JPH08111220A - High polymer solid electrolyte, battery and solid electric double layer capacitor using electrolyte, and manufacture of them - Google Patents

Abstract

PURPOSE: To provide high performance, high reliability battery and an electric double layer capacity by using a high polymer solid electrolyte composed of a composite material of an electrolyte and a high polymer having as a side chain an oxy-alkyl radical coupled by urethane bond. CONSTITUTION: 11.1g N-methacryloil isocyanate and 55g mono-methyl oligoethylene glycol having a mean molecular weight of 550 are dissolved in 100ml THF, and thereto 0.66g of dibutyltin dilaurate is added. The obtained substance is subjected to a reaction at 50 deg.C to produce N-methacryloyl carbamic acid ω-methyl oligooxyethyl ester, and 1.40g of this substance is dissolved in 100ml THF, whereto 0.14g LiCF3 SO3 is added followed by mixing well together. Then THF is removed, and application is made onto a glass plate followed by heating at 100 deg.C so that a high polymer solid electrolyte 2 and a film 9 are produced, which constitute the intended matter together with a positive and a negative electrode 1, 3, polarizing electrode 7, electricity collectors 4, 8, and spacers 5, 10. Thereby a battery and an electric double layer capacitor can be manufactured which present a high capacity, high performance, and high reliability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymer solid electrolyte having high ionic conductivity using a polymer having an oxyalkyl side chain having a urethane bond, an electrode using the polymer, and a method for producing the same. The present invention relates to a battery using the polymer solid electrolyte and / or the electrode, a manufacturing method thereof, an electric double layer capacitor using the polymer solid electrolyte, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Solid electrolytes are used as new ion conductors in place of conventional electrolyte solutions in the field of downsizing and solidification in the field of ionics, and are used as all-solid-state primary batteries, secondary batteries, and electric double layer capacitors. The application to is being actively attempted. Current batteries using electrolyte solutions have a problem in long-term reliability because liquid leakage to the outside of parts or elution of electrode substances is likely to occur. On the other hand, the product using the solid electrolyte does not have such a problem and can be easily thinned. Further, the solid electrolyte is also excellent in heat resistance and is advantageous in the manufacturing process of products such as batteries.

In particular, the one using a solid electrolyte containing a polymer as a main component has an advantage that the flexibility of the battery is increased and it can be processed into various shapes as compared with an inorganic substance. However, what has been studied so far has a problem that the extraction current is small because the ionic conductivity of the solid polymer electrolyte is low. Examples of these polymer solid electrolytes include “British Polymer Journal (Br. Polym. J.), Vol. 319, pp. 137, 1975.
"Year" describes that a composite of polyethylene oxide and an inorganic alkali metal salt exhibits ionic conductivity, but its ionic conductivity at room temperature is as low as 10 ^-7 S / cm.

Recently, it has been reported that a comb polymer having oligooxyethylene introduced into its side chain enhances the thermal mobility of the oxyethylene chain, which is responsible for the ionic conductivity, and improves the ionic conductivity. There is. For example, “J. Phys. Chem., Vol. 89, p. 987, 1984” in “Journal of Physical Chemistry. The example which compounded is described. Furthermore,
"Journal of American Chemical Society, J. Am. Chem. Soc., Vol. 106, p. 6854,
1984 "describes an example in which a polyphosphazene having an oligooxyethylene side chain is complexed with an alkali metal salt.

Recently, LiCoO ₂ , LiNiO ₂ , Li
Many studies have been made on lithium secondary batteries using a metal oxide such as MnO ₂ or MoS ₂ or a metal sulfide as a positive electrode. For example, “Journal of Electrochemical Society (J. Electrochem. Soc.), Volume 138 (No.
3), p. 665, 1991 ", a battery having MnO ₂ or NiO ₂ as a positive electrode is reported. These have attracted attention because of their high capacity per weight or volume. In addition, there are many reports on batteries using a conductive polymer as an electrode active material. For example, a lithium secondary battery using a polyaniline as a positive electrode is described in, for example, “27th Battery Discussion Session, 3A05L and 3A06L, 1986”. As previously reported, it has already been put on the market by Bridgestone and Seiko as a coin-type battery for a backup power source. Polyaniline has been attracting attention as a positive electrode active material having a high capacity and excellent flexibility.

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 arranged between the carbon material has been widely used for a memory backup power source. . For example, in "Functional Materials, February 1989, p. 33", a capacitor using a carbon-based polarizable electrode and an organic electrolyte is described in "173rd Electrochemical Society Meeting Atlanta, Georgia, May, No." .1
8, 1988 ”describes an electric double layer capacitor using a sulfuric acid aqueous solution. Also, JP-A-63-24
Japanese Patent No. 4570 discloses Rb ₂ Cu having high electrical conductivity.
_A capacitor using ₃ I ₃ Cl ₇ as an inorganic solid electrolyte is disclosed.

However, the current electric double layer capacitor using the electrolyte solution is liable to leak to the outside of the capacitor for a long period of time during abnormal conditions such as long-term use and application of high voltage. There is a problem in use and reliability. On the other hand, the electric double layer capacitor using the conventional inorganic ion conductive material has a problem that the decomposition voltage of the ion conductive material is low and the output voltage is low.

Japanese Unexamined Patent Publication (Kokai) No. 4-253771 proposes to use a polyphosphazene type polymer as an ion conductive substance, and one using a solid ion conductive substance containing such a polymer as a main component The output voltage is higher than that of the inorganic ion conductive material, and it has the advantages that it can be processed into various shapes and can be easily sealed. However, in this case, the ionic conductivity of the solid polymer electrolyte is not sufficient as 10 ⁻⁴ to 10 ⁻⁶ S / cm, and there is a drawback that the extraction current is small. It is also possible to add a plasticizer to the polymer solid electrolyte to increase the ionic conductivity, but since it adds fluidity, it cannot be handled as a perfect solid, resulting in poor film strength and film formability. When it is applied to an electric double layer capacitor or a battery, a short circuit is likely to occur, and a sealing problem occurs like the liquid ion conductive material. On the other hand, when assembling a solid electrolyte together with a polarizable electrode into a capacitor, there is a problem that it is difficult to uniformly compound a carbon material having a large specific surface area because the solids are mixed with each other.

The ionic conductivity of polymer solid electrolytes generally studied is 10 ⁻⁴ to 10 ⁻⁵ S at room temperature.
Although it has been improved to about / cm, the level is still lower by two digits or more as compared with the liquid ion conductive material. Also,
At a low temperature of 0 ° C. or lower, the ionic conductivity further deteriorates. Furthermore, when incorporating these polymer solid electrolytes into elements such as electric double layer capacitors, or when incorporating these polymer solid electrolytes into thin films into batteries, processing techniques such as compounding with electrodes and ensuring contact are required. It is difficult and there are problems with the manufacturing method.

[0010]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a polymer solid electrolyte which has good strength even when formed into a film, has high ionic conductivity at room temperature and low temperature, and is excellent in processability. And Further, the present invention, by using this polymer solid electrolyte, thin film is easy, high capacity, high current can be operated in the primary battery and secondary battery, further good cycleability, reliability The objective is to develop a secondary battery excellent in Another object of the present invention is to provide an electrode having high electrochemical activity and flexibility and a battery using the electrode.

The present invention also provides an electrode used in an electric double layer capacitor, which has good polarizability, good strength when formed into a film, and good contact with a solid polymer electrolyte. With the goal. Furthermore, the present invention uses a polymer solid electrolyte having high ionic conductivity even at room temperature or lower temperature, and having excellent membrane strength and processability, so that the output voltage is high and the extraction current is large. Another object of the present invention is to provide an electric double layer capacitor having excellent workability and reliability.

[0012]

Means for Solving the Problems In the polymer having an oxyalkyl group introduced into the side chain, the present inventors have introduced a urethane bond into the side chain to obtain good membrane strength and ionic conductivity. It was found that a high polymer solid electrolyte can be obtained. In the description of the present specification, the expression "oxyalkyl" means at least one oxyalkylene group.
Also included are oligooxyalkylenes and polyoxyalkylenes containing more than one, and the expression "side chain" also includes cross-linked chains.

Furthermore, it has been found that by using this polymer solid electrolyte in a battery, the problems of ionic conductivity, membrane strength, processability and the like are improved. Furthermore, the inventors of the present invention, for example, when recognizing that it is important to reduce the thickness of the electrode when a thin solid battery is produced using this polymer solid electrolyte, the electrode active material Which is excellent as a conductive polymer, polyaniline and its derivatives, that is, aniline-based polymers soluble in organic solvents, or other conductive polymers, metal oxides, metal sulfides or carbon By using a material or other electrode active material (positive electrode active material or negative electrode active material) and a polymer into which an oxyalkyl side chain having a urethane bond is introduced, the electrochemical activity of the electrode active material is impaired. Can be formed into an electrode having high electrochemical activity and flexibility, and a thin film of the electrode can be formed by, for example, a solvent casting method or another method. It was found that.

Further, the inventors of the present invention have introduced a polarizable material used as a polarizable electrode of an electric double layer capacitor, such as a carbon material described below, and a polymer into which an oxyalkyl side chain having a urethane bond is introduced. By using, it is possible to form a polarizable electrode suitable for the capacitor without deteriorating the polarization characteristics of the polarizable material, and further, for example, a thin film film of the electrode can be formed by a solvent casting method or another method. I found that.

Furthermore, the inventors of the present invention can obtain an electric double layer capacitor having a high output voltage, a large extraction current, and excellent workability and reliability by using the above-mentioned polymer solid electrolyte, in particular, , And found that it can be an all-solid-state electric double layer capacitor.

That is, the present invention provides: 1) General formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO OR ² (1) ( In the formula, R ¹ represents hydrogen or a methyl group, R ² represents an organic chain containing at least one oxyalkylene group, and the organic chain may have a linear, branched or cyclic structure. , Elements other than carbon, hydrogen and oxygen are 1
More than one may be included. x and y each represent 0 or a number of 1 to 5, and z represents a number of 0 or 1 to 10.
However, when x = 0 and y = 0, z = 0. Also [O
(CH ₂ ) _x (CH (CH ₃ )) _y ] (CH ₂ ) in _z
And (CH (CH ₃ )) may be arranged irregularly. ), Which is obtained from at least one compound selected from the group consisting of N-acryloylcarbamic acid ester compounds (hereinafter abbreviated as ACE compounds) or N-methacryloylcarbamic acid ester compounds (hereinafter abbreviated as MCE compounds). From a composite containing a polymer and / or a copolymer containing the compound as a copolymerization component (hereinafter, such a polymer and the copolymer are collectively referred to as (M) ACE polymer) and at least one electrolyte. Polymer solid electrolyte,

2) General formula (2) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO O (R ³ O) _n R ⁴ (2) [In the formula, R ³ is “in the present invention,“ each independently ”]
The, are each independently (R ³ O) _n n months of R ³ of -
It means that the groups of (CH ₂ ) ₂ — and —CH (CH ₃ ) CH ₂ — can be arbitrarily selected. The same applies to R ⁶ below. 』
Represents — (CH ₂ ) ₂ — or —CH (CH ₃ ) CH ₂ —, R ⁴ represents an alkyl group having 1 to 10 carbon atoms,
_{CONH [O (CH 2) x} '(CH (CH 3)) y'] z 'O
_{COCH = CH 2, -CONH [O} (CH 2) x '(CH
_{(CH 3)) y ']} z' OCOC (CH 3) = CH 2, -C
ONHCOC (CH ₃₎ = CH ₂ or -CONHCO
It represents CH = CH _2, n represents a number of 1 or more. [O (C
_{H 2) x '(CH (} CH 3)) y'] z ' in (a _{CH 2) (CH (CH 3} )) may be irregularly arranged. x ′ and y ′ each represent 0 or a number of 1 to 5, and z ′ represents a number of 0 or 1 to 10. However, x '= 0 and y' = 0
Then z '= 0. Other symbols are the same as in general formula (1). ] A compound represented by or the general formula _{(3) CH 2 = C (} R 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCO O [(R 6 O) m CONHR 5 NHCOO ] _K (R ³ O) _n R ⁴ (3) [In the formula, R ¹ represents hydrogen or a methyl group, and R ³ and R ^3
6 are each independently - (CH _{2) 2} - or -CH (C
H ₃ ) CH ₂ —, R ⁵ represents an alkylene group, an arylene group, an arylene group or an oxyalkylene group having 1 to 20 carbon atoms, and n, m and k each represent a number of 1 or more. Other symbols are general formula (1) and general formula (2)
Same as. ] A compound represented by the following formula, a polymer obtained from at least one compound selected from the above, and / or a polymer solid electrolyte comprising a complex containing a copolymer having the compound as a copolymerization component and at least one electrolyte,

3) The solid polymer electrolyte according to 1) or 2) above, wherein the electrolyte is at least one compound selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts. ) The above 1) characterized in that a plasticizer is added
To 3), a solid polymer electrolyte, and

5) A battery characterized by using the polymer solid electrolyte as described in 1) to 4), 6) a negative electrode comprising lithium or a lithium alloy or an electrode containing a carbon material capable of inserting and extracting lithium ions,
5) The lithium ion battery according to 5), 7) The positive electrode comprises an electrode containing an organic solvent-soluble aniline polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material. 6) The battery described above, and

8) A polymerizable monomer mixture containing at least one compound selected from ACE compounds or MCE compounds and at least one electrolyte, or a polymerizable monomer mixture containing a plasticizer added thereto is used for battery construction. 9. A method for producing a battery, which comprises a step of polymerizing the polymerizable monomer mixture by placing it in a structure or arranging it on a support, and 9) the formula (2) or the formula (3) Polymerizable monomer mixture containing at least one compound and at least one electrolyte selected from the compound, or a polymerizable monomer mixture with a plasticizer added thereto,
Put it in the structure for battery construction, or place it on the support,
A method for producing a battery, comprising a step of polymerizing the polymerizable monomer mixture,

10) An electrode characterized by containing an (M) ACE polymer and an electrode active material or a polarizable material, and 11) a compound represented by the general formula (2) or the general formula (3). And an electrode comprising a polymer obtained from at least one compound and / or a copolymer containing the compound as a copolymerization component and an electrode active material or a polarizable material, and 12) an electrode active material or polarizable material. The material is an organic solvent-soluble aniline-based polymer or other conductive polymer, metal oxide, metal sulfide or carbon material 10).
Or the electrode according to 11),

13) A polymerizable monomer mixture containing at least one compound selected from ACE compounds or MCE compounds and an electrode active material or a polarizable material,
Or a method for producing an electrode, which comprises a step of polymerizing a polymerizable monomer mixture to which a plasticizer is added, 14) a compound represented by the general formula (2) or the general formula (3) A polymerizable monomer mixture containing at least one compound and an electrode active material or a polarizable material, or a method for producing an electrode, which comprises a step of polymerizing a polymerizable monomer mixture to which a plasticizer is added, 15) The electrode active material or polarizable material is an organic solvent-soluble aniline-based polymer or other conductive polymer, metal oxide, metal sulfide or carbon material 13).
Or a method for producing the electrode according to 14), and

16) An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the ion conductive substance is the polymer solid electrolyte described in 1) to 4) above. Double layer capacitor, and 17) an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the polarizable electrode is composed of a composite containing a carbon material and the (M) ACE polymer. A characteristic electric double layer capacitor, 18) In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, the polarizable electrode is composed of a carbon material and the general formula (2) or the general formula (3). It is composed of a polymer obtained from at least one compound selected from the compounds represented and / or a composite containing a copolymer having the compound as a copolymerization component. Electric double layer capacitor according to symptoms, 19) in the electric double layer capacitor at a polarizable electrode via the ion conductive material, the polarizable electrode, ACE
An electric double layer capacitor, which is a polarizable electrode produced by polymerizing a polymerizable monomer mixture containing a carbon material and at least one compound selected from the group compounds or MCE compounds, 20) Ion conduction In an electric double layer capacitor in which a polarizable electrode is arranged via a polar substance, the polarizable electrode comprises at least one compound selected from compounds represented by the general formula (2) or the general formula (3) and a carbon material. An electric double layer capacitor, which is a polarizable electrode produced by polymerizing a polymerizable monomer mixture containing the same, and

21) A polymerizable monomer mixture containing at least one compound selected from ACE compounds or MCE compounds and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added,
22. A method for producing an electric double layer capacitor, which comprises a step of placing the electric double layer capacitor in a structure for constituting an electric double layer capacitor or arranging it on a support and polymerizing the polymerizable monomer mixture, 22) General formula (2) Alternatively, a polymerizable monomer mixture containing at least one compound selected from the compounds represented by the general formula (3) and at least one electrolyte, or a polymerizable monomer mixture containing a plasticizer added thereto is used as an electric double layer. 23. A method for producing an electric double layer capacitor, comprising: placing in a structure for forming a capacitor or disposing on a support, and polymerizing the polymerizable monomer mixture, and 23) a carbon material and the above (M). A pair of polarizable electrodes made of a composite containing an ACE polymer is arranged to face each other, and an ACE compound or M A step of injecting a polymerizable monomer mixture containing at least one compound selected from E-based compounds and at least one electrolyte, or a polymerizable monomer mixture having a plasticizer added thereto, and polymerizing the polymerizable monomer mixture. The above object was achieved by developing a manufacturing method of an electric double layer capacitor characterized by having. In addition, in the present specification, “oligooxyalkyl” means —CH ₂
The CH ₂ O- or -CH (CH ₃₎ 2 divalent group units composed of CH ₂ O- represents an oxyalkylene chain comprising at least one or more.

The present invention will be described in detail below. The ACE compound and the MCE compound which are the compounds represented by the general formulas (1) to (3) used in the present invention include a compound having one polymerizable group, a compound having two polymerizable groups, and A compound having a plurality of urethane groups such as a compound represented by the general formula (3), or the above general formula (1)
Compounds in which R ^{2 in (2)} contains a cyclic oxyalkylene group such as crown ether are mentioned.

A monomer for producing the (M) ACE polymer contained in the solid polymer electrolyte of the present invention,
The ACE-based compound or MCE-based compound, which is the compound represented by the general formula (1), or the compound represented by the general formula (2) can be obtained by the following reaction (wherein R ¹ , R ³ and R ⁴ are each represented by the general formula (2)
Same as. ). ^{_{CH 2 = C (R 1)}} CO [O (CH 2) x (CH (CH 3)) y] z NCO + O (R 3 O) n R 4 ─ → ACE compound or MCE based compounds for example, the general formula The compounds represented by (1) to (3) having one polymerizable group include methacryloyl isocyanate compounds (hereinafter abbreviated as MIs) or acryloyl isocyanate compounds (hereinafter abbreviated as AIs). ) And a monoalkylalkylene glycol. Further, as the compounds represented by the general formulas (1) to (3) having two polymerizable groups, MIs and / or AIs are reacted with oligoalkylene glycol at a molar ratio of 2: 1. Therefore, it can be easily obtained.

Furthermore, the compound having a plurality of urethane groups represented by the general formula (3) can be prepared by reacting two compounds such as hexamethylene diisocyanate and tolylene diisocyanate according to the following two reaction schemes. B mol of a product is obtained by reacting a mol of a compound having an isocyanate group with a mol of alkylene glycol and b mol of a monoalkylalkylene glycol, and then reacting the product with an equimolar amount of the above MIs or AIs. It is obtained by (However, in the following reaction scheme, R
³ , R ⁴ , R ⁵ , R ⁶ , k, m, and n are the same as in the general formula (3), and a and b each represent a number. )

A (OCNR ⁵ NCO) + a (HO (R ⁶ O) _m H) + b (HO (R ³ O) _n R ⁴ )-→ bHO {(R ⁶ O) _m CONHR ⁵ NHCOO} _{a / b} (R ³ O) _n R ⁴ (where a ≧ b and a / b = k) HO {(R ⁶ O) _m CONHR ⁵ NHCOO} _k (R ³ O) _n R ⁴ + MI type or Compounds of AIs-> (3) As another synthetic method of the compound represented by the general formula (3), the following two reaction schemes may be followed. Ie 2
There is also a method in which c mol of a compound having one isocyanate group is reacted with alkylene glycol (c + d) mol to obtain d mol of a product, and then the product is reacted with 2 times mol of MIs or AIs. c (OCNR ⁵ NCO) + (c + d) (HO (R ⁶ O) _m H) ─── → dHO {(R ⁶ O) _m CONHR ⁵ NHCOO} _{c / d} (R ⁶ O) _m H (in the formula, c and d are numbers, and have a relationship of c> d and c / d = k.) HO {(R ⁶ O) _m CONHR ⁵ NHCOO} _k (R ⁶ O) _m H +2 (MIs or AIs) ) ── → Compound of the general formula (3)

In the description of the present specification, the expression "alkylene glycol" also includes oligoalkylene glycol and polyalkylene glycol. Similarly, the expression "monoalkyl alkylene glycol" also includes monoalkyl oligoalkylene glycols and monoalkyl polyalkylene glycols.
Among the compounds represented by the general formula (1), the compound represented by the general formula (2) is preferable because more urethane groups and oxyalkylene groups can be introduced into the side chains of the obtained polymer.

The (M) ACE polymer contained in the polymer solid electrolyte of the present invention is represented by A represented by the general formula (1).
It is obtained by polymerizing at least one compound selected from CE-based compounds or MCE-based compounds, or by polymerizing the compound as a copolymerization component. For the polymerization, a general method utilizing the polymerizability of the acryloyl group or methacryloyl group of these monomers can be adopted. That is, these monomers, or a mixture of these monomers and other polymerizable compounds such as methacrylic acid (or acrylic acid) ester, acrylamide, styrene, N-vinylacetamide, etc., azobisisobutyronitrile, benzoylperoxide, etc. Radical polymerization catalysts such as oxides, protic acids such as CF ₃ COOH, BF
Radical, cationic or anionic polymerization can be carried out using a cationic polymerization catalyst such as Lewis acid such as ₃ , AlCl ₃ or the like, or an anionic polymerization catalyst such as butyllithium, sodium naphthalene or lithium alkoxide. It is also possible to polymerize such a polymerizable monomer mixture after being formed into a film-like shape. When the (M) ACE polymer is used in the polymer solid electrolyte as in the present invention, it is particularly advantageous to polymerize the polymerizable monomer mixture after film formation, as described above.

That is, ACE compound or MCE
A mixture of at least one compound selected from the group of compounds and at least one electrolyte such as an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt or a transition metal salt, and in some cases, further other polymerizable compound and / or Alternatively, a plasticizer and / or a solvent is added and mixed, and the polymerizable monomer mixture is polymerized in the presence or absence of the catalyst, and in some cases, irradiation with electromagnetic waves such as heating and / or light. In particular, after the polymerizable monomer mixture is formed into a film-like shape or the like, the film is polymerized by, for example, heating and / or irradiation of electromagnetic waves such as light to form a film-like polymer. This is a great advantage in application. When a solvent is used, it depends on the kind of the compound represented by the general formula (1) and the presence or absence of a polymerization catalyst, but any solvent may be used as long as it does not inhibit the polymerization, for example, tetrahydrofuran, acetonitrile, toluene and the like. Can be used.

The temperature for the polymerization depends on the kind of the compound represented by the general formula (1), but it may be any temperature at which the polymerization occurs, and it is usually carried out in the range of 0 ° C to 200 ° C. In the case of polymerizing by irradiation with electromagnetic waves, it depends on the kind of the compound represented by the general formula (1), but for example, an initiator such as benzylmethyl ketal or benzophenone is used, and ultraviolet light of several mW or more Can be irradiated to polymerize.

Used in the solid polymer electrolyte of the present invention (M)
As described above, the ACE polymer is a homopolymer of the ACE compound or the MCE compound represented by the general formula (1), or a copolymer of two or more ACE compounds or MCE compounds. Or it may be a copolymer of at least one ACE compound or MCE compound and another polymerizable compound. Further, the polymer used in the solid polymer electrolyte of the present invention may be a mixture of such (M) ACE polymer and another polymer. For example,
(M) ACE polymer, polyethylene oxide, polyacrylonitrile, polybutadiene, polymethacrylic (or polyacrylic) acid esters, polystyrene,
A mixture with a polymer such as polyphosphazene, polysiloxane or polysilane may be used in the solid polymer electrolyte of the present invention. The amount of the structural unit derived from the ACE compound or the MCE compound represented by the general formula (1) contained in the above copolymer or polymer mixture is 20% by weight of the copolymer or polymer mixture. If it is at least 50%, the characteristics of the urethane bond can be sufficiently exhibited, and it is preferably at least 50% by weight.

The molecular weight of the (M) ACE polymer used in the solid polymer electrolyte of the present invention is preferably 1,000 or more and 1,000,000 or less, and particularly preferably 5,000 or more and 50,000 or less.
When the molecular weight of the polymer becomes high, the film properties such as the film strength after processing become good, but on the other hand, the restriction of thermal motion important for carrier ion movement is caused, the ion conductivity is lowered, and it becomes difficult to dissolve in a solvent. It is disadvantageous in terms of processing. On the contrary, when the molecular weight is too low, the film forming property, the film strength and the like are deteriorated and the basic physical properties are deteriorated.

One of the compounds represented by the general formulas (1) to (3) used for obtaining the (M) ACE polymer used in the polymer solid electrolyte of the present invention has a polymerizable group. If there is a comb-shaped polymer due to polymerization,
A polymer having one polymerizable group can be obtained by polymerizing a network polymer. Therefore, by appropriately mixing these, it is possible to obtain a polymer having high thermal mobility and good film strength. The number of oxyalkylene chains in the oxyalkyl group serving as the side chain of the polymer (that is, the above general formula (1)
R ² and [O (CH ₂ ) _x (CH ₂ CH (CH
₃ )) _y ] The number of oxyalkylene groups contained in _z , or, for example, (R ³ O) _n in the general formula (2).
And [O (CH ₂ ) _x (CH ₂ CH (CH ₃ )) _y ] _z
The number of oxyalkylene groups contained therein, or (R ³ O) _n in the general formula (3),

Embedded image And [O (CH ₂ ) _x (CH ₂ CH (CH ₃ )) _y ] _z
The number of oxyalkylene groups contained therein is preferably in the range of 1 to 1000, particularly preferably in the range of 5 to 50.

The ACE compounds and MCE compounds of the present invention have the general formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO OR ^{2 In} (1), (a) x is 0 or 1, y is 0 or 1, z
Is 0 or 1 (however, z = 0 when x = 0 and y = 0), the corresponding isocyanate compound CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH
₃ )) _y ] _z NCO has high reactivity and can easily react with various oxyalkylene compounds. Further, these compounds are liquid and have low viscosity, and have an advantage that they can be easily reacted in a solvent system. On the other hand, in the ACE compound or the MCE compound, (b)
x = 3 to 5, y = 0, z = 1 to 10, (c) x = 1 to
5, the compound of y = 1-5 (random arrangement), z = 1-10 or (d) x = 0, y = 1-5, z = 1-10,
Generally, since the melting point is high and the polymerizability is low, the storage stability is good, and the handleability as a prepolymer is good. Especially in the cases of (c) and (d), when an oxypropylene group is introduced, the dielectric constant is lowered, but the melting point and the viscosity are not increased even with a high molecular weight, and it is an extremely advantageous polymer depending on the application. . Therefore, by utilizing the characteristics of these prepolymers, it is possible to obtain a polymer solid electrolyte suitable for use by appropriately combining prepolymers or by combining with other polymers.

By adding an organic compound as a plasticizer to the polymer solid electrolyte of the present invention,
The ionic conductivity is further improved. As the organic compound to be added, a compound having good compatibility with the (M) ACE polymer, a large dielectric constant, a boiling point of 100 ° C. or higher, and a wide electrochemical stability range is suitable. Such plasticizers include oligoethers such as triethylene glycol methyl ether and tetraethylene glycol dimethyl ether, carbonates such as ethylene carbonate, propylene carbonate, diethyl carbonate, vinylene carbonate, and aromatic nitriles such as benzonitrile and tolunitrile. , Sulfur compounds such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone and sulfolane, and phosphoric acid esters. Of these, oligoethers and carbonates are preferable, and carbonates are particularly preferable.

The larger the amount of the plasticizer added, the higher the ionic conductivity of the solid polymer electrolyte, but if it is too large, the mechanical strength of the solid polymer electrolyte decreases. The preferable addition amount is not more than 5 times the weight of the (M) ACE polymer. Further, by copolymerizing a polymerizable compound such as vinylene carbonate or N-vinylpyrrolidone as a plasticizer with a non-polymerizable plasticizer in an appropriate amount to copolymerize with ACE or MCE,
The ionic conductivity can be improved by increasing the amount of the plasticizer added without lowering the mechanical strength.

The above (M) in the solid polymer electrolyte of the present invention
The composite ratio of the ACE polymer and the electrolyte used for the composite is 2 to 100 ether oxygen atoms in the side chain to 1 electrolyte molecule.
A ratio of individual pieces is preferable. When the electrolyte used for the combination is present at a ratio of 1/2 or more of the ether oxygen atom, the migration of ions is significantly inhibited, and conversely, at a ratio of 1/100 or less, the absolute amount of ions is insufficient and the ionic conductivity is reduced. It becomes smaller, which is not preferable.

Further, the composite ratio is more preferably a ratio of one electrolyte molecule to 4 to 100 side chain ether oxygen atoms. If the electrolyte used for the composite is present at a ratio of 1/4 or more of the ether oxygen atom, the migration of ions is hindered. On the contrary, if the ratio is 1/100 or less, the absolute amount of ions is insufficient and the ionic conductivity is small. Therefore, it is not preferable. The type of electrolyte used in the composite is not particularly limited, it is possible to use an electrolyte containing ions to be used as carriers in the charge, it is desirable that the dissociation constant in the solid polymer electrolyte is large, alkali metal salt, (CH
₃ ) ₄ NBF _{4 and} other quaternary ammonium salts, (CH ₃ ) ₄
A quaternary phosphonium salt such as PBF _4, a transition metal salt such as AgClO ₄ or a protic acid such as hydrochloric acid, perchloric acid or borofluoric acid is recommended.

Examples of the negative electrode active material used in the battery of the present invention include alkali metals, alkali metal alloys, and
By using a material with a low redox potential that uses an alkali metal ion as a carrier, such as a carbon material, a high voltage,
It is preferable because a high capacity battery can be obtained. Therefore, an alkali metal salt is required as an electrolyte in the polymer solid electrolyte when using such a negative electrode in a battery using alkali metal ions as a carrier. Examples of the alkali metal salt include, for example, LiCF ₃ SO ₃ , LiPF ₆ ,
LiClO ₄ , LiI, LiBF ₄ , LiSCN, Li
AsF ₆ , NaCF ₃ SO ₃ , NaPF ₆ , NaClO
₄ , NaI, NaBF ₄ , NaAsF ₆ , KCF ₃ SO
₃ , KPF ₆ , KI and the like can be mentioned. Among these, it is most preferable to use lithium or a lithium alloy as the alkali metal, since it has a high voltage and a high capacity and can be formed into a thin film. In the case of a carbonaceous material negative electrode, not only alkali metal ions but also quaternary ammonium salts, quaternary phosphonium salts, transition metal salts, and various protic acids can be used.

The type of the electrolyte used for the composite in the case of the solid electric double layer capacitor is not particularly limited, and a compound containing an ion to be used as a charge carrier may be used, but the dissociation constant in the polymer electrolyte is It is desirable to include ions that are large and that easily form an electric double layer with the polarizable electrode. Such compounds include (CH ₃ ) ₄ NB
F ₄ , quaternary ammonium salts such as (CH ₃ CH ₂ ) ₄ NClO ₄ , transition metal salts such as AgClO ₄ , (CH ₃ ) ₄ P
Quaternary phosphonium salt such as BF ₄ , LiCF ₃ SO ₃ , L
iPF ₆ , LiClO ₄ , LiI, LiBF ₄ , LiS
CN, LiAsF ₆ , NaCF ₃ SO ₃ , NaPF ₆ ,
NaClO ₄ , NaI, NaBF ₄ , NaAsF ₆ , K
Examples thereof include alkali metal salts such as CF ₃ SO ₃ , KPF ₆ and KI, organic acids such as paratoluene sulfonic acid and salts thereof, and inorganic acids such as hydrochloric acid and sulfuric acid. Among these, a quaternary ammonium salt, a quaternary phosphonium salt, and an alkali metal salt are preferable because they can have a high output voltage and a large dissociation constant. Among the quaternary ammonium salts, (CH ₃ CH ₂ )
Those having different substituents on the nitrogen of the ammonium ion, such as (CH ₃ CH ₂ CH ₂ CH ₂ ) ₃ NBF ₄ , are preferable from the viewpoint of high solubility in the solid polymer electrolyte or dissociation constant.

In the structure of the battery of the present invention, by using an electrode active material having a low redox potential (negative electrode active material) such as a carbon material having an alkali metal, an alkali metal alloy, or an alkali metal ion as a carrier in the negative electrode, It is preferable because a high voltage and high capacity battery can be obtained. Among such electrode active materials, lithium metal or lithium alloys such as lithium / aluminum alloy, lithium / lead alloy, lithium / antimony alloy and the like are particularly preferable because they have the lowest redox potential. Further, the carbon material is also particularly preferable in that it has a low redox potential when occluding Li ions, and is stable and safe. Examples of carbon materials capable of occluding and releasing Li ions include natural graphite, artificial graphite, vapor phase graphite,
Examples thereof include petroleum coke, coal coke, pitch-based carbon, polyacene, and fullerenes such as C ₆₀ and C ₇₀ .

In the battery of the present invention, by using an electrode active material (positive electrode active material) having a high redox potential such as a metal oxide, a metal sulfide, a conductive polymer or a carbon material for the positive electrode, This is preferable because a battery having a high voltage and a high capacity can be obtained. Among such electrode active materials, metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, and molybdenum oxide, molybdenum sulfide, and molybdenum sulfide are included in terms of high packing density and high volume capacity density.
Metal sulfides such as titanium sulfide and vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide and the like are particularly preferable from the viewpoint of high capacity and high voltage. In addition, a conductive polymer such as polyaniline is particularly preferable because it is flexible and can be easily formed into a thin film. Examples of the conductive polymer 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, and polyfurylene. And derivatives thereof, polyselenophenylene and derivatives thereof, polyparaphenylene vinylene, polythienylene vinylene, polyfurylene vinylene, polynaphthylene vinylene, polyselenophenylene vinylene, polyarylene vinylene such as polypyridinediyl vinylene, and derivatives thereof. Is mentioned.

Examples of the carbon material include natural graphite, artificial graphite, vapor grown graphite, petroleum coke, coal coke, fluorinated graphite, pitch carbon, polyacene, fullerenes such as C ₆₀ and C _70. . The method for producing a metal oxide or a metal sulfide is not particularly limited, and for example, a general electrolysis method or heating method as described in “Electrochemistry, Vol. 22, 574, page 1954”. Manufactured by. When these are used in a lithium battery as an electrode active material, for example, Li _x CoO ₂ may be used at the time of manufacturing the battery.
It is preferable to use the Li element in the form of (composite) in a metal oxide or a metal sulfide in the form of Li _x MnO ₂ or the like. The method of inserting the Li element in this way is not particularly limited, and examples thereof include a method of electrochemically inserting Li ions and a salt such as Li ₂ CO ₃ as described in US Pat. No. 4,357,215. It can be carried out by mixing a metal oxide and heat treatment.

The conductive polymer used as the electrode active material in the battery or electrode of the present invention is produced by the chemical or electrochemical method described below or other known methods. Further, as the carbon material used as an electrode active material in the battery or electrode of the present invention, a commercially available carbon material can be used, or it can be produced according to a known method.

The use of an organic solvent-soluble aniline polymer as the electrode active material in the electrode or battery of the present invention is advantageous because molding can be performed by solution coating, and is particularly advantageous when a thin film battery is produced. Is. Examples of the aniline-based polymer include polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-anisidine, poly-m-anisidine, polyxylidines, poly-
2,5-dimethoxyaniline, poly-2,6-dimethoxyaniline, poly-2,5-diethoxyaniline, poly-2,6-diethoxyaniline, poly-o-ethoxyaniline, poly-m-ethoxyaniline and Although these copolymers can be mentioned, they are not particularly limited thereto, and any polymer having a repeating unit derived from an aniline derivative may be used. In addition, the introduction amount of the side chain in the organic solvent-soluble aniline-based polymer is more convenient in terms of solubility as the amount is larger, but as the introduction amount increases, the capacity per weight as the positive electrode decreases. A surface appears. Therefore, preferable aniline-based polymers include, for example, polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-anisidine, and poly-m.
-Anisidine, polyxylidines.

The polymerization method of the aniline polymer used in the present invention is not particularly limited, but generally, for example, "Journal of Chemical Society, Chemical Communication, page 1784 (1)
987) "and the like, aniline, o-
Examples thereof include a method of electrochemically or chemically oxidizing and oxidizing an aniline derivative such as anisidine. The molecular weight of the aniline polymer used in the present invention obtained by such a method is not particularly limited, but it is usually preferably 2000 or more. The aniline-based polymer obtained by such a method is generally obtained in a state where the anion in the polymerization solution is contained as a dopant, which is disadvantageous in terms of solubility and capacity per weight. Therefore, it is preferable that these anions be dedoped and further reduced to a reduced form, for example, by a film forming method before forming the electrode. The dedoping method is not particularly limited, but a method of treating with a base such as aqueous ammonia or sodium hydroxide is generally used. Also, there is no particular limitation on the reduction method,
General chemical or electrochemical reduction may be performed. For example, regarding the chemical reduction method, the aniline-based polymer dedoped by treatment with a base in a hydrazine or phenylhydrazine solution can be easily reduced by dipping or stirring at room temperature.

The dedoped or reduced aniline-based polymer thus obtained is soluble in various organic solvents, and in solution, at least one ACE-based polymer represented by the above general formula (1). Compound or a polymerizable monomer solution containing an MCE compound can be mixed, and a mixture prepared in such a manner can be used to form a thin film on various supports, for example, electrodes by a coating method or the like. The electrode can be manufactured by molding into a shape. The solvent in which the aniline-based polymer is dissolved depends on the kind of the substituent on the benzene ring, and is not particularly limited, but pyrrolidones such as N-methylpyrrolidone, amides such as dimethylformamide, m-cresol,
Easily soluble in polar solvents such as dimethyl propylene urea.

Next, an example of the method of manufacturing the electrode and the battery of the present invention will be described in detail. The electrode of the present invention is, for example, an ACE-based compound represented by the general formula (1) or MC
At least one compound selected from E-based compounds is further added with another polymerizable compound and / or a plasticizer, as the case may be, and mixed with the above electrode active material (positive electrode active material or negative electrode active material). In that case, the ratio of each component to be mixed should be appropriate for the intended battery. The polymerizable monomer / electrode active material mixture thus obtained is molded into a film-like shape and then polymerized to produce an electrode. In this method, the polymerization can be performed by the same polymerization method as in the case of obtaining the (M) ACE polymer from the above-mentioned ACE-based compound or MCE-based compound, for example, the polymerization can be performed by heating and / or electromagnetic wave irradiation. . When the electrode active material is, for example, an organic solvent-soluble aniline-based polymer, a polymerizable monomer / liquid monomer having high fluidity
When the electrode active material mixture is provided, the mixture is coated on a current collector or other support such as glass to form a film, which is then molded and polymerized to produce an electrode.

The electrode containing the above-mentioned electrode active material produced in this manner is used as at least one electrode, and the electrode containing the other electrode active material produced in the same manner or another commonly used electrode is used as the other electrode. , Both electrodes are placed in a battery structure structure or placed on a support so that they do not contact each other. For example, the positive electrode and the negative electrode are laminated to each other through a spacer having an appropriate thickness at the end of the electrode and put in the structure, and then, between the positive electrode and the negative electrode, the ACE compound represented by the general formula (1). Alternatively, at least one compound selected from MCE compounds and at least one electrolyte selected from the above-mentioned electrolytes such as alkali metal salts are mixed, and in some cases, other polymerizable compounds and / or plasticizers are added and mixed. After injecting the polymerizable monomer mixture prepared by, for example, by polymerization by heating and / or electromagnetic wave irradiation, by a polymerization method similar to the above-mentioned (M) ACE polymer to obtain a polymerization method, Alternatively, further, after polymerization, if necessary, a polyolefin resin,
By sealing with an insulating resin such as an epoxy resin, a battery in which the electrodes and the electrolyte are in good contact can be obtained. When such an electrode obtained by polymerizing the above-mentioned polymerizable monomer mixture is used, a battery in which the electrode and the electrolyte are in excellent contact can be obtained. When preparing such a polymerizable monomer mixture, the ratio of each component to be mixed should be appropriate for the intended battery. The battery structure 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. The shape is not limited, and may be any shape such as a tubular shape, a box shape, and a sheet shape.

As described above, by polymerizing the polymerizable monomer mixture obtained by mixing at least one ACE compound or MCE compound represented by the general formula (1) with at least one electrolyte, ( M) ACE
The method for producing a polymer solid electrolyte comprising a polymer and a composite containing at least one electrolyte is particularly useful for producing a thin film battery. 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 manufactured in this way. In the figure, 1 is a positive electrode, 2 is a solid polymer electrolyte, 3 is a negative electrode, 4 is a current collector, 5 is an insulating resin film which is a spacer, and 6 is an insulating resin sealant. In the case of manufacturing a wound type battery, the positive electrode and the negative electrode are laminated and wound through a polymer solid electrolyte sheet that has been prepared in advance, and the polymerized monomer is further wound after being inserted into the structure for battery construction. It is also possible to inject the mixture and polymerize it.

Next, the solid-state electric double layer capacitor of the present invention will be described. In the solid electric double layer capacitor of the present invention, the use of the polymer solid electrolyte of the present invention provides an all solid electric double layer capacitor having a high output voltage, a large extraction current, or excellent processability and reliability. To be done.

FIG. 2 shows a schematic sectional view of an example of the solid-state electric double layer capacitor of the present invention. This example is 1 cm in size
A thin cell having a size of 1 cm and a thickness of about 0.5 mm, 8 is a current collector, a pair of polarizable electrodes 7 is arranged inside the current collector, and a solid polymer electrolyte membrane 9 is arranged between them. ing. 10 is a spacer, an insulating film is used in this example, 11 is an insulating resin sealant, and 12 is a lead wire. The current collector 8 is preferably made of a material having electronic conductivity and electrochemical corrosion resistance, and a material having a large specific surface area as much as possible. For example, various metals and their sintered bodies, electron conductive polymers, carbon sheets and the like can be mentioned.

The polarizable electrode 7 may be an electrode made of a polarizable material such as a carbon material usually used in electric double layer capacitors, and a composite of the polymer solid electrolyte of the present invention with such a carbon material. preferable. The carbon material as the polarizable material is not particularly limited as long as it has a large specific surface area, but the larger the specific surface area, the larger the capacity of the electric double layer, which is preferable. For example, carbon blacks such as furnace black, thermal black (including acetylene black) and channel black, activated carbon such as coconut palm charcoal, natural graphite, artificial graphite, so-called pyrolytic graphite produced by a vapor phase method, polyacene and C _Examples include fullerenes such as ₆₀ and C ₇₀ .

Next, an example of a method for manufacturing the solid-state electric double layer capacitor of the present invention will be described. As described above, by polymerizing a polymerizable monomer mixture obtained by mixing at least one ACE compound or MCE compound represented by the general formula (1) with at least one electrolyte, (M) ACE The method for producing a composite containing a polymer and at least one electrolyte is particularly useful for producing the solid state electric double layer capacitor of the present invention.

When a polarizable electrode containing a polarizable material such as a carbon material and the (M) ACE polymer, which is preferably used in the solid electric double layer capacitor of the present invention, is manufactured, first, for example, the general formula (1) is used. At least one compound selected from the ACE-based compound and the MCE-based compound represented by the formula (3) is added to the polarizable material by adding another polymerizable compound and / or a plasticizer in some cases.
In that case, the ratio of each component to be mixed should be appropriate depending on the intended condenser. The polymerizable monomer / polarizable material mixture thus obtained is formed into a film on a support, for example, a current collector, and then polymerization is performed, for example, by heating and / or electromagnetic wave irradiation. A polarizable electrode is produced by polymerizing by the same method as that for obtaining the ACE polymer. According to this method, a composite thin film electrode that is in good contact with the current collector can be manufactured.

The two polarizable electrodes manufactured in this manner are placed in a structure for forming a capacitor or arranged on a support so as not to contact each other. For example, attach both electrodes to the end of the electrode through a spacer of appropriate thickness,
The ACE-based compound represented by the general formula (1) or the MC is placed between the two polarizable electrodes in the structure.
At least one compound selected from E-based compounds and at least one electrolyte selected from the above-mentioned electrolytes such as alkali metal salts are mixed, and in some cases, other polymerizable compounds and / or plasticizers are added and mixed. After injecting the polymerizable monomer mixture prepared by, by polymerizing by the same method as described above, or, further, after polymerization by sealing with an insulating resin such as a polyolefin resin or an epoxy resin, if necessary, An electric double layer capacitor in which the electrodes and the electrolyte are in good contact can be obtained. When preparing such a monomer mixture, the ratio of each component to be mixed is
Appropriate for the target capacitor. By this method, a particularly thin all-solid-state electric double layer capacitor can be manufactured. The capacitor structure 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, but is particularly made of these materials. However, the shape is not limited to the above, and may be any shape such as a tubular shape, a box shape, and a sheet shape.

As for 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 laminated body of a polarizable electrode and a polymer solid electrolyte is wound into a cylindrical shape to form a cylindrical tubular shape. Put it in the structure for capacitor construction,
It may be a cylindrical type manufactured by sealing. In the case of manufacturing a wound capacitor, the above-mentioned polarizable electrode is bonded through a polymer solid electrolyte sheet prepared in advance, wound, and inserted into the capacitor structure, and then the polymerizable monomer mixture is further added. Is injected and polymerized.

[0060]

The solid polymer electrolyte of the present invention is, as described above,
Easy film formation from the polymerizable monomer mixture that is the raw material,
A highly ion-conductive solid electrolyte consisting of a comb-type polymer or a network-like polymer with an oxyalkyl group having a urethane bond that can be compounded introduced into the side chain, with good film strength and excellent thin film processability. I have.

In the battery of the present invention, by using the above-mentioned polymer solid electrolyte as the ion conductive material, it is easy to process it into a thin film, there is no fear of short circuit even in the thin film, the extraction current is large and the reliability is high. It is a battery, and can be an all-solid-state battery in particular. Further, the battery of the present invention, in which the negative electrode is composed of an electrode containing an active material such as lithium or a lithium alloy or a carbon material capable of inserting and extracting lithium ions, can be formed into a thin film by using the polymer solid electrolyte as an ion conductive material. It is a battery that is easy to process, has no fear of short-circuiting even with a thin film, has a large extraction current, and has high reliability, and in particular can be an all-solid-state battery.

Further, in the present invention, the positive electrode is the above (M) ACE.
A polymer and an organic solvent-soluble aniline-based polymer or other conductive polymer, an electrode containing an active material such as a metal oxide, a metal sulfide or a carbon material, and the use of the polymer solid electrolyte as an electrolyte The featured battery is easy to process such as thin film, there is no fear of short circuit even with thin film, large withdrawal current, high capacity, high reliability, especially all-solid-state battery ..

Furthermore, the above-mentioned (M) ACE polymer and organic solvent-soluble aniline polymer or other conductive polymer, electrode active material such as metal oxide, metal sulfide or carbon material of the present invention is used. In the electrode and the method for producing the electrode, which does not impair the electrochemical activity of the electrode active material having excellent activity as an electrode, to provide an electrode having flexibility as necessary, For example, it can be a thin film electrode, and is useful as an electrode for various batteries. Further, according to the battery manufacturing method of the present invention, batteries of various shapes can be manufactured, and in particular, the battery can be easily thinned, can operate at high capacity and high current, or has good cycleability. A battery with excellent reliability can be manufactured, and in particular, an all-solid-state battery can be manufactured.

The electric double layer capacitor of the present invention can be easily formed into a film from a polymerizable monomer mixture and can be composited to form a comb polymer or a network polymer in which an oxyalkyl group having a urethane bond is introduced into a side chain. Polymerized by dissolving an electrolyte in a monomer mixture, produced by using as a high ion conductivity and good polymer solid electrolyte polymer solid electrolyte as an ion conductive material, there is no short circuit even in a thin film, It is an electric double layer capacitor having a high output voltage and a large extraction current and high reliability, and in particular, it can be an all-solid-state electric double layer capacitor. In particular, according to the electric double layer capacitor and the method of manufacturing the same of the present invention,
Good contact between the polarizable electrode and the solid polymer electrolyte, which is an ion-conductive substance, has no short circuit even in a thin film.
An electric double layer capacitor having high output voltage and extraction current and high reliability is provided, and in particular, an all-solid-state electric double layer capacitor is provided.

[0065]

The present invention will be described in more detail below by showing typical examples. It should be noted that these are merely examples for explanation, and the present invention is not limited to these.

Example 1 (1) Synthesis of N-methacryloylcarbamic acid ω-methyloligooxyethyl ester (MME (550)) (in the general formula (2), R ¹ ═R ⁴ ═CH ₃ and R ³ ═)
(CH ₂ ) ₂ , z = 0) N-methacryloyl isocyanate (MAI) 0.1 m
Ol (11.1 g) and 0.1 mol (55 g) of monomethyl oligoethylene glycol having an average molecular weight of 550 are dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and then 0.66 g of dibutyltin dilaurate is added. After that, by reacting at 50 ° C. for about 3 hours,
MME (550) was obtained as a colorless viscous liquid. Part ¹
From the results of 1 H-NMR, IR and elemental analysis, MAI and monomethyl oligoethylene glycol reacted in a one-to-one relationship,
Further, it was found that the isocyanate group of MAI disappeared and a urethane bond was formed.

(2) Preparation and Evaluation of MME (550) Polymer Solid Electrolyte 1.40 g of MME (550) was dissolved in 100 ml of THF, and 0.14 g of LiCF ₃ SO ₃ was added and well mixed. Then THF was removed at room temperature under reduced pressure to remove MME
A (550) / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. When this mixture was coated on a glass plate under an argon atmosphere and heated at 100 ° C. for 1 hour, MME (55
0) The polymer / LiCF ₃ SO ₃ composite was obtained as a transparent film of about 200 μm. 25 ℃ of this film
The ionic conductivity at 8 was measured by the impedance method and was 8 × 10 ⁻⁵ S / cm.

Example 2 (1) N-methacryloylcarbamic acid N-methacryloylcarbamoyloligooxyethyl ester (MEM)
(1000)) (in the general formula (2), R ¹ = CH ₃ , R ³ = (CH
₂ ) ₂ , R ⁴ = CONHOCOC (CH ₃ ) = CH ₂ ,
z = 0) N-methacryloyl isocyanate (MAI) 0.2 m
Ol (22.2 g) and 0.1 mol (100 g) of oligoethylene glycol having an average molecular weight of 1000 were dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and
Add 66 g of dibutyltin dilaurate. Then, MEM (1000) was obtained as a colorless viscous liquid by making it react at 50 degreeC for about 3 hours. Part ¹ H-N
From the results of MR, IR and elemental analysis, it was found that MAI and oligoethylene glycol reacted in a ratio of 2: 1 and further, the isocyanate group of MAI disappeared and a urethane bond was formed.

(2) MME (550) / MEM (100
0) Preparation and Evaluation of Copolymeric Polymer Solid Electrolyte 2.00 g of MME (550) synthesized in Example 1 and 0.40 g of MEM (1000) synthesized in Example 2 (1) were dissolved in 20 ml of THF, and LiCF was added. ₃ SO ₃ 0.14
g was added and mixed well. Then, THF was removed at room temperature under reduced pressure, and MME (550) / MEM (1000) /
A LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. After coating this mixture on a glass plate under an argon atmosphere,
When heated at ℃ for 1 hour, MME (550) / MEM
(1000) copolymer / LiCF ₃ SO ₃ composite is about 1
It was obtained as a transparent free-standing film of 00 μm. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 1 × 10 ⁻⁵ S / cm.

Example 3 Instead of LiCF ₃ SO ₃ used in Example 1, NaCF
_A solid electrolyte was produced in the same manner as in Example 1 except that 0.15 g of ₃ SO ₃ was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by the impedance method, it was 7 × 10 ⁻⁵ S / cm.

Example 4 Instead of LiCF ₃ SO ₃ used in Example 1, LiI
A solid electrolyte was produced in the same manner as in Example 1 except that 0.11 g was used. The ionic conductivity of this solid electrolyte at 25 ° C. was measured by the impedance method to be 1 × 1.
It was 0 ⁻⁴ S / cm.

Example 5 (1) Synthesis of N-methacryloylcarbamic acid N-methacryloylcarbamoyl oligooxyethyl / oligooxypropyl ester polymer (MEPM (800)) (in the general formula (2), R ¹ = CH ₃ , R ³ = (CH
₂ ) ₂ and / or (CH (CH ₃ ) CH ₂ ), R ⁴
_{= CONHOCOC (CH 3) = CH} 2, z = 0) N-
Methacryloyl isocyanate (MAI) 0.2 mol
(22.2 g), 0.1 mol of an oligoethylene glycol / propylene glycol copolymer having an average molecular weight of 800
(80 g) was well purified in a nitrogen atmosphere THF100
After dissolving in ml, add 0.66 g dibutyltin dilaurate. Then, by reacting at 50 ° C. for about 3 hours, MEPM (800) was obtained as a colorless gel solid.
I got From the results of ¹ H-NMR, IR and elemental analysis, MI and oligoethylene glycol / propylene glycol copolymer were reacted in a ratio of 2 to 1, further, the isocyanate group of MI disappeared and a urethane bond was formed. I found out that

(2) MME (550) / MEPM (80
0) Preparation and Evaluation of Copolymer Solid Electrolyte 2.00 g of MME (550) synthesized in Example 1 and ME
0.40 g of PM (800) was dissolved in 20 ml of THF, and 0.14 g of LiCF ₃ SO ₃ was added and mixed well. Then THF was removed at room temperature under reduced pressure to remove MME
A (550) / MEPM (800) / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. After coating this mixture on a glass plate in an argon atmosphere and heating at 100 ° C. for 1 hour, a transparent self-supporting film in which the MME (550) / MEPM (800) copolymer / LiCF ₃ SO ₃ composite was about 100 μm. Was obtained as. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method,
It was 1 × 10 ⁻⁴ S / cm.

Example 6 (1) Synthesis of N-methacryloylcarbamic acid ω-methyloligooxypropyl ester (MMP (440)) (in the general formula (2), R ¹ ═R ⁴ ═CH ₃ and R ³ ═C)
H ₂ CH (CH ₃ ), z = 0) MAI 0.1 mol (11.1 g), average molecular weight 440
0.1 mol of monomethyl oligopropylene glycol
(44 g) well purified in a nitrogen atmosphere THF100
After dissolving in ml, add 0.66 g dibutyltin dilaurate. Then, by reacting at 50 ° C for about 3 hours, MMP (440) was obtained as a single yellow viscous liquid.
I got From the results of ¹ H-NMR, IR and elemental analysis, it was found that MAI and monomethyloligopropylene glycol react with each other in a one-to-one manner, the isocyanate group of MAI disappears, and a urethane bond is formed. .

(2) MMP (440) / MEM (100
0) Preparation and Evaluation of Copolymeric Polymer Solid Electrolyte 1.84 g of MMP (440) and ME synthesized in Example 2
0.40 g of M (1000) was dissolved in 20 ml of THF, 0.14 g of LiCF ₃ SO ₃ was added and mixed well. Then THF was removed at room temperature under reduced pressure to remove MMP
A (440) / MEM (1000) / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. Under an argon atmosphere, after applying the mixture onto a glass plate, it was heated at 100 ℃, MMP (440) / MEM (1000) a transparent, free-standing film of a copolymer / LiCF ₃ SO ₃ complex of about 100μm Was obtained as. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method,
It was 2 × 10 ⁻⁵ S / cm.

Example 7 Instead of LiCF ₃ SO ₃ used in Example 5, tetrabutylammonium tetrafluoroborate (TBAB) was used.
A solid electrolyte was obtained as a 100 μm transparent self-supporting film in the same manner as in Example 10 except that 0.30 g was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by the impedance method, it was 7 × 10 ⁻⁵ S / cm.

Example 8 Instead of LiCF ₃ SO ₃ used in Example 5, AgI was used.
A solid electrolyte was obtained as a transparent self-supporting film of about 100 μm in the same manner as in Example 5 except that 0.30 g was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by the impedance method, it was 9 × 10 ⁻⁴ S / cm.

Example 9 MME (550) 1.40 synthesized in Examples 1 and 2
g, MEM (1000) 0.40 g, propylene carbonate (PC) 1.5 g, and LiCF ₃ SO ₃ 0.2
8 g was mixed well in an argon atmosphere, and MME (55
A 0) / MEM (1000) / PC / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. Under an argon atmosphere, after applying the mixture onto a glass plate, was heated at 100 ℃, MME (550) / MEM (1000) copolymer / PC / LiCF ₃ SO ₃ complex of about 300μm transparent Obtained as a free-standing film. 25 of this film
When the ionic conductivity at ° C was measured by the impedance method, it was 1 x 10 ^-3 S / cm.

Example 10 MME (550) / MEM (1000) was prepared in the same manner as in Example 9 except that tetraglyme (TG) was used in place of the propylene carbonate used in Example 9.
About 350μ of copolymer / TG / LiCF ₃ SO ₃ composite
m transparent self-supporting film. 2 of this film
When the ionic conductivity at 5 ° C. was measured by the impedance method, it was 5 × 10 ⁻⁴ S / cm.

Example 11 In the same manner as in Example 9 except that diethyl carbonate (DEC) was used instead of propylene carbonate used in Example 9, MME (550) / MEM (5
50) Copolymer / DEC / LiCF ₃ SO ₃ composite was obtained as a transparent self-supporting film of about 250 μm. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 2 × 10 ⁻³ S / cm.

Example 12 (in the general formula (3), R ¹ = R ⁴ = CH ₃ , R ⁵ =
(CH ₂ ) ₆ , R ³ = R ⁶ = (CH ₂ ) ₂ , z = 0) Hexamethylene diisocyanate 0.1 mol (16.
8 g), 0.1 mol (40 g) of polyethylene glycol having an average molecular weight of 400, and 0.1 mol (16.4 g) of triethylene glycol monomethyl ether were thoroughly purified in a nitrogen atmosphere. Tetrahydrofuran (THF) 10
After dissolution in 0 ml, 0.66 g dibutyltin dilaurate was added. Then, a colorless viscous liquid product was obtained by reacting at 60 ° C. for about 1 hour. Part ¹ H
From the results of NMR and IR, it was found that the isocyanate group of hexamethylene diisocyanate disappeared and a urethane bond was formed. In addition, as a result of measuring this product by gel filtration chromatography (GPC), the average molecular weight of the obtained product in terms of polyethylene glycol was about 750. 37.5 g of this compound
And N-methacryloyl isocyanate (MAI) 0.0
After dissolving 5 mol (5.55 g) in 100 ml of well-purified THF in a nitrogen atmosphere, 0.33 g of dibutyltin dilaurate was added. After that, about 3 at 50 ℃
The product was obtained as a colorless viscous liquid by reacting for a time. From the results of ¹ H-NMR, IR and elemental analysis, it was found that the isocyanate group of MAI disappeared and the urethane bond increased. 2.69 g of this monomer was dissolved in 10 ml of THF, and LiCF ₃ S was added.
O ₃ 0.14 g added thereto and mixed well, and the polymerizable monomer mixture was prepared. Next, this mixture was applied onto a glass plate under an argon atmosphere and then heated at 100 ° C. for 1 hour for polymerization to obtain a polymer solid electrolyte as a transparent self-supporting film of about 100 μm. 2 of this film
When the ionic conductivity at 5 ° C. was measured by the impedance method, it was 1 × 10 ⁻⁵ S / cm.

Example 13 Preparation of Polymerizable Monomer Mixture MME (550) 2.00 synthesized in Examples 1 and 2
g, MEM (1000) 0.51 g, propylene carbonate (PC) 2.0 g, ethylene carbonate (E
C) 2.0 g and LiBF ₄ 0.40 g were mixed well in an argon atmosphere, and MME (550) / MEM (10
00) / PC / EC / LiBF ₄ mixture was obtained as a viscous liquid. After coating this polymerizable monomer mixture on a glass plate under an argon atmosphere, 1
When heated at 00 ° C for 1 hour, MME (550) / M
The EM (1000) copolymer / PC / EC / LiBF ₄ composite was obtained as a transparent self-supporting film of about 300 μm. When the ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by the impedance method,
It was 3 × 10 ⁻³ and 1 × 10 ⁻³ S / cm.

Example 14 (1) 1-Methyl-2-methacryloyloxyethylcarbamic acid ω-methyloligooxyethyl ester (M
Synthesis of MME (550) (in the general formula (2), R ¹ = R ⁴ = CH ₃ , R ³ =
(CH ₂ ) ₂ , x = y = 1, z = 1) 1-methyl-2-methacryloyloxyethyl isocyanate (MMOI) 0.1 mol (16.9 g), monomethyl oligoethylene glycol having an average molecular weight of 550,
After dissolving 0.1 mol (55 g) in 100 ml of well-purified THF in a nitrogen atmosphere, 0.66 g of dibutyltin dilaurate is added. Then, by reacting at 50 ° C. for about 3 hours, MMM is obtained as a colorless viscous liquid.
E (550) was obtained. From the results of ¹ H-NMR, IR and elemental analysis, it was found that MMOI and monomethyloligoethylene glycol reacted in a one-to-one manner, the isocyanate group of MMOI disappeared, and a urethane bond was formed.

(2) MMME (550) / MEM (10
00) Preparation and Evaluation of Copolymeric Polymer Solid Electrolyte 2.00 g of MMME (550) and M synthesized in Example 2
0.40 g of EM (1000) was dissolved in 20 cc of THF, and 0.09 g of LiBF ₄ was added and mixed well. The THF was then removed at room temperature under reduced pressure and MMME (55
A 0) / MEM (1000) / LiBF ₄ mixture was obtained as a viscous liquid. When this mixture was applied onto a glass plate in an argon atmosphere and heated at 100 ° C. for 1 hour, MM
ME (550) / MEM (1000) copolymer / LiB
The F ₄ composite was obtained as a transparent self-supporting film of about 100 μm. The ionic conductivity of this film at 25 ° C. was measured by the impedance method to be 2 × 10 ⁻⁵ S / c
It was m.

Example 15 (1) 3-acryloyloxypropylcarbamic acid ω
-Methyl oligooxyethyl ester (550) APM
Synthesis of E (550) (In the general formula (2), R ¹ = R ⁴ = CH ₃ , R ³ =
(CH ₂ ) ₂ , x = 3, y = 0, z = 1) 3-acryloyloxypropyl isocyanate (AP
I) 0.1 mol (15.5 g), monomethyl oligoethylene glycol having an average molecular weight of 550, 0.1 mol
(55 g) well purified in a nitrogen atmosphere THF100
After dissolving in ml, add 0.66 g dibutyltin dilaurate. Then, by reacting at 50 ° C. for about 3 hours, APME (550) was obtained as a colorless viscous liquid.
I got From the results of ¹ H-NMR, IR and elemental analysis, API and monomethyl oligoethylene glycol were 1
It was found that the reaction was carried out in pair 1, the isocyanate group of API disappeared, and a urethane bond was formed.

(2) APME (550) / MEM (10
00) Preparation and Evaluation of Copolymeric Polymer Solid Electrolyte 2.00 g of APME (550) and M synthesized in Example 2
0.40 g of EM (1000) was dissolved in 20 cc of THF, and 0.09 g of LiBF ₄ was added and mixed well. The THF was then removed at room temperature under reduced pressure and APME (55
A 0) / MEM (1000) / LiBF ₄ mixture was obtained as a viscous liquid. After coating this mixture on a glass plate under an argon atmosphere and heating at 100 ° C. for 1 hour, AP
ME (550) / MEM (1000) copolymer / LiB
The F ₄ composite was obtained as a transparent self-supporting film of about 100 μm. The ionic conductivity of this film at 25 ° C. was measured by the impedance method to be 1 × 10 ⁻⁵ S / c
It was m.

Example 16 2.10 g of APME (550) synthesized in Example 15, 0.40 g of MEM (1000) synthesized in Example 2, 1.3 g of propylene carbonate (PC), and ethylene carbonate (EC) 1. 3g and LiBF ₄ 0.56g were mixed well in an argon atmosphere, and APME (550) /
A MEM (1000) / PC / EC / LiBF ₄ mixture was obtained as a viscous liquid. This polymerizable monomer solution was applied onto a glass plate under an argon atmosphere and then heated at 100 ° C. for 1 hour. As a result, APME (550) / MEM (100
0) Copolymer / PC / EC / LiBF ₄ composite is about 30
It was obtained as a 0 μm transparent self-supporting film. The ionic conductivities of this film at 25 ° C. and −10 ° C. were measured by the impedance method to be 2.5 × 10 ⁻³ ,
It was 0.8 × 10 ⁻³ S / cm.

Example 17 (1) Methacryloyloxymethylcarbamic acid ω-methyl oligooxyethyl ester (MMME (55
0)) (in the general formula (2), R ¹ = R ⁴ = CH ₃ , R ³ =
(CH ₂ ) ₂ , x = 1, y = 0, z = 1) Methacryloyloxymethyl isocyanate (MMI)
0.1 mol (14.1 g), monomethyl oligoethylene glycol having an average molecular weight of 550, 0.1 mol (55
g) is dissolved in 100 ml of well-purified THF in a nitrogen atmosphere and then 0.66 g of dibutyltin dilaurate is added. Then, MMME (550) was obtained as a colorless viscous liquid by making it react at 50 degreeC for about 3 hours. From the ¹ H-NMR, IR and elemental analysis results,
1: 1 for MMI and monomethyl oligoethylene glycol
Then, it was found that the isocyanate group of MMI disappeared and a urethane bond was formed.

(2) MMME (550) / MEM (10
00) Preparation and Evaluation of Copolymeric Polymer Solid Electrolyte 2.00 g of MMME (550) and M synthesized in Example 2
0.40 g of EM (1000) was dissolved in 20 cc of THF, and 0.09 g of LiBF ₄ was added and mixed well. The THF was then removed at room temperature under reduced pressure and MMME (55
A 0) / MEM (1000) / LiBF ₄ mixture was obtained as a viscous liquid. When this mixture was applied onto a glass plate in an argon atmosphere and heated at 100 ° C. for 1 hour, MM
ME (550) / MEM (1000) copolymer / LiB
The F ₄ composite was obtained as a transparent self-supporting film of about 100 μm. The ionic conductivity of this film at 25 ° C. was measured by the impedance method to be 2 × 10 ⁻⁵ S / c
It was m.

Example 18 Production of Cobalt Oxide Positive Electrode 22 g of Li ₂ CO ₃ and 24 g of Co ₃ O ₄ were mixed well,
Li ₂ CoO ₂ powder was obtained by heating at 800 ° C. for 24 hours in an oxygen atmosphere and then pulverizing. This Li ₂ CoO
_{The two} powders and the polymerizable monomer mixture prepared in Example 13 were mixed in a weight ratio of 7: 3 under an argon atmosphere and applied onto a stainless steel foil in a thickness of 1 × 1 cm and a thickness of about 200 μm. Further, by heat-polymerizing at about 100 ° C. for 1 hour, a cobalt oxide / polymer solid electrolyte composite positive electrode (65 m
g) was obtained.

Example 19 Production of Polymer Solid Electrolyte Secondary Battery A 75 μm thick lithium foil was cut into 1 × 1 cm (5.3 mg) in an argon atmosphere glove box, and a polyimide film of 10 μm was cut at each end of about 1 mm. Film
Coated as a spacer. Next, 15 mg of the polymerizable monomer mixture prepared in Example 13 was applied onto a lithium foil, and the cobalt oxide positive electrode prepared in Example 18 was laminated thereon, and after heating at 100 ° C. for 1 hour, the battery end portion was covered with an epoxy resin. Sealing was performed to obtain a lithium / cobalt oxide solid secondary battery having a structure shown in FIG. This battery, operating voltage 2.0 ~
When charging and discharging were repeated at 4.3 V and a current of 0.1 mA,
The maximum discharge capacity was 4.0 mAh, and the cycle life until the capacity decreased to 50% was 153 times.

Example 20 Production of Polyaniline Positive Electrode 1 × 1 using a 0.5 M aqueous solution of aniline and 1.5 M HBF ₄ as a polymerization solution and a graphite foil as a counter electrode.
cm Stainless steel foil with a constant current method of 1mA, about 100μ
Electrolytically oxidatively polymerized to a thickness of m. Then, after washing with methanol, vacuum drying was performed at 80 ° C. for 24 hours. Then, this membrane (15 mg) was transferred into a glove box in an argon atmosphere, soaked with the polymerizable monomer mixture prepared in Example 13, and polymerized at 100 ° C. for 1 hour to give a polyaniline / polymer solid electrolyte composite positive electrode. (45 mg) was obtained.

Example 21 Production of Polymer Solid Electrolyte Secondary Battery The procedure of Example 19 was repeated except that the polyaniline positive electrode produced in Example 20 was used in place of the cobalt oxide positive electrode.
A lithium / polyaniline solid state secondary battery was obtained. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.0 V and a current of 0.1 mA, the maximum discharge capacity was 1.0 mAh.
The cycle life until the capacity was reduced to 50% was 351 times.

Example 22 Production of a vapor-phase graphite negative electrode 10 g of a vapor-phase graphite fiber (average fiber diameter 0.3 μm, average fiber length 2.0 μm, 2700 ° C. heat-treated product) manufactured by Showa Denko and 2.5 M butyllithium-containing hexane 200 ml of the solution was mixed and stirred at room temperature for 8 hours. Then, it was washed with hexane and dried to obtain a graphite fiber in which lithium ions were preliminarily inserted. C / Li atomic ratio calculated by elemental analysis 1
It was 2/1. 6 g of the lithium-containing graphite fiber thus obtained and 4 g of the polymerizable monomer mixture prepared in Example 13 were mixed under an argon atmosphere, and a part of the mixture was taken and placed on a stainless steel foil at a thickness of 1 × 1 cm and a thickness of about 150 μm. Applied to Further, by heat-polymerizing at about 100 ° C. for 1 hour, a vapor-phase method graphite / polymer solid electrolyte composite negative electrode (21 m
g) was obtained.

Example 23 Manufacture of Polymer Solid Electrolyte Secondary Battery Vapor phase graphite / oxidation was performed in the same manner as in Example 19 except that the vapor phase graphite negative electrode manufactured in Example 22 was used instead of the lithium foil. A cobalt solid secondary battery was obtained. When this battery was repeatedly charged and discharged at an operating voltage of 1.5 to 4.3 V and a current of 0.1 mA, the maximum discharge capacity was 3.8 mAh, and the cycle life until the capacity decreased to 50% was 183 times. there were.

Example 24 Synthesis of Polyaniline Soluble in Organic Solvent A thermometer, a stirrer, and a condenser were attached to a 1-liter four-necked flask, and 500 ml of 1N HCl aqueous solution was attached.
1 l was added, and 20.3 g of aniline was dissolved while nitrogen was bubbled. Then, with stirring, with nitrogen bubble, 11.
5 g of ammonium persulfate was added as a solid over about 30 minutes. The reaction temperature was maintained at about 22 ° C. After the addition, the mixture was further reacted for 22 hours and then filtered, and the filter residue was washed with 500 ml of distilled water. Then, the product was transferred to a beaker and stirred with 500 ml of 5% aqueous ammonia for about 1 hour,
By filtering, washing with distilled water, and drying under reduced pressure, about 16 g of polyaniline powder in a dedoped state was obtained. Next 300m
Hydrazine monohydrate, 150 ml in a 3-necked flask
Was added, and the above-mentioned dedoped polyaniline powder was added at room temperature over about 1 hour while stirring and flowing nitrogen. After stirring under a nitrogen flow for about 10 hours at room temperature, the mixture was filtered in a nitrogen atmosphere and dried under reduced pressure. Purification T under nitrogen atmosphere
By washing with HF and purified ether and drying under reduced pressure,
About 14 g of reduced polyaniline powder was obtained. The elemental analysis values of this reduced polyaniline powder are carbon, hydrogen,
The total amount of nitrogen was 98%, and the element ratio of carbon / hydrogen / nitrogen was 6.00 / 4.95 / 1.01, which was almost the same as the theoretical value. This powder was dissolved in purified N-methylpyrrolidone (NMP) under an argon atmosphere to a concentration of about 5 wt%. The number average molecular weight of polyaniline determined by GPC measurement of this solution was about 20,000 in terms of polystyrene.

Example 25 Preparation of Polyaniline Positive Electrode The polymerizable monomer mixture prepared in Example 13 was prepared in Example 24 in an argon atmosphere glove box.
The wt% polyaniline / NMP solution was mixed so that the weight ratio of polyaniline and the polymerizable monomer mixture was 1: 1. Add this mixture to a 50 μm polyimide film
It was attached to the four end portions with a width of mm, and applied to a portion surrounded by a polyimide film on a stainless steel foil having a size of 15 × 15 mm and a thickness of 100 μm. Then 60 ℃, 80 ℃, 10
By heating at 0 ° C. for 1 hour each, drying and polymerization were performed to obtain a polyaniline positive electrode (68 mg).

Example 26 Manufacture of Polymer Solid Electrolyte Secondary Battery A 25 μm thick lithium foil was cut into 12 × 12 mm (2.6 mg) in an argon atmosphere glove box, and
About 2 mm square of the end portion was covered with a polyimide film of 10 μm as a spacer. Next, the polymerizable monomer mixture prepared in Example 13 was applied onto a lithium foil,
Further, the polyaniline positive electrode produced in Example 25 was laminated, heated at 100 ° C. for 1 hour, and the battery end was sealed with an epoxy resin to obtain a lithium / polyaniline solid secondary battery having the structure shown in FIG. This battery was operated at an operating voltage of 2.0-4.
When charging and discharging were repeated at 0 V and a current of 0.1 mA, the maximum discharge capacity was 1.4 mAh, and the cycle life until the capacity decreased to 50% was 221 times.

Example 27 Preparation of Poly-o-anisidine Positive Electrode Instead of the aniline used in Example 24, 27.0 g of o-
18 g of reduced poly-o-anisidine powder was synthesized and treated in the same manner as in Example 24 except that anisidine was used. The elemental analysis value of this reduced poly-o-anisidine powder was that the sum of carbon, hydrogen and nitrogen was 98%, and the element ratio of carbon / hydrogen / nitrogen was 7.00 / 6.91 /.
It was 1.03, which was almost the same as the theoretical value. This powder was converted into purified N-methylpyrrolidone (NMP) in an argon atmosphere to about 8%.
Dissolved to a concentration of wt%. The number average molecular weight of poly-o-anisidine obtained by GPC measurement of this solution was about 15,000 in terms of polystyrene. Then, Example 2
A poly-o-anisidine positive electrode (62 mg) was produced in the same manner as in Example 25 except that the 8 wt% poly-o-anisidine / NMP solution was used instead of the 5 wt% polyaniline / NMP solution used in Example 5. .

Example 28 Production of Solid Electrolyte Secondary Battery The polyaniline prepared in Example 27 was used in place of the polyaniline positive electrode.
Example 26 except that 62 mg of o-anisidine positive electrode was used.
A lithium / poly-o-anisidine solid state secondary battery was obtained in the same manner as in. This battery has an operating voltage of 1.8 to 3.8.
When charging and discharging were repeated at V and a current of 0.1 mA, the maximum discharge capacity was 1.1 mAh, and the cycle life until the capacity decreased to 50% was 232 times.

Example 29 Manufacture of Polyaniline Positive Electrode The polymerizable monomer solution prepared in Example 16 was prepared in Example 24 in a glove box under an argon atmosphere to prepare 5w.
The t% polyaniline / NMP solution was mixed so that the weight ratio of polyaniline and the polymerizable monomer solution was 1: 1. This mixed solution is mixed with 50 μm of polyimide film.
It was attached to the four end portions with a width of mm, and applied to a portion surrounded by a polyimide film on a stainless steel foil having a size of 15 × 15 mm and a thickness of 100 μm. Then 60 ℃, 80 ℃, 10
It was dried and polymerized by heating at 0 ° C. for 1 hour each.

Example 30 Production of Polymer Solid Electrolyte Secondary Battery A lithium / polyaniline solid secondary battery was obtained in the same manner as in Example 21 except that the polyaniline positive electrode produced in Example 29 was used as the polyaniline positive electrode. This battery
When charging and discharging were repeated at an operating voltage of 2.0 to 4.0 V and a current of 0.1 mA, the maximum discharge capacity was 1.4 mAh, and the cycle life until the capacity decreased to 50% was 180 times.

Example 31 Preparation of Polymerizable Monomer Mixture MME (550) 2.00 synthesized in Examples 1 and 2
g, MEM (1000) 0.51 g, propylene carbonate (PC) 2.0 g, ethylene carbonate (E
C) 2.0 g and ethyltributylammonium perchlorate (EBAP) 0.90 g were mixed well in an argon atmosphere, and MME (550) / MEM (1000) /
A polymerizable monomer mixture consisting of PC / EC / EBAP was obtained as a viscous liquid. This polymerizable monomer mixture was applied onto a glass plate under an argon atmosphere and then heated at 100 ° C. for 1 hour to polymerize the mixture. MME (550) / MEM
A (1000) copolymer / PC / EC / EBAP composite was obtained as a transparent self-supporting film of about 300 μm. The ionic conductivity of the film at 25 ° C. and −10 ° C. was measured by an impedance method to find that it was 3.5.
The values were × 10 ^-3 and 1.0 × 10 ^-3 S / cm.

Example 32 Production of Activated Carbon Electrode Coconut shell activated carbon and the polymerizable monomer mixture prepared in Example 31 were mixed at a weight ratio of 1: 1 under an argon atmosphere,
Approximately 150μ in size of 1cm x 1cm on stainless steel foil
It was applied to a thickness of m. Further, by heating at about 100 ° C. for 1 hour to polymerize, 13 mg of activated carbon / polymer solid electrolyte composite electrode was obtained.

Example 33 Production of Solid Electric Double Layer Capacitor In an argon atmosphere glove box, the activated carbon electrode (13 mg) produced in Example 32 had 1 cm × 1 cm end of about 1 mm square and a polyimide film having a thickness of 10 μm as a spacer. Coated. Next, 15 mg of the polymerizable monomer mixture prepared in Example 31 was applied onto the electrode, and another electrode was attached to the electrode. After heating at 100 ° C. for 1 hour,
The end of the capacitor was sealed with an epoxy resin to manufacture a solid electric double layer capacitor as shown in FIG. When this capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.1 mA, the maximum capacity was 210 mF. In addition, even if the charge and discharge were repeated 50 times under these conditions, there was almost no change in the capacity.

Example 34 Preparation of Solid Electric Double Layer Capacitor Instead of the salt EBAP used in the polymerizable monomer mixture prepared in Example 31, lithium perchlorate (LiC
A polymerizable monomer mixture was prepared using 0.3 g of 10 ₄ ). A solid-state electric double-layer capacitor was manufactured in the same manner as in Example 33 except that this polymerizable monomer mixture was used. When this capacitor was charged and discharged at an operating voltage of 0 to 2.0 V and a current of 0.1 mA, the maximum capacity was 1
It was 35 mF. In addition, even if the charge and discharge were repeated 50 times under these conditions, there was almost no change in the capacity.

Example 35 Production of acetylene black electrode Acetylene black and the polymerizable monomer mixture produced in Example 31 were mixed in a weight ratio of 6: 4 under an argon atmosphere, and the mixture was placed on a stainless steel foil in a size of 1 cm × 1 cm. , About 1
It was applied to a thickness of 50 μm. Further, by heat-polymerizing at 100 ° C. for 1 hour, 14 mg of acetylene black / polymer solid electrolyte composite electrode was obtained.

Example 36 Production of Solid Electric Double Layer Capacitor The acetylene black electrode produced in Example 35 (14 m
A solid-state electric double layer capacitor was manufactured in the same manner as in Example 33 except that g) was used. When this capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.1 mA, the maximum capacity was 55 mF. In addition, even if the charge and discharge were repeated 50 times under these conditions, there was almost no change in the capacity.

Example 37 Production of Activated Carbon Electrode Coconut shell activated carbon and the polymerizable monomer solution synthesized in Example 16 were mixed in a weight ratio of 1: 1 under an argon atmosphere, and the mixture was placed on a stainless steel foil in a size of 1 × 1 cm to about 150 μm. It was applied to a thickness. Further, the activated carbon / solid electrolyte composite electrode was obtained by heat-polymerizing at about 100 ° C. for 1 hour.

Example 38 Manufacture of solid-state electric double layer capacitor In an argon atmosphere glove box, the activated carbon electrode manufactured in Example 37 1 × 1 cm with an end of about 1 mm square 10
A μm polyimide film was coated as a spacer. Next, the polymerizable monomer solution prepared in Example 16 was applied on the electrode, and another electrode was attached to the electrode, and 1
After heating at 00 ° C. for 1 hour, the end of the capacitor was sealed with an epoxy resin to obtain a solid electric double layer capacitor as shown in FIG. When this capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.1 mA, the maximum capacity was 2
It was 00 mF. In addition, even if the charge and discharge were repeated 50 times under these conditions, there was almost no change in the capacity.

[0111]

The solid polymer electrolyte of the present invention comprises a composite of a polymer having an oxyalkyl group in its side chain bonded by a urethane bond and at least one electrolyte, and is a thin film having good membrane strength. It is easy to obtain as
It has the feature of high ionic conductivity. Batteries and 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. Batteries and capacitors can be manufactured.

The polymer of the present invention having an oxyalkyl group bonded by a urethane bond in its side chain and an organic solvent-soluble polyaniline polymer or other conductive polymer, metal oxide, metal sulfide or carbon material, etc. An electrode containing the electrode active material or polarizable material of
We can provide electrodes with high electrochemical activity and flexibility,
In particular, a thin electrode can be provided, and it is useful as an electrode used in various batteries or electric double layer capacitors, and a manufacturing method thereof.

The battery of the present invention is an all-solid-state battery that can operate with high capacity and high current, or has good cycleability, and is excellent in safety and reliability. It can be used as a power supply for electric products such as backup power supply, a large power supply for electric vehicles, and load leveling. Further, since it can be easily made into a thin film, it can be used as a paper battery such as an identification card. Furthermore, the electric double layer capacitor of the present invention has high voltage, high capacity,
It is an electric double layer capacitor that can operate at high current or has good cycleability, and is excellent in safety and reliability, and can be an all-solid-state electric double layer capacitor having such characteristics. Therefore, it can be used not only as a backup power source but also as a power source for various electric products when used together with a small battery. Further, since it has excellent workability such as thinning, it can be expected to be used in applications other than the conventional solid-state electric double layer capacitors.

[Brief description of drawings]

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

FIG. 2 is a schematic cross-sectional view of an example of the solid-state electric double layer capacitor of the present invention.

[Explanation of symbols]

 1 Positive Electrode 2 Polymer Solid Electrolyte 3 Negative Electrode 4 Current Collector 5 Spacer 6 Insulating Resin Sealant 7 Polarizing Electrode 8 Current Collector 9 Polymer Solid Electrolyte Membrane 10 Spacer 11 Insulating Resin Sealant 12 Lead Wire

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication H01M 4/02 A 6/18 E 10/36 A

Claims (23)

[Claims] 1. General formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO OR ² (1) [wherein R ¹ is It represents hydrogen or a methyl group, and R ² represents an organic chain containing at least one oxyalkylene group. The organic chain may have a linear, branched or cyclic structure, and an element other than carbon, hydrogen and oxygen is 1
More than one may be included. x and y each represent 0 or a number of 1 to 5, and z represents a number of 0 or 1 to 10.
However, when x = 0 and y = 0, z = 0. Also [O
(CH ₂ ) _x (CH (CH ₃ )) _y ] (CH ₂ ) in _z
And (CH (CH ₃ )) may be arranged irregularly. ] A polymer solid electrolyte comprising a polymer obtained from at least one of the compounds represented by and / or a composite containing a copolymer containing the compound as a copolymerization component and at least one electrolyte. 2. General formula (2) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO O (R ³ O) _n R ⁴ (2) [In the formula, each R ³ independently represents — (CH ₂ ) ₂ — or —CH (CH ₃ ) CH ₂ —, and R ⁴ has 1 carbon atom.
An alkyl group in the range of from 10 to -CONH [O (CH
_{2) x '(CH (CH} 3)) y'] z 'OCOCH = CH 2,
_{-CONH [O (CH 2) x} '(CH (CH 3)) y'] z '
_{OCOC (CH 3) = CH 2} , -CONHCOC (CH
₃₎ = represents CH ₂ or -CONHCOCH = CH _2, n represents a number of 1 or more. [O (CH ₂ ) _{x '} (CH
(CH ₃ )) _{y '} ] _z' (CH ₂ ) and (CH (CH
₃ )) may be arranged irregularly. x ′ and y ′ each represent 0 or a number of 1 to 5, and z ′ represents a number of 0 or 1 to 10. However, when x '= 0 and y' = 0, z '
= 0. Other symbols are the same as in general formula (1). ] A compound represented by or the general formula _{(3) CH 2 = C (} R 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCO O [(R 6 O) m CONHR 5 NHCOO ^{_{] k (R 3 O) n}} R 4 ... (3) [ wherein, R ⁶ is independently - (CH _{2) 2} - or -CH (CH ₃₎ CH ₂ - represents, R ⁵ is C 1 -C Represents an alkylene group, an arylene group, an arylene group, or an oxyalkylene group in the range of 20 to 20, and n, m, and k each represent a number of 1 or more. Other symbols are the same as those in the general formula (1) and the general formula (2). ] A polymer solid electrolyte comprising a polymer obtained from at least one compound selected from the following: and / or a copolymer containing the compound as a copolymerization component and at least one electrolyte. 3. The polymer solid electrolyte according to claim 1, wherein the electrolyte is at least one compound selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts. 4. A plasticizer is added to claim 1.
The polymer solid electrolyte described. 5. A battery using the solid polymer electrolyte according to claim 1. 6. The battery according to claim 5, wherein the negative electrode of the battery according to claim 5 comprises an electrode containing lithium, a lithium alloy or a carbon material capable of inserting and extracting lithium ions. 7. The positive electrode of the battery according to claim 5, wherein the positive electrode of the battery comprises an electrode containing an organic solvent-soluble aniline polymer or other conductive polymer, a metal oxide, a metal sulfide or a carbon material. Battery described. 8. The general formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO OR ² (1) (wherein the symbol is a request The same meaning as in item 1)), a polymerizable monomer mixture containing at least one compound represented by the formula (1) and at least one electrolyte, or a polymerizable monomer mixture obtained by adding a plasticizer to the polymerizable monomer mixture. Or a step of polymerizing the polymerizable monomer mixture, the method comprising the steps of: 9. The general formula (2) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO O (R ³ O) _n R ⁴ (2) (The symbols in the formula have the same meanings as in claim 2.) or the compound represented by the general formula (3) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )). _y ] _z NHCO O [(R ⁶ O) _m CONHR ⁵ NHCOO] _k (R ³ O) _n R ⁴ (3) (wherein the symbols have the same meanings as in claim 2) , A polymerizable monomer mixture containing at least one compound selected from the following, and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added to the polymerizable monomer mixture is placed in the structure for battery construction or placed on a support. And a battery having a step of polymerizing the polymerizable monomer mixture. Method. 10. General formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO OR ² (1) (wherein the symbol is a request The same meaning as in item 1)) and / or a polymer obtained from at least one compound represented by the formula (1) and / or a copolymer containing the compound as a copolymerization component and an electrode active material or a polarizable material. Electrode to do. 11. General formula (2) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO O (R ³ O) _n R ⁴ (2) (The symbols in the formula have the same meanings as in claim 2.) or the compound represented by the general formula (3) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )). _y ] _z NHCO O [(R ⁶ O) _m CONHR ⁵ NHCOO] _k (R ³ O) _n R ⁴ (3) (wherein the symbols have the same meanings as in claim 2) An electrode comprising a polymer obtained from at least one compound selected from, and / or a copolymer containing the compound as a copolymerization component and an electrode active material or a polarizable material. 12. The electrode according to claim 10, wherein the electrode active material or polarizable material is an organic solvent-soluble aniline polymer or other conductive polymer, metal oxide, metal sulfide or carbon material. . 13. General formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO OR ² (1) (wherein the symbol is a request And a polymerizable monomer mixture containing at least one compound represented by the formula (1) and an electrode active material or a polarizable material, or a polymerizable monomer mixture to which a plasticizer is added. A method for manufacturing an electrode, comprising: 14. General formula (2) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO O (R ³ O) _n R ⁴ (2) (The symbols in the formula have the same meanings as in claim 2.) or the compound represented by the general formula (3) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )). _y ] _z NHCO O [(R ⁶ O) _m CONHR ⁵ NHCOO] _k (R ³ O) _n R ⁴ (3) (wherein the symbols have the same meanings as in claim 2) , A polymerizable monomer mixture containing at least one compound selected from the following and an electrode active material or a polarizable material, or an electrode characterized by having a step of polymerizing a polymerizable monomer mixture to which a plasticizer is added. Production method. 15. The electrode according to claim 13 or 14, wherein the electrode active material or polarizable material is an organic solvent-soluble aniline polymer or other conductive polymer, metal oxide, metal sulfide or carbon material. Manufacturing method. 16. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the ion conductive substance is the polymer solid electrolyte according to any one of claims 1 to 4. Multilayer capacitor. 17. In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, the polarizable electrode comprises a carbon material and a general formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO OR ² (1) (wherein the symbols have the same meanings as in claim 1), a polymer obtained from at least one compound and And / or a composite containing a copolymer containing the compound as a copolymerization component. 18. In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, the polarizable electrode comprises a carbon material and a general formula (2) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO O (R ³ O) _n R ⁴ (2) (wherein the symbols have the same meanings as in claim 2) or a general compound. equation _{(3) CH 2 = C (} R 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCO O [(R 6 O) m CONHR 5 NHCOO] k (R 3 O) n R ⁴ (3) (wherein the symbols have the same meanings as those in claim 2), a polymer obtained from at least one compound selected from the group consisting of compounds represented by the formula, and / or the compound as a copolymerization component. An electric double layer capacitor comprising a composite containing the above-mentioned copolymer. 19. In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, the polarizable electrode has the general formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x. (CH (CH ₃ )) _y ] _z NHCO OR ² (1) (wherein the symbols have the same meanings as in claim 1), a polymerizable monomer containing at least one compound and a carbon material. An electric double layer capacitor, which is a polarizable electrode produced by polymerizing a mixture. 20. In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, the polarizable electrode has the general formula (2) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x. (CH (CH ₃ )) _y ] _z NHCO O (R ³ O) _n R ⁴ (2) (wherein the symbols have the same meanings as in claim 2) or the compound represented by the general formula (3) ^{_{) CH 2 = C (R 1}} ) CO [O (CH 2) x (CH (CH 3)) y] z NHCO O [(R 6 O) m CONHR 5 NHCOO] k (R 3 O) n R 4 ... (3) A compound represented by the formula (wherein the symbols have the same meanings as in claim 2), and a polymerizable monomer mixture containing at least one compound selected from the group consisting of a carbon material and a polymerizable monomer mixture. An electric double layer capacitor, which is a polarizable electrode. 21. General formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO OR ² (1) (the symbol in the formula is The same meaning as in item 1)), a polymerizable monomer mixture containing at least one compound represented by the formula (1) and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added to the polymerizable monomer mixture. A method for producing an electric double layer capacitor, which comprises a step of placing it in a structure for use or placing it on a support and polymerizing the polymerizable monomer mixture. 22. General formula (2) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO O (R ³ O) _n R ⁴ (2) (The symbols in the formula have the same meanings as in claim 2.) or the compound represented by the general formula (3) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )). _y ] _z NHCO O [(R ⁶ O) _m CONHR ⁵ NHCOO] _k (R ³ O) _n R ⁴ (3) (wherein the symbols have the same meanings as in claim 2) A polymerizable monomer mixture containing at least one compound selected from the following, and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added thereto is placed in a structure for constructing an electric double layer capacitor,
Alternatively, the method for producing an electric double layer capacitor comprises the step of disposing on a support and polymerizing the polymerizable monomer mixture. 23. Carbon material and general formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCO OR ² (1) (wherein The symbol has the same meaning as in claim 1.) A polarizable electrode pair comprising a polymer obtained from at least one compound represented by the formula (1) and / or a composite containing a copolymer containing the compound as a copolymerization component. And a polymerizable monomer mixture containing at least one compound represented by the general formula (1) and at least one electrolyte, or a plasticizer added thereto. A method for producing an electric double layer capacitor, comprising the steps of injecting a monomer mixture and polymerizing the polymerizable monomer mixture.