JP2003324037A - Gelatinous-electrolyte forming composition and gelatinous electrolyte - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gelatinous-electrolyte forming composition for forming a gelatinous electrolyte which can be crosslinked by heating or irradiating ultraviolet light, electron rays, etc., and has a high electrolyte-maintaining rate, therefore, has high ion conductivity and is excellent in a durability to high temperature, and the gelatinous electrolyte by which the composition is crosslinked. <P>SOLUTION: The gelatinous-electrolyte forming composition contains a monovinyl monomer and a crosslinking agent as a polymeric component. The crosslinking agent is an oligomer which contains a monovinyl compound and an aromatic divinyl compound, a polymerized polymer can form the gelatinous electrolyte having the electrolyte maintaining rate 12 times as large as the polymer weight or more. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gel-like electrolytic solution forming composition and a gel-like electrolytic solution which can be used as an electrochemical element such as a battery and a capacitor, and are particularly suitable for an aluminum electrolytic capacitor.

[0002]

2. Description of the Related Art Among capacitors, an aluminum electrolytic capacitor, when an overvoltage higher than the rating is applied during its use and the temperature rises, the organic solvent that constitutes the driving electrolyte used in the capacitor element is Hydrogen gas is generated by vaporization and electrochemical reaction. as a result,
Since the internal pressure of the metal case made of aluminum may rise and the liquid organic solvent may be ejected, a conventional liquid electrolyte may not be used.

Further, the liquid electrolyte has no shape-retaining property,
The manufacturing process of batteries and capacitors is limited, and special consideration must be given to the liquid leakage resistance of products, and improvements have been required.

As a technique for improving the resistance to liquid leakage and maintaining the degree of freedom of processing, there is a method of making the electrolytic solution non-fluidized to meet the above-mentioned demand. By mixing a crosslinked vinyl polymer and the electrolytic solution. A technique using a gel electrolyte is disclosed in Japanese Patent Laid-Open No. 5-325.
It is disclosed in Japanese Patent No. 986.

[0005]

However, in the gel electrolyte disclosed in the above publication, the ratio of the electrolyte after synthesizing the polymer, that is, the electrolyte retention is about 4 to 5 by weight. However, the proportion of the polymer component having a higher specific resistance than that of the electrolytic solution was large, and therefore the ionic conductivity of the electrolyte was not sufficiently high.

Further, the gel electrolyte disclosed in the above-mentioned publication is one in which a polymer is synthesized, then purified and dried, and then the electrolyte is mixed. Since the electrolytic solution is mixed, there is a problem that the degree of freedom in processing is small, for example, in order to apply it to a capacitor or the like, it is necessary to separately manufacture different sizes depending on the type.

In the manufacturing and processing steps of batteries and capacitors, the degree of freedom in processing is high. Therefore, after the electrodes and separators are arranged in the case in a configuration required for various batteries, capacitors, etc., the electrolytic solution is formed. A battery and a capacitor are manufactured by pouring into a predetermined space and sealing. Therefore, even when using the gel electrolyte, in order to maintain the degree of freedom of processing, the gel electrolyte forming composition was poured into a predetermined space formed by the electrodes and separators arranged in the case. Workability is required so that the polymerizable component can be reacted and cured to form a gel later.

Particularly in recent years, capacitors and batteries excellent in higher temperature durability have been demanded, and high temperature durability required for gel electrolyte is also required.

The object of the present invention is to form a gel that can be crosslinked by heating or irradiation with energy rays such as ultraviolet rays and electron beams, has a high electrolyte retention rate, and thus has high ionic conductivity and excellent high temperature durability. It is intended to provide a gel electrolyte forming composition that forms an electrolyte, and a gel electrolyte that is obtained by crosslinking the same.

[0010]

Means for Solving the Problems The present invention provides a gel electrolyte solution-forming composition containing a monovinyl monomer and a crosslinking agent as the polymerizable components, wherein the crosslinking agent comprises a monovinyl compound and an aromatic divinyl compound as the polymerizable components. The polymer, which is an oligomer contained, is capable of forming a gel electrolyte having an electrolyte retention of 12 times or more the weight of the polymer, and relates to a gel electrolyte forming composition.

By using a polymerizable component having such a composition, it can be crosslinked by heating or irradiation with energy rays such as ultraviolet rays and electron beams, and a lactone organic solvent such as γ-butyrolactone and an alcohol organic solvent such as ethylene glycol. , Gel-like electrolysis with high retention rate (electrolytic solution content weight ratio to resin) of electrolytic solution using electrolytic solution using mixed solvent of lactone organic solvent and alcohol organic solvent, and excellent high temperature durability It is possible to obtain a gel electrolyte forming composition that forms a liquid.

The electrolyte retention of the gel electrolyte is preferably as high as possible, but if too high, gel may not be formed, and the electrolyte retention is preferably 16 times or less.

In the present invention, the monovinyl compound is at least one of unsaturated carboxylic acid compounds and styrene compounds, and the aromatic divinyl compound is at least one of divinylbenzene and divinyltoluene.
It is preferably a seed.

The monovinyl compound / aromatic divinyl compound molar ratio is preferably 200/1 to 1/1. When the molar ratio of the monovinyl compound is more than 200/1, the gelling ability is low, and when it is less than 1/1, the intramolecular crosslinking reaction is highly generated, and the number of vinyl groups that react effectively during the formation of the gel electrolyte is It is not preferable because it decreases.

In the present invention, the cross-linking agent preferably has a weight average molecular weight of 1,000 to 100,000. When it is less than 1000, the gelling ability is low and the electrolytic solution content cannot be improved. On the other hand, if it is more than 100,000, the viscosity of the gel electrolyte forming composition increases, and it is impossible to fill the inside of the capacitor with the gel electrolyte forming composition.

Further, the content ratio of the aromatic divinyl compound is preferably 0.5 to 50 mol% in all the compounds of the monovinyl monomer, the monovinyl compound and the aromatic divinyl compound. With this configuration, a gel electrolyte having a high electrolytic solution retention rate, stability at 150 ° C., and excellent high-temperature durability can be reliably formed. When the content of the aromatic divinyl compound is less than 0.5 mol%, a gel electrolyte is not formed, and when it is more than 50 mol%, the content of the electrolyte is reduced and the ionic conductivity is reduced, which is not preferable.

The above-mentioned gel electrolyte forming composition preferably further contains an electrolyte in which an electrolyte is dissolved in an organic solvent, and it is also preferable that the composition further contains a radical polymerization initiator.

By mixing the electrolytic solution, the gel-like electrolytic solution can be formed by being polymerized and cured by an active energy ray such as an electron beam as it is, and by adding a radical polymerization initiator, the gel-like electrolytic solution can be heated. Can be formed.

The gel electrolyte of the present invention is obtained by cross-linking and copolymerizing the gel electrolyte-forming composition according to any one of claims 1 to 5 to which an electrolyte is added. It is characterized by

Such a gel electrolyte has an electrolyte retention of 1
It can be doubled or more, and therefore has high ionic conductivity and excellent high temperature durability.

The gel electrolyte solution-forming composition can be crosslinked and copolymerized by heating or irradiation with energy rays such as ultraviolet rays and electron beams to cause gelation. In particular, a radical polymerization initiator is added to the electrolyte solution. In the case of a gel-type electrolytic solution-forming composition to which is added, the gel-type electrolytic solution can be formed in the capacitor in a simple process by heating at the same time as the manufacturing process of the capacitor, thereby simultaneously crosslinking and copolymerizing and gelling. can do.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Raw materials used in the present invention will be described. As the polymerizable component that constitutes the polymer component of the gel electrolyte of the present invention, a monovinyl monomer and a crosslinking agent are used.

As the monovinyl monomer, known compounds can be used without limitation as long as the characteristics of the gel electrolyte of the present invention are not significantly impaired. For example, methyl acrylate,
Examples thereof include acrylic compounds such as methyl methacrylate, vinyl halides such as vinyl chloride, vinyl ethers, and vinyl ester compounds such as vinyl acetate. In particular, it is preferable to use a hydrophilic group-containing monomer because it has a high affinity with an organic solvent and a gel electrolyte having a high electrolyte retention rate can be obtained. Examples of the hydrophilic group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, acrylamide, and methacrylamide.

Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates, specifically hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate and the like. These may be used alone or in combination of two or more.

Examples of the carboxyl group-containing monomer include acrylic acid and methacrylic acid as the monocarboxylic acid, and maleic acid and itaconic acid as the dicarboxylic acid. These may be used alone or in combination of two or more.

The cross-linking agent is an oligomer containing a monovinyl compound and an aromatic divinyl compound as polymerizable components.

As the monovinyl compound, the above-mentioned compounds can be used without limitation as long as the characteristics of the gel electrolyte of the present invention are not significantly impaired. In particular, at least unsaturated carboxylic acid compounds and styrene compounds are used. It is preferably one type.

Examples of unsaturated carboxylic acid compounds include (meth) acrylic acid, (meth) acrylamide, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, polyethylene glycol (meth) acrylate and the like. The alkyl group is specifically methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-, i.
-, As well as neo-pentyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, lauryl, stearyl and the like. Further, the terminal of polyethylene glycol (meth) acrylate may be a hydroxyl group, an alkyl ether group such as methyl ether, or the like. These may be used alone or in combination of two or more.

Examples of the styrene compound include styrene, α-methylstyrene, β-methylstyrene, o-
Methylstyrene, p-methylstyrene, p-tert-
Butyl styrene, 2,4-dimethyl styrene, vinyl naphthalene, vinyl anthracene, 1,1-diphenyl ethylene and the like. These may be used alone 2
You may use together 1 or more types.

As the aromatic divinyl compound, known compounds can be used without limitation as long as the characteristics of the gel electrolyte of the present invention are not significantly impaired, but at least one of divinylbenzene and divinyltoluene is particularly preferable. It is preferable.

The method of polymerizing a monovinyl compound and an aromatic divinyl compound to produce an oligomer crosslinking agent can be carried out by a commonly used method.

As the organic solvent used in the polymerization step,
Various known solvents can be used. For example,
Examples thereof include amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol and ethanol. These may be used alone or in combination of two or more.

As the polymerization initiator, known radical polymerization is used.
Initiating peroxide polymerization initiator or azo polymerization initiator
A starter etc. can be used. Specifically, start peroxide polymerization
Examples of the agent include benzoyl peroxide, methyl
Ethyl ketone peroxide, t-butyl peroxide
Barrate, diisopropyl peroxycarbonate, di
Cumyl peroxide, di-t-butyl peroxide,
t-butyl hydroperoxide, t-butyl peroxide
Xybenzoate and the like, as an azo-based polymerization initiator
For example, 2,2'-azobis (2-isobutyronito)
Lil), 2,2'-azobisisobutyronitrile, 2,
2'-azobis (2,4-dimethylvaleronitrile),
1,1'-azobis (cyclohexane-1-carbonite
Lil) and the like. These can be used alone
Or two or more kinds may be used in combination. The amount of polymerization initiator used is
Although not particularly limited, for gel electrolyte forming composition
10 ^-Four˜1 mol / L is preferably used, especially 10
^-3-10^-2It is preferable to use mol / L.

In the polymerization reaction, it is preferable to use a chain transfer agent such as lauryl mercaptan and thiomalic acid. Although the amount of the chain transfer agent used is not particularly limited, it is preferably used in 1/1000 to 1/2 mol, and particularly preferably in 1/100 to 1/10 mol with respect to 1 mol of the polymerizable component. When the chain transfer agent is not used, the molecular weight becomes high and the target oligomer tends not to be obtained, and the viscosity of the gel electrolyte forming composition increases, which is not preferable.

In the polymerization reaction, a monomer having high alternating copolymerizability such as maleic anhydride may be added. By adding the monomer, the rate of continuous polymerization of the aromatic divinyl compound decreases, and an oligomer having a more uniform crosslinked structure can be obtained.

The polymerization temperature is not particularly limited as long as it is a temperature usually used in the polymerization reaction, but is preferably 150 ° C. or lower, more preferably 125 ° C. or lower.

The polymerization reaction is preferably carried out in an inert gas such as nitrogen or argon, but may be carried out under other conditions.

The polymer component of the gel electrolyte is obtained by polymerizing the monovinyl monomer and the oligomer crosslinking agent. Incidentally, divinylbenzene or divinyltoluene may be appropriately used in combination as a polymerizable component.

As the initiator to be polymerized by heating, the above-mentioned polymerization initiator can be used without particular limitation. The addition amount of these thermal polymerization initiators is not limited as long as a gel electrolyte is obtained, but is generally 10 with respect to the gel electrolyte forming composition from the viewpoint of electrical characteristics as an electrolyte. ^{-4 to 1} mol / L.

When the composition is irradiated with energy rays such as visible rays, ultraviolet rays and electron rays to be cured, it is preferable to use a photosensitizer together. As such a photosensitizer, known photosensitizers can be used without limitation, and benzoin-based photosensitizers, acetophenone-based photosensitizers, benzyl ketal-based photosensitizers and the like can be used. It is illustrated. Specifically, acetophenone, benzophenone, 4-methoxybenzophenone, benzoin methyl ether, 2,2-dimethoxy-
2-phenyldimethoxy-2-phenylacetophenone, benzyl, benzoyl, 2-methylbenzoin, 2
-Hydroxy-2-methyl-1-phenyl-1-one,
1- (4-isopropylphenyl-2-hydroxy-2
-Methylpropan-1-one, triphenylphosphine, 2-chlorothioxanthone and the like are exemplified. These may be used alone or in combination of two or more.
The amount of these photosensitizers added is not limited as long as it exerts a sensitizing action, but is generally 10 ^{−4 to 1} mol / mole with respect to the gel electrolyte forming composition like the initiator. It is L.

The initiator and photosensitizer may be added to the gel electrolyte forming composition from the beginning or before use.

As the organic solvent that constitutes the electrolytic solution, one that can dissolve the electrolyte to the required concentration is used. Specifically, a highly polar organic solvent such as a lactone solvent such as γ-butyrolactone or an alcohol solvent such as ethylene glycol, preferably a liquid organic solvent at room temperature is used. When two or more organic solvents are used in combination, it is also preferable that the mixture be liquid at room temperature. As the alcohol solvent, alcohols that are liquid at room temperature can be used without limitation, and n-butanol,
Examples include monoalcohols such as i-butanol and methyl cellosolve, and polyhydric alcohols such as ethylene glycol, propylene glycol and diethylene glycol.
Specific examples of the lactone solvent include γ-butyrolactone, γ-valerolactone, δ-valerolactone, 3-methyl-1,3-oxazolidin-2-one, 3-ethyl-1,3-oxazolidine-2-. ON and the like are exemplified.

Organic solvents that can be used in place of or in combination with the lactone-based solvent and the alcohol-based solvent include carbonate-based solvents such as ethylene carbonate and propylene carbonate, and pyrrolidone-based solvents such as N-methylpyrrolidone. Solvent, amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, 1,2
-Ether solvents such as dimethoxyethane and dibutyl ether, nitrile solvents such as acetonitrile and 3-methoxypropionitrile, imidazolidinone solvents such as 1,3-dimethyl-2-imidazolidinone, sulfolane,
Examples thereof include sulfolane-based solvents such as 3-methylsulfolane. These may be used alone or in combination of two or more. Among these non-aqueous solvents, it is particularly preferable to use carbonate-based solvents, ether-based solvents and cyclic ether-based solvents.

The organic solvent used in the electrolytic solution preferably does not contain water, but may contain a small amount of water depending on the use of the capacitor.

The gel electrolyte forming composition of the present invention and the electrolyte as a constituent of the gel electrolyte may be an alkali metal salt, a quaternary ammonium salt or an alkaline earth metal depending on the intended use of the gel electrolyte. It is appropriately selected without limitation from known electrolytes such as metal salts.

Specifically, examples of the alkali metal salt include
For example, LiClO_Four , LiSCN, LiBF_Four , LiA
sF₆ , LiCF₃ SO₃ , NaI, NaSCN, Na
ClO_Four , NaBF_Four , NaAsF₆ , KSCN, etc.
You can Examples of the quaternary ammonium salt include (CH₃ )
_Four NBF_Four , (C₂ H_Five )_Four NBF_Four , (N-C_Four H
₉ )_Four NBF_Four , (C₂ H_Five )_Four NBr, (C₂ H_Five )
_Four NClO_Four , (N-C _Four H₉ )_Four NClO_Four Etc.
To be Further, as the alkaline earth metal salt, for example,
Mg (ClO_Four )₂ , Ca (ClO_Four )₂ , Mg (BF
_Four )₂ , Ca (BF_Four )₂ , Imidazolium phthalate
Polybasic acids such as salts and quaternary ammonium phthalate
Included are primary ammonium salts. These electrolytes alone
May be used, or two or more types may be used in combination
It

The amount of the electrolyte added to the organic solvent is not particularly limited as long as it functions as an electrolyte and depends on the solubility of the electrolyte in the solvent, but it is 0.5 with respect to the organic solvent.
~ 2mol / L, preferably 0.7-1.5mo
1 / L.

The gel electrolyte used in capacitors, batteries, etc. is, for example, aluminum foil or the like arranged in a predetermined form, and the gel electrolyte forming composition is poured into the voids formed by the aluminum foil, and then heated. It is formed by reaction curing by means such as energy beam irradiation. It can also be produced by coating an aluminum foil with a gel electrolyte forming composition to a predetermined thickness, reacting the mixture by heating and irradiation with energy rays, and winding the obtained laminate.

In the conventional manufacturing process of batteries and capacitors, there is a process of heating in the range of 100 to 140 ° C. for about 1 hour. In the heating process, a gel electrolyte is formed from the gel electrolyte forming composition. The conventional process,
This is extremely preferable because a battery or capacitor excellent in high temperature durability can be manufactured without significantly changing the equipment. Therefore, the gel electrolyte forming composition of the present invention is 100 to 1
A composition that forms a gel electrolyte by heating at 40 ° C. for 1 hour is preferable.

[0050]

EXAMPLES Examples and the like specifically showing the constitution and effects of the present invention will be described below. The weight average molecular weights described in Examples and Comparative Examples were measured by a light scattering method, and the ionic conductivity was measured by an AC impedance method (measurement temperature 30 ° C.).

(Example 1) Acrylic acid (made by Nakarai) 1
4.7 g, divinylbenzene (made by Nakarai) 5.3 g,
Further, 1.0 g of lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 8.9 g of tetrahydrofuran (hereinafter abbreviated as THF), and 0.49 g of 2,2′-azobisisobutyronitrile (manufactured by Nakarai) as a polymerization initiator. Was added and polymerized at 50 ° C. for 30 minutes in a nitrogen atmosphere. After the completion of the polymerization, the polymerization product was precipitated in 50 g of hexane, the precipitate was dissolved in as little THF as possible, and purified by reprecipitation with 20 times the amount of hexane as the cross-linking agent A (weight average molecular weight: Thirteen
500) was obtained. Next, acrylic acid (made by Nakarai) 0.4
3 g and a crosslinking agent A (0.57 g) were mixed to obtain a polymerizable component B. 12 g of an electrolytic solution obtained by dissolving γ-butyrolactone (hereinafter, abbreviated as GBL) in the above polymerizable component B (1 g) as an electrolyte so that the imidazolium phthalate salt is 1 mol / L, and t-as a radical polymerization initiator. 0.04 g of butyl peroxybenzoate (trade name: Perbutyl Z, manufactured by NOF CORPORATION) was added to obtain a gel electrolyte forming composition. The obtained gel electrolyte forming composition is heated to 105 ° C.
By heating for 1 hour, a gel electrolyte b was obtained. The ionic conductivity of this gel electrolyte b is 6.4 × 1.
It was 0 ⁻³ (S / cm). About gel electrolyte b
When a heat resistance test was performed at 50 ° C. for 1000 hours, the gel shape was retained even after the test, and high heat resistance shape stability was exhibited. (Example 2) A crosslinking agent A was produced in the same manner as in Example 1. Further, 0.47 g of methacrylic acid (manufactured by Nakarai) and a crosslinking agent A (0.53 g) were mixed to obtain a polymerizable component C. In the above-mentioned polymerizable component C (1 g), 12 g of an electrolytic solution prepared by dissolving imidazolium phthalate salt as an electrolyte in GBL at 1 mol / L, and t-butylperoxybenzoate (0.04 g) as a radical polymerization initiator. )
Was added to obtain a gel electrolyte forming composition. The obtained gel electrolyte forming composition was heated at 105 ° C. for 1 hour to obtain a gel electrolyte c. This gel electrolyte c
Had an ionic conductivity of 6.6 × 10 ⁻³ (S / cm). When the gel electrolyte c was subjected to a heat resistance test at 150 ° C. for 1000 hours, the gel shape was retained even after the test, and high heat resistance shape stability was exhibited.

(Example 3) Acrylic acid (made by Nakarai) 1
4.7 g, divinylbenzene (made by Nakarai) 5.3 g,
And 0.7 g of thiomalic acid (manufactured by Wako Pure Chemical Industries) in THF
Dissolved in (8.9 g), the above 2,2 'as a polymerization initiator
-Add azobisisobutyronitrile (0.49g),
Polymerization was carried out at 50 ° C. for 30 minutes in a nitrogen atmosphere. After completion of the polymerization, the polymerization product was precipitated in 50 g of hexane, and the precipitate was dissolved in as little THF as possible, and the THF
The product was purified by reprecipitation with 0 times the amount of hexane to obtain a crosslinking agent D (weight average molecular weight: 11300). Next, 0.47 g of methacrylic acid (made by Nakarai) and a cross-linking agent D (0.53 g) were mixed to obtain a polymerizable component E. The above polymerizable component E (1 g)
To the GBL, 12 g of an electrolyte solution in which an imidazolium phthalate salt was dissolved as an electrolyte to 1 mol / L, and the t-butylperoxybenzoate (0.04 g) as a radical polymerization initiator were added to the gel electrolyte solution. A forming composition was obtained. The obtained gel electrolyte forming composition is heated to 105 ° C.
By heating for 1 hour, a gel electrolyte e was obtained. The ionic conductivity of this gel electrolyte e is 7.2 × 1.
It was 0 ⁻³ (S / cm). Gel electrolyte 150
When a heat resistance test was conducted at 1000C for 1000 hours, the gel shape was retained even after the test, and high heat resistance shape stability was exhibited.

Example 4 A polymerizable component B was produced in the same manner as in Example 1. Electrolyte solution 1 obtained by dissolving quaternary ammonium phthalate salt as an electrolyte in ethylene glycol at 1 mol / L in the above polymerizable component B (1 g).
2 g of the above-mentioned t-butyl peroxybenzoate (0.04 g) was added as a radical polymerization initiator to obtain a gel electrolyte forming composition. The gel electrolyte forming composition thus obtained was heated at 105 ° C. for 1 hour to obtain a gel electrolyte f. The ionic conductivity of this gel electrolyte f is
It was 2.1 × 10 ⁻³ (S / cm). Gel electrolyte f
When subjected to a heat resistance test at 150 ° C. for 1000 hours, the gel shape was retained even after the test, and high heat resistance shape stability was exhibited.

Example 5 A polymerizable component C was produced in the same manner as in Example 2. Electrolyte solution 1 obtained by dissolving quaternary ammonium phthalate salt as an electrolyte in ethylene glycol in the above-mentioned polymerizable component C (1 g) at a concentration of 1 mol / L.
2 g of the above-mentioned t-butyl peroxybenzoate (0.04 g) was added as a radical polymerization initiator to obtain a gel electrolyte forming composition. The obtained gel electrolyte forming composition was heated at 105 ° C. for 1 hour to obtain gel electrolyte g. The ionic conductivity of this gel electrolyte g is
It was 1.8 × 10 ⁻³ (S / cm). Gel electrolyte g
When subjected to a heat resistance test at 150 ° C. for 1000 hours, the gel shape was retained even after the test, and high heat resistance shape stability was exhibited.

Example 6 A polymerizable component E was produced in the same manner as in Example 3. Electrolytic solution 1 in which the quaternary ammonium phthalate salt as an electrolyte was dissolved in the above-mentioned polymerizable component E (1 g) in an amount of 1 mol / L as an electrolyte.
2 g of the above-mentioned t-butyl peroxybenzoate (0.04 g) was added as a radical polymerization initiator to obtain a gel electrolyte forming composition. The obtained gel electrolyte forming composition was heated at 105 ° C. for 1 hour to obtain a gel electrolyte h. The ionic conductivity of this gel electrolyte h is
It was 1.6 × 10 ⁻³ (S / cm). Gel electrolyte h
When subjected to a heat resistance test at 150 ° C. for 1000 hours, the gel shape was retained even after the test, and high heat resistance shape stability was exhibited.

Comparative Example 1 Acrylic acid (made by Nakarai)
0.85 g, and divinylbenzene (made by Nakarai).
15 g was mixed to obtain a polymerizable component I. In the above polymerizable component I (1 g), 12 g of an electrolytic solution prepared by dissolving imidazolium phthalate salt as an electrolyte in GBL at 1 mol / L, and t-butylperoxybenzoate (0.04 g) as a radical polymerization initiator. ) Was added to obtain a gel electrolyte forming composition. The obtained gel electrolyte forming composition was heated at 105 ° C. for 1 hour, but no gel electrolyte was formed.

Comparative Example 2 Methacrylic acid (made by Nakarai)
0.87 g, and divinylbenzene (made by Nakarai) 0.
13 g was mixed to obtain a polymerizable component J. In the above polymerizable component J (1 g), 12 g of an electrolytic solution prepared by dissolving imidazolium phthalate salt as an electrolyte in GBL at 1 mol / L, and t-butylperoxybenzoate (0.04 g) as a radical polymerization initiator. ) Was added to obtain a gel electrolyte forming composition. The obtained gel electrolyte forming composition was heated at 105 ° C. for 1 hour, but no gel electrolyte was formed.

Comparative Example 3 A polymerizable component I was obtained in the same manner as in Comparative Example 1. 12 g of an electrolytic solution prepared by dissolving quaternary ammonium phthalate salt as an electrolyte in ethylene glycol in the above polymerizable component I (1 g) at a concentration of 1 mol / L,
The above-mentioned t-butylperoxybenzoate (0.04 g) was added as a radical polymerization initiator to obtain a gel electrolyte forming composition. The obtained gel electrolyte forming composition was mixed with 10
When heated at 5 ° C. for 1 hour, no gel electrolyte was formed.

Comparative Example 4 A polymerizable component J was obtained in the same manner as in Comparative Example 2. 12 g of an electrolytic solution prepared by dissolving quaternary ammonium phthalate salt as an electrolyte in ethylene glycol in the above-mentioned polymerizable component J (1 g) so as to be 1 mol / L.
The above-mentioned t-butylperoxybenzoate (0.04 g) was added as a radical polymerization initiator to obtain a gel electrolyte forming composition. The obtained gel electrolyte forming composition was mixed with 10
When heated at 5 ° C. for 1 hour, no gel electrolyte was formed.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshio Mimura             1-17-18 Edobori, Nishi-ku, Osaka City, Osaka Prefecture             Toyo Tire & Rubber Co., Ltd. (72) Inventor Akira Matsumoto             Kansai, 3-3-35 Yamate-cho, Suita City, Osaka Prefecture             Faculty of Engineering, Department of Applied Chemistry F term (reference) 5H024 BB11 FF21 GG01 HH00 HH01                 5H029 AJ06 AJ14 AM02 AM03 AM04                       AM05 AM07 AM16 CJ11 DJ09                       HJ02 HJ11

Claims (8)

[Claims] 1. A gel electrolyte forming composition containing a monovinyl monomer and a crosslinker as a polymerizable component, wherein the crosslinker is an oligomer containing a monovinyl compound and an aromatic divinyl compound as the polymerizable component. The polymer is capable of forming a gel electrolyte having an electrolyte retention rate of 12 times or more the weight of the polymer, thereby forming a gel electrolyte forming composition. 2. The monovinyl compound is at least one of an unsaturated carboxylic acid compound and a styrene compound, and the aromatic divinyl compound is at least one of divinylbenzene and divinyltoluene. Item 2. The gel electrolyte forming composition according to Item 1. 3. The gel electrolyte forming composition according to claim 1, wherein the molar ratio of monovinyl compound / aromatic divinyl compound is 200/1 to 1/1. 4. The cross-linking agent has a weight average molecular weight of 1,000.
It is 100-100,000, The gel electrolyte forming composition in any one of Claims 1-3 characterized by the above-mentioned. 5. The content of the aromatic divinyl compound in all compounds of the monovinyl monomer, the monovinyl compound, and the aromatic divinyl compound is 0.5 to 50 mol%, any one of claims 1 to 4 characterized in that The gel electrolyte forming composition as described in 1. 6. The gel-like electrolytic solution forming composition according to claim 1, further comprising an electrolytic solution in which an electrolyte is dissolved in an organic solvent, in an amount of 12 times or more the weight of the polymerizable component. 7. The gel electrolyte forming composition according to claim 1, further comprising a radical polymerization initiator. 8. A gel electrolyte solution obtained by cross-linking and copolymerizing the gel electrolyte solution-forming composition according to claim 6 or 7 to form a gel.