JPH0696770A - Chemical battery - Google Patents

Abstract

PURPOSE:To prevent the dropping-out of an active material and provide satisfactory characteristic by containing a polymer having a functional group and a compound having, in one molecule, at least two functional groups reactive with the polymer having the functional group in a positive electrode mix and/or negative electrode mix. CONSTITUTION:Determined functional groups are shown by a formula. A polymer having at least one of them is used. In the formula, R<1>, R<2>, R<3>, R<4> represent H, C1-C6 alkyl groups, C6-C12 aryl groups, or aralkyl groups, X represents a connecting group -O- or -N(R<5>)-, and R<5> represents H, a C1-C6 alkyl group or a C6-C12 aralkyl group. Y, Z represents amino groups which may be substituted by alkoxy groups or their salts, and at least one of Y and Z is a halogen. The functional group possessed by the compound is at least one kind of the groups, which is reacted with the polymer and chemically connected thereto. When this compound is contained in a positive electrode mix and/or negative electrode mix, the dropping-out of an electrode active material is prevented in a chemical battery, and satisfactory charge/discharge characteristic can be provided.

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 in which charge and discharge cycle characteristics are improved by using an electrode in which an 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 and carboxymethyl cellulose are used as binders for electrode active materials (JP-A-1-175171 and JP-A-1-105471). , JP-A-51-5538, 50-2
6500), hydroxypropyl cellulose (JP-A-63-245859, JP-A-54-49541), regenerated cellulose (JP-A-61-91872), polyvinyl chloride, polyvinyl pyrrolidone, etc. are used, and non-aqueous materials such as lithium batteries are used. Teflon or the like is generally used in the electrolytic solution. (“Battery Handbook” published by Denki Shoin, 1980) In particular, in a secondary battery, the positive electrode or the negative electrode repeatedly expands or contracts in volume during charging and discharging, so that active material particles and conductive agents fall off, resulting in a short charge and discharge cycle life. However, the selection of a binder is important as a means for preventing this. However, the above-mentioned binder was insufficient to prevent the active material and the like from falling off. On the other hand, JP-A-3-1082
No. 63 discloses a positive electrode binder that prevents the active material from falling off, and it is stated that the charge / discharge cycle life is improved. However, the binder has an affinity for aqueous and non-aqueous electrolytes. Poor, low utilization of active material, and insufficient charge / discharge cycle life. Further, there is a drawback that the internal resistance remarkably increases when the added amount is increased.

As described above, the charge / discharge cycle life and the utilization rate of the active material (that is, the discharge capacity) are contradictory performances, and a binder technology that makes them compatible has been desired. In addition, as for the primary battery, a lithium battery adopts a spiral structure in which a sheet-shaped electrode is wound in order to reduce the internal resistance. Some are made of metal foil. However,
If the adhesion of the coating of the active material coated on the current collector is weak, the active material may peel off or fall off during battery assembly such as winding, resulting in many defective products. A binder is a factor that improves the adhesive strength between the active material and the current collector. Japanese Patent Laid-Open No. 3-222258 discloses a binder that improves the adhesive strength, but its performance is still insufficient.

[0004]

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 above-mentioned object is to provide a polymer having a functional group as a binder and a reaction with the functional group of the polymer in a chemical battery comprising a positive electrode active material, a negative electrode active material, and an electrolyte having ion conductivity. This could be achieved by incorporating a compound having at least two possible functional groups in one molecule into the positive electrode mixture and / or the negative electrode mixture.

The functional groups contained in the polymer and the compound include, for example, functional groups represented by the formula 1. The reaction of these polymers with polyfunctional compounds having two or more functional groups is commonly known as the cross-linking reaction of polymers, thereby forming a three-dimensional network of polymers.

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]

[Chemical 5]

(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,
A residue containing an aryl group, an aralkyl group, or a functional group described in Formula 1, wherein one or two of R ¹ , R ² , R ³ , and R ⁴ is a functional group represented by Formula 1. It is a residue that has. ) ・ General formula (2)

[0010]

[Chemical 6]

(However, in the formula, R ¹ , R ² , R ³ , R ⁴ , R
⁵ , R ⁶ , R ⁷ and R ⁸ are a hydrogen atom, a hydroxyl group and a carbon number of 1 to
6 is a hydroxyalkyl group, an acyloxy group, an acyloxymethyl group, an alkyl group, an alkoxy group, a carboxyalkyl group or a residue having the functional group represented by Formula 1. ) ・ General formula (3)

[0012]

[Chemical 7]

However, in the formula, L ₁ represents an alkylene group having 1 to 12 carbon atoms, L ₂ represents an arylene group or an alkylarylene group having 6 to 12 carbon atoms, and has a functional group represented by the formula 1 as a substituent. - Formula ^{(4) - (NR 1 -L} 1 -NR 1 -CO-L 2 -CO) - 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, and contains a functional group of formula 1. - 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, and contains a functional group of the formula 1. -General formula (6)-(L-O)-However, L is a C2-C6 alkylene group and C6 in the formula.
~ 12 represents an arylene group or an alkylarylene group, and contains the functional group shown in Formula 1.

Among the above general formulas, the more preferable structure is the general formula (1) or (2). Examples of the polymer used in the present invention include natural or semisynthetic polymers such as cellulose having a hydroxyl group (-OH) and its derivatives, that is, cellulose acetate having a degree of substitution of less than 3, cellulose acetate butyrate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose and the like. And polymers of hydroxyethylmethacrylate alone or with other monomers and synthetic polymers such as polyvinyl alcohol and polyvinyl butyral.

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

The constitutional units of the polymer having other functional groups are shown below, but these may be copolymerized with other monomers, and may have two or more functional groups. The present invention is not limited to these.

[0017]

[Chemical 8]

Examples of the monomer copolymerizable with the above-mentioned reactive functional group-containing monomer include ethylene, propylene, butadiene, styrene, acrylonitrile, ethylidene norbornene, 1,4-hexadiene, dicyclopentadiene and methyl vinyl ether. ,
Examples include N-vinylpyrrolidone, methyl methacrylate, butyl acrylate, vinyl acetate, vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylidene fluoride.

The above-mentioned polymers are all polymers of ethylenically unsaturated compounds, but they may be polymers containing other heteroatoms in the polymer main chain and containing reactive functional groups in their side chains. Examples thereof include polymers having at least one of polyester, polyamide, polyether, polyurethane, polyurea, polysulfone, polyimine, and polysiloxane as a main chain. Also,
The preferred molecular weight of the polymer used in the present invention is 5,000.
~ 1,000,000.

Next, more preferable examples of the polymer according to the present invention will be shown, but the polymer is not limited thereto.

[0021]

[Chemical 9]

[0022]

[Chemical 10]

The "compound having at least two sites capable of reacting with the functional group of the polymer in one molecule" in the present invention is generally called a crosslinking agent or a curing agent, and the reaction between the polymer and the crosslinking agent. To form a three-dimensional network structure.
As a preferable reaction, there is a reaction represented by the following formula.

[0024]

[Chemical 11]

Among these, a particularly preferable reaction is
,,and so on. Any combination of these reactive functional groups may be contained 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]

[Chemical 12]

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 more bonds represented by R-, -NRCOO-, and -OP (OR) (O) O-. R is a hydrogen atom, 1 to 1
It represents an alkyl group, an aryl group or an aralkyl group having a pentavalent carbon atom.

Further, -NR-, -CONR-, -SO ₂ N
When two or more R- and -NRCOO- are included, those R
May be the same or different, and 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, an alphamoyl group, an alkyl group and an aryl group. Further, the substituent is represented by the above formula 2
One or a plurality of groups represented by may be included. The following can be mentioned as a typical example of L.

[0029]

[Chemical 13]

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, and is particularly preferably 2.
d and g are numbers from 0 to 100, and preferably 0 to 20.
Specific examples of the compound represented by the general formula (7) are shown below.

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

2) General formula (8)

[0035]

[Chemical 17]

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.
R ¹ and R ² are preferably 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 are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and 6 to 1 carbon atoms
It is an aryl group of 0 and may be substituted. As the substituent, a halogen atom, an alkoxy group, an aryloxy group and the like are preferable. Further, R ³ and R ⁴ may combine to form a ring.

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

[0038]

[Chemical 18]

3) General formula (9) X ¹ -SO ₂ -L-SO ₂ -X ^{2 In the} above general formula, X ¹ and X ² are -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 which is substituted by a nucleophilic group or which can be eliminated by a base in the form of HY (eg, halogen atom, sulfonyloxy, sulfuric acid monoester, etc.). L is a divalent linking group and may be substituted.

Specific examples of X ¹ and X ² include 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, an alkyl group having 1 to 15 carbon atoms, an aralkyl group, or an aryl group.
Or, -NR ^1- , -SO ₂ NR ^1- , -CONR
_When two or more ^1- and -NR ¹ CO ₂ -are contained, their R ^{1 s} may be the same or different.
Also, they may be bonded to 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 with 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 example may be an integer of 1 to 10, and only d may be 0. y is an integer of 2 to 6.

[0042]

[Chemical 19]

Of these, d, k, l, p and u are 1 to 3
Is preferable, and those other than d, k, l, p and u of a to x are preferably 1 or 2. Further, y is preferably 2. R ¹ is a hydrogen atom or 1 to 6
Alkyl groups having 4 carbon atoms are preferred, with hydrogen, methyl and ethyl groups being especially preferred. Regarding the vinyl sulfone compounds represented by the general formula (9), for example, JP-B-47-24259 and 50-358.
07, JP-A-49-24435 and JP-A-53-4122.
No. 1, No. 59-18944 and the like have detailed descriptions.

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

[0045]

[Chemical 20]

[0046]

[Chemical 21]

4) General formula (10)

[0048]

[Chemical formula 22]

In the formula, R ¹ is a hydroxyl group, —OM (M group is a monovalent metal atom), alkyl group, —N (R ² ) R ³ group (R ² and R ³ are 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 a methyl group, an ethyl group, a butyl group or the like, and the alkoxy group is preferably a methoxy group, an ethoxy group or a butoxy group. The -N (R ₂₎ Examples of R ₃ groups -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 a sodium atom, a potassium atom or the like.

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

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

[0052]

[Chemical formula 23]

5) General formula (11)

[0054]

[Chemical formula 24]

In the formula, R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms,
It represents an alkyl group, an aryl group or an aralkyl group, and 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 preferable, and a hydrogen atom is particularly preferable.

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

[0057]

[Chemical 25]

6) General formula (12)

[0059]

[Chemical formula 26]

In the formula, R ¹ and R ² are each an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, 2-ethylhexyl group, etc.), aryl group having 6 to 15 carbon atoms (eg, phenyl group, naphthyl group). Etc.) or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl group, phenethyl group, etc.), and they may be the same or different. It is also preferable that R ¹ and R ² are bonded to each other to form a heterocycle with a nitrogen atom. Examples of forming a ring 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, an 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 sulfooxy group, a sulfoamino group and a ureido group. X ⁻ represents an anion and serves as a counter ion of the N-carbamoylpyridinium salt. When the substituent of R ³ contains a sulfo group, a sulfooxy group or a sulfoamino group, it may form an inner salt and X ⁻ may not be present. As a preferable example of the anion, a detailed description of a carbamoyl ammonium salt-based cross-linking agent represented by the general formula (12) such as halide ion, sulfate ion, sulfonate ion, ClO ₄ ⁻ , BF ₄ ⁻ , and PF ₆ ⁻ is given. Japanese Patent Publication Sho 56-1285
3, JP-A-58-32699, JP-A-49-51945.
No. 51-59625 and 61-9641.

7) General formula (13)

[0062]

[Chemical 27]

[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]

[Chemical 28]

R ¹ , R ² , R ³ and R ⁴ have 1 to 1 carbon atoms.
20 alkyl groups (eg, methyl group, ethyl group, butyl group, 2-ethylhexyl group, dodecyl group, etc.), aralkyl groups having 6 to 20 carbon atoms (eg, benzyl group, phenethyl group, 3-pyridylmethyl group), or Carbon number 5
20 aryl groups (eg, 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, and examples of the substituent include a halogen atom, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. Group, N, N-disubstituted carbamoyl group and the like.

It is also preferable that any ^{two of} R ¹ , R ² , R ³ and R ⁴ are bonded to form a ring. For example, R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form a ring together with a nitrogen atom, which may be a pyrrolidine ring, a piperazine ring, a perhydroazepine ring or a morpholine ring. Examples of R ¹ and R ³ or R ² and R ^{4 which} are bonded to each other to form a ring with two nitrogen atoms and a carbon atom sandwiched between them include an imidazoline ring, a tetrahydropyrimidine ring and a tetrahydrodiazepine. Examples include the case of forming a ring.

X represents a group capable of leaving when the compound represented by the general formula (14) reacts with a nucleophile, and preferable examples thereof include a halogen atom, a sulfonyloxy group and 1
-Pyridiniumyl group and the like. Y ⁻ represents an anion, and a halide ion, a sulfonate ion, a sulfate ion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^{− and the} like are preferable. When Y ⁻ represents a sulfonate ion, it may combine with X, R ¹ , R ² , R ³ or R ⁴ to form an inner 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]

[Chemical 29]

In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, 2-ethylhexyl group), a cycloalkyl group having 5 to 8 carbon atoms (eg, cyclohexyl group), carbon number 3-10 alkoxyalkyl groups (eg methoxyethyl group) or 7 carbon atoms
Represents an aralkyl group of ˜15 (eg, benzyl group, phenethyl group, etc.). In addition to the group defined for R ¹ , R ² is preferably a group represented by —R ³ (R ⁴ ) N (R ⁵ ) R ^{6 +} X ⁻ . R ³ represents an alkylene group having 2 to 4 carbon atoms (for example, ethylene group, propylene group, trimethylene group, etc.). R ⁴ and R ⁵ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, etc.). Also, R ⁴ and R ⁵
Is preferably bonded to form a heterocycle (eg, pyrrolidine ring, piperazine ring, morpholine ring, etc.) together with the nitrogen atom. 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 it is also preferably substituted. As examples of the substituent, a substituted or unsubstituted carbamoyl group, a sulfo group and the like are preferable. X ⁻ represents an anion, a halide ion,
Sulfonate ion, a sulfate ion, ClO ₄ ^-, BF ₄
^-, PF ₆ ^- and the like are preferable. When R ⁶ is substituted with a sulfo group, it may form an inner salt and X ⁻ may not be present.

Details of these carbodiimide type crosslinking agents are described in JP-A-51-126125 and JP-A-52-48311. 10) General formula (16)

[0072]

[Chemical 30]

In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, butyl group), an aryl group having 6 to 15 carbon atoms (eg, phenyl group, naphthyl group), or carbon It represents an aralkyl group of formulas 7 to 15 (eg, benzyl group, 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 a hydrogen atom, a halogen atom, an acylamido 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, and the like, and each is the same. It can be different. It is also preferable that R ² and R ³ are bonded to each other 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) reacts with a nucleophile, and a preferable example thereof is a halogen atom, a sulfonyloxy group or --OP (O) (OR ⁴ ) ₂ A group represented by (R ⁴
Represents an alkyl group or an aryl group. ) Can be given. When X represents a sulfonyloxy group, X and R
It is also preferred that ¹ is attached.

Y ⁻ represents an anion, and is a halide ion, sulfonate ion, sulfate ion, Cl
O ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^{− and the} like are preferable. Also R ¹
When is substituted with a sulfo group, it forms an inner salt,
Y ⁻ does not have to 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]

[Chemical 31]

In the formula, R ¹ and R ² are defined by the general formula (12).
Are exactly the same as the definitions of R ¹ and R ² in R ³ , and R ³ is an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, butyl group, etc.), aryl group having 6 to 15 carbon atoms (eg, phenyl group). , Naphthyl group) or having 7 to 7 carbon atoms
Represents 15 aralkyl groups (eg, benzyl group, phenethyl group, etc.). X ⁻ is an anion, which is a halide ion, a sulfonate ion, a sulfate ion, 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 above general formulas (7) to (17), JP-A-50-38540, JP-A-52-93470, and JP-A-52-93470, The compounds described in JP-A-56-43353, JP-A-58-113929, JP-A-61-9650 and US Pat. No. 3,321,313 are also preferable.

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

[0081]

[Chemical 32]

[0082]

[Chemical 33]

[0083]

[Chemical 34]

Specific examples of the compound according to the general formula (13)

[0085]

[Chemical 35]

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

[0087]

[Chemical 36]

Specific examples of the compound according to the general formula (15)

[0089]

[Chemical 37]

Specific examples of the compound according to the general formula (16)

[0091]

[Chemical 38]

Specific examples of the compound according to the general formula (17)

[0093]

[Chemical Formula 39]

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

[0095]

[Chemical 40]

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

[0097]

[Chemical 41]

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

[0099]

[Chemical 42]

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

[0101]

[Chemical 43]

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

[0103]

[Chemical 44]

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

[0105]

[Chemical formula 45]

[0106]

[Chemical formula 46]

[0107]

[Chemical 47]

Other examples of compounds

[0109]

[Chemical 48]

More preferred examples of the crosslinking agent in the present invention are 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 0.5 to 30% by weight of the polymer and 0.
05-10%, more preferably 1-
15% by weight, and the crosslinking agent is 0.1 to 5%.

When the unreacted functional group of the above-mentioned polymer or compound of the present invention interferes with 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, but especially for lithium secondary batteries, among inorganic compound positive electrodes or active materials, Co oxides (JP-A-52-12,424, DE2, 606,915), Li-Co oxide (US3,945,848, U)
S4, 340, 652), Li-Ni-Co oxide (EP243,926A, JP-A-63-114,06).
3, the same 63-211,565, the same 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 (electrochemistry 48, 432 (1).
980), Journal of Electrochemical Society, Volume 130, 1225 (1983), JP-A 2-12,769, etc.), Mn oxide (EP 269,8).
55, JP-A-63-58, 761 and the like), Li-Mn oxides (JP-A-56-136,464, 114,06).
4, the same 114,065, the same 148,550, the same 221,
559, Japanese Patent Application Laid-Open Nos. 1-5,459 and 1-109,66.
2, the same 1-128,371, the same 1-209,663, the same 2-27,660), Li-Ni-Mn oxides (JP-A-63-210,028, etc.) and the like.

In addition, Ni compounds are generally used in alkaline secondary batteries. ("Battery Handbook" published by Denki Shoin) In addition, among 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, etc.),
Pyrrole derivatives (Journal of Chemical Society Chemical Communication 854 (19
79), DE 3,223,544A3A, and 307,9.
54A, JP-A-62-225,517, 63-69,
824, JP-A-1-170,615, etc.), polythiophene derivatives (JP-A-58-187,432, JP-B-1-
12,775, etc.), polyacene derivatives (JP-A-58-58)
209, 864, etc.), polyparaphenylene derivatives and the like. Each derivative also includes a copolymer.

This organic polymer compound is described in detail in "Conductive Polymer", edited by Naoya Ogata, published by Kodansha Scientific (1990). The 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, 63-28.
2, the same 63-24, 555, the same 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).

When the compound of the present invention is added to this calcined carbonaceous compound, the group reactive with lithium contained in the compound of the present invention is eliminated by adding a compound which reacts with a hydroxyl group such as an isocyanate group. It is preferable to activate it. Examples of the secondary battery negative electrode active material that can contain the compound of the present invention include a hydrogen storage alloy (“hydrogen storage alloy”, published by Yono Shobo) in nickel-hydrogen secondary batteries.

The electrode mixture may usually contain a conductive material such as carbon, silver (JP-A-63-148,554) or polyphenylene derivative (JP-A-59-20,971). Examples of the negative electrode active material of the lithium secondary battery used with the positive electrode mixture of the present invention include lithium metal and lithium alloy (A
1, Al-Mn (US 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-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, phosphoric acid triester
0-23,973), trimethoxymethane (JP-A-61-61)
-4,170), 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, JP-A-62-290,071), and tetrahydrofuran derivatives (JP-A-63-32,87).
2), ethyl ether (JP-A-63,62,166),
1,3-propane sultone (Japanese Patent Laid-Open No. 63-102,17)
3) such as aprotic organic solvent mixed with at least one kind 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 carboxylic acid salts (JP-A-60-41,7)
73), AlCl ₄ ⁻ , Cl ⁻ , Br ⁻ , I ⁻ (JP-A 60-247,265), chloroborane compound (JP-A 61-165,957), tetraphenylboric acid (JP-A 6-165).
1-214, 376) and the like. Above all, a mixture of propylene carbonate and 1,2-dimethoxyethane was mixed with LiClO ₄ or LiBF _4.
An electrolytic solution containing ₆ is typical.

In addition to the electrolytic solution, the following solid electrolytes can be used. Solid electrolytes are classified into inorganic solid electrolytes and organic solid electrolytes. Li-nitrides, halides, oxyacid salts, and the like are well known as inorganic solid electrolytes. 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-49-81,8)
_{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.

In 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, or a polymer containing an ionic dissociative group (JP-A-62-254, 302, 62-254, 30).
3, 63-193,954), a mixture of a polymer containing an ion dissociative group and the aprotic electrolytic solution (US Pat. Nos. 4,792,504, 4,830,939, JP-A-6-63).
2-22, 375, 62-2, 376, 63-2
2, 375, 62-22, 776, and JP-A-1-95,
117), a phosphoric acid ester polymer (JP-A-61-25)
6,573) is effective. Furthermore, there is also a method of adding polyacrylonitrile to the electrolytic solution (JP-A-62-27).
8,774). Also known is a method in which an inorganic and organic solid electrolyte is used in combination (JP-A-60-1,768).

The separator has a high ion permeability,
An insulating thin film having a predetermined mechanical strength. Olefin-based non-woven fabrics such as polypropylene and glass fibers are used because of their resistance to organic solvents and hydrophobicity. It is also known to add the following compounds to the 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-57-57). 152, 684), ethylenediamine (JP-A-58-87,777), n-glyme (JP-A-58-87,778), hexaphosphoric acid triamide (JP-A-58-87,779), nitrobenzene derivative (JP-A-58-87,779). 58-214,281), sulfur (JP-A-59-8,2)
80), quinone imine dyes (JP-A-59-68, 18)
4), N-substituted oxazolidinone and N, N'-substituted imidazolidinone (JP-A-59-154,778), ethylene glycol dialkyl ether (JP-A-59-20)
5,167), a quaternary ammonium salt (JP-A-60-3).
0,065), polyethylene glycol (JP-A-60-
41,773), pyrrole (JP-A-60-79,67).
7), 2-methoxyethanol (JP-A-60-89,0)
75), AlCl ₃ (JP-A-61-88,466), and a monomer of a conductive polymer electrode active material (JP-A-61-16).
1, 673), triethylenephosphoramide (Japanese Patent Laid-Open No.
1-208,758), trialkylphosphine (JP 62-80976), morpholine (JP 62-758).
80,977), an aryl compound having a carbonyl group (JP-A-62-86,673), hexamethylphosphoric triamide and 4-alkylmorpholine (JP-A-6-76).
2-217,575), a bicyclic tertiary amine (Japanese Patent Application Laid-Open No. 6-58242).
2-217, 578), oil (JP-A-62-287,
580), a quaternary phosphonium salt (JP-A-63-121,
268), a tertiary sulfonium salt (JP-A-63-121,
269) and the like.

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. (JP-A-48-36,
632) Further, carbon dioxide gas can be included in the electrolytic solution in order to have suitability for high temperature storage. (JP-A-59-134,5
67) Further, the positive electrode active material may contain an electrolytic solution or an electrolyte. For example, the above-mentioned ion conductive polymer, nitromethane (JP-A-48-36,633) and addition of an electrolytic solution (JP-A-57-124,870) are 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-55-163,779) and a chelating agent (JP-A-55-163,780), and a conductive polymer (JP-A-5-163).
8-163, 188, 59-144, and 274), and treatment with polyethylene oxide and the like (JP-A-60-97, 561).

Further, 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), L
Examples of the treatment include iCl (JP-A-58-142,771) and ethylene carbonate (JP-A-59-31,573). As the carrier for the electrode active material, for the positive electrode, in addition to ordinary stainless steel, nickel, and aluminum, porous foam metal (JP-A-59-18,578) and titanium (JP-A-59-68,169). , Expanded metal (JP-A-61-264, 686), punched metal, negative electrode, in addition to ordinary stainless steel, nickel, titanium, aluminum, porous nickel (JP-A-58-18,
883), porous aluminum (JP-A-58-38,4).
66), an aluminum sintered body (JP-A-59-130,0).
74), a molded product of an aluminum fiber group (JP-A-59-1)
48,277), silver-plated stainless steel surface (JP-A-60-41,761), fired carbonaceous material such as phenol resin fired body (JP-A-60-112,264), Al.
-Cd alloy (JP-A-60-212,779), porous foam metal (JP-A-61-74,268), etc. are used.

The current collector may be any electron conductor that does not undergo a chemical change in the constructed battery. For example, in addition to commonly used stainless steel, titanium and nickel, nickel-plated copper (Japanese Patent Laid-Open No. 48-36,62).
7), the titanium-plated body of copper and the positive electrode active material of sulfide are treated with copper on stainless steel (JP-A-60-175,3).
73) and the like are used.

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

[0125]

The present invention will be described in more detail with reference to the following examples, but the invention is not limited to the following examples as long as the gist of the present invention is not exceeded. Example 1 V ₆ O ₁₃ as a positive electrode active material and acetylene black as a conductive agent were mixed at a ratio of 88 parts by weight and 6 parts by weight, respectively, and 4 and 2 parts by weight of a solid content of the present invention as a binder, respectively. After adding a solution of the polymer and the compound (crosslinking agent) and kneading, the solution was applied to both surfaces of an aluminum foil current collector having a thickness of 20 μm. As the solvent of the solution, water, acetone, toluene, or the like in which the binder was soluble was used. The above coated material was dried and compression-molded with a roller press to prepare a strip-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 binders of the present invention and the binders of Comparative Examples used.

A negative electrode sheet (2) was prepared by cutting a lithium-aluminum alloy (alloy ratio 80-20% by weight, thickness 150 μm) into strips. 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 Nos. 4 and 15, a part of the active material was peeled off, but this was not the case with the product of the present invention.

The wound body was housed in a bottomed cylindrical battery can (4) made of iron and plated with nickel, which also serves as a negative electrode terminal. Furthermore, 1 mol / liter LiB as an electrolyte
F ₄ a (equal volume mixture 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 the cylindrical battery. In addition, 7 is a safety valve.

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

[0129]

[Table 1]

* Comparative polymer Z-1: Polytetrafluoroethylene Z-2: Ethylene-propylene-dicyclopentadiene copolymer Example 2 Pitch coke 90 was prepared by using pulverized coal-based pitch coke as the negative electrode active material. 7 and 3 parts by weight of the polymer and the compound of the present invention are added as binders to parts by weight, and a suitable solvent such as toluene and acetone is added and kneaded to form a slurry, and both surfaces of a copper foil current collector having a thickness of 20 μm are added. Was applied to. The coated material was dried and compression-molded with a roller press to form a negative electrode sheet having a thickness of 230 μm.

Li _0.5 Co _0.5 V _0.5 as the positive electrode active material
0 _2.5 was mixed in a proportion of 88 parts by weight and 6 parts by weight of acetylene black as a conductive agent, and Example 1 as a binder.
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 except that a combination of 4 parts by weight of -1 and 2 parts by weight of compound b-3 was added and kneaded with a toluene or acetone solvent. A positive electrode sheet using Z-2 as a binder (A), a-1
Let (B) be the positive electrode sheet using and b-3.

A cylindrical battery was prepared in the same manner as in Example 1 using the above negative electrode sheet and positive electrode sheet. * Comparative Example Polymer 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. Shown in 2. The test conditions are the same as in Example 1.

[0133]

[Table 2]

[0134]

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

[Brief description of drawings]

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

[Explanation of symbols]

 1. Positive electrode 2. Negative electrode 3. Separator 4. Battery can 5. Battery cover 6. Gasket 7. safety valve

Claims (15)

[Claims] 1. A chemical battery comprising a positive electrode active material, a negative electrode active material, and an electrolyte having ion conductivity, a polymer having a functional group as a binder, and one molecule of a functional group capable of reacting with the functional group of the polymer. A chemical battery comprising a positive electrode mixture and / or a negative electrode mixture containing at least two compounds therein. 2. The chemical battery according to claim 1, wherein the functional group of the polymer is at least one selected from the group of functional groups represented by formula 1. Formula 1 (However, R ¹ , R ² , R ³ , and R ⁴ are hydrogen atoms and have 1 carbon atom.
To an alkyl group having from 6 to 6, an aryl group having from 6 to 12 carbons, or an aralkyl group, and X is a linking group -O- or -N.
(R ⁵ ) —, wherein R ⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aralkyl group having 6 to 12 carbon atoms. Y and Z represent 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 halogen. ) 3. A compound having a functional group of at least one selected from the group of functional groups represented by Formula 1, and capable of reacting with the polymer to form a chemical bond. 1. The chemical battery according to 1. 4. The functional group contained in the polymer is --OH.
2. The chemical battery according to claim 1, wherein the functional group contained in the compound is a functional group represented by Formula 2. Formula 2 5. The functional group contained in the polymer is --OH.
The functional group contained in the compound is —NHCH ₂ OR (wherein R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group). The chemical battery according to claim 1, wherein: 6. The functional group contained in the polymer is --OH.
2. The chemical battery according to claim 1, wherein the functional group contained in the compound is -NCO. 7. The functional group contained in the polymer is --COO.
The chemical battery according to claim 1, wherein the functional group contained in the compound with H is a functional group represented by the formula 2. 8. The chemical battery according to claim 1, wherein the functional group contained in the polymer is a functional group represented by formula 3 and the functional group contained in the compound is represented by a formula 2. Formula 3 9. The functional group contained in the polymer is the functional group represented by the formula 2, and the functional group contained in the compound is H ₂
N—R—NH ₂ (wherein 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 1. The chemical battery according to Item 1. 10. The functional group contained in the polymer has formula 2
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.
H, the functional group contained in the compound is —SO ₂ CH═C.
The chemical battery according to claim 1, which is H ₂ . 12. The functional group contained in the polymer is --O.
The chemical battery according to claim 1, wherein the functional group contained in the compound at H is a functional group represented by Formula 4. Formula 4 However, Y and Z represent halogen and an alkoxy group having 1 to 6 carbon atoms, and at least one of Y and Z is 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 carbon atom having 6 to 12 carbon atoms.
Represents an aryl group or an aralkyl group. 13. The functional group contained in the polymer is --N.
The chemical battery according to claim 1, wherein the functional group contained in the compound with H ₂ is a functional group represented by Formula 2. 14. The chemical battery according to claim 1, wherein the main chain of the polymer is a polymer of an ethylenically unsaturated compound. 15. The chemical battery according to claim 1, wherein the main chain of the polymer is a sugar chain.