ions, sulfonate ions, sulfate ion, Cl
O ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^{− and the} like are preferable. Also R ¹
Is substituted with a sulfo group to form an inner salt,
Y ^- may not exist. These pyridinium base crosslinking agents are described in detail in JP-B-58-50699, JP-A-57-44140 and JP-A-57-46538.

11) General formula (17)

[0077]

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In the formula, R ¹ and R ² are defined by the general formula (12)
Is exactly the same as the definition of R ¹ and R ² in R ³ , and R ³ is an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, butyl group, etc.) and an aryl group having 6 to 15 carbon atoms (for example, phenyl group , Naphthyl group, etc.)
15 aralkyl groups (for example, benzyl group, phenethyl group, etc.). X ^- is an anion, and includes a halide ion, a sulfonate ion, a sulfate ion, and ClO _{4
^{-, BF 4 -, PF 6}} - and the like are preferable.

The pyridinium salt-based crosslinking agent represented by the general formula (17) is described in detail in JP-A-52-54427. As the crosslinking agent used in the present invention, in addition to the compounds represented by the general formulas (7) to (17), JP-A-50-38540, JP-A-52-93470, and Compounds described in JP-A-56-43353, JP-A-58-113929, JP-A-61-9650, and U.S. Pat. No. 3,321,313 are also preferable.

Specific examples of the compound represented by the general formula (12)

[0081]

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[0082]

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[0083]

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Specific examples of the compound represented by the general formula (13)

[0085]

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Specific examples of the compound represented by the general formula (14)

[0087]

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Specific examples of the compound represented by the general formula (15)

[0089]

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Specific examples of the compound represented by the general formula (16)

[0091]

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Specific examples of the compound represented by the general formula (17)

[0093]

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Examples of compounds described in JP-A-50-38540

[0095]

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Examples of compounds described in JP-A-52-93470

[0097]

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Examples of compounds described in JP-A-56-43353

[0099]

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Examples of compounds described in JP-A-58-113929

[0101]

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Examples of compounds described in US Pat. No. 3,321,313

[0103]

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Examples of compounds described in JP-A-61-9650

[0105]

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[0106]

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[0107]

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Examples of other compounds

[0109]

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More preferred examples of the crosslinking agent in the present invention include b-3, b-6, b-7, b-10 and b-1.
3, c-1, c-2, c-3, c-6, d-3, d-
6, d-15, e-1, e-2, f-2, f-1 and the like. The preferred addition amount of the present invention is such that the amount of the polymer is 0.5 to 30% by weight and the amount of the crosslinking agent is 0.
And the polymer is preferably 1 to 10%.
15% by weight and 0.1 to 5% of a crosslinking agent.

When the unreacted functional group of the polymer or compound of the present invention hinders the subsequent battery reaction, it can be removed by an appropriate treatment (heating, washing with a solvent, etc.). The active material that can be used in the present invention may be any electrode material. In particular, for a lithium secondary battery, an inorganic compound positive electrode or an active material containing a Co oxide (JP-A-52-12424, DE2, 606,915, etc.), Li-Co oxide (US Pat. No. 3,945,848, U
S4, 340, 652), Li-Ni-Co oxide (EP243,926A, JP-A-63-114,066)
3, 63-211,565, 63-299,05
6, JP-A-1-120,765, etc.), V oxide (FR
21, 611, 796, JP-A-55-53,077, JP-A-62-140,362, JP-A-62-227,358, etc.), Li-V oxide (Electrochemical, Vol. 48, 432 (1)
980), Journal of Electrochemical Society, Vol. 130, No. 1225 (1983), JP-A No. 2-12,769), Mn oxide (EP 269,8)
55, JP-A-63-58,761, etc.) and Li-Mn oxides (JP-A-56-136,464, 114,06).
4, 114,065, 148,550, 221
559, JP-A Nos. 1-5,459 and 1-109,66
2, 1-128, 371, 1-109, 663, 2-27,660), and Li-Ni-Mn oxides (JP-A-63-210,028, etc.).

In the alkaline secondary battery, a Ni compound is generally used. (“Battery Handbook” published by Denki Shoin) Also, among the organic polymer positive electrode active materials, polyaniline derivatives (Molecular, Crystal and Liquid Crystal, 121, 173 (1985), JP-A-60-197,728, 63-46) , 223, 63
243, 131, JP-A-2-219,823),
Pyrrole derivatives (Journal of Chemical Society Chemical Communication 854 (19
79), DE 3,223,544A3A, 307,9
54A, JP-A-62-225517, 63-69,
824, JP-A-1-170,615, etc., polythiophene derivatives (JP-A-58-187,432, Japanese Patent Publication No.
12,775), polyacene derivatives (JP-A-58-1983)
209, 864) and polyparaphenylene derivatives. Each derivative includes a copolymer.

The organic polymer compound is described in detail in "Conductive Polymer", Naoya Ogata, Kodansha Scientific (1990). As a secondary battery negative electrode active material that can contain the compound of the present invention,
In a lithium secondary battery, a calcined carbonaceous compound capable of occluding lithium ions or lithium metal (JP-A-58-20)
9,864, 61-214,417, 62-88,
268, 62-216, 170, 63-13, 28
2, 63-24,555, 63-121,247,
63-121, 257, 63-155, 568, 63-276, 873, 63-314, 821, JP-A-1-204,361, 1-221,859, 1-
274, 360, etc.).

When the compound of the present invention is added to the calcined carbonaceous compound, for example, by adding a compound which reacts with a hydroxyl group such as an isocyanate group, a group which reacts with lithium contained in the compound of the present invention is lost. It is preferable to activate. As a negative electrode active material for a secondary battery that can contain the compound of the present invention, a nickel-hydrogen secondary battery includes a hydrogen storage alloy ("Hydrogen storage alloy", published by Yono Shobo).

The electrode mixture can usually contain a conductive material such as carbon, silver (JP-A-63-148,554) or polyphenylene derivative (JP-A-59-20,971). As the negative electrode active material of the lithium secondary battery used together with the positive electrode mixture of the present invention, in the case of a lithium secondary battery, lithium metal, lithium alloy (A
1, Al-Mn (U.S. Pat. No. 4,820,599), Al
-Mg (JP-A-57-98977), Al-Sn (JP-A-63-6,742), Al-In, Al-Cd (JP-A-1-144,573) and the like.

As the electrolyte, propylene carbonate, ethylene carbonate, diethylene carbonate,
γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolan, formamide, dimethylformamide, dioxolan, acetonitrile, nitromethane, phosphate triester (JP-A-6
0-23,973), trimethoxymethane (JP-A-61
-4,170), a dioxolane derivative (JP-A-62-1)
5,771, 62-22,372, 62-108,
474), sulfolane (JP-A-62-31959),
3-Methyl-2-oxazolidinone (JP-A-62-4)
4,961), propylene carbonate derivatives (JP-A-62-290,069 and JP-A-62-290,071), and tetrahydrofuran derivatives (JP-A-63-3287).
2), ethyl ether (JP-A-63-62166),
1,3-propane sultone (JP-A-63-10217)
3) a solvent in which at least one or more aprotic organic solvents are mixed and a lithium salt soluble in the solvent, for example, ClO ₄ ⁻ , BF ₆ ⁻ , PF ₆ ⁻ , CF ₃ S
O ₃ ⁻ , CF ₃ CO ₂ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , B
₁₀ C ₁₀ (JP-57-74,974), (1,2-dimethoxyethane) 2ClO ₄ ^- (JP 57-74,97
7), lower aliphatic carboxylate (JP-A-60-41,7
73), AlCl ₄ ⁻ , Cl ⁻ , Br ⁻ , I ⁻ (JP-A-60-247,265), chloroborane compounds (JP-A-61-165957), tetraphenylboric acid (JP-A-6-1987)
1-214, 376). In particular, LiClO ₄ or LiBF is added to a mixed solution of propylene carbonate and 1,2-dimethoxyethane.
_An electrolyte containing ₆ is typical.

In addition to the electrolytic solution, the following solid electrolyte can be used. Solid electrolytes are classified into inorganic solid electrolytes and organic solid electrolytes. Well-known inorganic solid electrolytes include nitrides, halides, and oxyacid salts of Li. Among them, Li ₃ N, LiI, Li ₅ N
_{I 2, Li 3 N-LiI} -LiOH, LiSiO 4, L
iSiO ₄ -LiI-LiOH (JP-A-49-811.8)
_{99), xLi 3 PO 4 -} (1-x) Li 4 SiO
₄ (JP-A-59-60,866), Li ₂ SiS ₃ (JP-A-60-501,731), phosphorus sulfide compound (JP-A-62-82,665) and the like are effective.

As the organic solid electrolyte, a polyethylene oxide derivative or a polymer containing the derivative (JP-A-63-1)
35,447), a polypropylene oxide derivative or a polymer containing the derivative, and a polymer containing an ion dissociating group (Japanese Patent Application Laid-Open Nos. 62-254,302 and 62-254,30).
3, 63-193, 954), a mixture of a polymer containing an ion-dissociating group and the aprotic electrolyte (U.S. Pat. Nos. 4,792,504 and 4,830,939;
2-22,375, 62-22,376, 63-2
2,375, 62-22,776, JP-A-1-95,
117), phosphate ester polymer (Japanese Patent Laid-Open No. 61-25 / 1986)
6,573) is effective. Furthermore, there is also a method of adding polyacrylonitrile to an electrolytic solution (Japanese Patent Application Laid-Open No. Sho 62-27).
8,774). In addition, a method using both an inorganic and an organic solid electrolyte is also known (JP-A-60-1768).

The separator has a high ion permeability,
An insulating thin film having a predetermined mechanical strength. Olefin-based nonwoven fabrics such as polypropylene and glass fibers are used because of their organic solvent resistance and hydrophobicity. It is known that the following compounds are added to an electrolyte for the purpose of improving discharge and charge / discharge characteristics. For example, pyridine (JP-A-49-108,525), triethylphosphite (JP-A-47-4,376), triethanolamine (JP-A-52-72,425), cyclic ether (JP-A-57-725,425) 152,684), ethylene diamine (JP-A-58-87,777), n-glyme (JP-A-58-87,778), hexaphosphoric triamide (JP-A-58-87,779), nitrobenzene derivative (JP-A-58-87,779) 58-214, 281), sulfur (Japanese Unexamined Patent Application Publication No.
80), quinone imine dyes (JP-A-59-68,18)
4), N-substituted oxazolidinone and N, N'-substituted imidazolidinone (JP-A-59-154778), ethylene glycol dialkyl ether (JP-A-59-20)
5,167), quaternary ammonium salts (JP-A-60-3)
0,065), polyethylene glycol (JP-A-60-1985)
41,773), pyrrole (JP-A-60-79,67).
7), 2-methoxyethanol (JP-A-60-89,0)
75), AlCl ₃ (JP-A-61-88,466), a monomer of a conductive polymer electrode active material (JP-A-61-16)
1,673), triethylene phosphoramide (JP-A-6
1-208,758), trialkylphosphine (JP-A-62-80,976), morpholine (JP-A-62-80,976).
80,977), aryl compounds having a carbonyl group (JP-A-62-86,673), hexamethylphosphoric triamide and 4-alkylmorpholine (JP-A-6-8663).
2-217,575), bicyclic tertiary amines (Japanese Unexamined Patent Publication No.
2-217,578), oil (JP-A-62-287,
580), quaternary phosphonium salts (JP-A-63-121,
268), tertiary sulfonium salts (JP-A-63-121,
269).

Further, in order to make the electrolytic solution nonflammable, a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride chloride can be contained in the electrolytic solution. (Japanese Patent Laid-Open No. 48-36,
632) In addition, carbon dioxide can be included in the electrolytic solution to make it suitable for high-temperature storage. (JP-A-59-1344.5)
67) Further, the positive electrode active material can contain an electrolytic solution or an electrolyte. For example, the addition of the ionic conductive polymer, nitromethane (JP-A-48-36,633), and an electrolytic solution (JP-A-57-124,870) is known.

The surface of the positive electrode active material can be modified. For example, the surface of a metal oxide is treated with an esterifying agent (JP-A-55-163779), a chelating agent (JP-A-55-163780), and a conductive polymer (JP-A-5-163780).
8-163,188, 59-14, 274) and polyethylene oxide (JP-A-60-97,561).

The surface of the negative electrode active material can be modified. For example, a method of providing an ion-conductive polymer or a polyacetylene layer (JP-A-58-111276);
iCl (JP-A-58-142,771) and treatment with ethylene carbonate (JP-A-59-31,573). As a carrier for the electrode active material, in addition to ordinary stainless steel, nickel, and aluminum, a porous foamed metal (JP-A-59-18,578) and titanium (JP-A-59-68,169) , Expanded metal (JP-A-61-264,686), punched metal, and negative electrode include porous nickel (JP-A-58-18, JP-A-58-18) in addition to ordinary stainless steel, nickel, titanium, and aluminum.
883), porous aluminum (JP-A-58-38,4).
66), aluminum sintered body (JP-A-59-130,0)
74), a molded product of an aluminum fiber group (Japanese Unexamined Patent Publication No.
48,277), the surface of stainless steel is silver-plated (JP-A-60-41,761), calcined carbonaceous materials such as phenol resin calcined bodies (JP-A-60-112,264), Al
-Cd alloy (JP-A-60-211,779), porous foamed metal (JP-A-61-74,268) and the like are used.

The current collector may be any electronic conductor that does not cause a chemical change in the constructed battery. For example, in addition to commonly used stainless steel, titanium and nickel, nickel-plated copper (JP-A-48-3662)
7) For copper titanium plating and sulfide positive electrode active material, stainless steel is treated with copper (JP-A-60-175,3).
73) and the like.

The shape of the battery can be applied to any of coins, buttons, sheets, cylinders, squares and the like.

[0125]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. Example 1 V ₆ O ₁₃ as a positive electrode active material and 88 parts by weight and 6 parts by weight of acetylene black as a conductive agent were mixed at a ratio of 4 parts by weight and 2 parts by weight, respectively, as a binder. After adding and kneading a solution of a polymer and a compound (crosslinking agent), the mixture was applied to both surfaces of a 20 μm-thick aluminum foil current collector. As a solvent of the solution, a solvent in which a binder such as water, acetone, and toluene was soluble was used. The coated material was dried and compression-molded by a roller press to prepare a belt-shaped positive electrode sheet (1). FIG. 1 shows the positive electrode sheet 1. The thickness of the positive electrode sheet after compression molding is 220 μm
Met. Table 1 shows the binder of the present invention used and the binder of the comparative example.

A negative electrode sheet (2) was prepared by cutting a lithium-aluminum alloy (alloy ratio: 80 to 20% by weight, thickness: 150 μm) into a belt shape. The positive electrode (1), the microporous polypropylene film separator (3), the negative electrode sheet (2) and the separator (3) are laminated in this order,
This was spirally wound. At this time, Comparative Examples 13 and 1
In 4 and 15, the active material was partially peeled off, but this was not the case with the product of the present invention.

This wound body was housed in a nickel-plated iron bottomed cylindrical battery can (4) also serving as a negative electrode terminal. Further, 1 mol / liter LiB is used as an electrolyte.
F ₄ (a mixture of equal volumes of propylene carbonate and 1,2-dimethoxyethane) was injected into the battery can. A battery lid (5) having a positive electrode terminal was caulked via a gasket (6) to produce a cylindrical battery. The positive electrode terminal (5) was connected to the positive electrode sheet (1), and the battery can (4) was connected to the negative electrode sheet by a lead terminal in advance. FIG. 1 shows a cross section of a cylindrical battery. In addition, 7 is a safety valve.

For this battery, the electrode density was 1 mA / cm ²
The charge and discharge cycle test was performed by repeating the operation of discharging to 2.4 V and then charging to 3.4 V.

[0129]

[Table 1]

* Polymer of Comparative Example Z-1: polytetrafluoroethylene Z-2: ethylene-propylene-dicyclopentadiene copolymer Example 2 The above-mentioned pitch coke 90 was prepared by using pulverized coal-based pitch coke as a negative electrode active material. 7 and 3 parts by weight of the polymer and the compound of the present invention, respectively, as a binder were added to the parts by weight, and an appropriate solvent such as toluene, acetone or the like was added and kneaded to obtain a slurry having a thickness of 20 μm. Was applied. After drying the applied material, it was compression-molded by a roller press machine to prepare a 230 μm-thick negative electrode sheet.

As the positive electrode active material, Li _0.5 Co _0.5 V _0.5
0 _2.5 88 parts by weight and acetylene black as a conductive agent in a ratio of 6 parts by weight were mixed together.
6 parts by weight of Z-2 or the polymer a of the present invention
A positive electrode sheet was prepared in the same manner as in Example 1, using a combination of 4 parts by weight of -1 and 2 parts by weight of compound b-3 and kneading with a toluene or acetone solvent. The positive electrode sheet using Z-2 as a binder was (A), a-1
And (B) a positive electrode sheet using b-3.

Using the above-mentioned negative electrode sheet and positive electrode sheet, a cylindrical battery was produced in the same manner as in Example 1. * Polymer of Comparative Example Z-3: polyvinylidene fluoride Z-4: trifluorochloroethylene-vinylidene fluoride copolymer The results of the charge / discharge cycle test of the binder and the battery of the present invention used in Example 2 are shown in the table. 2 is shown. The test conditions are the same as in Example 1.

[0133]

[Table 2]

[0134]

As is apparent from Examples 1 and 2, the electrode using the binder of the present invention prevents the active material from falling off, and has a considerably long life of the charge / discharge cycle in the secondary battery. Excellent discharge cycle characteristics. The electrode using the binder of the present invention may be only a positive electrode or a negative electrode, or may be used for both electrodes.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a general cylindrical battery.

[Explanation of symbols]

 1. 1. positive electrode Negative electrode 3. Separator 4. Battery can 5. Battery cover 6. Gasket 7. safety valve

Claims (14)

(57) [Claims] 1. A chemical battery comprising a positive electrode active material, a negative electrode active material, and an electrolyte having ion conductivity, wherein the binder has no ethylenically unsaturated group, and has no ethylenically unsaturated group.
A battery comprising a polymer having a functional group other than the above and a compound having at least two functional groups capable of reacting with the functional group of the polymer in one molecule in the positive electrode mixture and / or the negative electrode mixture. . 2. The chemical battery according to claim 1, wherein the functional group of the compound comprises at least one of a group of functional groups represented by Formula 1. Formula 1 (However, R ¹ , R ² , R ³ , and R ⁴ are a hydrogen atom, a carbon atom 1
X represents an alkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group, and X represents a linking group -O- or -N
(R ⁵⁾ - represents, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or aralkyl group having 6 to 12 carbon atoms. Y and Z each represent a halogen, an alkoxy group or a salt thereof or an amino group which may be substituted, and at least one of Y and Z is a halogen. ) 3. The method according to claim 1, wherein the functional group of the polymer is -OH,-
COOH, at least one of: Formula 2, Formula 3, -NH ₂
Cell of claim 1, wherein the consist like. Formula 2 Formula 3 4. The method according to claim 1, wherein the functional group contained in the polymer is -OH.
In chemical batteries according to claim 1, wherein the functional group to which the compound has is characterized in that a functional group represented by the formula 2. 5. The method according to claim 1, wherein the functional group contained in the polymer is —OH.
Wherein the functional group contained in the compound is —NHCH ₂ OR (where R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an aralkyl group having 6 to 12 carbon atoms). The chemical battery according to claim 1, wherein: 6. The polymer according to claim 1, wherein the functional group contained in the polymer is —OH.
The chemical battery according to claim 1, wherein the functional group contained in the compound is -NCO. 7. The method according to claim 1, wherein the functional group contained in the polymer is —COO.
2. The chemical battery according to claim 1, wherein the functional group contained in the compound in H is a functional group represented by Formula 2. 8. The chemical batteries according to claim 1, wherein the functional group containing functional group of the polymer contains the said compound with a functional group represented by formula 3, characterized in that the formula 2. 9. The functional group contained in the polymer is a functional group represented by Formula 2, and the functional group contained in the compound is H _2.
N-R-NH ₂ (where R is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms or an aralkylene group). Item 6. The chemical battery according to Item 1. 10. The functional group contained in the polymer is represented by formula 2
The chemical battery according to claim 1, wherein the functional group contained in the compound is -OH. 11. The functional group contained in the polymer is —O
In H, functional groups contained the compound -SO ₂ CH = C
_2. The chemical battery according to claim 1, wherein the chemical battery is H2. 12. The method according to claim 1, wherein the functional group contained in the polymer is —O
The chemical battery according to claim 1, wherein in H, the functional group contained in the compound is a functional group represented by Formula 4. Formula 4 However, Y and Z represent a halogen and an alkoxy group having 1 to 6 carbon atoms, and at least one of Y and Z is a halogen,
X represents a linking group -O- or -NR-, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a C 6 to 12
Represents an aryl group or an aralkyl group. 13. The method according to claim 13, wherein the functional group contained in the polymer is —N
_2. The chemical battery according to claim 1, wherein in H ₂ , the functional group contained in the compound is a functional group represented by Formula 2. 3. 14. The chemical battery according to claim 1, wherein the main chain of the polymer is a sugar chain.