JPH10340618A - High polymer solid electrolyte and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily form a thin film, and improve strength of the thin film of a solvent adding type, ion conductivity at a room temperature or less, workability, heat resistance and a large electric current characteristic by including one or more kinds of high polymers having a group of a poly or oligooxytetramethylene type in a cross-linking chain or a side chain and one or more kinds of electrolytes. SOLUTION: A group contained in a cross-linking chain and/or a side chain is expressed by formula I, and is desirably composed of a polymer containing one or more kinds of heat and/or active light beam polymerizing compounds having a group of the formula I and a polymerizing functional group of formula II formula III and one or more kinds of electrolyte salt. A carbonate type organic solvent and an alumina type inorganic oxide are desirably added, and composite electrolyte salt is selected from alkaline metal salt, quaternary ammonium salt and quaternary phosphonium salt. [In the formulas I, II, and III, (n) is an integer not less than 1; R<1> to R<4> are hydrogen and an alkyl group and/or an alkoxy group having the carbon number of 1 to 5; and R<5> and R<6> are hydrogen or an alkyl group; R<7> is a bivalent group having the carbon number not more than 10; (x) is 0 or 1 to 10].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a high ionic conductive polymer solid electrolyte including a polymer and an electrolyte having a crosslinked and / or side chain group mainly composed of a poly- or oligooxytetramethylene-based organic chain, The present invention relates to a battery using the polymer solid electrolyte and a method for manufacturing the same, and an electric double layer capacitor using the polymer solid electrolyte and a method for manufacturing the same.

[0002]

2. Description of the Related Art In the field of downsizing and all-solidification in the field of ionics, all-solid-state primary and secondary batteries and solid-state batteries using solid electrolytes as new ion conductors replacing conventional electrolyte solutions. Applications to electrochemical elements such as multilayer capacitors have been actively attempted. Current electrochemical devices using an electrolyte solution have a problem in long-term reliability because liquid leakage to the outside of a component or elution of an electrode active material easily occurs. On the other hand, a product using a solid electrolyte does not have such a problem, and it is easy to reduce the thickness. Further, the solid electrolyte is excellent in heat resistance, and is advantageous in a process of manufacturing a product such as a battery. In particular, those using a polymer solid electrolyte containing a polymer as a main component increase the flexibility of the battery as compared with inorganic substances,
There is an advantage that it can be processed into various shapes. However, those studied so far have a problem that the extraction current is small because the ionic conductivity of the solid polymer electrolyte is low.

Recently, LiCoO ₂ , LiNiO ₂ , Li
Many studies have been made on lithium secondary batteries using metal oxides such as MnO ₂ and MoS ₂ and metal sulfides for the positive electrode and lithium, lithium alloys, carbon materials and inorganic compounds capable of inserting and extracting lithium ions, and polymers for the negative electrode. Have been. For example,
"Journal of the Electrochemical Society
(J. Electrochem. Soc.), Vol. 138 (No. 3),
665, 1991 "states that MnO ₂ or NiO
A battery having a positive electrode of ₂ has been reported. These have attracted attention because of their high capacity per weight or volume.
Further, in recent years, an electric double layer capacitor in which a carbon material having a large specific surface area such as activated carbon or carbon black is used as a polarizable electrode and an ion conductive solution is disposed between the polarizable electrode and the memory backup power supply has been widely used. For example, in "Functional Materials, February 1989, p. 33", a capacitor using a carbon-based polarizable electrode and an organic electrolyte is described in "1.
73rd Electrochemical Society Meeting
Atlanta Georgia, May, No. 18,198
"Eight years" describes an electric double layer capacitor using a sulfuric acid aqueous solution. In Japanese Patent Application Laid-Open No. 63-244570, Rb ₂ Cu ₃ I ₃ Cl having high electrical conductivity is disclosed.
_A capacitor using ₇ as an inorganic solid electrolyte is disclosed.

However, in current batteries and electric double layer capacitors using an electrolyte solution, when the battery is used for a long period of time or when an abnormality such as a high voltage is applied, liquid leakage to the outside of the battery or the capacitor occurs. There is a problem in long-term use and reliability because of its easiness. On the other hand, batteries and electric double-layer capacitors using conventional inorganic ion-conductive substances have problems such as low decomposition voltage and low output voltage of the ion-conductive substance, and difficulty in forming an interface between the electrolyte and the electrode. There were problems such as processing. Japanese Patent Application Laid-Open No. Hei 4-253771 discloses that a polyphosphazene-based polymer is used as an ion-conductive substance for a battery or an electric double-layer capacitor. The used ones have the advantages that the output voltage is higher than that of the inorganic ion conductive material, that they can be processed into various shapes, and that the sealing is simple. However, in this case,
The ionic conductivity of the polymer solid electrolyte is 10 ^-4 to 10 ^-6 S /
cm, which is insufficient, and has a drawback that the take-out current is small. In addition, when assembling a solid electrolyte and a polarizable electrode into a capacitor, there is also a problem that it is difficult to uniformly combine the solid electrolyte with a carbon material having a large specific surface area because of mixing of solids.

[0005] The ionic conductivity of a polymer solid electrolyte generally studied is 10 ^-4 to 10 ^-5 S at room temperature.
/ Cm, but is still at least two orders of magnitude lower than liquid ion conductive materials. Also,
At a low temperature of 0 ° C. or lower, the ionic conductivity further decreases extremely. Furthermore, when these solid electrolytes are incorporated into an element such as an electric double layer capacitor, or when these solid electrolytes are incorporated into a battery as a thin film, processing techniques such as compounding with electrodes and securing contactability are difficult, and even in a manufacturing method. There was a problem. Examples of these solid polymer electrolytes are described in British Polymer Journal (Br. Polym. J.), No. 3
19, pp. 137, 1975] describes that a composite of polyethylene oxide and an inorganic alkali metal salt exhibits ionic conductivity, and the ionic conductivity at room temperature is 10 ⁻⁷ S / S. cm and low. Recently, it has been reported that a comb-shaped polymer in which oligooxyethylene is introduced into a side chain enhances the thermal mobility of an oxyethylene chain that is responsible for ionic conductivity and improves ionic conductivity. For example, "Journal of Physical Chemistry (J. Phys. Chem.), Vol. 89, p. 987, 1984"
In "Year", there is described an example in which oligooxyethylene is added to a side chain of polymethacrylic acid and an alkali metal salt is complexed. In addition, "Journal of American Chemical Society (J. Am. Chem. Soc.)
106, 6854, 1984 "describes an example in which a polyphosphazene having an oligooxyethylene side chain is complexed with an alkali metal salt, and the ionic conductivity is about 10 ^-5 S / cm. Still not enough.

US Pat. No. 4,357,401 discloses that a polymer solid electrolyte comprising a heteroatom-containing crosslinked polymer and an ionizable salt has reduced crystallinity, low glass transition point, and improved ionic conductivity. However, it was still insufficient at about 10 ⁻⁵ S / cm. J. A
ppl. Electrochem. , No. 5,63 ~
As described on page 69 (1975), it has been reported that a so-called polymer gel electrolyte obtained by adding a solvent and an electrolyte to a cross-linked polymer such as polyacrylonitrile or polyvinylidene fluoride gel has a high ionic conductivity. I have.
JP-B-58-36828 reports that a similar polymer gel electrolyte obtained by adding a solvent and an electrolyte to a polymethacrylate alkyl ester has a high ionic conductivity. However, although these polymer gel electrolytes have high ionic conductivity, they will impart fluidity, so they cannot be handled as completely solid, and have poor film strength and film formability.
When applied to an electric double layer capacitor or a battery, a short circuit easily occurs, and a sealing problem occurs as in the case of the liquid ion conductive material.

On the other hand, in US Pat. No. 4,792,504, the ionic conductivity is improved by using a crosslinked polymer solid electrolyte in which an electrolytic solution comprising a metal salt and an aprotic solvent is impregnated in a continuous network of poly (ethylene oxide). It has been proposed to be. However, even if a solvent is added, the ionic conductivity is still insufficient at 10 ^-4 S / cm, and there has been a problem that the film strength is reduced due to the addition of the solvent. Tokuho 3-73081,
U.S. Pat. No. 4,908,283 discloses a method for forming a polymer solid electrolyte by irradiating a composition comprising acryloyl-modified polyalkylene oxide such as polyethylene glycol diacrylate / electrolyte salt / organic solvent with actinic rays such as ultraviolet rays. Attempts have been made to shorten the polymerization time. In addition, US Pat. No. 4,830,939 and JP-A-5-109310 also disclose a composition comprising a crosslinkable polyethylene unsaturated compound / electrolyte salt / active light inert solvent by irradiating radiation such as ultraviolet ray or electron beam. A similar method for forming a solid polymer electrolyte containing an electrolyte is disclosed. In these systems, the amount of the electrolyte in the solid polymer electrolyte was increased, so that the ionic conductivity was improved, but it was still insufficient, and the membrane strength tended to deteriorate.

[0008] Solid State Ionics, 19
Issue 7, 1982, p. 75, Li, a polymer solid electrolyte
It has been reported that by further combining alumina particles with the ClO ₄ / polyethylene oxide composite, it is possible to achieve an improvement in the strength of the solid polymer electrolyte without lowering the ionic conductivity. Japanese Patent Application Laid-Open No. 6-140052 proposes a solid electrolyte in which a polyalkylene oxide / crosslinked isocyanate / inorganic oxide composite is impregnated with a non-aqueous electrolyte, and the strength of the electrolyte solid polymer electrolyte is improved. It is planned. However, these composite polymer solid electrolytes have insufficient properties of the polymer itself,
There were still problems in practical use in terms of ionic conductivity, workability, and stability.

[0009] In order to solve these problems, the present inventors have proposed an ionic conductivity using a composite comprising a polymer obtained from a (meth) acrylate prepolymer containing an oxyalkylene group having a urethane bond and an electrolyte. (JP-A-6-187822). Ion conductivity of this solid polymer electrolyte is a a high level of solvent is not added in 10 ^-4 S / cm (room temperature), the further addition of solvent, at room temperature or above a temperature lower by 10 ^-3 S / cm or more, and the film quality was good and improved to such an extent that it could be obtained as a free-standing film. In addition, this prepolymer has good polymerizability, and when applied to batteries,
There is also a processing advantage that it can be polymerized after being incorporated in a battery in a prepolymer state and solidified. However, these systems also have a problem that the membrane strength is insufficient for use as a separator of a battery or the like, and it is difficult to handle industrially. In addition, a small amount of impurities and oxygen in the battery system, such as water, decomposition products of electrolyte salts, and electrode material impurities, easily deteriorate the polymer, especially at high temperatures, the oxyalkylene moiety, which affects the battery life. . Further, when applied to a battery or an electric double layer capacitor, there is a problem that the capacity is greatly reduced at the time of high current discharge. This is thought to be because the oxyethylene group in the oxyalkylene group, in particular, tends to be complexed with the ion, which hinders the ion transfer when a large current is to be obtained.

[0010]

SUMMARY OF THE INVENTION The present invention has a good strength even when a thin film having a thickness of about several tens of μm is formed in a solvent-added system, has high ionic conductivity at room temperature and low temperature, and has excellent workability and heat resistance. An object of the present invention is to provide a polymer solid electrolyte having excellent high current characteristics. Another object of the present invention is to provide a primary battery and a secondary battery which can be easily formed into a thin film, can operate at a high capacity and a high current, and have excellent reliability, and a method for manufacturing the same.
Still another object of the present invention is to provide an electric double-layer capacitor having a high output voltage, a large take-out current, excellent workability and reliability, and a method for manufacturing the same.

[0011]

Means for Solving the Problems The present inventors have developed a polymer having a high ionic conductivity containing a polymer having a crosslinked chain and / or a side chain mainly composed of a poly or oligooxytetramethylene organic chain and an electrolyte. Molecular solid electrolyte has good membrane strength, high ionic conductivity, excellent workability, and high current characteristics compared to conventional polyoxyethylene and polyoxypropylene-based oligooxyalkylenes.
It has been found that the polymer solid electrolyte is particularly excellent in high-temperature durability. In addition, the present inventors have found that by using this polymer solid electrolyte, thinning is easy, and a high capacity,
It has been found that a primary battery and a secondary battery that can operate at a high current and have excellent reliability and stability can be obtained. Further, the present inventors, by using the polymer solid electrolyte described above, the output voltage is high, the extraction current is large,
It has been found that an electric double layer capacitor excellent in workability, reliability and stability can be obtained. That is, the present invention has achieved the above object by developing the following.

[1] It is characterized by containing at least one kind of polymer having at least a poly- or oligooxytetramethylene group represented by the following general formula (1) in a crosslinked chain or a side chain, and at least one kind of electrolyte. Polymer solid electrolyte.

Embedded image [In the formula, n is an integer of 1 or more, R ^{1 to} R ⁴ are a hydrogen atom, an alkyl group and / or an alkoxy group having 1 to 5 carbon atoms, which may be the same or different. [2] General formula (2) or general formula (3)

Embedded image

Embedded image Wherein R ⁵ and R ⁶ represent hydrogen or an alkyl group;
⁷ represents a divalent group having 10 or less carbon atoms. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x is 0 or 1
The numerical value of 10 is shown. However, R in a plurality of polymerizable functional groups represented by the general formula (2) or (3) in the same molecule
The values of ⁵ , R ⁶ , R ⁷ and x are each independent and need not be the same. ] At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by the general formula (1) and a poly or oligooxytetramethylene group represented by the general formula (1), and a polymerizable polymer containing at least one electrolyte salt The solid polymer electrolyte according to [1], obtained by polymerizing the composition.

[3] The polymer solid electrolyte according to the above [1] or [2], comprising at least one organic solvent. [4] The polymer solid electrolyte according to [3], wherein the at least one organic solvent is a carbonate compound. [5] The above-mentioned [1] containing at least one inorganic oxide.
The solid polymer electrolyte according to any one of [1] to [4]. [6] At least one kind of inorganic oxide has a crystal particle diameter of 0.1.
The above-mentioned [5], which is an alumina-based compound having a BET specific surface area of 1 m or less and a BET specific surface area of 50 m ² / g or more.
The solid polymer electrolyte according to the above. [7] The polymer solid electrolyte according to any one of [1] to [6], wherein the electrolyte salt is at least one selected from an alkali metal salt, a quaternary ammonium salt, and a quaternary phosphonium salt. [8] A battery using the solid polymer electrolyte according to any one of [1] to [7]. [9] The battery according to [8], wherein the negative electrode of the battery uses at least one material selected from lithium, a lithium alloy, a carbon material capable of inserting and extracting lithium ions, an inorganic oxide, an inorganic chalcogenide, and a conductive polymer. ] The battery according to the above. [10] In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, the ion conductive material is the polymer solid electrolyte according to any one of the above [1] to [7]. And electric double layer capacitor.

[11] The general formula (2) or the general formula (3)

Embedded image

Embedded image Wherein R ⁵ and R ⁶ represent hydrogen or an alkyl group;
⁷ represents a divalent group having 10 or less carbon atoms. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x is 0 or 1
The numerical value of 10 is shown. However, R in a plurality of polymerizable functional groups represented by the general formula (2) or (3) in the same molecule
The values of ⁵ , R ⁶ , R ⁷ and x are each independent and need not be the same. ] At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by the general formula (1) and a poly or oligooxytetramethylene group represented by the general formula (1), and a polymerizable polymer containing at least one electrolyte salt A method for producing a battery, comprising placing the composition in a structure for battery construction or disposing the composition on a support, and polymerizing the polymerizable composition.

[12] The method for producing a battery according to the above [11], wherein the polymerizable composition contains at least one organic solvent. [13] The method for producing a battery according to the above [11] or [12], wherein the polymerizable composition contains at least one inorganic oxide. [14] General formula (2) or general formula (3)

Embedded image

Embedded image Wherein R ⁵ and R ⁶ represent hydrogen or an alkyl group;
⁷ represents a divalent group having 10 or less carbon atoms. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x is 0 or 1
The numerical value of 10 is shown. However, R in a plurality of polymerizable functional groups represented by the general formula (2) or (3) in the same molecule
The values of ⁵ , R ⁶ , R ⁷ and x are each independent and need not be the same. ] At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by the general formula (1) and a poly or oligooxytetramethylene group represented by the general formula (1), and a polymerizable polymer containing at least one electrolyte salt A method for producing an electric double layer capacitor, comprising placing the composition in a structure for forming an electric double layer capacitor or disposing the composition on a support, and polymerizing the polymerizable composition. [15] The method for producing an electric double layer capacitor according to the above [14], wherein the polymerizable composition contains at least one organic solvent. [16] The method for producing an electric double layer capacitor according to the above [14] or [15], wherein the polymerizable composition contains at least one inorganic oxide.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [1] Polymer solid electrolyte (a) Polymer In the polymer solid electrolyte of the present invention, at least one of the polymers used for the polymer solid electrolyte has a crosslinked chain of an oxytetramethylene group represented by the following general formula (1) and / or Alternatively, it is characterized in that it is contained in a side chain.

Embedded image [In the formula, n is an integer of 1 or more, R ^{1 to} R ⁴ are a hydrogen atom, an alkyl group and / or an alkoxy group having 1 to 5 carbon atoms, which may be the same or different. ]

As a kind of general oxyalkylene,
Oxymethylene and oxyethylene have a high polarity and can promote the dissociation of the electrolyte salt and can be dissolved. In addition, the crystallinity is high, and the glass transition point of the polymer tends to be high. When the number of carbon atoms of the alkylene in the oxyalkylene is increased to propylene or tetramethylene, the interaction with the alkali metal ion is reduced. However, oxypropylene is still insufficient, and it is necessary to increase the number of carbon atoms to oxytetramethylene. However, if the number of carbon atoms is excessively increased, the polarity becomes small, and conversely, it becomes difficult to dissociate the electrolyte salt. Therefore, oxytetramethylene is most suitable as an oxyalkylene chain having a small interaction with a cation and a high dissociation ability of an electrolyte salt. The proportion of the oxytetramethylene group contained in the crosslinked chains and / or side chains in the polymer used in the polymer solid electrolyte of the present invention must be 50% by weight or more of the crosslinked chains or side chains containing the same. And 65% by weight or more is preferred. In this case, a portion other than the oxytetramethylene group in the crosslinked chain and / or the side chain may contain another oxyalkylene group. The number of repeating oxytetramethylene-based groups in one crosslinked chain and / or side chain containing an oxytetramethylene-based group in the polymer used in the polymer solid electrolyte of the present invention as a main component is 1 to 1.
000, preferably 5-100.
To 50 are particularly preferred.

The polymer used in the polymer solid electrolyte of the present invention has an oxytetramethylene group represented by the general formula (1) and has the following general formula (2) or (3)

Embedded image

Embedded image Wherein R ⁵ and R ⁶ represent hydrogen or an alkyl group;
⁷ represents a divalent group having 10 or less carbon atoms. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x is 0 or 1
The numerical value of 10 is shown. However, R in a plurality of polymerizable functional groups represented by the general formula (2) or (3) in the same molecule
The values of ⁵ , R ⁶ , R ⁷ and x are each independent and need not be the same. The polymer of at least one kind of heat- and / or actinic-ray-polymerizable compound having a polymerizable functional group represented by formula (I) is preferable because it can be easily processed with a solid polymer electrolyte and combined with an electrode used in various electrochemical devices. .

The method for synthesizing the polymerizable compound having the groups represented by the general formulas (1) and (2) is not particularly limited.
For example, it can be easily obtained by reacting acid chloride with oligooxytetramethyleneol having a hydroxyl group at a terminal as follows.

Embedded image

Embedded image

Embedded image

Embedded image Wherein R ⁵ is the same as in the general formula (2). R ⁸ is an alkyl group or ester group having 1 or more carbon atoms, and s and t are integers of 1 or more. And R in the general formula (1)
^{When 1 to} R ⁴ are not hydrogen atoms, they can be synthesized in the same manner.

The method for synthesizing the polymerizable compound having the groups represented by the general formulas (1) and (3) is not particularly limited.
For example,

Embedded image Wherein R ⁶ , R ⁷ , and x are the same as in the general formula (3). Can be easily obtained by reacting the isocyanate compound represented by the formula (1) with oligooxytetramethyleneol having a hydroxyl group at a terminal. As a specific method, the compound having one functional group represented by the general formula (3) is, for example, a methacryloyl isocyanate compound (hereinafter abbreviated as MI) or an acryloyl isocyanate compound (hereinafter abbreviated as AI). Yes.)
And monoalkyl oligotetramethylene glycol,
It can be easily obtained by reacting at a molar ratio of 1: 1 as in the following reaction.

Embedded image Wherein R ⁶ is the same as in the general formula (3). R ⁹ is an alkyl group or ester group having 1 or more carbon atoms, and u is an integer of 1 or more. ]

The compound having two functional groups represented by the general formula (3) can be easily prepared by reacting MIs or AIs with oligotetramethylene glycol in a molar ratio of 2: 1. Is obtained. Further, the compound having three functional groups represented by the general formula (3) is, for example, a compound obtained by adding MIs and / or AIs to a triol obtained by addition-polymerizing tetramethylene oxide to a trihydric alcohol such as glycerin. It is easily obtained by reacting at a molar ratio of 1: 1. Further, the compound having four functional groups represented by the general formula (3) is, for example, MI and / or AIs and tetraol obtained by addition polymerization of tetramethylene oxide to a tetrahydric alcohol such as pentaerythritol. It is easily obtained by reacting at a molar ratio of 4: 1.

Compounds having five functional groups represented by the general formula (3) include, for example, MIs and / or AIs and pentaol obtained by addition polymerization of α-D-glucopyranose with tetramethylene oxide. Can be easily obtained by reacting with a 5: 1 molar ratio. The compound having six functional groups represented by the general formula (3) is, for example, a 6: 1 molar mixture of MIs and / or AIs and hexaol obtained by addition polymerization of mannitol with tetramethylene oxide. It is easily obtained by reacting in a ratio.

Here, a polymer obtained by polymerizing a compound having only one functional group represented by the general formula (2) or (3) does not have a crosslinked structure and has insufficient film strength. Therefore, there is a great risk of short-circuiting when a thin film is used. Therefore, it is copolymerized with a polymerizable compound having two or more functional groups represented by the general formula (2) or (3) and crosslinked, or the functional group represented by the general formula (2) or (3) is It is preferable to use a polymer obtained from two or more polymerizable compounds in combination. When these polymers are used as a thin film, the number of functional groups represented by the general formula (2) or (3) contained in one molecule is more preferably three or more in consideration of its strength. Further, among the compounds having a functional group represented by the general formula (2), the compound having a functional group represented by the general formula (3) can introduce a urethane group and has good polymerizability;
In addition, a large amount of urethane groups can be introduced into the polymer, the dielectric constant increases, and the ionic conductivity of a polymer solid electrolyte increases, which is preferable. Further, the film strength when formed into a thin film is large, and the amount of the electrolyte contained is large, which is preferable.

The polymer which is preferable as a component of the polymer solid electrolyte of the present invention has an organic group represented by the general formula (1) and has a functional group represented by the general formula (2) or (3). In addition to a homopolymer of a compound having a group, a copolymer of two or more kinds belonging to the category, a copolymer of at least one kind of the compound and another polymerizable compound, and the like can be given. Examples of other polymerizable compounds having an organic group represented by the general formula (1) and copolymerizable with the compound having a functional group represented by the general formula (2) or (3) include No restrictions. For example, methyl methacrylate,
(Meth) acrylic acid alkyl esters such as n-butyl acrylate, various urethane (meth) acrylates, (meth) acrylic acid esters having oxyfluorocarbon chains and / or (meth) acrylic acid fluorinated alkyl esters, acrylamide, methacrylamide , N, N-
(Meth) acrylamide compounds such as dimethylacrylamide, N, N-dimethylmethacrylamide, vinylene carbonate, (meth) acryloylcarbonate, N-vinylpyrrolidone, acryloylmorpholine, methacryloylmorpholine, N, N-dimethylaminopropyl (meth) acrylamide And styrene compounds such as styrene and α-methylstyrene; N-vinylamide compounds such as N-vinylacetamide and N-vinylformamide; and alkyl vinyl ethers such as ethyl vinyl ether. Of these, (meth) acrylate, urethane (meth) acrylate, or (meth) acrylate having an oxyfluorocarbon chain is preferably used. Among these, urethane (meth) acrylate is particularly preferred from the viewpoint of polymerizability.

Having an organic group represented by the general formula (1),
For the polymerization of the compound having a functional group represented by the general formula (2) or (3), a general method utilizing the polymerizability of an acryloyl group or a methacryloyl group, which is a functional group, can be adopted. That is, a radical polymerization catalyst such as azobisisobutyronitrile and benzoyl peroxide, CF ₃ COO is added to these compounds alone or a mixture of these compounds and the other copolymerizable polymerizable compound.
Radical polymerization, cationic polymerization or anionic polymerization can be performed using a cationic polymerization catalyst such as a proton acid such as H, a Lewis acid such as BF ₃ or AlCl ₃ , or an anionic polymerization catalyst such as butyl lithium, sodium naphthalene, or lithium alkoxide. it can. It is also possible to polymerize such a polymerizable compound or polymerizable mixture after forming it into a film or the like. A polymer obtained from at least one compound having an organic group represented by the general formula (1) and having a functional group represented by the general formula (2) or (3) and / or When the copolymer as the polymerization component is used for the polymer of the solid polymer electrolyte as in the present invention, it is particularly advantageous to polymerize the polymerizable compound or the polymerizable mixture after forming the film as described above. .

That is, at least one compound having an organic group represented by the general formula (1) and having a functional group represented by the general formula (2) or (3) is combined with an alkali metal salt and a quaternary compound. Mixing with at least one electrolyte such as ammonium salts, quaternary phosphonium salts or transition metal salts,
In some cases, another polymerizable compound and / or a plasticizer and / or a solvent and / or an inorganic oxide are added and mixed to prepare a polymerizable composition, and the polymerizable composition is added in the presence or absence of the catalyst. In the presence, it is optionally polymerized by heating and / or irradiation with actinic radiation. Especially,
After shaping the polymerizable compound, the mixture, and the composition into a film-like shape, for example, by heating and / or irradiating with an actinic ray to polymerize to form a film-like polymer, the degree of freedom in a processed surface is increased. Spreading is a great advantage in application.

When a solvent is used for the polymerization, any solvent may be used as long as it does not inhibit the polymerization, for example, tetrahydrofuran, acetonitrile, toluene, etc., depending on the type of the polymerizable compound and the presence or absence of a polymerization catalyst. be able to. The polymerization temperature depends on the type of the compound having the organic group represented by the general formula (1) and the functional group represented by the general formula (2) or (3). And usually 0 ° C.
The temperature may be in the range of 200 to 200 ° C. When polymerizing by irradiation with actinic rays, it depends on the type of the compound having an organic group represented by the general formula (1) and a functional group represented by the general formula (2) or (3). For example, polymerization can be carried out by irradiating ultraviolet light of several mW or more, γ-ray, electron beam or the like using an initiator such as benzyl methyl ketal and benzophenone.

As described above, a preferred polymer used in the polymer solid electrolyte of the present invention has an organic group represented by the general formula (1) and is represented by the general formula (2) or (3). It may be a homopolymer of a compound having a functional group, a copolymer of two or more compounds belonging to the category, or a copolymer of at least one of the compounds and another polymerizable compound. You may. Further, a preferred polymer used for the polymer solid electrolyte of the present invention has an organic group represented by the general formula (1) and a functional group represented by the general formula (2) or (3). It may be a polymer obtained from at least one compound and / or a mixture of a copolymer having the compound as a copolymer component and another polymer. For example, a polymer having at least one compound having an organic group represented by the general formula (1) and having a functional group represented by the general formula (2) or (3) and / or the compound And a copolymer having the following components: polyethylene oxide, polypropylene oxide, polyacrylonitrile, polybutadiene, polymethacrylic (or acrylic) esters, polystyrene, polyphosphazenes, polysiloxane or polysilane,
A mixture with a polymer such as polyvinylidene fluoride and polytetrafluoroethylene may be used for the solid polymer electrolyte of the present invention.

When the copolymer is used, the amount of the structural unit derived from the compound having the organic group represented by the general formula (1) and having the functional group represented by the general formula (2) or (3) Depends on the type of other copolymer component or polymer mixture component, but in consideration of ionic conductivity and membrane strength, heat resistance, and current characteristics when used in a solid polymer electrolyte, this copolymer or polymer The content is preferably at least 40% by weight, more preferably at least 60% by weight, based on the total amount of the mixture.

(B) Solvent It is preferable to add a solvent to the solid polymer electrolyte of the present invention since the ionic conductivity of the solid polymer electrolyte is further improved. As a solvent that can be used, it has good compatibility with the compound having a group represented by the general formula (1) used in the polymer solid electrolyte of the present invention, a large dielectric constant, a boiling point of 60 ° C. or more, and Compounds with a wide range of chemical stability are suitable. Examples of such a solvent include ethers such as 1,2-dimethoxyethane, 2-methyltetrahydrofuran, crown ether, triethylene glycol methyl ether, tetraethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl. Carbonates such as methyl carbonate, aromatic nitriles such as benzonitrile and tolunitrile, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N
-Sulfur compounds such as vinylpyrrolidone and sulfolane, and phosphoric esters. Among them, ethers and carbonates are preferable, and carbonates are particularly preferable. Although the ionic conductivity of the polymer solid electrolyte increases as the amount of the solvent added increases, the mechanical strength of the polymer solid electrolyte decreases when the amount is too large. The preferable addition amount is 2 to 1 times the weight of the polymer used for the polymer solid electrolyte of the present invention.
A 5-fold amount and a 3- to 10-fold amount are particularly preferred.

(C) Composite Film When the polymer solid electrolyte of the present invention is used as a thin film, it may be used in combination with another porous film.
By doing so, the strength as a film is further increased, but depending on the type and amount of the film to be composited, a decrease in conductivity and a deterioration in stability are caused. Examples of the composite film include a porous polyolefin sheet such as a reticulated polyolefin sheet such as a polypropylene nonwoven fabric or a polyethylene net, a polyolefin microporous film such as Celgard (trade name), and a nylon nonwoven fabric. preferable. The porosity may be about 10 to 95%, but the porosity is preferably as large as possible as long as the strength allows. Therefore, the preferable porosity is in the range of 40 to 95%. . Although there is no particular limitation on the compounding method, for example, at least one of compounds having an organic group represented by the general formula (1) and having a functional group represented by the general formula (2) or (3), Or, after impregnating the porous polymer film with a polymerizable composition obtained by adding and mixing at least one type of electrolyte, and optionally, another polymerizable compound and / or a plasticizer and / or a solvent and / or an inorganic oxide, Such a method of polymerizing a (meth) acryloyl-based compound can be uniformly compounded, the film thickness can be easily controlled, and can be recommended.

(D) Inorganic Oxide It is preferable that various inorganic oxides are added to the polymer solid electrolyte of the present invention. This not only improves the strength and film thickness uniformity, but also causes fine pores to be formed between the inorganic oxide and the polymer. The free electrolyte is dispersed therein, and the ion conductivity and the mobility can be increased without impairing the strength increase. Also,
The addition of the inorganic oxide increases the viscosity of the polymerizable composition, and also has an effect of suppressing the separation of the polymer even when the compatibility between the polymer and the solvent is insufficient. As the inorganic oxide to be used, a non-electron conductive and electrochemically stable one is selected. Further, it is more preferable that the material has ion conductivity. Specific examples thereof include α, β, γ-alumina, silica, titania, magnesia, and composite oxides of two or more of these, and ion-conductive or non-conductive ceramic fine particles such as zeolite.

From the viewpoints of increasing the strength of the solid polymer electrolyte and increasing the amount of retained electrolyte, the inorganic oxide preferably has a secondary particle structure in which primary particles are aggregated. Examples thereof include ultrafine silica particles and ultrafine alumina particles such as Aerosil (manufactured by Nippon Aerosil Co., Ltd.), and ultrafine alumina particles are particularly preferable in terms of stability and composite efficiency. To increase the holding amount of the electrolyte solution of the polymer solid electrolyte, ion conductivity, the purpose of increasing the mobility, the specific surface area of the inorganic oxide is preferably as large as possible, or 10 m ² / g in BET method Preferably 50 m ² / g
The above is more preferred.

The crystal particle size of such an inorganic oxide is not particularly limited as long as it can be mixed with the polymerizable composition, but the size is preferably 0.001 μm to 10 μm.
0.001 μm to 0.1 μm is particularly preferred. In addition, various shapes such as a sphere, an egg, a cube, a rectangular parallelepiped, a cylinder or a rod can be used. If the amount of the inorganic oxide is too large, on the contrary, the strength and ionic conductivity of the solid polymer electrolyte are reduced, and the film is hardly formed. Therefore, the preferable addition amount is preferably 50 wt% or less, particularly preferably 0.1 to 30 wt% based on the solid polymer electrolyte.

(E) Electrolyte The composite ratio of the electrolyte in the solid polymer electrolyte of the present invention is preferably 0.1 to 50% by weight, and more preferably 1 to 50% by weight based on the weight of the polymer.
30% by weight is particularly preferred. The electrolyte used for the composite is 50
If it is present at a ratio of not less than% by weight, the movement of ions is greatly inhibited. Conversely, if the ratio is not more than 0.1% by weight, the absolute amount of ions becomes insufficient and the ion conductivity becomes small. The type of electrolyte used for the composite is not particularly limited,
An electrolyte containing an ion to be used as a carrier by an electric charge may be used. However, it is preferable that the dissociation constant in the solid polymer electrolyte is large, and LiCF ₃ SO ₃ and LiN (CF ₃ S
O ₂ ) ₂ , LiPF ₆ , LiClO ₄ , LiI, LiB
F ₄ , LiSCN, LiAsF ₆ , NaCF ₃ SO ₃ ,
NaPF ₆ , NaClO ₄ , NaI, NaBF ₄ , Na
Alkali metal salts such as AsF ₆ , KCF ₃ SO ₃ , KPF ₆ and KI; quaternary ammonium salts such as (CH ₃ ) ₄ NBF _4; quaternary phosphonium salts such as (CH ₃ ) ₄ PBF ₄ ;
A transition metal salt such as gClO ₄ or a protic acid such as hydrochloric acid, perchloric acid, or borofluoric acid is recommended.

As the negative electrode active material used in the battery of the present invention, an alkali metal, an alkali metal alloy,
A material having a low oxidation-reduction potential using an alkali metal ion such as a carbon material as a carrier is preferable because a high-voltage and high-capacity battery can be obtained. Therefore, when such a negative electrode is used in a battery using an alkali metal ion as a carrier, an alkali metal salt is required as an electrolyte in the solid polymer electrolyte. Examples of the kind of the alkali metal salt include LiCF ₃ SO ₃ , LiPF ₆ , LiClO ₄ , L
iBF ₄ , LiSCN, LiAsF ₆ , LiN (CF ₃
SO ₂ ) ₂ , NaCF ₃ SO ₃ , LiI, NaPF ₆ ,
NaClO ₄ , NaI, NaBF ₄ , NaAsF ₆ , K
CF ₃ SO ₃ , KPF ₆ , KI and the like can be mentioned. Among the negative electrodes, the use of lithium or a lithium alloy as the alkali metal is the most preferable because it has a high voltage, a high capacity, and can be formed into a thin film. Therefore, the electrolyte is preferably a Li salt among the alkali metal salts.

The type of electrolyte to be compounded when used in an electric double layer capacitor is not particularly limited, and a compound containing an ion to be used as a charge carrier may be used. It is desirable to include ions that are large and easily form a polarizable electrode and an electric double layer. Such compounds include (CH ₃ ) ₄ N
Quaternary ammonium salts such as BF ₄ , (CH ₃ CH ₂ ) ₄ ClO ₄ , transition metal salts such as AgClO ₄ , (CH ₃ ) ₄ P
Quaternary phosphonium salts such as BF ₄ , LiCF ₃ SO ₃ , L
iPF ₆ , LiClO ₄ , LiI, LiBF ₄ , LiS
CN, LiAsF ₆ , LiN (CF ₃ SO ₂ ) ₂ , Na
CF ₃ SO ₃ , NaPF ₆ , NaClO ₄ , NaI, N
aBF ₄ , NaAsF ₆ , KCF ₃ SO ₃ , KPF ₆ ,
Examples thereof include alkali metal salts such as KI, organic acids such as paratoluenesulfonic acid and salts thereof, and inorganic acids such as hydrochloric acid and sulfuric acid. Among them, quaternary ammonium salts, quaternary phosphonium salts, and alkali metal salts are preferable in that the output voltage can be increased and the dissociation constant is large. Among the quaternary ammonium salts, (CH ₃ CH ₂ ) (CH ₃ CH ₂ CH ₂ CH
₂₎ such as ₃ NBF _4, which is a substituent on the nitrogen of the ammonium ion are different, from the viewpoint that a large solubility or dissociation constant of the solid polymer electrolyte.

[2] Battery (a) Negative Electrode Active Material In the structure of the battery of the present invention, an alkali metal ion such as an alkali metal, an alkali metal alloy, a carbon material, a metal oxide, or a conductive polymer is used as a carrier for the negative electrode. It is preferable to use a low oxidation-reduction potential electrode active material (negative electrode active material) because a high-voltage, high-capacity battery can be obtained. Among such electrode active materials, lithium metal or lithium alloys such as lithium / aluminum alloy, lithium / lead alloy, and lithium / antimony alloy are particularly preferable because they have the lowest redox potential. Also, the carbon material is Li
Occlusion of ions is particularly preferred in that it has a low oxidation-reduction potential and is stable and safe. The carbon material of Li ions can occluding and releasing, natural graphite, artificial graphite, vapor grown graphite, petroleum coke, coal coke, pitch carbon, polyacene, C _60, C ₇₀ fullerenes, such as and the like.

(B) Positive electrode active material In the configuration of the battery of the present invention, a high oxidation-reduction potential electrode active material such as metal oxide, metal sulfide, conductive polymer or carbon material (positive electrode active material) Is preferable because a high-voltage, high-capacity battery can be obtained. Among such electrode active materials, metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, molybdenum oxide, molybdenum sulfide, and sulfide Titanium,
Metal sulfides such as vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide and the like are particularly preferable in terms of high capacity and high voltage. The method for producing the metal oxide or metal sulfide in this case is not particularly limited. It is manufactured by a heating method. When these are used for a lithium battery as an electrode active material, for example, Li _x CoO
Preferably, Li is used in a state of being inserted (composite) into a metal oxide or metal sulfide in the form of Li ₂ or Li _x MnO ₂ . The method of inserting the Li element in this way is not particularly limited. For example, a method of electrochemically inserting Li ions or a method of inserting a Li ion such as Li ₂ CO ₃ as described in US Pat. No. 4,357,215. It can be carried out by mixing and heating the metal oxide.

Also, in terms of being flexible and easy to form a thin film,
Conductive polymers are preferred. Examples of conductive polymers include:
Polyaniline, polyacetylene and its derivatives, polyparaphenylene and its derivatives, polypyrrole and its derivatives, polythienylene and its derivatives, polypyridinediyl and its derivatives, polyisothianaphthenylene and its derivatives, polyfurylene and its derivatives, polyselenophene and its Derivatives, polyarylenevinylenes such as polyparaphenylenevinylene, polythienylenevinylene, polyfurylenevinylene, polynaphthenylenevinylene, polyselenophenvinylene, polypyridinediylvinylene, and derivatives thereof, and the like. Among them, a polymer of an aniline derivative soluble in an organic solvent is particularly preferable. The conductive polymer used as an electrode active material in these batteries or electrodes is manufactured according to a chemical or electrochemical method described later or other known methods. The carbon materials include natural graphite, artificial graphite, vapor phase graphite, petroleum coke, coal coke, fluorinated graphite,
Pitch-based carbon, polyacene and the like can be mentioned.

(C) Manufacturing Method Next, an example of the method for manufacturing the battery of the present invention will be described in detail. The positive and negative electrodes are placed in the structure for battery construction so as not to come into contact with each other, or are arranged on a support. For example,
At the end of the electrode, a positive electrode and a negative electrode are attached to each other through a spacer having an appropriate thickness or a polymer solid electrolyte film prepared in advance, and put in the structure. At least one compound having an organic group represented by (1) and having a functional group represented by general formula (2) or (3), or at least one type of electrolyte; After injecting a polymerizable composition obtained by adding and mixing a polymerizable compound and / or a plasticizer and / or a solvent and / or an inorganic oxide, for example,
By polymerizing by heating and / or irradiating with actinic rays, or by further sealing with an insulating resin such as a polyolefin resin or an epoxy resin as necessary after the polymerization, a battery in which the electrode and the electrolyte are in good contact with each other can be obtained. can get.

The battery structure or the support may be made of a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. It is not limited to what is, and its shape is
It may be cylindrical, box-shaped, sheet-shaped or any other shape. FIG. 1 shows a schematic cross-sectional view of an example of a thin-film solid state secondary battery as an example of the battery of the present invention thus manufactured. In the figure, 1 is a positive electrode, 2 is a polymer solid electrolyte, 3 is a negative electrode, 4 is a current collector, and 5 is an insulating resin sealant. When a wound type battery is manufactured, the above positive electrode and negative electrode are pasted together through a polymer solid electrolyte film that has been prepared in advance, wound, and inserted into a battery structure, and then the polymerizable composition is further added. It is also possible to inject a substance and polymerize it.

[3] Electric Double Layer Capacitor (a) Configuration By using the polymer solid electrolyte of the present invention, an electric double layer capacitor having a high output voltage, a large take-out current, or excellent workability and reliability. Is provided. The electric double layer capacitor of the present invention can have the same configuration as a known electric double layer capacitor except that the solid polymer electrolyte of the present invention is used. FIG. 2 shows a schematic sectional view of an example of the electric double layer capacitor of the present invention. This example is a thin cell having a size of 1 cm × 1 cm and a thickness of about 0.5 mm. Reference numeral 7 denotes a current collector, and a pair of polarizable electrodes 6 are arranged inside the current collector. A molecular solid electrolyte 8 is provided. 9 is an insulating resin sealant, 10
Is a lead wire. The current collector 7 is preferably made of a material having electron conductivity and electrochemical corrosion resistance, and having a specific surface area as large as possible. For example, various metals and their sintered bodies, electron conductive polymers, carbon sheets and the like can be mentioned. The polarizable electrode 6 may be any electrode made of a polarizable material such as a carbon material usually used for an electric double layer capacitor. The carbon material as the polarizable material is not particularly limited as long as it has a large specific surface area. For example,
Carbon blacks such as furnace black, thermal black (including acetylene black) and channel black, activated carbon such as coconut charcoal, natural graphite, artificial graphite, so-called pyrolytic graphite produced by a gas phase method, polyacene and C ₆₀ , mention may be made of C _70.

(B) Manufacturing Method Next, an example of a method for manufacturing the electric double layer capacitor of the present invention will be described. The two polarizing electrodes are placed in a structure for forming a capacitor so as not to contact each other, or are arranged on a support. For example, a polarizable electrode is attached to the end of the electrode via a spacer having an appropriate thickness or a polymer solid electrolyte film prepared in advance, and the electrode is placed in the structure, and the organic group represented by the general formula (1) is attached. And at least one compound having a functional group represented by the general formula (2) or the general formula (3), or at least one electrolyte, and optionally another polymerizable compound and / or plasticizer. After injecting a polymerizable composition to which an agent and / or a solvent and / or an inorganic oxide are added and mixed, the mixture is polymerized, or further, after polymerization, if necessary, with an insulating resin such as a polyolefin resin or an epoxy resin. By sealing, an electric double layer capacitor in which the electrode and the electrolyte are in good contact is obtained. By this method, a particularly thin electric double layer capacitor can be manufactured. The structure for forming the capacitor or the support may be a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. However, the shape is not limited to this, and the shape may be cylindrical, box, sheet, or any other shape.

As the shape of the electric double layer capacitor, in addition to the sheet type as shown in FIG. 2, a coin type, or a sheet-like laminate of a polarizable electrode and a polymer solid electrolyte is wound into a cylindrical shape, and a cylindrical tubular It may be a cylindrical type or the like that is manufactured by sealing in a capacitor structure. In the case of manufacturing a wound capacitor, the polarizable electrode is pasted through a polymer solid electrolyte film which has been prepared in advance, wound, and after being inserted into the structure for forming a capacitor, the polymerizable composition is further added. Is injected and polymerized.

[0046]

The present invention will be described more specifically with reference to representative examples. These are merely examples for explanation, and the present invention is not limited to these.

Example 1 <Synthesis of Compound>

Embedded image

Embedded image [Where [X ¹ ] is (CH ₂ CH ₂ CH ₂ CH ₂ O)
_p (CH ₂ CH ₂ O) _q H, [X ² ]

Embedded image Is shown. Compound (average molecular weight: 4500, p / q is about 2/1) 4
After dissolving 5.0 g and 4.6 g of the compound in 100 ml of well-purified THF in a nitrogen atmosphere, 0.44 g of dibutyltin dilaurate is added. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a colorless product. ¹ H-NMR,
From the results of IR and elemental analysis, it was found that the compound reacted with the compound at a ratio of 1: 3, further the isocyanate group of the compound disappeared, a urethane bond was formed, and the compound was formed.

Example 2 1.0 g of compound, 1.8 g of ethylene carbonate (EC), 4.2 g of ethyl methyl carbonate (EMC), 0.60 g of LiPF ₆ (battery grade manufactured by Hashimoto Kasei), and 2,4,6-trimethylbenzoyl Diphenylphosphine oxide (trade name Lucillin TP
O, manufactured by BASF) was sufficiently mixed in an argon atmosphere to obtain a photopolymerizable composition. The water content of this composition (Karl Fischer method) was 30 ppm. This photopolymerizable composition was applied on a PET film under an argon atmosphere and then irradiated with a chemical fluorescent lamp (FL20S.BL manufactured by Sankyo Electric Co., Ltd.) for 10 minutes. Was obtained as a free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method,
They were 4.5 × 10 ⁻³ and 1.0 × 10 ⁻³ S / cm, respectively.

Example 3 1.0 g of compound at 1000 ° C.
(Crystal particle diameter 0.013 μm, average secondary particle diameter about 0.1 μm (observed by SEM), BET specific surface area 100 m ² /
g) 0.33g, EC 1.8g, EMC 4.2g LiPF ₆ (Hashimoto Chemical Battery grade) 0.60g and Luciline TPO
0.005 g (manufactured by BASF) was mixed well in an argon atmosphere to obtain a photopolymerizable composition. The water content of this composition (Karl Fischer method) was 35 ppm. After applying this photopolymerizable composition on a PET film under an argon atmosphere,
10 chemical fluorescent lamps (FL20S.BL manufactured by Sankyo Electric Co., Ltd.)
After irradiation for one minute, a compound polymer / aluminum oxide C composite film impregnated with an EC / EMC electrolytic solution was obtained as a free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, it was 5.5 × 10 ⁻³ and 1.2, respectively.
× 10 ^-3 S / cm.

Example 4 Lucylin TPO as initiator
Instead of benzoyl peroxide (BPO) 0.04g
In the same manner as in Example 3 except that
I got something. The water content of this composition (Karl Fischer
Method) was 35 ppm. This thermopolymerizable composition is
After coating on PET film under PP atmosphere, PP film
Coated and heated on hot plate at 80 ° C. for 1 hour
However, compound polymer impregnated with EC / EMC electrolyte
/ Aluminum oxide C composite film is about 30μm
As a free standing film 25 of this film
℃, ionic conductivity at -20 ℃ by impedance method
When measured, 5.0 × 10 ^-3, 0.8 × 10^-3S / cm
Met.

Example 5 LiBF ₆ was used instead of LiPF _6
4 (Hashimoto Kasei Battery Grade) A photopolymerizable composition was obtained in the same manner as in Example 3 except that 0.50 g was used. The water content (Karl Fischer method) of this composition was 50 ppm. This photopolymerizable composition was applied and irradiated with light in the same manner as in Example 3 to obtain a compound polymer impregnated with an electrolytic solution.
An aluminum oxide C composite film was obtained as a free standing film of about 30 μm. 25 ° C. of this solid electrolyte, −
When the ionic conductivity at 20 ° C. was measured by the impedance method, it was 4.0 × 10 ⁻³ and 0.6 × 10 ⁻³ S / cm.

Example 6 1.0 g of compound, 1.5 g of EC
, EMC 3.0g, diethyl carbonate (DEC) 1.5
g, LiPF ₆ (Hashimoto Kasei battery grade) 0.60g, 1
Aluminum oxide C 0.33 heat-treated at 000 ° C
g and Luciline TPO (manufactured by BASF) 0.005 g were mixed well in an argon atmosphere to obtain a photopolymerizable composition. The water content (Karl Fischer) of this composition was 35 ppm. This photopolymerizable composition was placed in an argon atmosphere using PET.
After coating on the film, the film was irradiated with a chemical fluorescent lamp for 10 minutes to obtain a compound polymer / aluminum oxide C composite film impregnated with an EC / EMC / DEC electrolyte as a self-supporting film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, they were 5.0 × 10 ⁻³ ,
0.7 × 10 ⁻³ S / cm.

Example 7 In place of LiPF ₆ , high-purity tetraethylammonium tetrafluoroborate (TE
AB) (Example 3) except that 1.00 g of (manufactured by Hashimoto Kasei) and 6.0 g of propylene carbonate were used instead of EC and EMC as the solvent.
In the same manner as in the above, a photopolymerizable composition was obtained. The water content of this composition (Karl Fischer method) was 100 ppm.
This photopolymerizable composition was applied and irradiated with light in the same manner as in Example 3 to obtain a compound polymer / aluminum oxide C composite film impregnated with a PC-based electrolyte solution of about 30 μm.
As a free standing film. 25 ℃ of this solid electrolyte,
The ionic conductivity at −20 ° C. was measured by an impedance method and found to be 9.5 × 10 ⁻³ and 1.5 × 10 ⁻³ S / cm.

[0054] [Example 8] <Synthesis of _{Compound> H (OCH 2 CH 2 CH} 2 CH 2) r OH + 2CH 2 = C (CH 3) COOCH 2 CH 2 NCO ( Compound) (compound) → CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ NHCO (OCH ₂ CH ₂ CH ₂ CH ₂ ) _r OCONHCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (Compound) 100 g of compound (average molecular weight 2000), 15.5 g of compound in a nitrogen atmosphere After dissolving in 200 ml of THF
0.66 g of dibutyltin dilaurate was added. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a solid colorless product. From the results of ¹ H-NMR, IR and elemental analysis, the compound and the compound reacted one to two, and further, the isocyanate group of the compound disappeared, and a urethane bond was generated, and the compound was generated. I understand.

Example 9 Compound 1.0 g, 1000 ° C.
-Purity γ-alumina heat-treated at room temperature (Showa Denko; UA5
805; crystal particle diameter 0.03 μm, average secondary particle diameter 1.
8 μm, BET specific surface area 80 m ² / g) 0.66 g, EC
1.8g, EMC 4.2g, LiPF ₆ (Hashimoto Chemical Co., Ltd. battery grade) 0.60g and Lucirin TPO (manufactured by BASF) 0.
005 g was mixed well in an argon atmosphere to obtain a photopolymerizable composition. Water content of this composition (Karl Fischer method)
Was 30 ppm. This photopolymerizable composition was applied on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp for 10 minutes. As a result, a compound polymer / UA5805 composite film impregnated with an EC / EMC-based electrolyte solution was reduced to about 3%.
Obtained as a 0 μm freestanding film. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 6.0 × 10 ⁻³ and 1.2 × 10 ⁻³ , respectively.
It was S / cm.

Example 10 Compound: CH ₃ (OCH ₂ CH ₂ ) _v OCOC (CH ₃ ) = CH ₂ (Nippon Oil & Fat, Blemmer AE-400, Mw 400) 0.3 g, compound 0.7 g synthesized in Example 8 UA heat treated at 1000 ° C
5805 (manufactured by Showa Denko KK) 0.66 g, EC 1.8 g, E
MC 4.2g, LiPF ₆ (Hashimoto Kasei battery grade) 0.
60 g and 0.005 g of Lucylin TPO (manufactured by BASF) were mixed well in an argon atmosphere to obtain a photopolymerizable composition. The water content (Karl Fischer method) of this composition is 80 ppm
Met. This photopolymerizable composition was placed in an argon atmosphere under PE
After application on a T film, the film was irradiated with a chemical fluorescent lamp for 10 minutes.
m2 free standing film. 25 of this film
° C., the ion conductivity at -20 ° C. was measured by the impedance method, respectively, 4.5 × 10 ^-3 , 1.0 × 10 ^-3 S / cm
Met.

Example 11 <Synthesis of Compound> H (OCH ₂ CH ₂ CH ₂ CH ₂ ) ₁ (OCH ₂ CH ₂ ) _k OH + ₂ CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ NCO (compound) (Compound) → CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ NHCO (OCH ₂ CH ₂ CH ₂ CH ₂ ) _l (OCH ₂ CH ₂ ) _k -OCONHCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (compound 90 g of compound (average molecular weight 1800, l / k = -1)
After dissolving 15.5 g in 100 ml of well-purified THF in a nitrogen atmosphere, 0.66 g of dibutyltin dilaurate was added. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a colorless product. From the results of ¹ H-NMR, IR and elemental analysis, the compound and the compound reacted one to two, and further, the isocyanate group of the compound disappeared, and a urethane bond was generated, and the compound was generated. I understand.

Example 12 Compound 1.0 g, 1000 ° C.
0.33g of aluminum oxide C heat-treated with EC, EC
1.8 g, EMC 4.2 g, LiPF ₆ (Hashimoto Chemicals battery grade) 0.60 g and Lucirin TPO (BASF) 0.00
5 g was mixed well in an argon atmosphere to obtain a photopolymerizable composition. The water content of this composition (Karl Fischer method) was 30 ppm. This photopolymerizable composition was applied on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp for 10 minutes. The compound polymer / aluminum oxide C composite film impregnated with an EC / EMC electrolyte solution was about 30 μm thick. Obtained as a free standing film. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, each was 4.5 × 1.
0 ^-3 and 1.1 × 10 ^-3 S / cm.

Example 13 Compound 1.0 g, 1000
Silica heat-treated at ℃ (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd., crystal particle diameter 0.012 μm, average secondary particle diameter about 0.1 μm (SEM observation), BET specific surface area 200 m ² /
g) 0.33 g, propylene carbonate (PC) 6.0 g, T
EAB 1.00g and Lucirin TPO (BASF) 0.
005 g was mixed well in an argon atmosphere to obtain a photopolymerizable composition. Water content of this composition (Karl Fischer method)
Was 120 ppm. This photopolymerizable composition was applied on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp for 10 minutes. As a result, a compound polymer / Aerosil 200 composite film impregnated with a PC-based electrolytic solution was about 30 minutes.
It was obtained as a μm freestanding film. 2 of this film
When the ionic conductivity at 5 ° C. and −20 ° C. was measured by the impedance method, 8.5 × 10 ⁻³ and 1.8 × 10 ⁻³ S /
cm.

Example 14 Lucilin TP as an initiator
Benzoyl peroxide (BPO) 0.04 instead of O
A thermopolymerizable composition was obtained in the same manner as in Example 13 except that g was added. The water content of this composition (Karl Fischer method) was 120 ppm. This thermopolymerizable composition was coated on a PET film under an argon atmosphere, coated with a PP film, and heated on a hot plate at 80 ° C. for 1 hour.
Aerosil 200 composite film was obtained as a free standing film of about 30 μm. 25 ° C, -20 ° C of this film
Was measured by an impedance method and found to be 8.5 × 10 ⁻³ and 1.8 × 10 ⁻³ S / cm, respectively.

Example 15 <Production of Lithium Cobaltate Cathode> 11 g of Li ₂ CO ₃
And 24 g of Co ₃ O ₄ are mixed well, and the mixture is
After heating at 0 ° C. for 24 hours, pulverization is performed to obtain LiCoO.
_Two powders were obtained. This LiCoO ₂ powder, acetylene black, and polyvinylidene fluoride were mixed at a weight ratio of 8: 1: 1, and an excess N-methylpyrrolidone solution was added to obtain a gel composition. This composition was applied and molded on an aluminum foil of about 25 μm to a thickness of 10 mm × 10 mm and a thickness of about 180 μm. Further, by heating and vacuum drying at about 100 ° C. for 24 hours, a lithium cobaltate positive electrode (75 mg) was obtained.

Example 16 <Production of Graphite Negative Electrode> MCMB graphite (manufactured by Osaka Gas), vapor-phase graphite fiber (manufactured by Showa Denko KK: average fiber diameter: 0.3 μm)
, Average fiber length, 2.0 μm, heat-treated at 2700 ° C.) and an excess of N-methylpyrrolidone solution were added to a mixture of polyvinylidene fluoride at a weight ratio of 8.6: 0.4: 1.0 to obtain a gel composition. This composition was coated on a copper foil of about 15 μm in a thickness of 10 mm ×
It was applied and molded to a thickness of 10 mm and a thickness of about 250 μm. further,
By heating and vacuum drying at about 100 ° C. for 24 hours, a graphite negative electrode (35 mg) was obtained.

Example 17 <Production of Li-ion secondary battery> The graphite negative electrode (10 m) produced in Example 16 was placed in a glove box under an argon atmosphere.
m × 10 mm) in the electrolyte (1M LiPF ₆ / EC + E)
MC (3: 7)), the compound polymer / aluminum oxide C composite film (12 mm × 12 mm) prepared in Example 3 was stuck on a graphite negative electrode, and the cobalt produced in Example 15 was further bonded. Electrolyte (1M LiPF ₆ ) is applied to the lithium oxide positive electrode (10 mm × 10 mm).
/ EC + EMC (3: 7)) were bonded together, and the battery end was sealed with an epoxy resin to obtain a graphite / cobalt oxide Li-ion secondary battery. FIG. 1 shows a cross-sectional view of the obtained battery. The battery was charged and discharged at 60 ° C. and 25 ° C. with an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA.
The maximum discharge capacities were 7.2 mAh and 7.2 mAh, respectively. Also, 2
When charge and discharge were repeated at 5 ° C., operating voltage 2.75 to 4.1 V, charge 0.5 mA, and discharge 3.0 mA, the maximum discharge capacity was 6.6 mAh, and the cycle life until the capacity was reduced to 50% was 430 times. .

Example 18 <Production of Li-ion secondary battery> Example 17 was repeated except that the compound polymer / UA5805 film produced in Example 9 was used instead of the compound polymer / aluminum oxide C composite film. L in the sectional view shown in FIG.
An i-ion secondary battery was manufactured. The battery was heated at 60 ° C, 2
When charging and discharging were performed at 5 ° C. at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA, the maximum discharge capacities were 7.2 mAh and 7.2 mAh, respectively. Also, 25 ° C, operating voltage 2.75 ~ 4.1V, charging 0.5mA,
When charging and discharging were repeated at 3.0 mA, the maximum discharging capacity was
At 7.0 mAh, the cycle life was 510 cycles before the capacity was reduced to 50%.

Example 19 <Production of Li-ion secondary battery> The graphite negative electrode (10 m) produced in Example 16 was placed in an argon atmosphere glove box.
m × 10 mm) in the electrolyte (1M LiPF ₆ / EC + E)
MC (3: 7)), and then the compound prepared in Example 12 / aluminum oxide C-based photopolymerizable composition was applied to a thickness of 30 μm, and a chemical fluorescent lamp was applied in an argon atmosphere to a thickness of 10 μm. After irradiation for one minute, a compound polymer / aluminum oxide C composite film impregnated with an electrolytic solution was formed directly on the graphite negative electrode. Further, the lithium cobaltate positive electrode (10 m
m × 10 mm) in the electrolyte (1M LiPF ₆ / EC + EM)
C (3: 7)) were bonded together, and the battery end was sealed with an epoxy resin to obtain a graphite / cobalt oxide-based Li-ion secondary battery shown in FIG. This battery is
When charging and discharging were performed at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 25 ° C. and 25 ° C., the maximum discharge capacities were 7.2 mAh and 7.2 mAh, respectively. In addition, 25 ° C, operating voltage 2.75 ~ 4.1V, charging 0.5m
A. When charging and discharging were repeated at a discharge of 3.0 mA, the maximum discharge capacity was 6.6 mAh, and the cycle life until the capacity was reduced to 50% was 460 times.

Example 20 <Production of Li-ion secondary battery> The graphite negative electrode (10 m) produced in Example 16 was placed in an argon atmosphere glove box.
m × 10 mm) impregnated with the thermopolymerizable composition prepared in Example 4, and the compound polymer prepared in Example 3 /
Aluminum oxide C composite film (12 mm x 1
2 mm) on a graphite negative electrode.
Lithium cobaltate positive electrode (10 mm × 10 m
m) impregnated with the thermopolymerizable composition prepared in Example 4 was adhered, and the end of the battery was sealed with an epoxy resin;
Further, the thermopolymerizable composition was cured at 80 ° C. for 1 hour to obtain a graphite / cobalt oxide-based Li-ion secondary battery. FIG. 1 shows a cross-sectional view of the obtained battery. The battery was heated at 60 ° C, 2
When charging and discharging were performed at 5 ° C. at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA, the maximum discharge capacities were 7.2 mAh and 7.0 mAh, respectively. Also, 25 ° C, operating voltage 2.75 ~ 4.1V, charging 0.5mA,
When charging and discharging were repeated at 3.0 mA, the maximum discharging capacity was
The capacity dropped to 50% at 4.2 mAh was 210 times.

Example 21 <Production of Activated Carbon Electrode> An excess N-methylpyrrolidone solution was added to a mixture of coconut palm activated carbon and polyvinylidene fluoride at a weight ratio of 9.0: 1.0 to obtain a gel composition. This composition was applied on a stainless steel foil in a size of 10 mm × 10 mm to a thickness of about 150 μm. After vacuum drying at about 100 ° C. for 10 hours, an activated carbon electrode (14.0 mg) was obtained.

Example 22 <Production of Electric Double Layer Capacitor> The activated carbon electrode (14) produced in Example 21 was placed in an argon atmosphere glove box.
mg) 10 mm x 10 mm with electrolyte (1 M TEAB /
Two electrodes impregnated with PC + EC (3: 1) were prepared. Next, the compound polymer / aluminum oxide C composite film (12 mm × 12 m
m) was attached to one of the electrodes, the other electrode was attached to the other electrode, and the capacitor end was sealed with an epoxy resin to produce an electric double layer capacitor as shown in FIG. When the capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.2 mA at 60 ° C. and 25 ° C., the maximum capacity was 470 mF and 470 mF.
The maximum capacity at 25 ° C. and 2.5 mA is 400 mF.
Thus, there was almost no change in the capacity even when charging and discharging were repeated 50 times.

Example 23 <Production of Electric Double Layer Capacitor> Example 22 was repeated except that the compound polymer / Aerosil 200 composite film (12 mm × 12 mm) produced in Example 13 was used as the polymer solid electrolyte film. An electric double layer capacitor was manufactured in the same manner as described above. When the capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.2 mA at 60 ° C. and 25 ° C., the maximum capacity was 470 mF and 460 mF. The maximum capacity at 25 ° C. and 2.5 mA is 380 m
At F, there was almost no change in the capacity even when charging and discharging were repeated 50 times.

Example 24 <Production of Electric Double Layer Capacitor> In the argon atmosphere glove box, the activated carbon electrode (14
mg) Two electrodes of 10 mm × 10 mm impregnated with the thermopolymerizable composition prepared in Example 14 were prepared. Next, the compound polymer produced in Example 13 / Aerosil 200
A composite film (12 mm × 12 mm) was stuck to one electrode, and the other electrode was stuck together. The end of the capacitor was sealed with epoxy resin.
By heating and polymerizing at 0 ° C. for 1 hour, an electric double layer capacitor as shown in FIG. 2 was produced. The capacitor was operated at 60 ° C. and 25 ° C. with an operating voltage of 0 to 2.5 V and a current of 0.
When charging / discharging was performed at 2 mA, the maximum capacity was 460 m.
F, 410 mF. Further, the maximum capacity at 25 ° C. and 2.5 mA was 230 mF, and there was almost no change in capacity even when charging and discharging were repeated 50 times.

[0071]

According to the present invention, the high ionic conductive polymer solid electrolyte containing a polymer having a crosslinked chain and / or a side chain containing a poly or oligooxytetramethylene organic chain as a main component and an electrolyte has a membrane strength. Is a polymer solid electrolyte which has good ionic conductivity, high ionic conductivity, excellent workability, and excellent high current characteristics and high-temperature durability as compared with conventional oligooxyalkylenes. Batteries and electric double layer capacitors using the polymer solid electrolyte of the present invention can be used stably for a long time without danger of liquid leakage because the ion conductive substance is a solid, and using this solid electrolyte This allows the manufacture of thin batteries and capacitors

By using the polymer solid electrolyte of the present invention, it is easy to make a thin film, it can be operated with a large capacity, has a long life, and has a large current characteristic, high temperature durability, reliability, stability, and workability. An excellent secondary battery can be obtained. In addition, the battery of the present invention is a battery that can operate at high capacity and high current as an all solid type, or has good cyclability, and is excellent in safety and reliability. It can be used as a power supply for electric appliances, electric vehicles, and large power supplies for road leveling. Further, since it can be easily thinned, it can be used as a paper battery for an identification card or the like. Further, the battery of the present invention can be efficiently manufactured by the method for manufacturing a battery of the present invention.

Further, by using the solid polymer electrolyte of the present invention, an electric double layer capacitor having a high output voltage, a large take-out current, a long life, and excellent in high-temperature durability, workability, reliability and stability. Is obtained. The electric double layer capacitor of the present invention, even compared to the conventional capacitor,
It is an electric double layer capacitor that can be operated at high voltage, high capacity, high current, or has good cycling characteristics, and is excellent in safety and reliability. It can be used as a power supply for electrical products. In addition, it is excellent in workability such as thinning, and can be expected for uses other than the use of conventional electric double layer capacitors. Further, the electric double layer capacitor of the present invention can be efficiently manufactured by the method for manufacturing an electric double layer capacitor of the present invention.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an example of a thin battery shown as an example of the battery of the present invention.

FIG. 2 is a schematic sectional view of an embodiment of the electric double layer capacitor of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Polymer solid electrolyte 3 Negative electrode 4 Current collector 5 Insulating resin sealing agent 6 Polarized electrode 7 Current collector 8 Polymer solid electrolyte 9 Insulating resin sealing agent 10 Lead wire

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI H01M 10/40 H01G 9/00 301G

Claims (16)

[Claims] 1. A high-molecular-weight composition comprising at least one polymer having at least one poly- or oligooxytetramethylene-based group represented by the following general formula (1) in a crosslinked chain or a side chain, and at least one electrolyte: Molecular solid electrolyte. Embedded image [In the formula, n is an integer of 1 or more, R ^{1 to} R ⁴ are a hydrogen atom, an alkyl group and / or an alkoxy group having 1 to 5 carbon atoms, which may be the same or different. ] 2. General formula (2) or general formula (3) Embedded image Wherein R ⁵ and R ⁶ represent hydrogen or an alkyl group;
⁷ represents a divalent group having 10 or less carbon atoms. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x is 0 or 1
The numerical value of 10 is shown. However, R in a plurality of polymerizable functional groups represented by the general formula (2) or (3) in the same molecule
The values of ⁵ , R ⁶ , R ⁷ and x are each independent and need not be the same. ] At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by the general formula (1) and a poly or oligooxytetramethylene group represented by the general formula (1), and a polymerizable polymer containing at least one electrolyte salt The polymer solid electrolyte according to claim 1, which is obtained by polymerizing the composition. 3. The polymer solid electrolyte according to claim 1, comprising at least one organic solvent. 4. The solid polymer electrolyte according to claim 3, wherein the at least one organic solvent is a carbonate compound. 5. The solid polymer electrolyte according to claim 1, comprising at least one inorganic oxide. 6. The polymer solid according to claim 5, wherein the at least one inorganic oxide is an alumina-based compound having a crystal particle diameter of 0.1 μm or less and a BET specific surface area of 50 m ² / g or more. Electrolytes. 7. The polymer solid electrolyte according to claim 1, wherein the electrolyte salt is at least one selected from alkali metal salts, quaternary ammonium salts, and quaternary phosphonium salts. 8. A battery using the polymer solid electrolyte according to claim 1. 9. The battery according to claim 9, wherein the negative electrode is lithium, a lithium alloy,
9. The battery according to claim 8, wherein at least one material selected from a carbon material capable of inserting and extracting lithium ions, an inorganic oxide, an inorganic chalcogenide, and a conductive polymer is used. 10. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the ion conductive substance is the solid polymer electrolyte according to any one of claims 1 to 7. Electric double layer capacitor. 11. The general formula (2) or the general formula (3) Embedded image Wherein R ⁵ and R ⁶ represent hydrogen or an alkyl group;
⁷ represents a divalent group having 10 or less carbon atoms. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x is 0 or 1
The numerical value of 10 is shown. However, R in a plurality of polymerizable functional groups represented by the general formula (2) or (3) in the same molecule
The values of ⁵ , R ⁶ , R ⁷ and x are each independent and need not be the same. ] At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by the general formula (1) and a poly or oligooxytetramethylene group represented by the general formula (1), and a polymerizable polymer containing at least one electrolyte salt A method for producing a battery, comprising placing the composition in a structure for battery construction or disposing the composition on a support, and polymerizing the polymerizable composition. 12. The method according to claim 11, wherein the polymerizable composition contains at least one organic solvent. 13. The method according to claim 11, wherein the polymerizable composition contains at least one inorganic oxide. 14. The general formula (2) or the general formula (3) Embedded image Wherein R ⁵ and R ⁶ represent hydrogen or an alkyl group;
⁷ represents a divalent group having 10 or less carbon atoms. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x is 0 or 1
The numerical value of 10 is shown. However, R in a plurality of polymerizable functional groups represented by the general formula (2) or (3) in the same molecule
The values of ⁵ , R ⁶ , R ⁷ and x are each independent and need not be the same. ] At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by the general formula (1) and a poly or oligooxytetramethylene group represented by the general formula (1), and a polymerizable polymer containing at least one electrolyte salt A method for producing an electric double layer capacitor, comprising placing the composition in a structure for forming an electric double layer capacitor or disposing the composition on a support, and polymerizing the polymerizable composition. 15. The method for manufacturing an electric double layer capacitor according to claim 14, wherein the polymerizable composition contains at least one organic solvent. 16. The method according to claim 14, wherein the polymerizable composition contains at least one kind of inorganic oxide.