JP2002260962A - Electric double-layer capacitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electric double-layer capacitor which has superiority in safety such as tolerance to external pressure and in electric characteristics. SOLUTION: The electric double-layer capacitor ahs polarizing electrodes opposite across a compound polymer electrolyte obtained by uniting an electric insulating porous thin film and a polymer electrolyte together; and the polymer electrolyte contains a polymer obtained by causing a compound which has an Si-H group at both terminals, a compound shown by a formula (A) or a compound shown by a formula (D) react and the compound type polymer electrolyte has sticking strength of >=1 N and ion conductivity of >=1&times;10<-3> s/cm at 25 deg.C and >=1&times;10<-4> s/cm at -30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electric double layer capacitor excellent in safety.

[0002]

2. Description of the Related Art An electric double layer capacitor utilizing an electric double layer generated at an interface between a polarizable electrode and an electrolytic solution is used as a power supply for a backup of a personal computer or the like, a power supply for a hybrid vehicle,
It is used as a power source for starting cell motors.

An electric double layer capacitor has a structure in which an electrolytic solution is filled between polarizable electrodes facing each other in a cell via a separator. As the electrolytic solution, an aqueous electrolytic solution such as a sulfuric acid aqueous solution or a non-aqueous electrolytic solution is used. In an electric double layer capacitor using a non-aqueous electrolyte, the non-aqueous electrolyte evaporates in a high-temperature atmosphere, the internal pressure rises, the shape of the capacitor is deformed, the characteristics deteriorate, and a fire may occur. Sometimes. In addition, although electric double layer capacitors using an aqueous electrolyte have better heat resistance than those using a non-aqueous electrolyte, when the cell is damaged by external pressure, an acidic electrolyte leaks out. There was danger.

[0004] In order to enhance the safety of the electric double layer capacitor, an electric double layer capacitor using a polymer electrolyte such as a gel electrolyte containing an electrolytic solution or an all solid electrolyte has been proposed. Although all solid electrolytes have excellent mechanical strength, their ionic conductivity is low, so that there are few practically available ones. For this reason, a gel electrolyte containing an electrolytic solution is mainly used. However, there is a drawback that the handleability in assembling the electric double layer capacitor is poor due to low mechanical strength. Therefore, a composite polymer electrolyte integrated with an electrically insulating porous thin film has been proposed. Since the composite polymer electrolyte is integrated with the electrically insulating porous thin film, problems such as a decrease in ionic conductivity and an increase in the internal resistance of the electric double layer capacitor occur. There was something.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problem of cell breakage in electric double layer capacitors which have recently been used in fields requiring higher safety, such as automobiles and heavy machinery. It is another object of the present invention to provide a high-performance electric double layer capacitor which does not cause liquid leakage even when it is used, is excellent in safety such as heat resistance, and exhibits high electric characteristics.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found the following invention.

That is, (1) In an electric double layer capacitor in which polarizable electrodes face each other via a composite polymer electrolyte in which an electrically insulating porous thin film and a polymer electrolyte are integrated, Compound having terminal Si-H group and formula (A)

[0008]

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Wherein R ¹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ² independently represents a substituted or unsubstituted Represents a substituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, a substituted or unsubstituted arylene alkylene group, a dialkyl (poly) silylene group, a diaryl (poly) silylene group, or a direct bond. , Z ¹
Polyoxyalkylene group, (poly) carbonate group,
It represents a (poly) ester group, an alkylene group, a heteroatom-containing organic group, a divalent group derived from polyacrylate or polymethacrylate, or a direct bond. At least a linear polymer obtained by an addition reaction with the compound represented by formula (I), the composite polymer electrolyte has a puncture strength of 0.1 N or more,
1 × 10 ⁻³ S / cm or more at −30 ° C. and 1 × 10 ⁻⁴ S / cm at −30 ° C.
Electric double layer capacitor characterized by having an ionic conductivity of at least 1 cm

(2) Through a composite polymer electrolyte in which an electrically insulating porous thin film and a polymer electrolyte are integrated,
In an electric double layer capacitor in which polarizable electrodes face each other, a polymer electrolyte comprises a compound having Si—H groups at both ends and a compound represented by the formula (A):

[0011]

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Wherein R ¹ , R ² and Z ¹ are as defined in claim 1. Formula (D) having three or more ethylenic double bonds in a linear polymer having two terminal hydrosilyl groups obtained by an addition reaction with a compound represented by the following formula:

[0013]

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[In the formula, R ⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ⁵ independently represents a substituted or unsubstituted aryl group. Represents a substituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, a heteroatom-containing organic group, or a direct bond, n ² is an integer of 3 or more, and Z ² is n ² A linking group having the same valence as: carbon atom, alkylene group, alkane polyyl group, polyvalent aromatic carbocyclic group, alkane polyoxy group, silicon atom, monosubstituted trivalent silicon atom,
Aliphatic group, hetero atom-containing organic group, benzene polycarboxy group, phosphate group, oxyphosphate group, cyclic alkylpolysiloxane group, or alkylarylpolysiloxane group, (poly) carbonate, (poly) ester, polyacrylate or poly R ⁹ represents a group derived from methacrylate, or a direct bond, wherein R ⁹ is, independently of each other,
R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group,
A substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, a heteroatom-containing organic group, or a direct bond; n ³ represents an integer of 2 to 30; Represents an integer of 0 to 3, Z ⁴ is a linking group having the same valence as n ³ ,
Carbon atom, alkylene group, alkynyl group, polyvalent aromatic carbocyclic group, alkanepolyoxy group, silicon atom, monosubstituted 3
Valence silicon atom, aliphatic group, hetero atom-containing organic group, benzene polycarboxy group, phosphate group, oxyphosphate group,
Groups derived from (poly) carbonates, (poly) esters, polyacrylates or polymethacrylates,
Or indicate a direct bond. And at least a crosslinked polymer obtained by subjecting the compound represented by the formula
With a puncture strength of at least N and 1 × 10 at 25 ° C.
An electric double layer capacitor having an ionic conductivity of at least ^-3 S / cm and at least 1 x 10 ^-4 S / cm at -30 ° C.

(3) The electric double layer capacitor according to the above (1) or (2), wherein the composite polymer electrolyte has a tensile strength in the longitudinal direction of 200 N / m or more.

(4) The electric double layer capacitor as described in any of (1) to (3) above, wherein the electrically insulating porous thin film is a nonwoven fabric.

(5) The electric device according to any one of (1) to (4) above, wherein the electrically insulating porous thin film is a nonwoven fabric in which some of the constituents are bonded by hydrogen bonding. Multilayer capacitor

(6) The above (1) to (1), wherein the electrically insulating porous thin film is a nonwoven fabric produced by a wet method.
The electric double layer capacitor according to any one of (5) and (5).

(7) The electric double layer capacitor according to any one of the above (1) to (6), wherein the electrically insulating porous thin film is a nonwoven fabric containing heat-resistant organic fibers.

(8) Part of the heat-resistant organic fiber has a fiber diameter of 1 μm.
m. The electric double layer capacitor as described in (7) above, wherein

(9) The electric double layer capacitor according to the above (7) or (8), wherein the heat-resistant organic fiber is a liquid crystalline polymer fiber.

(10) The electric double layer capacitor according to the above (9), wherein the liquid crystalline polymer fiber is a wholly aromatic polyamide fiber.

(11) The electric double layer capacitor according to the above (9), wherein the liquid crystalline polymer fiber is a wholly aromatic polyester fiber.

(12) The electric double layer capacitor according to the above (7), wherein the heat-resistant organic fiber is a polyester fiber.

(13) The electric double layer capacitor according to the above (12), wherein the average fiber diameter of the polyester fibers is 5 μm or less.

(14) The electric double layer capacitor as described in any one of (1) to (13) above, wherein the electrically insulating porous thin film is a nonwoven fabric containing glass fibers.

(15) The electric double layer capacitor according to the above (14), wherein the glass fiber is a micro glass fiber having an average fiber diameter of 3 μm or less.

(16) The electric double layer capacitor as described in any one of (1) to (15) above, wherein the electrically insulating porous thin film is a nonwoven fabric containing fibrillated cellulose.

(17) The electric double layer capacitor according to the above (16), wherein the fibrillated cellulose is fibrillated with a high-pressure homogenizer.

(18) The electric double layer capacitor according to the above (16), wherein the fibrillated cellulose is bacterial cellulose.

A polymer electrolyte containing at least a linear polymer obtained by an addition reaction between a compound having Si—H groups at both ends and a compound represented by the formula (A), and having a Si—H group at both ends A cross-linked polymer obtained by reacting a linear polymer having two terminal hydrosilyl groups obtained by an addition reaction between a compound and a compound represented by the formula (A) with a polyfunctional compound of the formula (D) is used. At least the contained polymer electrolyte has high ionic conductivity over a wide temperature range. Since the polymer electrolyte can maintain high ionic conductivity even when integrated with the electrically insulating porous thin film, the electric characteristics of the electric double layer capacitor are not reduced. The ionic conductivity of the composite polymer electrolyte is 1 × 10 ⁻³ at 25 ° C.
It has been found that it suffices that it be S / cm or more and 1 × 10 ⁻⁴ S / cm or more at −30 ° C.

When the composite polymer electrolyte has a puncture strength of 0.1 N or more, an electric double layer capacitor excellent in resistance to external pressure and hardly leaking liquid can be obtained.

According to the electric double layer capacitor of the present invention,
The tensile strength in the longitudinal direction of the composite polymer electrolyte is 200 N /
When it is at least m, not only a square laminated electric double layer capacitor but also a cylindrical wound electric double layer capacitor can be stably manufactured.

In the electric double layer capacitor of the present invention, the porosity of the electrically insulating porous thin film is preferably higher in order to increase the content of the polymer electrolyte in the composite polymer electrolyte. However, when the porosity is increased, there arises a problem that the mechanical strength of the electrically insulating porous thin film decreases. When the electrically insulating porous thin film is a nonwoven fabric, as a method for improving the mechanical strength, there is a method of adding a heat fusible fiber or an adhesive to heat and fuse the fibers constituting the nonwoven fabric. To improve mechanical strength more easily than this,
It is preferable that the electrically insulating porous thin film is a nonwoven fabric in which some of the components are bonded by hydrogen bonding.

When the nonwoven fabric is manufactured by a wet method, the uniformity is excellent, so that there is an advantage that the electrical characteristics and mechanical strength of the composite polymer electrolyte become uniform. In the wet method, a nonwoven fabric is manufactured by drying a web formed by dispersing fibers in water. As the water adsorbed on the fibers is removed in the drying process, the functional groups having the ability to form hydrogen bonds that are present in the fibers come closer, and finally hydrogen bonds are formed, creating a nonwoven fabric with excellent mechanical strength. Obtainable. In the dry method, it is difficult to obtain a nonwoven fabric in which some of the components are bonded by hydrogen bonding because water is not used, but the mechanical strength is increased by using heat-fusible fibers and adhesives. Can be expressed.

In the electric double layer capacitor of the present invention,
In order for the insulating porous thin film to be a nonwoven fabric in which some of the components are bonded by hydrogen bonds, as a component,
Wholly aromatic polyamide fiber, wholly aromatic polyester fiber,
It is preferable to contain polyester fiber, glass fiber and fibrillated cellulose fiber. As the fibrillated cellulose fiber, fibrillated cellulose fibrillated by a high-pressure homogenizer or bacterial cellulose can be used.

According to the electric double layer capacitor of the present invention,
Since the electrically insulating porous thin film is a nonwoven fabric containing heat-resistant organic fibers, it can withstand higher temperatures during assembly and operation than conventional electric double layer capacitors. In addition, since a part of the heat-resistant organic fibers is fibrillated to a fiber diameter of 1 μm or less, a composite polymer electrolyte having uniform and high puncture strength can be obtained.

When the heat-resistant organic fiber is a liquid crystalline polymer fiber, a fibrillated fiber having a low twist can be easily obtained. As the liquid crystalline polymer fiber, aromatic polyamide fiber or aromatic polyester fiber can be used advantageously.

When the electrically insulating porous thin film is a nonwoven fabric containing glass fibers, the dimensional stability is improved, and a constant porosity can be maintained even at a high temperature. When the glass fiber is a micro glass fiber having an average fiber diameter of 3 μm or less, a nonwoven fabric having a uniform and high piercing strength can be obtained.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The electric double layer capacitor according to the present invention has a structure in which polarizable electrodes face each other via an electrically insulating porous thin film and a polymer electrolyte.

In one embodiment of the polymer electrolyte relating to the electric double layer capacitor of the present invention, the polymer electrolyte comprises a compound having a Si—H group at both terminals and a compound of the formula (A)

[0042]

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[In the formula, R ¹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ² independently represents a substituted or unsubstituted group. Represents a substituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, a substituted or unsubstituted arylene alkylene group, a dialkyl (poly) silylene group, a diaryl (poly) silylene group, or a direct bond. , Z ¹
Polyoxyalkylene group, (poly) carbonate group,
It represents a (poly) ester group, an alkylene group, a heteroatom-containing organic group, a divalent group derived from polyacrylate or polymethacrylate, or a direct bond. At least a linear polymer obtained by an addition reaction with the compound represented by the formula:

Another embodiment of the polymer electrolyte relating to the electric double layer capacitor of the present invention is obtained by an addition reaction of a compound having a Si—H group at both terminals and a compound represented by the formula (A). To the linear polymer having two hydrosilyl groups at the terminal
Formula (D) having at least one

[0045]

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[In the formula, R ⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ⁵ independently represents a substituted or unsubstituted aryl group. Represents a substituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, a heteroatom-containing organic group, or a direct bond, n ² is an integer of 3 or more, and Z ² is n ² A linking group having the same valence as: carbon atom, alkylene group, alkane polyyl group, polyvalent aromatic carbocyclic group, alkane polyoxy group, silicon atom, monosubstituted trivalent silicon atom,
Aliphatic group, hetero atom-containing organic group, benzene polycarboxy group, phosphate group, oxyphosphate group, cyclic alkylpolysiloxane group, or alkylarylpolysiloxane group, (poly) carbonate, (poly) ester, polyacrylate or poly R ⁹ represents a group derived from methacrylate, or a direct bond, wherein R ⁹ is, independently of each other,
R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group,
A substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, a heteroatom-containing organic group, or a direct bond; n ³ represents an integer of 2 to 30; Represents an integer of 0 to 3, Z ⁴ is a linking group having the same valence as n ³ ,
Carbon atom, alkylene group, alkynyl group, polyvalent aromatic carbocyclic group, alkanepolyoxy group, silicon atom, monosubstituted 3
Valence silicon atom, aliphatic group, hetero atom-containing organic group, benzene polycarboxy group, phosphate group, oxyphosphate group,
Groups derived from (poly) carbonates, (poly) esters, polyacrylates or polymethacrylates,
Or indicate a direct bond. At least a crosslinked polymer obtained by subjecting the compound represented by the formula (1) to an addition reaction.

As the compound having Si—H bonds at both ends, compounds represented by formulas (B-1) and (B-2) can be used.

[0048]

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[0049] [wherein, R ³ independently of one another represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, R ⁶
Each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group; R ⁷ independently of one another, a substituted or unsubstituted alkylene group; a substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, dialkyl (poly) silylene group, diaryl (poly) silylene group, a dialkyl silylene bis (alkylene) group or a direct bond,, Z ³ is a divalent A divalent substituted divalent silicon atom, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a heteroatom-containing organic group, a benzene polycarboxy group, a phosphate group, a polyoxyalkylene group, (Poly) carbonate group, (poly) ester group, polyacrylate or polymethacrylate And n ¹ represents an integer of 0 to 500. ]

In the formula (B-1), the alkyl group represented by R ³ includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, and the like. Examples include a benzyl group, a phenethyl group and the like, and examples of the aryl group include a phenyl group, a toluyl group, a naphthyl group and the like. The substituted alkyl group represented by R ³ includes, for example, a halogenated alkyl group such as a trifluoropropyl group and a chloropropyl group, and a cyanoalkyl group such as a 2-cyanoethyl group.

In the compound represented by the formula (B-2),
Examples of the alkyl group and the aryl group represented by R ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group,
It includes an octyl group, a dodecyl group, a phenyl group, a toluyl group, a naphthyl group and the like. The aralkyl group represented by R ⁶ includes, for example, a benzyl group, a phenethyl group and the like.

The alkylene group represented by R ⁷ includes a methylene group, an ethylene group, a propylene group, a butylene group, an octylene group, a dodecylene group and the like, and the arylene group includes, for example, a phenylene group, a toluylene group,
A naphthylene group and the like are included, and an arylalkylene group includes, for example, a phenylmethylene group, a phenylethylene group, a phenylethylidene group and the like. The alkyl group of the dialkyl (poly) silylene group preferably has 1 to 6 carbon atoms, and includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and the like, and the aryl group of the diaryl (poly) silylene group is , Preferably having 6 to 10 carbon atoms,
For example, a phenyl group, a toluyl group, a naphthyl group and the like are included.

The alkyl group of the dialkylsilylenebis (alkylene) group represented by R ⁷ is an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms;
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Even if the two alkylene groups are the same as each other,
It may be different. Preferred dialkylsilylene bis (alkylene) groups include dimethylsilylene (methylene)
Examples include an ethylene group, dimethylsilylene (ethylene) ethylene group, and dimethylsilylene (ethylene) butylene group.

In the formula (B-2), the substituent of the disubstituted divalent silicon atom represented by Z ³ includes an alkyl group or an aryl group, preferably has 1 to 6 carbon atoms, more preferably 1 carbon atom. To 3 alkyl groups, most preferably a methyl group. Accordingly, a preferred disubstituted divalent silicon atom is a dialkylsilyl group, most preferably a dimethylsilyl group. Examples of the alkylene group and the arylene group represented by Z ³ include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, a phenyl group, a toluyl group, a naphthyl group, and the like.

The hetero atom-containing organic group represented by Z ³ is a group containing an oxygen, sulfur or nitrogen atom as a hetero atom, and these hetero atoms are present between carbon atoms to form ether, thioether and It may form a secondary amino group, may be present on a carbon atom to form a carbonyl, thiocarbonyl and / or imino group, or may be a mixture thereof. Therefore, the hetero atom-containing organic group includes an amide group. Also,
The hetero atom-containing organic group may have a substituent such as a halogen or a cyano group. The polyoxyalkylene group is preferably a group derived from a polymer of an alkylene oxide having 1 to 6 carbon atoms, for example, poly (oxymethylene), poly (oxyethylene), poly (oxypropylene), poly (oxypropylene) Butylene), poly (oxypentylene), and copolymers thereof. The (poly) carbonate group may be a glycol or polyglycol, such as ethylene glycol or propylene glycol, or an arylene diol or polyarylene diol, such as phenylene diol.
(CO) O- is a divalent group linked via O-, glycol preferably has 1 to 12, more preferably 2 to 8, most preferably 2 to 6 carbon atoms, and arylene diol is preferably Has a carbon number of 6 to 10, more preferably 6 to 8, and most preferably 6. The (poly) ester group may be a dicarboxylic acid such as glycolic acid, adipic acid, phthalic acid or terephthalic acid, and a glycol or polyglycol such as ethylene glycol or propylene glycol, or an arylene diol or polyarylene diol such as phenylene diol. And a divalent group obtained by dehydration condensation with As the glycol and arylene diol in this case, the same ones as in the case of the (poly) carbonate group can be used. The molecular weight of a divalent group derived from a polyoxyalkylene group, a (poly) carbonate group, a (poly) ester group, a heteroatom-containing organic group, polyacrylate and polymethacrylate is 6
It is 0 to 30,000, preferably 100 to 10,000. Preferably, Z ³ is a poly (oxyethylene) having a dimethylsilyl group, an alkylene group, a phenylene group.
Groups, poly (oxypropylene) groups, and polyoxyalkylene groups, such as copolymers thereof, (poly) carbonate groups, and (poly) ester groups.

R ⁶ , R ⁷ and Z ³ in the formula (B-2)
Examples of such substituents, when has substituents, include halogens such as chlorine, fluorine and bromine, and cyano groups. Specific groups having a substituent include halogenated alkyl groups such as a trifluoropropyl group and a chloropropyl group, and cyanoalkyl groups such as a 2-cyanoethyl group.

Specific examples of the compound having Si—H bonds at both terminals include:

[0058]

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[0059]

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[0060]

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And the like.

In the compound represented by the formula (A) relating to the electric double layer capacitor of the present invention, the alkyl group represented by R ¹ includes, for example, methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group And the like, and the aryl group includes, for example, a phenyl group, a toluyl group, a naphthyl group and the like. The alkylene group represented by R ² includes, for example, a methylene group, an ethylene group, a propylene group, a butylene group, an octylene group, a dodecylene group, and the like, and an arylene group includes, for example, a phenylene group,
Tolylene group, naphthylene group and the like, and the arylalkylene group includes, for example, a phenylmethylene group,
Examples include a phenylethylene group and a phenylethylidene group. The alkylene group represented by Z ¹ is the same as that described for R ² . Preferably, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 4 carbon atoms or a direct bond, and Z ¹ is an alkylene group, a polyoxyalkylene group, or a (poly) carbonate group. , (Poly) ester groups, polyacrylates,
It is a divalent group derived from polymethacrylate or polysiloxane.

In the compound represented by the formula (A), Z ¹
Is preferably a divalent group derived from a polymer of an alkylene oxide having 1 to 6 carbon atoms, for example, poly (oxymethylene), poly (oxyethylene), poly (oxypropylene) ), Poly (oxybutylene), poly (oxypentylene), and copolymers thereof. The (poly) carbonate group may be a glycol or polyglycol, such as ethylene glycol or propylene glycol, or an arylene diol or polyarylene diol, such as phenylene diol, may be -O (CO) O.
-Is a divalent group linked through-, glycol preferably has 1 to 12, more preferably 2 to 8, most preferably 2 to 6 carbon atoms, and arylene diol preferably has 6 to 10 carbon atoms. , More preferably 6 to 8, most preferably 6 carbon atoms. The (poly) ester group may be a dicarboxylic acid such as glycolic acid, adipic acid, phthalic acid or terephthalic acid, and a glycol or polyglycol such as ethylene glycol or propylene glycol, or an arylene diol or polyarylene diol such as phenylene diol. And a divalent group obtained by dehydration condensation with As the glycol and arylene diol in this case, the same ones as in the case of the (poly) carbonate group can be used. The hetero atom-containing organic group is
Groups containing an oxygen, sulfur or nitrogen atom as a heteroatom, which heteroatoms may be present on carbon atoms even if they are present between carbon atoms to form ether, thioether and / or secondary amino groups. To form a carbonyl, thiocarbonyl and / or imino group, or a mixture thereof. Therefore, this heteroatom-containing organic group includes an amide group. The hetero atom-containing organic group may have a substituent such as a halogen or a cyano group. The molecular weight of the divalent group derived from a polyoxyalkylene group, a (poly) carbonate group, a (poly) ester group, a heteroatom-containing organic group, polyacrylate and polymethacrylate is 60 to 30,00.
0, preferably 100 to 10,000. Preferably, Z ¹ is a polyoxyalkylene group having a molecular weight of 300 to 4,000, and poly (oxyethylene)
Group, poly (oxypropylene) group, or a copolymer thereof.

When R ¹ , R ² , and Z ¹ in the formula (A) have a substituent, the substituent includes a halogen such as chlorine, fluorine and bromine, and a cyano group. Specific groups having a substituent include a halogenated alkyl group such as a trifluoropropyl group and a chloropropyl group,
And a cyanoalkyl group such as a 2-cyanoethyl group.

The bond between the terminal alkenyl group and Z ¹ in these compounds is determined by the type of Z ¹ chain.
For example, when Z ¹ is a polyoxyalkylene chain, the terminal alkenyl group is bonded by an ether bond, and when Z ¹ is a polyester chain, the terminal alkenyl group is bonded by an ether bond or an ester bond.

Specific examples of the compound represented by the formula (A) include:

[0067]

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[0068]

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[0069]

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And the like.

In the compound represented by the formula (D) relating to the electric double layer capacitor of the present invention, examples of the alkyl group represented by R ⁴ include, for example, methyl group, ethyl group, propyl group, butyl group, octyl group, Including a dodecyl group,
The aryl group includes, for example, a phenyl group, a toluyl group, a naphthyl group and the like. The alkylene group represented by R ⁵ includes a methylene group, an ethylene group, a propylene group, a butylene group, an octylene group, a dodecylene group, and the like, and the arylene group includes, for example, a phenylene group, a toluylene group, and a naphthylene group. Included, and the arylalkylene group includes, for example, a phenylmethylene group, a phenylethylene group, a phenylethylidene group and the like. The hetero atom-containing organic group represented by R ⁵ is a group containing an oxygen, sulfur or nitrogen atom as a hetero atom, and these hetero atoms are present between carbon atoms to form ether, thioether and / Or 2
It may form a primary amino group, may be present on a carbon atom to form a carbonyl, thiocarbonyl and / or imino group, or may be a mixture thereof. Therefore, this heteroatom-containing organic group includes an amide group. The hetero atom-containing organic group may have a substituent such as a halogen or a cyano group. Further, an alkyl-polyoxyalkylene-alkyl group is also included. The alkyl group includes an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, and specifically, methyl-poly (oxyethylene) -methyl, methyl-poly (oxypropylene) -methyl , Methyl-poly (oxyethylene) -propyl, ethyl-poly (oxybutylene) -ethyl, ethyl-poly (oxypentylene) -propyl, and copolymers thereof.

In the compound represented by the formula (D), Z ²
The methylene group, ethylene group, propylene group, butylene group, octylene group, dodecyl group and the like are included in the alkylene group represented by. The alkanepolyyl group represented by Z ² includes a methynyl group, an ethynyl group, a propynyl group,
In addition to an alkynyl group such as a butynyl group, an octyl group and a dodecynyl group, a 1,2,3-propanetriyl group and the like are included. The polyvalent aromatic carbocyclic group represented by Z ² includes
It includes a benzenetriyl group, a naphthalenetriyl group and the like. The alkane polyoxy group represented by Z ² includes
1,2,3-propanetrioxy group, 1,2,3,4-
Butanetetraoxy group, 1,2,3,4,5,6-hexanehexoxy group and the like. The monosubstituted trivalent silicon atom represented by Z ² includes, for example, ≡Si-alkyl. In the hetero atom-containing organic group represented by Z ² , the hetero atom means an aliphatic or aromatic group containing an oxygen, sulfur or nitrogen atom. These heteroatoms may exist between carbon atoms to form ether, thioether and / or secondary amino groups, but still exist on carbon atoms to form carbonyl, thiocarbonyl and / or
Alternatively, an imino group may be formed, or a mixture thereof. Amide groups can also be used. Specifically, a methyleneoxymethynyl group, a methyleneoxyethynyl group, a methyleneoxypropynyl group, an ethyleneoxypropynyl group,
An alkylene group, an arylene group or an arylenedialkylene group such as a methyleneoxyethyleneoxymethynyl group, an ethyleneoxyethyleneoxyethynyl group, a propyleneoxyethyleneoxypropynyl group, a phenylenebis (methyloxyethynyl) group is an alkynyl with an ether bond. Includes groups bonded to groups, trioxotriazine groups, and those in which some of the oxygen atoms have been replaced by sulfur and / or nitrogen atoms. The benzene polycarboxy group represented by Z ² includes groups derived from benzenetricarboxylic acid and benzenetetracarboxylic acid. Porioki and an alkylene group represented by Z ^2, (poly) carbonate group, examples of the (poly) ester groups are the same as those indicated for Z ¹ in formula (A). Polyoxyalkylene group represented by Z ^2, (poly) carbonate groups, (poly) ester group, a hetero atom-containing organic group, the molecular weight of divalent group derived from polyacrylates and polymethacrylates, 60～30,00
0, preferably 100 to 10,000. Preferably, Z ¹ is a polyoxyalkylene group having a molecular weight of 300 to 4,000, and is a poly (oxyethylene) group, a poly (oxypropylene) group, or a copolymer thereof. Desirable n ¹ is an integer of 3 to 10.

Examples of R ^{9 in} formula (D) are the same as those described for R ⁴ except that R ⁹ is not a hydrogen atom, and examples of R ¹⁰ are the same as those described for R ⁵ .
And examples of Z ⁴ are the same as those shown for the Z ^2.
Preferred examples of R ⁹ , R ¹⁰ and Z ⁴ are also
^4, is similar to that shown for R ⁵ and Z ^2. Preferred n ³ is an integer of 2 to 10, especially 2 to 6.

The following are specific examples of the compound represented by the formula (D).

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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In the electric double layer capacitor of the present invention,
In the first embodiment, the reaction between the compound having the Si-H bond at both ends and the compound represented by the formula (A), and the compound having the Si-H bond at both ends and the formula ( Addition reaction between a linear polymer having two terminal hydrosilyl groups obtained by reaction with the compound represented by A) and a compound represented by formula (D) having three or more ethylenic double bonds ( The hydrosilylation reaction) can be promoted by mixing and heating at room temperature or lower because the reaction rate has a large temperature dependence. The heating temperature in this case is about 50 to 150 ° C., preferably 60 to 12 ° C.
It is about 0 ° C. As a catalyst that can be used in the hydrosilylation reaction, compounds such as platinum, ruthenium, rhodium, palladium, osmium, and iridium are known. Of these, the platinum compound is predominantly used because the reaction proceeds rapidly and does not adversely affect the electrical characteristics. Examples of platinum compounds include chloroplatinic acid, platinum alone,
Solid platinum supported on a carrier such as alumina, silica or carbon black, a platinum-vinylsiloxane complex, a platinum-phosphine complex, a platinum-phosphite complex, a platinum alcoholate catalyst or the like can be used. The platinum catalyst is added in an amount of about 0.0001 to 0.1% by mass as platinum.

In the electric double layer capacitor of the present invention, a composite polymer electrolyte in which a polymer electrolyte is integrated with an electrically insulating porous thin film is used. As the electrically insulating porous thin film, a porous film, a nonwoven fabric, or the like can be used. As the porous film, for example, a film obtained by forming a porous film from a thermoplastic resin such as polyolefin, polyester, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, polyamide, and fluororesin by a uniaxial stretching method or the like can be used.

The electric double-layer capacitor according to the present invention contains a plurality of fibers having different materials, fiber diameters, fiber lengths, etc., so that the porosity, mechanical strength, heat resistance, etc. Nonwoven fabrics capable of controlling the properties of the nonwoven fabric can be advantageously used.

Examples of the nonwoven fabric relating to the electric double layer capacitor of the present invention include polyolefin fibers, polyester fibers, polyvinyl chloride fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, polyamide fibers, fluororesin fibers, and recycled fibers. , Semi-synthetic fibers, natural fibers and the like. The fibers constituting the nonwoven fabric may be fibrillated.

In the electric double layer capacitor of the present invention,
A hydrogen bond of a nonwoven fabric in which a part of fibers is bonded by a hydrogen bond is a bond in which atoms V and W having a high electronegativity are connected via a hydrogen bond, and is represented by the general formula (H).

[0088]

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Here, V is nitrogen, oxygen, phosphorus, sulfur,
Represents an atom such as halogen. W represents an atom such as nitrogen, oxygen, phosphorus, sulfur, and halogen, as well as a heterocyclic ring and an unsaturated bond. In order for a part of the fibers to be bonded by a hydrogen bond, a fiber containing a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphate group, an oxyphosphate group, or an amide group is used as the fiber having a VH group. I do. As the fiber having the atom W, a fiber having a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an oxyphosphoric acid group, an amide group, a hetero atom-containing alkyl group, an unsaturated bond, a heterocyclic ring, or the like is used. In order to form hydrogen bonds, of the above fibers,
Cellulose fiber, polyamide fiber, polyester fiber, polyvinyl chloride fiber, polyvinyl alcohol fiber, acrylonitrile fiber, fluororesin fiber, glass fiber and the like can be mentioned.

In the electric double layer capacitor of the present invention,
Nonwoven fabric that can be used as an electrically insulating porous thin film can be manufactured by any of a dry method and a wet method,
It is preferable to use a nonwoven fabric manufactured by a wet method in order to obtain a nonwoven fabric that is compatible with thinning and in which some of the components are bonded by hydrogen bonding. In the wet method, usually, fibers are uniformly dispersed in water using a dispersing aid, a thickener, and the like to form a slurry, and water is added to the slurry to form an aqueous slurry having an appropriate concentration. It is a method of obtaining a nonwoven fabric by using the sheet to form a sheet. As the wet method, a fourdrinier paper machine, a round paper machine, an inclined paper machine, or a combination machine combining two or more types can be used.

As the heat-resistant organic fiber relating to the electric double layer capacitor of the present invention, a fiber whose tensile strength reduction rate is within 10% even when it is kept at 200 ° C. for 3 days or more can be preferably used. As a polymer constituting such a fiber, wholly aromatic polyamide (aramid), polyphenylene sulfide, polyetheretherketone, polyethersulfone, polyetherimide, polyester, wholly aromatic polyester, or the like can be used. These fibers may be used alone or in combination of two or more.

Among these, a wholly aromatic polyamide fiber and a wholly aromatic polyester fiber which are particularly excellent in heat resistance can be used advantageously. The fiber diameter is preferably 1 to 30 μm.

In the electric double layer capacitor of the present invention,
In order to obtain a uniform nonwoven fabric, it is preferable to use fibrillated fibers as constituent fibers. As a method for producing the fibrillated fibers, for example, a method of adding a precipitant of the polymer solution to the polymer solution constituting the fibers and applying a shearing force is used. Examples thereof include a method of applying a shearing force by introducing the suspension into a high-pressure homogenizer for producing an emulsion or a dispersion, and a method of applying a mechanical shearing force such as beating to a molded product made of a polymer constituting a fiber. Among them, a method using a high-pressure homogenizer can be advantageously used. Bacterial cellulose can also be used as the fibrillated cellulose fiber.

The glass fibers relating to the electric double layer capacitor of the present invention are those produced by a vapor spraying method, a spinning method, a flame insertion method, a rotary method or the like, and particularly, the average fiber diameter is preferably 5 μm or less. preferable.

The basis weight of the electrically insulating porous thin film according to the electric double layer capacitor of the present invention is not particularly limited.
Preferably 50 g / m ^2, is used more preferably 10 to 30 g / m ^2. The thickness is also not particularly limited, but is preferably thinner from the viewpoint of miniaturization of the electric double layer capacitor, and more preferably 10 to 200 μm, and more preferably 1
5 to 100 μm. The thickness of the electrically insulating porous thin film can be adjusted by calendering such as a super calender, a machine calender, a thermal calender, a soft calender, and a thermal soft calender.

The porosity of the electrically insulating porous thin film according to the electric double layer capacitor of the present invention is preferably 20 to 80%. If the porosity is less than 20%, a sufficient polymer electrolyte cannot be maintained. If the porosity is more than 80%, the mechanical strength of the composite polymer electrolyte is low, and the safety of the electric double layer capacitor is low. Can not be enhanced. The porosity in the present invention can be determined by (specific gravity of insulating porous thin film−density of insulating porous thin film) / specific gravity of insulating porous thin film × 100 [%].

The polymer electrolyte according to the present invention includes:
Either an all-solid electrolyte containing no electrolyte or a gel electrolyte containing an electrolyte may be used.

In the electric double layer capacitor of the present invention,
When the polymer electrolyte is a gel electrolyte, use an aprotic polar solvent with a high dielectric constant or a low viscosity, or an organic solvent that is electrochemically stable and dissolves the electrolyte salt, as the medium of the electrolyte solution. I do. For example, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, carbonates such as ethyl methyl carbonate, lactones such as γ-butyrolactone, dimethylformamide, amide solvents such as dimethylacetamide, sulfolane, acetonitrile,
Dimethyl sulfoxide, tetrahydrofuran, dimethoxyethane and the like can be mentioned. These electrolytes are
In the polymer electrolyte relating to the electric double layer capacitor of the present invention, it is present at 0 to 99% by mass.

The electric power related to the electric double layer capacitor of the present invention
As the decomposing salt, metal cation, ammonium ion,
Select from amidinium ion and guanidinium ion
Cations, chlorine ions, bromine ions, iodine ions
ON, perchlorate ion, thiocyanate ion, tetraf
Fluoroborate ion, nitrate ion, AsF₆ ^-, P
F ₆ ^-, Stearyl sulfonate ion, octyl sulfone
Acid ion, dodecylbenzenesulfonic acid ion, naphtha
Lensulfonic acid ion, dodecylnaphthalenesulfonic acid
Ion, 7,7,8,8-tetracyano-p-quinodime
Tanion, X¹SO_Three ^-, [(X¹SO_Two) (X^TwoSO_Two)
N]^-, [(X¹SO_Two) (X^TwoSO_Two) (X^ThreeSO_Two) C]^-
And [(X¹SO_Two) (X^TwoSO_Two) YC]^-Chosen from
And an anion. Where X
¹, X^Two, X^ThreeAnd Y are electron-withdrawing groups. further,
Preferably X¹, X^TwoAnd X^ThreeHave each independently a carbon number
1 to 6 perfluoroalkyl groups or perfluoroa
Y is a nitro group, a nitroso group, a carbon
A carboxyl group or a cyano group. X¹,
X^TwoAnd X^ThreeMay be the same or different
No. These electrolytes are used in the electric double layer capacitor of the present invention.
0.1 to 60% by mass in the polymer electrolyte concerned
Or 1.0 to 40% by mass.

Further, a polyalkylene oxide compound such as tetraethylene glycol dimethyl ether and tetrapropylene glycol dimethyl ether, a modified polyacrylate having a polyalkylene oxide as a structural unit,
An ion conductive polymer such as modified polyphosphazene having a structural unit of polyacrylonitrile, polyvinylidene fluoride, or polyalkylene oxide can also be blended.

In order for the electric double layer capacitor of the present invention to exhibit high charge / discharge characteristics, the composite polymer electrolyte integrated with the electrically insulating porous thin film must be 1 × 1 at 25 ° C.
0 ^-3 S / cm or more, 1 x 10 ^-4 S / c at -30 ° C
It preferably has an ionic conductivity of at least m. When the polymer electrolyte is a gel electrolyte, the polymer electrolyte preferably has an ion conductivity of 40% or more of the electrolyte.

In the electric double layer capacitor of the present invention,
The composite polymer electrolyte integrated with the electrically insulating porous thin film preferably has a puncture strength of 0.1 N or more in order to obtain sufficient safety of the electric double layer capacitor. The puncture strength can be adjusted by the type, concentration, molecular weight, type, thickness, basis weight, porosity, etc. of the polymer used for the polymer electrolyte. Also, considering the workability of assembling the electric double layer capacitor, the tensile strength of the composite polymer electrolyte is 200 N / m
It is preferable that it is above.

In the electric double layer capacitor of the present invention,
The method of integrating the polymer electrolyte and the insulating porous thin film is as follows: (a) A method of doping the polymer with the electrolyte, heating and melting, directly applying to the insulating porous thin film, and then cooling and solidifying. Method of directly coating and impregnating the solution mixed with the electrolyte on the insulating porous thin film and solidifying it by cooling (c) Polymerization reaction after directly coating and impregnating the polymer raw material and electrolyte on the insulating porous thin film (D) Coating the raw material of the polymer directly on the insulating porous thin film
Method of performing polymerization reaction after impregnation, and swelling with electrolyte solution (e) Method of dissolving polymer raw material in electrolyte solution, directly coating and impregnating insulating porous thin film, then performing polymerization reaction ( F) Method of directly coating and impregnating the raw material of the polymer and the electrolyte salt on the insulating porous thin film, and then performing a polymerization reaction and swelling with the medium of the electrolytic solution. A method of assembling an electric double layer capacitor and then injecting a raw material of a polymer and an electrolyte salt into the capacitor and performing a polymerization reaction (h) Using an insulating porous thin film and a polarizable electrode, an electric double layer After assembling the capacitor, there is a method of injecting a polymer raw material / electrolyte solution into the capacitor and performing a polymerization reaction.

In the electric double layer capacitor of the present invention, both the positive electrode and the negative electrode use a carbonaceous electrode mainly composed of a carbon material. Activated carbon, carbon black, polyacene and the like can be used as the carbon material. If necessary, a conductive material may be added to the carbonaceous electrode to increase conductivity, and an organic binder resin is added to form a sheet on a metal current collector and integrated with the current collector. Formed electrodes. As the organic binder resin, polyvinylidene fluoride, polytetrafluoroethylene, a polyimide resin, a polyamideimide resin, or the like can be used. Further, as the metal current collector, a foil, a net, or the like of aluminum, stainless steel, or the like can be used.

[0105]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 Production of Electrically Insulating Porous Thin Film Polypropylene having a fineness of 0.8 dtex and a fiber length of 5 mm
Polyethylene core sheath fiber 40% by mass, polyethylene synthetic pulp 30% by mass, fineness 0.8dtex, fiber length 10mm
Was dispersed in water using a pulper together with a dispersing aid and then diluted with water to a predetermined concentration to prepare a slurry. From this slurry, a basis weight of 28 g / m ² and a thickness of 73 μm were obtained by a wet method using a round paper machine.
Was manufactured. 15 for this wet nonwoven
A heat calendering treatment was performed at 0 ° C. to heat-bond the fibers and to adjust the thickness. Obtained electrically insulating porous thin film a
Had a basis weight of 28 g / m ² , a thickness of 50 μm, and a porosity of 60%.

Production of Composite Polymer Electrolyte The polymer electrolyte compositions shown in Table 1 were uniformly mixed.
The mixed solution was impregnated and squeezed with an electrically insulating porous thin film a dried at 120 ° C. for 10 hours, kept at 90 ° C. for 2 hours, and then cooled to room temperature to prepare a composite polymer electrolyte A. . The obtained composite polymer electrolyte A was 98 g /
m ² and thickness 52 μm.

[0108]

[Table 1]

Example 2 Production of Composite Polymer Electrolyte The raw materials shown in Table 2 were mixed and reacted at 80 ° C. under a nitrogen atmosphere, and then toluene was removed to obtain a linear block having hydrosilyl groups at both ends. A copolymer (C-1) was synthesized.

[0110]

[Table 2]

The above block copolymer (C-1) and each compound were mixed as shown in Table 3. To this mixture, 12
The electrically insulating porous thin film a dried at 0 ° C. for 10 hours was impregnated and squeezed, kept at 90 ° C. for 2 hours, and then cooled to room temperature to prepare a composite polymer electrolyte B. The obtained composite polymer electrolyte B had a thickness of 95 g / m ² and a thickness of 51 μm.
Met.

[0112]

[Table 3]

Example 3 Production of Composite Polymer Electrolyte The raw materials shown in Table 4 were mixed and reacted at 80 ° C. under a nitrogen atmosphere, and then toluene was removed to obtain a linear block having hydrosilyl groups at both ends. A copolymer (C-2) was synthesized.

[0114]

[Table 4]

The above block copolymer (C-2) and each compound were mixed as shown in Table 5. To this mixture, 12
The electrically insulating porous thin film a dried at 0 ° C. for 10 hours was impregnated and squeezed, kept at 90 ° C. for 2 hours, and cooled to room temperature to prepare a composite polymer electrolyte C. The obtained composite polymer electrolyte C was 97 g / m ² and had a thickness of 53 μm.
Met.

[0116]

[Table 5]

Example 4 Production of Electrically Insulating Porous Thin Film At least a portion of fibrillated polypropylene fiber having a fiber diameter of 1 μm or less 30% by mass, fineness 0.7 dtex, fiber length 10 mm, polypropylene / polyethylene core-sheath fiber 4
30% by mass of polypropylene short fibers of 0% by mass, a fineness of 1.7 dtex and a fiber length of 10 mm were dispersed in water using a pulper together with a dispersing agent, and then diluted to a predetermined concentration with water to prepare a slurry. From this slurry, a wet nonwoven fabric having a basis weight of 30 g / m ² and a thickness of 90 μm was produced by a wet method using a circular paper machine. 140 for this wet nonwoven
A heat calendering treatment was performed at a temperature of 0 ° C. to thermally fuse the fibers and adjust the thickness. The obtained electrically insulating porous thin film b
Had a basis weight of 30 g / m ² , a thickness of 50 μm, and a porosity of 57%.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film b dried at 120 ° C. for 10 hours in the mixed solution of Table 5, held at 90 ° C. for 2 hours, and then cooled to room temperature Thus, a composite polymer electrolyte D was prepared. 99 g of the obtained composite polymer electrolyte D
/ M ² and a thickness of 51 μm.

Example 5 Production of Electrically Insulating Porous Thin Film A dry type was prepared by using 40 mass% of polypropylene short fibers having a fineness of 0.8 dtex and a fiber length of 10 mm and 60 mass% of polypropylene / polyethylene core-sheath long fibers having a fineness of 1.7 dtex. A dry nonwoven fabric having a basis weight of 20 g / m ² and a thickness of 90 μm was prepared by the method. This dry nonwoven fabric was subjected to a heat calender treatment at 120 ° C. The obtained electrically insulating porous thin film c
Had a basis weight of 20 g / m ² , a thickness of 40 μm, and a porosity of 64%.

Preparation of Composite Polymer Electrolyte The impregnated and squeezed liquid of the electrically insulating porous thin film c dried at 120 ° C. for 10 hours was mixed with the mixed solution shown in Table 5, and kept at 90 ° C. for 2 hours. Thus, a composite polymer electrolyte E was prepared. The obtained composite polymer electrolyte E weighed 72 g.
/ M ² and a thickness of 41 μm.

Example 6 Production of an Electrically Insulating Porous Thin Film A dry type was prepared by using 40 mass% of para-aramid short fibers having a fineness of 1.4 dtex and a fiber length of 6 mm and 60 mass% of para-aramid long fibers having a fineness of 3.3 dtex. Basis weight 16g / m by method
^2. A dry nonwoven fabric having a thickness of 70 μm was prepared. This dry nonwoven fabric was subjected to a heat calender treatment at 180 ° C. The obtained electrically insulating porous film d had a basis weight of 16 g / m ² , a thickness of 50 μm, and a porosity of 77%.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film d dried at 200 ° C. for 2 hours in the mixed solution of Table 5, held at 90 ° C. for 2 hours, and then cooled to room temperature Thus, a composite polymer electrolyte F was prepared. The obtained composite polymer electrolyte F was 67 g /
m ² and thickness 52 μm.

Example 7 Production of an Electrically Insulating Porous Thin Film A fully durable polyester short fiber having a fineness of 1.5 dtex and a fiber length of 10 mm was 50% by mass and a fully aromatic polyester filament having a fineness of 2.2 dtex was 50% by mass. A dry nonwoven fabric having a basis weight of 20 g / m ² and a thickness of 60 μm was prepared by a dry method. This dry nonwoven fabric was subjected to a heat calender treatment at 180 ° C. The obtained electrically insulating porous film e has a basis weight of 2
0 g / m ² , thickness 35 μm, and porosity 59%.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film e dried at 200 ° C. for 2 hours, and kept at 90 ° C. for 2 hours, then cooled to room temperature. Thus, a composite polymer electrolyte G was prepared. The obtained composite polymer electrolyte G was 82 g /
m ² and thickness 35 μm.

Example 8 Production of Electrically Insulative Porous Thin Film A fineness of 1.6 dtex, a fiber length of 10 mm, a melting point of 255% polyester short fiber 40% by mass, and a fineness of 1.7 dte
x, 40% by mass of polyester short fiber having a fiber length of 20 mm and a melting point of 255 ° C, and 20% by mass of a polyester having a fineness of 1 dtex and a fiber length of 3mm and a modified polyester core and sheath fiber having a melting point of 110 ° C and a melting point of 110 ° C together with a dispersing agent. And then diluted with water to a predetermined concentration to prepare a slurry. From this slurry, a wet nonwoven fabric having a basis weight of 25 g / m ² and a thickness of 83 μm was produced by a wet method using a circular paper machine. This wet nonwoven fabric was subjected to a heat calender treatment at 180 ° C. The obtained electrically insulating porous thin film f had a basis weight of 25 g / m ² , a thickness of 50 μm, and a porosity of 5
8%.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film f dried at 200 ° C. for 2 hours in the mixed solution of Table 5, held at 90 ° C. for 2 hours, and then cooled to room temperature Thus, a composite polymer electrolyte H was prepared. The obtained composite polymer electrolyte H was 99 g /
m ² and thickness 53 μm.

Example 9 Production of Electrically Insulating Porous Thin Film 30 d% of polyester fiber having a fineness of 0.1 dtex, fiber length of 3 mm, melting point of 255 ° C., 40 d% of polyester fiber having a fineness of 1.7 dtex, fiber length of 10 mm, and fiber length 3m
A polyester having a melting point of 255 ° C./modified polyester core-sheath fiber having a melting point of 110 ° C./30% by mass was dispersed in water using a pulper together with a dispersing agent, and then diluted to a predetermined concentration with water to prepare a slurry. From the slurry, a basis weight of 20 g / m ² and a thickness of 60 μm were obtained by a wet method using a circular paper machine.
m was prepared. 1 for this wet nonwoven
Heat calendering was performed at 80 ° C. The obtained electrically insulating porous thin film g had a basis weight of 20 g / m ² , a thickness of 50 μm,
The porosity was 71%.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film g dried at 200 ° C. for 2 hours, and kept at 90 ° C. for 2 hours, then cooled to room temperature Thus, a composite polymer electrolyte I was prepared. The obtained composite polymer electrolyte I was 77 g /
m ² , and the thickness was 51 μm.

Example 10 Production of Electrically Insulating Porous Thin Film Fine Fiber 0.1 dtex, Fiber Length 3 mm, Polyester Fiber with Melting Point 255 ° C. 40% by Mass, Fineness 1.38 dtex, Para-Aramid Short Fiber with Fiber Length 6 mm 50% by Mass Then, 10% by mass of vinylon fiber as a binder was dispersed in water using a pulper together with a dispersing aid, and then diluted to a predetermined concentration with water to prepare a slurry. From this slurry, a basis weight of 25 g / m ² and a thickness of 70 were obtained by a wet method using a round paper machine.
A wet nonwoven fabric of μm was produced. This wet nonwoven fabric was subjected to a heat calender treatment at 180 ° C. The obtained electrically insulating porous thin film h had a basis weight of 25 g / m ² and a thickness of 50 μm.
m, and the porosity was 64%.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film h dried at 200 ° C. for 2 hours in the mixed solution of Table 5, held at 90 ° C. for 2 hours, and then cooled to room temperature Thus, a composite polymer electrolyte J was prepared. The obtained composite polymer electrolyte J was 89 g /
m ² and thickness 52 μm.

Example 11 Production of Electrically Insulating Porous Thin Film At least a portion of fibrillated para-aramid fiber having a fiber diameter of 1 μm or less is 30% by mass, fineness is 0.1 dtex, fiber length is 3 mm, and polyester fiber having a melting point of 255 ° C. is 40% by mass. %, A para-aramid short fiber having a fineness of 1.38 dtex and a fiber length of 6 mm was dispersed in water using a pulper together with a dispersing aid, and then diluted with water to a predetermined concentration to prepare a slurry. From this slurry, a wet nonwoven fabric having a basis weight of 30 g / m ² and a thickness of 80 μm was produced by a wet method using a circular paper machine. This wet nonwoven fabric was subjected to a heat calender treatment at 180 ° C. The obtained electrically insulating porous thin film i had a basis weight of 30 g / m ² , a thickness of 50 μm, and a porosity of 57%.
Met.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film i dried at 200 ° C. for 2 hours in the mixed solution of Table 5, held at 90 ° C. for 2 hours, and then cooled to room temperature Thus, a composite polymer electrolyte K was prepared. The obtained composite polymer electrolyte K was 93 g /
m ² , and the thickness was 51 μm.

Example 12 Production of Electrically Insulating Porous Thin Film 30% by mass of a wholly aromatic polyester fiber in which at least a part thereof was fibrillated to a fiber diameter of 1 μm or less, and a fineness of 0.1 d
tex, 3 mm in fiber length, 40% by mass of polyester fiber having a melting point of 255 ° C., fineness of 1.38 dtex, and 30% by mass of para-aramid short fiber having a fiber length of 6 mm are dispersed in water using a pulper together with a dispersing agent, and then with water. The slurry was diluted to a predetermined concentration to prepare a slurry. From the slurry, a basis weight of 25 g / m ² and a thickness of 80 μm were obtained by a wet method using a round paper machine.
m was prepared. 1 for this wet nonwoven
Heat calendering was performed at 80 ° C. The obtained electrically insulating porous thin film j had a basis weight of 25 g / m ² , a thickness of 50 μm,
The porosity was 64%.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film j dried at 200 ° C. for 2 hours, and kept at 90 ° C. for 2 hours, then cooled to room temperature Thus, a composite polymer electrolyte H was prepared. The obtained composite polymer electrolyte H was 81 g /
m ² and thickness 50 μm.

Example 13 Production of Electrically Insulating Porous Thin Film 5% by mass of fibrillated para-aramid fiber, fineness 0.1 d
tex, 30% by mass of a polyester fiber having a fiber length of 3 mm,
0.5 dtex fineness, 30% by mass of polyester fiber having a fiber length of 3 mm, fineness 1 dtex, melting point 25 having a fiber length of 3 mm
5% polyester / 30% by mass of modified polyester core-sheath fiber having a melting point of 110 ° C., and 5% by mass of micro glass fiber having an average fiber diameter of 3 μm are dispersed in water with a dispersing agent using a pulper, and then diluted to a predetermined concentration with water. Thus, a slurry was prepared. From this slurry, a wet nonwoven fabric having a basis weight of 18 g / m ² and a thickness of 100 μm was produced by a wet method using a circular paper machine. This wet nonwoven fabric was subjected to a heat calendering treatment at 150 ° C. to thermally fuse the fibers and adjust the thickness. The obtained electrically insulating porous thin film k has a basis weight of 18 g.
/ M ² , thickness 50 μm, and porosity 74%.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film k dried at 200 ° C. for 2 hours, and kept at 90 ° C. for 2 hours, then cooled to room temperature Thus, a composite polymer electrolyte M was prepared. The obtained composite polymer electrolyte M was 72 g /
m ² and thickness 50 μm.

Example 14 Production of Electrically Insulating Porous Thin Film Fibrillated cellulose fiber 10% by mass, at least a portion of which was a fibrillated polyethylene fiber 20 having a fiber diameter of 1 μm or less.
Mass%, fineness 0.1 dtex, fiber length 3 mm, melting point 25
5% polyester fiber 40% by mass, fineness 0.8 dte
x, 30% by mass of polypropylene / polyethylene short core fiber having a fiber length of 10 mm was dispersed in water using a pulper together with a dispersing aid, and then diluted with water to a predetermined concentration to prepare a slurry. From this slurry, a wet nonwoven fabric having a basis weight of 30 g / m ² and a thickness of 80 μm was prepared by a wet method using a circular paper machine. This wet nonwoven fabric was subjected to a heat calender treatment at 180 ° C. The obtained electrically insulating porous thin film 1 had a basis weight of 30 g / m ² , a thickness of 50 μm, and a porosity of 57%.
Met.

Preparation of Composite Polymer Electrolyte The impregnated and squeezed liquid of the electrically insulating porous thin film 1 dried at 120 ° C. for 10 hours was mixed with the mixed solution shown in Table 5, and kept at 90 ° C. for 2 hours. Thus, a composite polymer electrolyte N was prepared. 89 g of the obtained composite polymer electrolyte N was obtained.
/ M ² and a thickness of 51 μm.

Example 15 Preparation of Bacterial Cellulose CSL- having the composition of Table 6 from glycerol stock
BPR2001 strain (Acetobacter xylinum) was placed in a 750 ml roux flask charged with 100 ml of Fru medium.
1% of Subsby Seeds schrofermentance)
The cells were inoculated and cultured at 28 ° C. for 3 days. Table 7 shows CSL-
It is a composition of a vitamin mixture of a Fru medium. Table 8
Is the composition of the salt mixture of the CSL-Fru medium. After the culture, the roux flask was shaken well to remove the cells from the cellulose membrane, and 12.5 ml of the bacterial solution was inoculated into a 500 ml flask containing 112.5 ml of the medium, and was inoculated at 28 ° C and 180 rpm.
m for 3 days. The culture is aseptically disintegrated with a blender, and 60 ml of the culture is mixed with 540 ml of CSL-Fru.
Inoculate 11 jars containing the medium and adjust the pH to 4.9 to 5.1 with ammonia (gas) and 1N sulfuric acid so that the dissolved oxygen (DO) becomes 3.0% or more. Main culture was performed by aeration and agitation culture while automatically controlling the number of revolutions. After completion, the obtained culture solution was diluted about 5 times with an acetate buffer, and then centrifuged to collect a precipitate. The precipitate was suspended in an 8 times volume of 0.1 N sodium hydroxide solution and heated at 80 ° C. for 20 minutes to lyse the cells. After the lysis, the precipitate was recovered by centrifugation. Thereafter, the precipitate was suspended in 8 volumes of distilled water, heated at 80 ° C. for 20 minutes, centrifuged after heating, and the precipitate was collected to wash the cellulose. Washing was performed three times in the same process to obtain purified bacterial cellulose.

[0140]

[Table 6]

[0141]

[Table 7]

[0142]

[Table 8]

990 g of water was added to 10 g (dry weight) of the purified bacterial cellulose, and the mixture was disintegrated at 5,000 rpm for 3 minutes using a high-speed mixer to prepare a 1.0% suspension of disintegrated bacterial cellulose.

Production of Electrically Insulating Porous Thin Film Fineness 0.1 dtex, Fiber length 3 mm, 20% by mass of polyester fiber having a melting point of 255 ° C., Fineness 1.7 dtex, Short polypropylene fiber 10% in fiber length 50% by mass, Fineness 0.8 dtex 15% by weight of a polypropylene / polyethylene core-sheath fiber having a fiber length of 5 mm, bacterial cellulose 1
5% by mass was dispersed in water using a pulper together with a dispersing aid, and then diluted to a predetermined concentration with water to prepare a slurry. From this slurry, the wet method using a round paper machine,
A wet nonwoven fabric having a basis weight of 25 g / m ² and a thickness of 70 μm was prepared. This wet nonwoven fabric was subjected to a heat calender treatment at 140 ° C. The obtained electrically insulating porous thin film m had a basis weight of 25 g / m ² , a thickness of 50 μm, and a porosity of 64%.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film m dried at 120 ° C. for 12 hours in the mixed solution of Table 5, held at 90 ° C. for 2 hours, and then cooled to room temperature Thus, a composite polymer electrolyte O was prepared. 95 g of the obtained composite polymer electrolyte O
/ M ² and thickness 50 μm.

Example 16 Production of Electrically Insulative Porous Thin Film Softwood bleached kraft pulp was beaten with a refiner to 280 ml of Canadian Standard Freeness (CSF), 70% by mass, and 20% by mass of polyester fiber having a fineness of 0.1 dtex and a fiber length of 3 mm % And 10% by mass of microfibrillated cellulose fibrillated with a high-pressure homogenizer were dispersed in water using a pulper, and then diluted with water to a predetermined concentration to prepare a slurry. From this slurry, a basis weight of 18 g / m ² and a thickness of 75 μm were obtained by a wet method using a round paper machine.
m was obtained. This wet nonwoven fabric is calendered to a basis weight of 18 g / m ² , a thickness of 50 μm, and a porosity of 7
4% of an electrically insulating porous thin film h was obtained.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film h dried at 120 ° C. for 10 hours, and kept at 90 ° C. for 2 hours, then cooled to room temperature. Thus, a composite polymer electrolyte P was prepared. 63 g of the obtained composite polymer electrolyte P
/ M ² and thickness 50 μm.

Example 17 Production of Electrically Insulating Porous Thin Film Fineness 0.1 dtex, 40% by mass of 3 mm fiber length polyester fiber, 20% by mass of bacterial cellulose produced in the same manner as in Example 15, fineness 1.4 dtex, fiber length 6m
m-para-aramid short fiber 40% by mass was dispersed in water using a pulper together with a dispersing aid, and then diluted with water to a predetermined concentration to prepare a slurry. From the slurry, a basis weight of 15 g / m ² and a thickness of 75 were obtained by a wet method using a circular paper machine.
A wet nonwoven fabric of μm was manufactured. This wet nonwoven fabric was subjected to a calender treatment. The obtained electrically insulating porous thin film o had a basis weight of 15 g / m ² , a thickness of 50 μm, and a porosity of 79.
%Met.

Preparation of Composite Polymer Electrolyte Impregnated and squeezed with the electrically insulating porous thin film o dried at 200 ° C. for 2 hours, and kept at 90 ° C. for 2 hours, then cooled to room temperature Thus, a composite polymer electrolyte Q was prepared. The obtained composite polymer electrolyte Q was 65 g /
m ² and thickness 50 μm.

Example 18 Production of Electrically Insulating Porous Thin Film Polypropylene having a fineness of 0.8 dtex and a fiber length of 5 mm was prepared.
Microfibrillated cellulose 30 fibrillated by high-pressure homogenizer, 40% by mass of polyethylene core-sheath fiber
A slurry was prepared by dispersing 30% by mass of a polypropylene fiber having a mass% of 0.8 dtex and a fineness of 0.8 dtex and a fiber length of 10 mm together with a dispersing agent in water using a pulper and then diluting to a predetermined concentration with water. From this slurry, a wet nonwoven fabric having a basis weight of 28 g / m ² and a thickness of 63 μm was produced by a wet method using a circular paper machine. This wet nonwoven fabric was subjected to a heat calendering treatment at 150 ° C. to thermally fuse the fibers and adjust the thickness. The obtained electrically insulating porous thin film p had a basis weight of 28 g / m ² , a thickness of 50 μm, and a porosity of 60%.

Preparation of Composite Polymer Electrolyte
Impregnated with the electrically insulating porous thin film p dried for 10 hours
After the solution was squeezed and kept at 90 ° C. for 2 hours, it was cooled to room temperature to prepare a composite polymer electrolyte R. The obtained composite polymer electrolyte K had a thickness of 107 g / m ² and a thickness of 50 μm.
Met.

Example 19 Production of Composite Polymer Electrolyte A microporous polypropylene membrane (15 g / m ² , thickness 50 μm, porosity 67%) dried at 120 ° C. for 12 hours was impregnated and squeezed into the mixed solution shown in Table 5. The mixture was kept at 90 ° C. for 2 hours, and then cooled to room temperature to prepare a composite polymer electrolyte S. The obtained composite polymer electrolyte S was 56 g / m2.
^{2. The} thickness was 51 μm.

Comparative Example 1 The polymer electrolyte compositions shown in Table 1 were uniformly mixed.
This mixed solution was cast on a polyethylene terephthalate sheet, kept at 90 ° C. for 2 hours, cooled to room temperature, and peeled off to prepare a polymer electrolyte single membrane having a basis weight of 75 g / m ² and a thickness of 55 μm.

Comparative Example 2 The polymer electrolyte compositions shown in Table 3 were uniformly mixed.
This mixed solution was cast on a polyethylene terephthalate sheet, kept at 90 ° C. for 2 hours, cooled to room temperature, and peeled off to prepare a polymer electrolyte single membrane having a basis weight of 70 g / m ² and a thickness of 50 μm.

Comparative Example 3 The polymer electrolyte compositions shown in Table 5 were uniformly mixed.
This mixed solution was cast on a polyethylene terephthalate sheet, kept at 90 ° C. for 2 hours, cooled to room temperature, and peeled off to prepare a polymer electrolyte single membrane having a basis weight of 70 g / m ² and a thickness of 50 μm.

The following evaluation was performed on the composite polymer electrolyte of the above example and the polymer electrolyte of the comparative example.
The results are summarized in Tables 10 and 11.

(I) Ionic conductivity: A composite polymer electrolyte or a polymer electrolyte was sandwiched between platinum electrodes of 20 mmφ, and the frequency dependence of the impedance at 10 Hz to 10 kHz was measured by the AC impedance method.
The ionic conductivity [S / cm] in Hz was determined.

(II) Puncture strength: A composite polymer electrolyte or a polymer electrolyte was set in a 25 mmφ fixed frame,
A puncture needle having a tip radius of 1 mmφ was pierced at 100 mm / min, and a load [N] when a defect such as a hole occurred in the polymer electrolyte was obtained, and the safety was evaluated for the electric double layer capacitor.

(III) Tensile strength: The tensile strength of the composite polymer electrolyte or the polymer electrolyte in the longitudinal (production flow) direction was measured. According to JIS-P-8113, the tensile strength is 5 cm wide and 20 c long from each composite polymer electrolyte.
m of the test piece was taken, and the load at break was set to 1 using a Tensilon measuring instrument (manufactured by Orientec; HTM-100).
The measurement was performed 0 times, and the average value was shown.

(IV) Electric characteristics of electric double layer capacitor:
80 g of highly activated carbon having a non-surface area of 2000 m ² / g and an average particle size of 8 μm, 10 g of acetylene black, and 12 g
% Concentration of PVDF (N-methylpyrrolidone solution) 100
g and 150 g of N-methylpyrrolidone were mixed to prepare an activated carbon-containing liquid. This liquid was applied on an aluminum foil to produce a capacitor electrode. This electrode was laminated with the composite polymer electrolyte of the example or the polymer electrolyte of the comparative example to produce a square laminated electric double layer capacitor. As electric characteristics of the electric double layer capacitor, the electric double layer capacitor was charged at 2.5 V for 24 hours, then discharged to 0 V, and the leakage current [μA] and the internal resistance [mΩ] were measured.

(V) Stable Productivity of Electric Double Layer Capacitor: A cylindrical wound electric double layer using the electrode described in (IV) above and the composite polymer electrolyte of the example or the polymer electrolyte of the comparative example. The stable productivity of the capacitor was confirmed.

(VI) Safety of Electric Double Layer Capacitor: A rectangular laminated electric double layer capacitor was produced by the method described in (IV) above, using the composite polymer electrolyte of the example. Liquid leakage was observed when a 3 mmφ metal rod was pierced into the electric double layer capacitor. As a comparative example, the same test was performed using a commercially available capacitor separator and an electric double layer capacitor manufactured using an electrolyte shown in Table 12 instead of using the composite polymer electrolyte of the example.

[0163]

[Table 9]

[0164]

[Table 10]

[0165]

[Table 11]

Table 12 shows the decrease in tensile strength when the heat-resistant organic fibers used in Examples of the present invention were kept at 200 ° C. for 3 days. When the polypropylene fiber and the polypropylene / polyethylene core-sheath fiber were kept at 200 ° C. for 3 days, they melted and did not stay in the original form. The polyester fibers, para-aramid fibers, and wholly aromatic polyester fibers, which are heat-resistant organic fibers, retained high mechanical strength even after being kept at 200 ° C. for 3 days. The electrically insulating porous thin films dl and o containing these fibers are used for producing a composite polymer electrolyte.
The assembly operation was completed in a short time because it could be processed at a high temperature of ℃.

[0167]

[Table 12]

The ionic conductivity of the composite polymer electrolytes A to S integrated with the electrically insulating porous thin film according to the electric double layer capacitor of the present invention was 25 ° C. and −30 ° C., as compared with Comparative Examples 1 to 4. It was comparable to the ionic conductivity of only the polymer electrolyte shown.

Although the electric double layer capacitor of the present invention uses the composite type polymer electrolyte, the leakage current and the internal resistance were at values that allowed the electric double layer capacitor to operate without any problem.

The composite polymer electrolyte of the example exhibited higher piercing strength and tensile strength than the polymer electrolyte of the comparative example. Therefore, when the polymer electrolyte of the comparative example was used, a cylindrical wound electric double layer capacitor could not be manufactured, but when the composite polymer electrolyte of the example was used, the operation was stable. An electric double layer capacitor was obtained.

By containing fibers made of polypropylene or polyethylene and fibrillated cellulose,
The composite polymer electrolyte R using the electrically insulating porous thin film p, which is a nonwoven fabric in which some of the components are bonded by hydrogen bonding, comprises polypropylene fibers, polyethylene fibers, and fibrillated polyethylene fibers that do not form hydrogen bonds. The mechanical strength such as the puncture strength and the tensile strength was improved as compared with the composite polymer electrolyte C using the contained electrically insulating porous thin film a. In addition, when the polymer electrolyte is impregnated, in the electrically insulating porous thin film a, the propylene carbonate serving as the medium sometimes partially dissociates the thermal fusion points of the fibers. Since the fibers were firmly bonded by hydrogen bonding, the mechanical strength could be maintained. Electrically insulating porous thin films a, b, f produced by a wet method
To p are electrically insulating porous thin films c to e produced by a dry method.
And had a more homogeneous formation.

In the electric double layer capacitor of the present invention,
The composite polymer electrolytes K to M using the electrically insulating porous thin films i to k containing heat-resistant organic fibers partially fibrillated to 1 μm or less contain heat-resistant organic fibers that are not fibrillated. High puncture strength was shown as compared with the composite polymer electrolytes F to J using the electrically insulating porous thin films d to h. In addition, the electrically insulating porous thin film M using the electrically insulating porous thin film k containing the microglass fiber exhibited higher piercing strength and also produced a cylindrical wound electric double layer capacitor. The yield was high.

In the electric double layer capacitor of the present invention using the electrically insulating porous thin films A to S, the electrolyte did not leak when the metal rod was pierced. In the electric double layer capacitor manufactured using the commercially available capacitor separator and the electrolytic solution shown in Table 12 instead of using the composite polymer electrolyte of the example, liquid leakage was confirmed.

[0174]

As described above, since the electric double layer capacitor of the present invention uses the composite polymer electrolyte integrated with the electrically insulating porous thin film, there is little danger of liquid leakage and the like. It has an excellent effect of also exhibiting excellent electrical characteristics.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenji Hyodo 3-4-2 Marunouchi, Chiyoda-ku, Tokyo F-term in Mitsubishi Paper Mills Co., Ltd. (reference) 4J035 JA01 JB01 JB02 LB20

Claims (18)

[Claims] An electric double layer capacitor in which polarizable electrodes face each other through a composite polymer electrolyte in which an electrically insulating porous thin film and a polymer electrolyte are integrated,
The polymer electrolyte comprises a compound having Si—H groups at both ends and a compound represented by the formula (A): [Wherein, R ¹ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ² independently represents a substituted or unsubstituted alkylene Z ¹ represents a group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, a substituted or unsubstituted arylene alkylene group, a dialkyl (poly) silylene group, a diaryl (poly) silylene group, or a direct bond; Is a group derived from a polyoxyalkylene group, a (poly) carbonate group, a (poly) ester group, an alkylene group, a heteroatom-containing organic group, polyacrylate or polymethacrylate.
Shows a valence group or a direct bond. And at least a linear polymer obtained by an addition reaction with the compound represented by formula (1), the composite polymer electrolyte has a puncture strength of 0.1 N or more, and 1 × 10 ⁻³ S at 25 ° C.
An electric double layer capacitor having an ionic conductivity of not less than 1 × 10 ⁻⁴ S / cm at −30 ° C. or more at −30 ° C. 2. An electric double-layer capacitor in which polarizable electrodes face each other via a composite polymer electrolyte in which an electrically insulating porous thin film and a polymer electrolyte are integrated,
The polymer electrolyte comprises a compound having Si—H groups at both ends and a compound represented by the formula (A): Wherein R ¹ , R ² and Z ¹ are as defined in claim 1. A linear polymer having two terminal hydrosilyl groups obtained by an addition reaction with a compound represented by the formula:
Formula (D) having three or more ethylenic double bonds: [Wherein, R ⁴ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ⁵ independently represents a substituted or unsubstituted alkylene A substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, a heteroatom-containing organic group, or a direct bond, n
² is an integer of 3 or more, and Z ² is a linking group having the same valence as n ^2, and is a carbon atom, an alkylene group, an alkane polyyl group, a polyvalent aromatic carbocyclic group, an alkane polyoxy group. , Silicon atom, monosubstituted trivalent silicon atom, aliphatic group,
Heteroatom-containing organic group, benzene polycarboxy group, phosphate group, oxyphosphate group, cyclic alkylpolysiloxane group, or alkylarylpolysiloxane group, derived from (poly) carbonate, (poly) ester, polyacrylate or polymethacrylate R ⁹ independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; R ¹⁰ represents independently a substituted or unsubstituted An alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, a heteroatom-containing organic group, or a direct bond;
³ represents an integer of 2 to 30; a represents an integer of 0 to 3; Z ⁴ is a linking group having the same valence as n ^3, and is a carbon atom, an alkylene group, an alkynyl group, a polyvalent group; Aromatic carbocyclic group, alkane polyoxy group, silicon atom, monosubstituted trivalent silicon atom, aliphatic group, hetero atom-containing organic group, benzene polycarboxy group, phosphate group, oxyphosphate group, (poly) carbonate, ( Shows groups derived from poly) esters, polyacrylates or polymethacrylates, or direct bonds. And at least a composite polymer electrolyte having a puncture strength of 0.1 N or more and 1 × 10 ⁻³ S at 25 ° C.
An electric double layer capacitor having an ionic conductivity of not less than 1 × 10 ⁻⁴ S / cm at −30 ° C. or more at −30 ° C. 3. The composite polymer electrolyte according to claim 1, wherein the tensile strength in the longitudinal direction is 200 N / m or more.
Or the electric double layer capacitor according to 2. 4. The electric double layer capacitor according to claim 1, wherein the electrically insulating porous thin film is a non-woven fabric. 5. The electric double layer capacitor according to claim 1, wherein the electrically insulating porous thin film is a nonwoven fabric in which a part of the constituents is bonded by hydrogen bonding. 6. The electric double layer capacitor according to claim 1, wherein the electrically insulating porous thin film is a nonwoven fabric manufactured by a wet method. 7. The non-woven fabric according to claim 1, wherein the electrically insulating porous thin film contains a heat-resistant organic fiber.
7. The electric double layer capacitor according to any one of claims 6 to 6. 8. A heat-resistant organic fiber partly fibrillated to a fiber diameter of 1 μm or less.
The electric double layer capacitor as described in the above. 9. The electric double layer capacitor according to claim 7, wherein the heat-resistant organic fiber is a liquid crystalline polymer fiber. 10. The electric double layer capacitor according to claim 9, wherein the liquid crystalline polymer fiber is a wholly aromatic polyamide fiber. 11. The electric double layer capacitor according to claim 9, wherein the liquid crystalline polymer fiber is a wholly aromatic polyester fiber. 12. The electric double layer capacitor according to claim 7, wherein the heat-resistant organic fiber is a polyester fiber. 13. The polyester fiber having an average fiber diameter of 5 μm.
13. The electric double layer capacitor according to claim 12, wherein m is equal to or less than m. 14. The electrically insulating porous thin film is a nonwoven fabric containing glass fibers.
14. The electric double layer capacitor according to any one of claims 13 to 13. 15. The glass fiber is a micro glass fiber having an average fiber diameter of 3 μm or less.
The electric double layer capacitor as described in the above. 16. The electric double layer capacitor according to claim 1, wherein the electrically insulating porous thin film is a nonwoven fabric containing fibrillated cellulose. 17. The electric double layer capacitor according to claim 16, wherein the fibrillated cellulose is fibrillated with a high-pressure homogenizer. 18. The electric double layer capacitor according to claim 16, wherein the fibrillated cellulose is bacterial cellulose.