JP3161906B2 - Polymer solid electrolyte, battery and solid electric double layer capacitor using the same, and methods for producing them - Google Patents

Abstract

PURPOSE:To obtain a solid polyelectrolyte having a satisfactory film strength,a high ionic conductivity, and an excellent processability by using a composite comprising an electrolyte and a (co)polymer obtained from at least one specific compound. CONSTITUTION:The electrolyte is made of a composite comprising a (co)polymer (a) and at least one electrolyte selected preferably from among alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts (e.g. LiCF3), the (co)polymer (a) being a polymer of at least one compound (b) selected from among 2-(meth)acryloyloxyethyl carbamates represented by the formula, CH2=C(R<1>)COO(CH2)2NHCOOR<2> (wherein R<1> us H or CH3 and R<2> is a linear, branched, or cyclic organic group which has one or more alkylene groups and may contain one or more elements other than C, H, and O) and/or a copolymer of the compound (b) with other monomer(s).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid polymer electrolyte having high ionic conductivity using a polymer into which an oxyalkyl side chain having a urethane bond is introduced, 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 and a method for manufacturing the same, and an electric double layer capacitor using the polymer solid electrolyte and a method for manufacturing the same.

[0002]

2. Description of the Related Art In the field of downsizing and solidification of solid electrolytes in the field of ionics, all-solid primary batteries, secondary batteries and electric double-layer capacitors have been used as new ion conductors instead of conventional electrolyte solutions. The application to is being actively tried. A battery using a current electrolyte solution has a problem in long-term reliability because liquid leakage to the outside of a component or elution of an electrode material easily occurs. On the other hand, a product using a solid electrolyte does not have such a problem, and it is easy to reduce the thickness. Further, the solid electrolyte is excellent in heat resistance, and is advantageous in a process of manufacturing a product such as a battery.

[0003] In particular, those using a solid electrolyte containing a polymer as a main component have the advantage that the flexibility of the battery is increased and that it can be processed into various shapes as compared with inorganic materials. However, those studied so far have a problem that the extraction current is small because the ionic conductivity of the solid polymer electrolyte is low. Examples of these solid polymer electrolytes are described in "British Polymer Journal (Br. Polym. J.), Vol. 319, p. 137, 1975."
The publication 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.

[0004] Recently, it has been reported that a comb polymer in which oligooxyethylene is introduced into a side chain enhances the thermal mobility of an oxyethylene chain which is responsible for ionic conductivity and improves ionic conductivity. I have. For example, "Journal of Physical Chemistry (J. Phys. Chem.), Vol. 89, p. 987, 1984" discloses that an alkali metal salt is obtained by adding oligooxyethylene to a side chain of polymethacrylic acid. Are described. further,
"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 metal oxides such as MnO ₂ and MoS ₂ and metal sulfides for the positive electrode. For example, "Journal of Electrochemical Society (J. Electrochem. Soc.), Vol. 138 (No.
3), p. 665, 1991 ", a battery using 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 Symposium, 3A05L and 3A06L, 1986”. As previously reported, Bridgestone and Seiko have already launched coin-cell batteries for backup power. In addition, polyaniline has been attracting attention as a positive electrode active material having high capacity and excellent flexibility.

Further, in recent years, electric double-layer capacitors 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 them for use as a memory backup power supply or the like have been frequently used. . For example, "Functional Materials, February 1989, p. 33"
Discloses a capacitor using a carbon-based polarizable electrode and an organic electrolyte, "173rd Electrochemical Society Meeting Atlanta Georgia, May, No.
18, 1988 "describes an electric double layer capacitor using a sulfuric acid aqueous solution. Also, JP-A-63-2
No. 44570 discloses Rb ₂ C having high electrical conductivity.
A capacitor using u ₃ I ₃ Cl ₇ as an inorganic solid electrolyte is disclosed.

However, in the current electric double layer capacitor using an electrolyte solution, when the capacitor is used for a long period of time or when an abnormal condition such as a high voltage is applied, liquid leakage to the outside of the capacitor is likely to occur. There is a problem with use or 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 Patent Application Laid-Open No. Hei 4-253771 discloses that a polyphosphazene-based polymer is used as an ion-conductive substance. It has the advantages that the output voltage is higher than that of the inorganic ion conductive material, that it can be processed into various shapes, and that sealing is simple. However, in this case, the ionic conductivity of the solid polymer electrolyte is not enough, that is, 10 ⁻⁴ to 10 ⁻⁶ S / cm, and there is a drawback that the takeout current is small. It is also possible to increase the ionic conductivity by adding a plasticizer to the polymer solid electrolyte, but since it imparts fluidity, it cannot be treated as a complete solid and has poor film strength and film formability. When applied to an electric double layer capacitor or a battery, a short circuit easily occurs, and a sealing problem occurs as in the case of the liquid ion conductive material. On the other hand, when assembling a solid electrolyte together with a polarizable electrode into a capacitor, there is also a problem that it is difficult to uniformly combine the solid electrolyte with a carbon material having a large specific surface area because of mixing of solids.

The ionic conductivity of a polymer solid electrolyte generally studied is 10 ⁻⁴ to 10 ⁻⁵ S at room temperature.
/ Cm, but is still at least two orders of magnitude lower than liquid ion conductive materials. Also,
At a low temperature of 0 ° C. or lower, the ionic conductivity is further extremely reduced. Furthermore, when these polymer solid electrolytes are incorporated into an element such as an electric double layer capacitor, or when these polymer solid electrolytes are incorporated into a battery in the form of a thin film, processing techniques such as compounding with electrodes and securing contactability are required. It is difficult and there is a problem even in the manufacturing method.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer solid electrolyte which has good strength even when formed into a membrane, has high ionic conductivity at room temperature and low temperature, and has excellent workability. And In addition, the present invention provides a primary battery and a secondary battery that can be easily formed into a thin film, can operate at a high capacity and a high current by using the polymer solid electrolyte, and have good cycleability and reliability. The aim is to develop a secondary battery with excellent performance. Another object of the present invention is to provide an electrode having high electrochemical activity and flexibility, and a secondary battery using the same.

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

[0012]

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

Furthermore, it has been found that the use of the solid polymer electrolyte in a battery improves the problems of the above-described ionic conductivity, membrane strength, workability, and the like. Further, the present inventors, for example, when using this polymer solid electrolyte to make a thin solid-state battery, and made a study with the recognition that thinning of the electrodes is important, the electrode active material Polyaniline and its derivatives, which are excellent as conductive polymers, that is, aniline-based polymers that are soluble in organic solvents, or other conductive polymers, metal oxides, metal sulfides or carbon The use of a material or another electrode active material (a positive electrode active material or a negative electrode active material) and a polymer into which an oxyalkyl side chain having a urethane bond is introduced impairs the electrochemical activity of such an electrode active material. It is possible to form an electrode having high electrochemical activity and flexibility without any problem, and it is possible to form a thin film of the electrode by, for example, a solvent casting method or another method. I found the door.

Further, the present inventors have developed a polarizable material used as a polarizable electrode of an electric double layer capacitor, a carbon material as described below, and a polymer having an oxyalkyl side chain having a urethane bond introduced therein. By using, a polarizable electrode suitable for the capacitor can be obtained without impairing the polarization characteristics of such a polarizable material, and further, for example, a thin film of the electrode can be formed by a solvent casting method or another method. Was found.

Further, the present inventors have obtained that by using the above-mentioned polymer solid electrolyte, it is possible to obtain an electric double layer capacitor having a high output voltage, a large take-out current, and excellent workability and reliability. It has been found that an all-solid-state electric double layer capacitor can be obtained.

That is, the present invention relates to the following: [1] General formula (1) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) (wherein R ¹ represents hydrogen or a methyl group; R ² represents an organic chain containing at least one oxyalkylene group, which may have any of a linear, branched, or cyclic structure, and containing one or more elements other than carbon, hydrogen, and oxygen.
More than one may be included. ) Represented by 2-acryloyloxyethyl carbamate (hereinafter referred to as ACE)
Abbreviated. ) Or a polymer obtained from at least one compound selected from 2-methacryloyloxyethylcarbamate (hereinafter abbreviated as MCE) and / or
Alternatively, a copolymer containing the compound as a copolymer component (hereinafter, such a polymer and a copolymer are collectively abbreviated to (M) ACE polymer) and 2 to 100 ether oxygen atoms in the side chain are added. A battery comprising a polymer solid electrolyte comprising a composite containing at least one electrolyte in a proportion of the solid electrolyte.

[2] General formula (2) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO (R ³ O) _n R ⁴ (2) (wherein, R ¹ represents hydrogen or a methyl group. , R ³ is-
(CH ₂ ) ₂ — or —CH (CH ₃ ) CH ₂ —, wherein R ⁴ is an alkyl group having 1 to 10 carbon atoms;
_{CONH (CH 2) 2 OCOCH =} CH 2 or -CO
NH (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ ,
n represents one or more numbers. 2-methacryloyloxyethylcarbamic acid ω-alkyl oligooxyalkyl ester (hereinafter abbreviated as MCOA) and 2-acryloyloxyethylcarbamic acid ω-alkyl oligooxyalkyl ester (hereinafter abbreviated as ACOA) 2-methacryloyloxyethylcarbamic acid 2-methacryloyloxyethylcarbamoyl oligooxyalkyl ester (hereinafter abbreviated as MCMC), 2
-Acryloyloxyethylcarbamic acid 2-acryloyloxyethylcarbamoyl oligooxyalkyl ester (hereinafter abbreviated as ACAC), 2-acryloyloxyethylcarbamic acid 2-methacryloyloxyethylcarbamoyl oligooxyalkyl ester (hereinafter abbreviated as ACMC), or the general formula _{(3) CH 2 = C (} R 1) COO (CH 2) 2 NHCOO {(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 ⁶ are each independently — (CH ₂ ) ₂ — or —CH
(CH ₃ ) CH ₂ —, wherein R ⁴ has 1 to 10 carbon atoms
Range alkyl group, -CONH (CH _{2) 2} OCOC
H = CH ₂ or —CONH (CH ₂ ) ₂ OCOC (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 1 or more. A) a polymer obtained from at least one compound selected from the group consisting of a compound represented by formula (1) and a copolymer containing the compound as a copolymer component, and a ratio of 1 to 2 to 100 side chain ether oxygen atoms. [3] A battery characterized by using a solid polymer electrolyte comprising a composite containing at least one electrolyte of [3] wherein the solid polymer electrolyte is an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, or The battery according to the above [1] or [2], which is at least one compound selected from transition metal salts. [4] The battery according to the above [1] to [3], wherein a plasticizer is added to the polymer solid electrolyte. [5] The lithium battery according to any one of the above [1] to [4], wherein the negative electrode is an electrode containing lithium or a lithium alloy. [6] The negative electrode is a lithium ion. [1] The lithium ion battery according to any one of [1] to [4], comprising an electrode containing a carbon material capable of inserting and extracting carbon. [7] The positive electrode is an organic solvent-soluble aniline polymer or other conductive polymer. [1] to [6], comprising an electrode containing a metal oxide, a metal sulfide or a carbon material.
The battery according to any of the above,

[8] A polymerizable monomer mixture containing at least one compound selected from ACE or MCE and at least one electrolyte per 2 to 100 side chain ether oxygen atoms, or a polymerizable monomer mixture containing the same. A method for producing a battery, comprising the steps of: placing the polymerizable monomer mixture to which the agent has been added into the structure for battery construction or disposing the mixture on a support, and polymerizing the polymerizable monomer mixture. ] MCOA, ACOA, MCMC, ACAC, A
Polymerizable monomer mixture containing at least one compound selected from CMC or the compound represented by the general formula (3) and at least one electrolyte in a ratio of 2 to 100 ether oxygen atoms in the side chain. Or a polymerizable monomer mixture to which a plasticizer has been added, placed in a structure for battery construction, or placed on a support, and a step of polymerizing the polymerizable monomer mixture. Production method,

[10] An electrode comprising (M) an ACE polymer and an electrode active material or a polarizable material. [11] MCOA, ACOA, MCMC, ACAC, A
Including a polymer obtained from CMC or at least one compound selected from the compounds represented by the general formula (3) and / or a copolymer containing the compound as a copolymer component and an electrode active material or a polarizable material [12] The electrode according to [10], wherein the electrode active material or the polarizable material is an organic solvent-soluble aniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material. ] Or the electrode according to [11].

[13] A step of polymerizing a polymerizable monomer mixture containing at least one compound selected from ACE or MCE and an electrode active material or a polarizable material, or a polymerizable monomer mixture having a plasticizer added thereto. [14] MCOA, ACOA, MCMC, ACAC,
A polymerizable monomer mixture containing ACMC or at least one compound selected from the compounds represented by the general formula (3) and an electrode active material or a polarizable material, or a polymerizable monomer mixture obtained by adding a plasticizer to the mixture. A method for producing an electrode, comprising a step of polymerizing, [15] the electrode active material or the polarizable material is an organic solvent-soluble aniline-based polymer or other conductive polymer, a metal oxide, or a metal sulfide Or the method for producing an electrode according to the above [13] or [14], which is a carbon material;

[16] In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, a polymer obtained by using at least one kind of compound selected from ACE and MCE and / or the compound is used. A polymer solid electrolyte comprising a composite comprising: a copolymer containing as a copolymer component and at least one electrolyte in a proportion of 2 to 100 side chain ether oxygen atoms. [17] An electric double-layer capacitor in which a polarizable electrode is arranged via an ion-conductive substance, wherein the ion-conductive substance is MCOA, ACOA, MCMC, ACAC, ACMC.
Alternatively, a polymer obtained from at least one compound selected from the compounds represented by the general formula (3) and / or a copolymer having the compound as a copolymer component and 2 to 100 side chain ether oxygen atoms An electric double layer capacitor, characterized in that it is a polymer solid electrolyte comprising a composite containing at least one electrolyte in a ratio of one to 18. [18] An electrolyte of the polymer solid electrolyte is an alkali metal salt, a quaternary electrolyte. The electric double layer capacitor according to the above [16] or [17], which is at least one compound selected from a ammonium salt, a quaternary phosphonium salt and a transition metal salt, [19] wherein a plasticizer is added to the polymer solid electrolyte. The electric double layer capacitor according to any one of the above [16] to [18],

[20] An electric double layer capacitor in which a polarizable electrode is arranged via an ion-conductive substance, wherein the polarizable electrode is made of a composite containing a carbon material and an (M) ACE copolymer. And electric double layer capacitor. [21] In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, the polarizable electrode is made of a carbon material and MCOA, ACOA, MCMC, ACAC, A
A polymer obtained from CMC or at least one compound selected from the compounds represented by the general formula (3) and / or a composite containing a copolymer containing the compound as a copolymer component. Electric double layer capacitor. [22] In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, the polarizable electrode is A
An electric double layer capacitor comprising a polarizable electrode produced by polymerizing a polymerizable monomer mixture containing at least one compound selected from CE or MCE and a carbon material. [23] In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, the polarizable electrode is
A polarizable electrode manufactured by polymerizing a polymerizable monomer mixture containing a carbon material and at least one compound selected from COA, ACOA, MCMC, ACAC, ACMC or the compound represented by the general formula (3). An electric double-layer capacitor,

[24] A polymerizable monomer mixture containing at least one compound selected from ACE or MCE and at least one electrolyte per 2 to 100 side chain ether oxygen atoms, or a polymerizable monomer mixture containing the same. The polymerizable monomer mixture to which the agent has been added is placed in a structure for forming an electric double layer capacitor, or placed on a support, and the step of polymerizing the polymerizable monomer mixture is provided. [25] MCOA, ACOA, MCMC, ACAC,
A polymerizable monomer mixture containing at least one compound selected from ACMC or a compound represented by the general formula (3) and at least one electrolyte in a ratio of 2 to 100 ether oxygen atoms in a side chain; Alternatively, a polymerizable monomer mixture to which a plasticizer is added is placed in a structure for forming an electric double layer capacitor, or placed on a support, and a step of polymerizing the polymerizable monomer mixture is provided. [26] A method of manufacturing an electric double-layer capacitor, [26] a pair of polarizable electrodes made of a composite containing a carbon material and (M) ACE are disposed to face each other, and at least one selected from ACE or MCE is provided between the facing electrodes. And a polymerizable monomer containing at least one electrolyte in a ratio of 2 to 100 ether oxygen atoms in the side chain Method for producing an electric double layer capacitor characterized by having a compound, or its plasticizer injecting the added polymerizable monomer mixture, polymerizing the polymerization monomer mixture step,

[27] A polymer obtained from at least one compound selected from ACE or MCE and / or
Or a solid polymer electrolyte comprising a copolymer containing the compound as a copolymer component and at least one electrolyte in a proportion of 2 to 100 ether oxygen atoms in a side chain; [28] , An alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, or a transition metal salt, the polymer solid electrolyte according to the above [27], and [29] a plasticizer. The above object has been achieved by developing the solid polymer electrolyte according to the above [27] or [28]. In this specification, M
COA, ACOA, MCMC, ACAC, -CH 2 CH 2 and "oligo oxyalkyl" in the name of ACMC
The O- or -CH (CH ₃₎ 2 divalent group units composed of CH ₂ O- represents an oxyalkylene chain comprising at least one or more.

Hereinafter, the present invention will be described in detail. ACE which is a compound represented by the general formula (1) used in the present invention
And specific examples of MCE include compounds having one polymerizable group such as MCOA and ACOA represented by the general formula (2), and compounds having two polymerizable groups such as MCMC, ACAC and ACMC. A compound having a plurality of urethane groups, such as a compound represented by the general formula (3), or a compound in which R ^{2 in the} general formula (1) includes a cyclic oxyalkylene group such as a crown ether; And the like.

A monomer for producing the (ACE) polymer contained in the solid polymer electrolyte of the present invention,
ACE or MCE, which is a compound represented by the general formula (1), or ACOA or MCOA, which is a compound represented by the general formula (2), can be obtained by the following reaction (where R ¹ , R ³ and R ⁴ are the same as those in the general formula (2).) ^{_{CH 2 = C (R 1)}} COO (CH 2) 2 NCO + H
O (R ³ O) _n R ⁴ ───── → ACE (or A
COA) or MCE (or MCOA) For example, MCOA or ACOA is 2-methacryloyloxyethyl isocyanate (hereinafter abbreviated as MOI) or 2-acryloyloxyethyl isocyanate (hereinafter abbreviated as AOI) and mono. It is easily obtained by reacting with an alkylalkylene glycol. MCMC represented by the general formula (2);
ACAC or ACMC is the MOI and / or A
It can be easily obtained by reacting OI and oligoalkylene glycol at a molar ratio of 2: 1.

Furthermore, the compound having a plurality of urethane groups represented by the general formula (3) can be used, for example, by using two compounds such as hexamethylene diisocyanate and tolylene diisocyanate according to the following two reaction schemes. The reaction of kmol of a compound having an isocyanate group with jmol of alkylene glycol (2kj) and jmol of monoalkylalkyleneglycol gives j mole of the product, and then equimolar MOI or AOI with such a product. It is obtained by reacting. (However, in the following reaction scheme, R ³ , R ⁴ , R ⁵ , R ⁶ , k, m, and n are the same as those in the general formula (3), and j and (2k-
j) indicates a number. )

K (OCNR ⁵ NCO) + (2k−j) (HO (R ⁶ O) _m H) + j (HO (R ³ O) _n R ⁴ ) → jHO ｛(R ⁶ O) _m CONHR ⁵ NHCOO ｝ _K (R ³ O) _n R ⁴ HO ｛(R ⁶ O) _m CONHR ⁵ NHCOOO｝ _k (R ³ O) _n R ⁴ + MOI or AOI → (3)

In the present specification, the expression "alkylene glycol" includes oligoalkylene glycol and polyalkylene glycol. Similarly, the expression “monoalkylalkylene glycol” includes monoalkyl oligoalkylene glycol and monoalkyl polyalkylene glycol. Among the compounds represented by the general formula (1), the compound represented by the general formula (2) can introduce more urethane groups and oxyalkylene groups into side chains in the obtained polymer, preferable.

The (M) ACE polymer contained in the solid polymer electrolyte of the present invention is a polymer represented by the general formula (1):
It can be obtained by polymerizing at least one compound selected from CE or MCE, or polymerizing the compound as a copolymer component. For the polymerization, a general method utilizing the polymerizability of an acryloyl group or a methacryloyl group of these monomers can be employed. That is,
These monomers, or these monomers and other polymerizable compounds, such as methacrylic acid (or acrylic acid)
After mixing an ester, acrylamide, styrene, N-vinylacetamide, etc., a radical polymerization catalyst such as azobisisobutyronitrile, benzoyl peroxide, a protonic acid such as CF ₃ COOH, BF ₃ , AlCl
Radical, cationic or anionic polymerization can be carried out using a cationic polymerization catalyst such as a Lewis acid such as ₃ 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 forming it into a film or the like. When the (M) ACE polymer is used for the solid polymer electrolyte as in the present invention, it is particularly advantageous to polymerize the polymerizable monomer mixture after film formation.

That is, for example, MCOA, ACOA, MCMC, ACA selected from ACE or MCE
C, mixing at least one compound selected from ACMC 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 polymerizing compound and A plasticizer and / or a solvent are added and mixed, and the polymerizable monomer mixture is polymerized in the presence or absence of the catalyst by irradiation with electromagnetic waves such as heating and / or light depending on the case. In particular, after the polymerizable monomer mixture is formed into a film-like shape or the like, for example, heating and / or irradiation of electromagnetic waves such as light is performed to polymerize the polymerizable monomer mixture into a film-like polymer, so that the degree of freedom in the processing surface is increased. Spreading is a great advantage in application. In the case of using a solvent, any solvent may be used as long as it does not inhibit polymerization, for example, tetrahydrofuran, acetonitrile,
Toluene or the like can be used.

The temperature for the polymerization depends on the kind of the compound represented by the general formula (1), but may be any temperature at which the polymerization takes place. In the case of polymerizing by electromagnetic wave irradiation, depending on the type of the compound represented by the general formula (1), for example, an initiator such as benzyl methyl ketal, benzophenone or the like may be used to emit ultraviolet light or γ-rays of several mW or more. To polymerize.

(M) used in the solid polymer electrolyte of the present invention
As described above, the ACE polymer may be a homopolymer of ACE or MCE represented by the general formula (1), a copolymer of two or more ACEs or MCEs, or at least one ACE or MCE. Of ACE or MCE and other polymerizable compounds. Further, the polymer used for the solid polymer electrolyte of the present invention may be a mixture of the (M) ACE polymer and another polymer. For example,
(M) A mixture of an ACE polymer and a polymer such as polyethylene oxide, polyacrylonitrile, polybutadiene, polymethacrylic (or acrylic) esters, polystyrene, polyphosphazenes, polysiloxane or polysilane, is used as the polymer solid electrolyte of the present invention. May be used. ACE or MCE represented by the general formula (1) contained in the above copolymer or polymer mixture
The amount of the structural unit derived from the copolymer or the polymer mixture is preferably 20% by weight or more of the copolymer or polymer mixture because the urethane bond characteristics can be sufficiently exhibited, and more preferably 50% by weight or more.

The molecular weight of the ACE polymer (M) used in the solid polymer electrolyte of the present invention is preferably from 1,000 to 1,000,000, particularly preferably from 5,000 to 50,000.
When the molecular weight of the polymer increases, the film properties such as the film strength after processing become good, but on the other hand, the thermal motion important for carrier ion transfer is restricted, the ionic conductivity is reduced, and it becomes difficult to dissolve in the solvent, It is disadvantageous in processing. Conversely, if the molecular weight is too low, film formability, film strength, and the like will deteriorate, and basic physical properties will be inferior.

The MCOA or ACOA used for obtaining the (M) ACE polymer used in the polymer solid electrolyte of the present invention has one polymerizable group.
Since a comb polymer is obtained by polymerization, and MCMC, ACAC or ACMC has two polymerizable groups, a network polymer is obtained by polymerization. Therefore, a polymer having high thermal motility and good film strength can be obtained by appropriately mixing these. The number of oxyalkylene chains in the oxyalkyl group serving as a side chain of the polymer (that is, the number of oxyalkylene groups contained in R ² in the general formula (1), or, for example, n in the general formula (2) or M × k + in the general formula (3)
n) is preferably in the range of 1 to 1000, particularly preferably in the range of 5 to 50.

Preferably, an organic compound as a plasticizer is added to the solid polymer 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 ACE polymer (M), a large dielectric constant, a boiling point of 100 ° C. or higher, and a wide electrochemical stability range is suitable. Examples of such a plasticizer include oligoethers such as triethylene glycol methyl ether and tetraethylene glycol dimethyl ether, carbonates such as ethylene carbonate, propylene carbonate, diethyl carbonate, and vinylene carbonate, benzonitrile, and aromatic nitriles such as tolunitrile. , Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone, sulfur compounds such as sulfolane, and phosphoric esters. Of these, oligoethers and carbonates are preferred, and carbonates are particularly preferred.

Although the ionic conductivity of the polymer solid electrolyte increases as the amount of the plasticizer added increases, the mechanical strength of the polymer solid electrolyte decreases if the amount is too large. A preferable addition amount is 5 times or less the weight of the (M) ACE polymer. Further, by polymerizing a polymerizable compound such as vinylene carbonate and N-vinylpyrrolidone as a plasticizer with ACE or MCE or the like in combination with an appropriate non-polymerizable plasticizer,
The ionic conductivity can be improved by increasing the amount of the plasticizer added without reducing 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 such that the number of electrolyte molecules per one to two to 100 ether oxygen atoms in the side chain is
Is preferred. If the electrolyte used for the composite is present at a ratio of 1/2 or more of the ether oxygen atom, the movement of ions is greatly inhibited. It is not preferable because it becomes smaller.

The compound ratio is more preferably a ratio of one electrolyte molecule to four to 100 ether oxygen atoms in the side chain. When the electrolyte used for the composite is present at a ratio of 1/4 or more of the ether oxygen atom, the movement of ions is hindered. On the other hand, at a ratio of 1/100 or less, the absolute amount of ions becomes insufficient and the ion conductivity becomes small. This is not preferred. The type of electrolyte used for the composite is not particularly limited, and an electrolyte containing an ion to be used as a carrier with a charge may be used.It is preferable that the dissociation constant in the solid polymer electrolyte be large, and an alkali metal salt, (CH
₃ ) ₄ Quaternary ammonium salts such as ₄ NBF ₄ , (CH ₃ ) ₄
Quaternary phosphonium salts PBF _4, etc., a transition metal salt or hydrochloric such AgClO _4, perchloric acid, protonic acids such as tetrafluoroboric acid are recommended.

As the negative electrode active material used in the battery of the present invention, an alkali metal, an alkali metal alloy,
By using a material having a low oxidation-reduction potential using an alkali metal ion such as a carbon material as a carrier, a high voltage,
This is preferable because a high-capacity battery can be obtained. Therefore, when such a negative electrode is used in a battery using an alkali metal ion as a carrier, an alkali metal salt is required as an electrolyte in the solid polymer electrolyte. Examples of the kind of the alkali metal salt include LiCF ₃ SO ₃ , LiPF ₆ ,
LiClO ₄ , 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 and KI. Among them, the use of lithium or a lithium alloy as the alkali metal is the most preferable because it has a high voltage, a high capacity, and can be formed into a thin film. In the case of a carbon material negative electrode, not only alkali metal ions but also quaternary ammonium salts, quaternary phosphonium salts, transition metal salts, and various protonic acids can be used.

In the case of a solid electric double layer capacitor, the type of electrolyte used for the composite is not particularly limited, and a compound containing an ion to be used as a charge carrier may be used. It is desirable to include ions that are large and easily form a polarizable electrode and an electric double layer. Such compounds include (CH ₃ ) ₄ NB
Quaternary ammonium salts such as F ₄ , (CH ₃ CH ₂ ) ₄ ClO ₄ , transition metal salts such as AgClO ₄ , (CH ₃ ) ₄ PB
Quaternary phosphonium salts such as F ₄ , LiCF ₃ SO ₃ , Li
PF ₆ , LiClO ₄ , LiI, LiBF ₄ , LiSC
N, LiAsF ₆ , NaCF ₃ SO ₃ , NaPF ₆ , N
aClO ₄ , NaI, NaBF ₄ , NaAsF ₆ , KC
Examples include alkali metal salts such as F ₃ SO ₃ , KPF ₆ and KI, organic acids and salts thereof such as paratoluenesulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. Among them, quaternary ammonium salts, quaternary phosphonium salts, and alkali metal salts are preferable because they can provide a high output voltage and have 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 in view of their high solubility in polymer solid electrolytes or large dissociation constants.

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

In the structure of the battery of the present invention, by using an electrode active material having a high oxidation-reduction potential (a positive electrode active material) such as a metal oxide, a metal sulfide, a conductive polymer, or a carbon material for the positive electrode, It is preferable because a battery with high voltage and 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,
Metal sulfides such as titanium sulfide and vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide and the like are particularly preferable in terms of high capacity and high voltage. In addition, a conductive polymer such as polyaniline is particularly preferable in that it is flexible and 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, polyparaphenylenevinylene, polythienylenevinylene, polyfurylenevinylene, polynaphthylenevinylene, polyarylenevinylene such as polyselenophenylenevinylene, polypyridinediylvinylene, and derivatives thereof, and the like. Is mentioned.

Examples of the carbon material include natural graphite, artificial graphite, vapor-grown graphite, petroleum coke, coal coke, fluorinated graphite, pitch-based carbon, polyacene, and fullerenes such as C ₆₀ and C _70. . The method for producing a metal oxide or metal sulfide is not particularly limited, and for example, a general electrolytic method or a heating method as described in “Electrochemistry, Vol. 22, pp. 574, 1954”. Manufactured by When these are used in a lithium battery as an electrode active material, for example, Li _x CoO ₂
And Li _x MnO ₂ or the like is preferably used in a state where the Li element is inserted (composite) into the metal oxide or metal sulfide. The method of inserting the Li element in this way is not particularly limited. For example, a method of electrochemically inserting Li ions or a method of inserting a Li ion such as Li ₂ CO ₃ as described in US Pat. No. 4,357,215. It can be carried out by mixing and heating the metal oxide.

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

The use of an organic solvent-soluble aniline-based polymer as the electrode active material in the electrode or the battery of the present invention is advantageous because molding can be carried out by solution coating, and is particularly advantageous when a thin film battery is manufactured. It is. Examples of the aniline-based polymer include polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-anisidine, poly-m-anisidine, polyxylidines, and poly-lysine.
2,5-dimethoxyaniline, poly-2,6-dimethoxyaniline, poly-2,5-diethoxyaniline, poly-2,6-diethoxyaniline, poly-o-ethoxyaniline, poly-m-ethoxyaniline and Examples of these copolymers include, but are not particularly limited to, any polymer having a repeating unit derived from an aniline derivative. 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, preferred aniline polymers include, for example, polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-anisidine, poly-m
-Anisidine, polyxylidines.

The method of polymerizing the aniline polymer used in the present invention is not particularly limited, but is generally, for example, as described in “Journal of Chemical Society, Chemical Communication, p.
Aniline, o-
A method in which an aniline derivative such as anisidine is electrochemically or chemically oxidized and polymerized. The electrochemical oxidative polymerization is performed by anodic oxidation and has a current density of about 0.01.
A constant current method, a constant voltage method, or any other method can be used in a range of 50 mA / cm ² and an electrolysis voltage of 0.1 to 30 V. The polymerization is carried out in an aqueous solution, an organic solvent or a mixed solvent thereof. Electrolyte p
H is not particularly limited, but preferably has a pH of 3 or less, particularly preferably 2 or less. Specific examples of the acid used for pH adjustment include HCl, HBF ₄ , and CF ₃ COO.
Examples include strong acids such as H, H ₂ SO ₄ , HNO ₃ , and paratoluenesulfonic acid, but are not particularly limited thereto.

In the case of chemical oxidative polymerization, for example, the aniline derivative can be oxidatively polymerized with an oxidizing agent such as a peroxide or a persulfate in an acidic solution. As the acid used in this case, the same acid as that used in the case of electrochemical oxidation polymerization can be used, but it is not limited thereto. Although the molecular weight of the aniline-based polymer used in the present invention obtained by such a method is not particularly limited, it is usually preferable that the molecular weight be 2000 or more. An aniline-based polymer obtained by such a method is generally obtained in many cases in which an anion in a 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 are dedoped before being formed into an electrode by, for example, a film formation method, and further reduced. The method of undoping is not particularly limited, but generally a method of treating with a base such as aqueous ammonia or sodium hydroxide is used. Also, there is no particular limitation on the reduction method, and general chemical or electrochemical reduction may be performed. For example, in the case of a chemical reduction method, an aniline-based polymer dedoped by treating a hydrazine or phenylhydrazine solution with a base can be easily reduced by immersion or stirring at room temperature.

The undoped or reduced aniline polymer thus obtained is soluble in various organic solvents, and in solution, at least one type of ACE or ACE represented by the general formula (1). It can be mixed with a polymerizable monomer solution containing MCE, and using the mixture thus prepared,
For example, an electrode can be manufactured by forming a thin film on various supports, for example, an electrode by a coating method or the like, or forming the electrode into another shape. The solvent in which the aniline-based polymer dissolves is not particularly limited because it depends on the type of the substituent on the benzene ring. It is easily dissolved in polar solvents such as propylene urea.

According to the present invention, as described above, even if a soluble conductive polymer such as an organic solvent-soluble aniline-based polymer is used, a flexible thin film can be obtained by using the (M) ACE polymer. The conductive polymer that can be used in the electrode or the battery of the present invention may be soluble or insoluble in an organic solvent.

Next, an example of the method for manufacturing the electrode and the battery of the present invention will be described in detail. The electrode of the present invention is obtained, for example, by adding at least one compound selected from ACE or MCE represented by the general formula (1), and optionally adding another polymerizable compound and / or a plasticizer. With an electrode active material (a positive electrode active material or a negative electrode active material). In that case, the ratio of each component to be mixed is determined to be more appropriate for the intended battery. The polymerizable monomer / electrode active material mixture thus obtained is shaped into a film or the like and then polymerized to produce an electrode. In this method, the polymerization is carried out from the aforementioned ACE or MCE (M)
The polymerization can be performed in the same manner as in the case of obtaining the ACE polymer. For example, the polymerization can be performed by heating and / or irradiation with electromagnetic waves. When the electrode active material gives a highly flowable polymerizable monomer / electrode active material mixture as in the case of, for example, an organic solvent-soluble aniline-based polymer, the mixture is treated with a current collector or other glass or the like. An electrode is produced by forming the film by applying it on a support and forming a film, and then polymerizing.

The electrode containing the above-mentioned electrode active material manufactured as described above is used as at least one electrode, and the electrode containing another electrode active material manufactured in the same manner or another commonly used electrode is used as the other electrode. The two electrodes are placed in a structure for battery construction so as not to contact each other, or are arranged on a support. For example, a positive electrode and a negative electrode are attached to the end of the electrode via a spacer having an appropriate thickness, and the positive electrode and the negative electrode are put into the structure. Next, an ACE or MCE represented by the general formula (1) is placed between the positive electrode and the negative electrode. At least one compound selected from the group consisting of at least one electrolyte selected from the above-mentioned electrolytes such as alkali metal salts, and in some cases, was prepared by adding and mixing another polymerizable compound and / or a plasticizer. After injecting the polymerizable monomer mixture,
For example, by polymerizing by a method similar to the polymerization method for obtaining the (M) ACE polymer described above, such as by heating and / or irradiation with electromagnetic waves, or further, after polymerization, if necessary, an epoxy resin or the like. By sealing with the insulating resin described above, a battery in which the electrode and the electrolyte are in good contact can be obtained. When an electrode obtained by polymerizing the above-mentioned polymerizable monomer mixture is used, a battery in which the electrode and the electrolyte are in particularly good contact is obtained. When preparing such a polymerizable monomer mixture, the ratio of the components to be mixed is determined to be appropriate for the intended battery. Incidentally, the structure for the battery 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 the shape may be cylindrical, box, sheet, or any other shape.

As described above, the (M) ACE weight is obtained by polymerizing a polymerizable monomer mixture obtained by mixing at least one kind of ACE or MCE represented by the general formula (1) with at least one kind of electrolyte. A method for producing a solid polymer electrolyte comprising a composite containing a coalesced substance and at least one electrolyte is particularly useful for producing a thin film battery. FIG. 2 is a schematic cross-sectional view of an example of a thin-film solid state secondary battery as an example of the battery of the present invention thus manufactured.
Shown in In the figure, 1 is a positive electrode, 2 is a polymer solid electrolyte, 3 is a negative electrode, 4 is a current collector, 5 is an insulating resin film serving as a spacer, and 6 is an insulating resin sealing agent. When manufacturing a wound type battery, the positive electrode and the negative electrode are pasted together through a previously prepared polymer solid electrolyte sheet, rolled up, and further inserted into the battery structure. It is also possible to inject the mixture and polymerize it.

Next, the solid 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 take-out current, or excellent workability and reliability. Is done.

FIG. 3 is a schematic sectional view showing an example of the solid electric double layer capacitor of the present invention. This example is 1cm ×
A thin cell of 1 cm and a thickness of about 0.5 mm, 8 is a current collector, a pair of polarizable electrodes 7 are arranged inside the current collector, and a polymer solid electrolyte membrane 9 is arranged between them. ing. Reference numeral 10 denotes 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 electron conductivity and electrochemical corrosion resistance, and having a specific surface area as large as possible. For example, various metals and their sintered bodies, electron conductive polymers, carbon sheets and the like can be mentioned.

The polarizable electrode 7 may be an electrode made of a polarizable material such as a carbon material usually used for an electric double layer capacitor. preferable. The carbon material as the polarizable material is not particularly limited as long as it has a large specific surface area. However, the larger the specific surface area, the larger the capacity of the electric double layer. For example, carbon blacks such as furnace black, thermal black (including acetylene black), and channel black; activated carbon such as coconut charcoal; natural graphite; artificial graphite; so-called pyrolytic graphite produced by a gas phase method; _60, fullerenes such as C ₇₀ and the like.

Next, an example of a method for manufacturing the solid 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 kind of ACE or MCE represented by the general formula (1) with at least one kind of electrolyte,
A method for producing a composite comprising a CE polymer and at least one electrolyte is particularly useful for producing the solid electric double layer capacitor of the present invention.

When manufacturing a polarizable material 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, first, for example, the general formula (1) At least one compound selected from the group consisting of ACE and MCE is mixed with a polarizable material, if necessary, by further adding another polymerizable compound and / or a plasticizer. In that case, the ratio of the components to be mixed is determined to be more appropriate for 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 polymerized by heating and / or irradiation with electromagnetic waves. A polarizable electrode is produced by polymerizing in the same manner as the polymerization method 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 as described above are placed in a structure for forming a capacitor so as not to be in contact with each other, or are arranged on a support. For example, by bonding both electrodes to the end of the electrode via a spacer of appropriate thickness,
Then, between the two polarizable electrodes, at least one compound selected from ACE or MCE represented by the general formula (1) and the above electrolyte such as an alkali metal salt are put between the two polarizable electrodes. At least one selected electrolyte is mixed, and if necessary, a polymerizable monomer mixture prepared by adding and mixing another polymerizable compound and / or a plasticizer is injected, and then polymerized by the same method as described above. Alternatively, after the polymerization, if necessary, the resultant structure is sealed with an insulating resin such as an epoxy resin to obtain an electric double layer capacitor in which the electrodes and the electrolyte are in good contact. When preparing such a monomer mixture, the ratio of each component to be mixed is determined to be more appropriate for the intended condenser. By this method, a particularly thin all-solid-state electric double layer capacitor can be manufactured. The capacitor structure or the support may be made of a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. However, the shape is not limited to this, and the shape may be cylindrical, box, sheet, or any other shape.

The shape of the electric double layer capacitor is not only a sheet type as shown in FIG. Put in the structure for capacitor construction,
It may be a cylindrical type or the like manufactured by sealing. When manufacturing a wound capacitor, the polarizable electrode is pasted through a polymer solid electrolyte sheet that has been prepared in advance, wound, and inserted into a structure for forming a capacitor, and then the polymerizable monomer mixture is further added. Is injected and polymerized.

[0061]

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-type polymer in which an oxyalkyl group having a urethane bond capable of being compounded is introduced into the side chain, and has excellent film strength and excellent thin film processing property. I have.

The battery of the present invention can be easily formed into a thin film by using the solid polymer electrolyte as the ion-conductive substance. It is a battery, in particular, an all-solid-state battery. Further, the battery of the present invention, in which the negative electrode comprises 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. Such a battery is easy to process, has no risk of short circuit even in a thin film, has a large take-out current, and has high reliability, and in particular, can be an all solid-state battery.

In the present invention, the positive electrode is preferably the (M) ACE
An electrode containing an active material such as a polymer and an organic solvent-soluble aniline-based polymer or other conductive polymer, metal oxide, metal sulfide or carbon material, and using the polymer solid electrolyte as an electrolyte. The featured battery is easy to process such as thinning, there is no danger of short circuit even in thin film, it has a large take-out current, high capacity, and highly reliable battery, and it can be particularly an all solid-state battery .

Further, the (M) ACE polymer and an electrode active material such as an organic solvent-soluble aniline polymer or other conductive polymer, a metal oxide, a metal sulfide or a carbon material of the present invention may be used. In the method for producing an electrode and the electrode including, without impairing the electrochemical activity of the electrode active material excellent in activity as an electrode, to provide an electrode having flexibility as needed, For example, it can be a thin film electrode, and is useful as an electrode of various batteries. Further, according to the method for producing a battery of the present invention, batteries of various shapes can be produced, and in particular, the battery can be easily thinned, can operate at a high capacity and a high current, or has good cyclability. A highly reliable battery 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 formed into a comb-shaped polymer or a network polymer having an oxyalkyl group having a urethane bond introduced into a side chain. Manufactured by polymerizing a solution in which an electrolyte is dissolved in a monomer mixture, and using a solid polymer electrolyte having high ionic conductivity and good film strength as an ion conductive material. This is a highly reliable electric double-layer capacitor having a large output voltage and a high current, and in particular, 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,
The contact between the polarizable electrode and the solid polymer electrolyte, which is an ion-conductive substance, has been made well.
An electric double layer capacitor having a high output voltage and a large take-out current and having high reliability is provided. In particular, an all-solid-state electric double layer capacitor is provided.

[0066]

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

Example 1 (1) 2-acryloyloxyethylcarbamic acid ω-
Methyl oligooxyethyl ester (ACOA (35
0)) Synthesis of 2-acryloyloxyethyl isocyanate (AO
I) 0.1 mol (14.1 g), monomethyl oligoethylene glycol 0.1 mol (3
5 g) in a nitrogen atmosphere, 100 ml of well-purified THF
After dissolution, 0.66 g of dibutyltin dilaurate is added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain ACOA (350) as a colorless viscous liquid. From the results of ¹ H-NMR, IR and elemental analysis,
AOI and monomethyl oligoethylene glycol are one to one.
Further, it was found that the isocyanate group of the AOI disappeared and a urethane bond was generated.

(2) Preparation and Evaluation of ACOA (350) Polymer Solid Electrolyte 1.46 g of ACOA (350) was dissolved in 100 ml of THF, and 0.14 g of LiCF ₃ SO ₃ was added and mixed well. The THF was then removed at room temperature under reduced pressure and the ACO
An A (350) / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. This mixture was applied to a glass plate under an argon atmosphere and heated at 100 ° C. for 1 hour.
(350) Polymer / LiCF ₃ SO ₃ complex is about 200
Obtained as a μm transparent film. The ionic conductivity of the film measured at 25 ° C. by an impedance method was 2 × 10 ⁻⁴ S / cm.

Example 2 (1) 2-acryloyloxyethylcarbamic acid 2-
Synthesis of acryloyloxyethyl carbamoyl oligooxyethyl ester (ACAC (400)) 2-acryloyloxyethyl isocyanate (AO
I) After dissolving 0.2 mol (28.2 g) and 0.1 mol (40 g) of oligoethylene glycol having an average molecular weight of 400 in 100 ml of well-purified THF in a nitrogen atmosphere, 0.66 g of dibutyltin dilaurate is added. Then, by reacting at 50 ℃ for about 3 hours,
ACAC (400) was obtained as a colorless viscous liquid. That
^From the results of ¹ H-NMR, IR and elemental analysis, AOI and oligoethylene glycol reacted 2: 1,
It was found that the isocyanate group of the AOI disappeared, and a urethane bond was formed.

(2) ACOA (350) / ACAC (4
00) Preparation and Evaluation of Copolymer Type Polymer Solid Electrolyte 1.46 g of ACOA (350) synthesized in Example 1 and 0.40 g of ACAC (400) synthesized in Example 2 (1)
Was dissolved in 20 ml of THF, and LiCF ₃ SO ₃ 0.1
4 g was added and mixed well. The THF was then removed at room temperature under reduced pressure and ACOA (350) / ACAC (40
0) / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid.
After applying this mixture on a glass plate under an argon atmosphere,
After heating at 100 ° C for 1 hour, ACOA (350)
The / ACAC (400) copolymer / LiCF ₃ SO ₃ composite was obtained as a transparent free-standing film of about 100 μm. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 2 × 10 ⁻⁵ S / cm.

Example 3 In place of LiCF ₃ SO ₃ used in Example 1, NaCF
_A solid electrolyte was prepared in the same manner as in Example 1 except that 0.15 g of ₃ SO ₃ was used. The ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method and found to be 2 × 10 ⁻⁴ S / cm.

Example 4 In place of LiCF ₃ SO ₃ used in Example 1, LiI
A solid electrolyte was prepared in the same manner as in Example 1 except that 0.11 g was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, 3 × 1
It was 0 ^-4 S / cm.

Example 5 (1) 2-methacryloyloxyethylcarbamic acid ω
-Methyl oligooxyethyl ester (MCOA (55
0)) Synthesis of 2-methacryloyloxyethyl isocyanate (MO
I) 0.1 mol (15.5 g), 0.1 mol (5 mol) of monomethyl oligoethylene glycol having an average molecular weight of 550
5 g) in a nitrogen atmosphere, 100 ml of well-purified THF
After dissolution, 0.66 g of dibutyltin dilaurate is added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain MCOA (550) as a colorless viscous liquid. From the results of ¹ H-NMR, IR and elemental analysis,
MOI and monomethyl oligoethylene glycol are 1: 1
Further, it was found that the isocyanate group of the MOI disappeared and a urethane bond was generated.

(2) Preparation and evaluation of MCOA (550) polymer solid electrolyte 2.09 g of MCOA (550) was dissolved in 10 ml of THF, and 0.14 g of LiCF ₃ SO ₃ was added and mixed well. The THF was then removed at room temperature under reduced pressure and the MCOA
A (550) / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. This mixture was applied on a glass plate under an argon atmosphere and heated at 100 ° C. for 1 hour.
50) Polymer / LiCF ₃ SO ₃ composite is about 200 μm
Was obtained as a transparent free standing film. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 3 × 10 ⁻⁵ S / cm.

Example 6 (1) 2-acryloyloxyethylcarbamic acid 2-
Synthesis of acryloyloxyethyl carbamoyl oligooxyethyl ester (ACAC (600)) 2-acryloyloxyethyl isocyanate (AO
I) 0.2 mol (28.2 g) and 0.1 mol (60 g) of oligoethylene glycol having an average molecular weight of 600 are dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and 0.66 g of dibutyltin dilaurate is added. Then, by reacting at 50 ℃ for about 3 hours,
ACAC (600) was obtained as a colorless gel solid. That
^From the results of ¹ H-NMR, IR and elemental analysis, AOI and oligoethylene glycol reacted 2: 1,
It was found that the isocyanate group of the AOI disappeared, and a urethane bond was formed.

(2) MCOA (550) / ACAC (6
00) Preparation and Evaluation of Copolymer Type Polymer Solid Electrolyte 2.10 g of MCOA (550) and ACAC (600)
0.61 g was dissolved in THF 20 ml, and LiCF ₃ S
0.14 g of O ₃ was added and mixed well. Then, THF
At room temperature under reduced pressure to give MCOA (550) / ACA
A C (600) / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere and heated at 100 ° C. for 1 hour.
(550) / ACAC (600) copolymer / LiCF ₃
The SO ₃ composite was obtained as a clear free standing film of about 100 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 7 (1) 2-acryloyloxyethylcarbamic acid ω-
Methyl oligooxyethyl ester (ACOA (16
4)) Synthesis AOI 0.1 mol (14.1 g), average molecular weight 164
0.1 mol of monomethyltriethylene glycol (1
6g) in 100 ml of THF which is well purified in a nitrogen atmosphere
After dissolution, 0.66 g of dibutyltin dilaurate is added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain ACOA (164) as a single yellow viscous liquid. From the results of ¹ H-NMR, IR and elemental analysis, AOI and monomethyl oligoethylene glycol were
It was found that the reaction was performed in pairs, and further, the isocyanate group of the AOI disappeared, and a urethane bond was generated.

(2) ACOA (164) / ACAC (4
00) Preparation and Evaluation of Copolymer Type Polymer Solid Electrolyte 0.95 g of ACOA (164) and A synthesized in Example 2
0.40 g of CAC (400) was dissolved in 20 ml of THF, and 0.14 g of LiCF ₃ SO ₃ was added and mixed well. The THF was then removed at room temperature under reduced pressure and ACOA
A (164) / ACAC (400) / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour. The ACOA (164) / ACAC (400) copolymer / LiCF ₃ SO ₃ composite was a transparent free-standing film of about 100 μm. Was obtained as The ionic conductivity of this film measured at 25 ° C. by an impedance method was 8 × 10 ⁻⁶ S / cm.

Example 8 Instead of LiCF ₃ SO ₃ used in Example 7, NaCF was used.
_A solid electrolyte was prepared in the same manner as in Example 7, except that 0.13 g of ₃ SO ₃ was used. The ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, and was 9 × 10 ⁻⁶ S / cm.

Example 9 Instead of LiCF ₃ SO ₃ used in Example 7, 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 7 except that 0.30 g was used. The ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method and found to be 8 × 10 ⁻⁵ S / cm.

Example 10 (1) 2-acryloyloxyethylcarbamic acid ω-
Methyl oligooxypropyl ester (ACOA (44
AOI 0.1 mol (14.1 g), average molecular weight 440
0.1 mol of monomethyl oligopropylene glycol
(44 g) in a nitrogen atmosphere, well purified THF100
After dissolving in ml, 0.66 g of dibutyltin dilaurate is added. Thereafter, by reacting at 50 ° C. for about 3 hours, ACOA (44) was obtained as a single yellow viscous liquid.
0) was obtained. From the results of ¹ H-NMR, IR and elemental analysis, it was found that AOI and monomethyl oligopropylene glycol reacted one-to-one, and further, the isocyanate group of AOI disappeared, and a urethane bond was formed. .

(2) ACOA (440) / ACAC (4
00) Preparation and Evaluation of Copolymer Type Polymer Solid Electrolyte 1.84 g of ACOA (440) and A synthesized in Example 2
0.40 g of CAC (400) was dissolved in 20 ml of THF, and 0.14 g of LiCF ₃ SO ₃ was added and mixed well. The THF was then removed at room temperature under reduced pressure and ACOA
A mixture of (440) / ACAC (400) / LiCF ₃ SO ₃ was obtained as a viscous liquid. Under an argon atmosphere, after applying the mixture to a glass plate, it was heated at 100 ℃, ACOA (440) / ACAC (400) a transparent, free-standing film of a copolymer / LiCF ₃ SO ₃ complex of about 100μm Was obtained as The ionic conductivity of this film measured at 25 ° C. by an impedance method was 3 × 10 ⁻⁵ S / cm.

Example 11 Instead of LiCF ₃ SO ₃ used in Example 10, tetrabutylammonium tetrafluoroborate (TBA
B) 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 an impedance method, it was 9 × 10 ⁻⁶ S / c.
m.

Example 12 0.48 g of ACOA (164) synthesized in Example 7, 2.05 g of MCOA (550) synthesized in Example 5, and 0.40 g of ACAC (400) synthesized in Example 2 were added to THF.
It was dissolved in 10 ml, and 0.17 g of LiCF ₃ SO ₃ was added and mixed well. The THF was then removed at room temperature under reduced pressure and ACOA (164) / MCOA (550) / AC
An AC (400) / LiCF ₃ SO ₃ mixture was obtained as a highly viscous semi-solid. This mixture was applied to a glass plate under an argon atmosphere and heated at 100 ° C. for 1 hour.
OA (164) / MCOA (550) / ACAC (40
0) Copolymer / LiCF ₃ SO ₃ composite is about 150 μm
Was obtained as a transparent free standing film. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 1 × 10 ⁻⁵ S / cm.

Example 13 The temperature change of the ionic conductivity of the solid electrolyte film produced in Example 1 was measured by an impedance method, and the result was as shown in FIG. The vertical axis of FIG. 1 shows a logarithmic ionic conductivity, the horizontal axis in Arrhenius plot showing the temperature 1000 / absolute temperature, ions of the slope ACOA (350) polymer / LiCF ₃ SO ₃ based solid electrolyte It represents the activation energy of movement.

Example 14 ACOA (350) 1.46 synthesized in Examples 1 and 2
g, ACAC (400) 0.40 g, propylene carbonate (PC) 1.5 g, and LiCF ₃ SO ₃ 0.2
8 g were mixed well in an argon atmosphere, and ACOA (35
0) / ACAC (400) / PC / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere and heated at 100 ° C. for 1 hour. The ACOA (350) / ACAC (400) copolymer / PC / LiCF ₃ SO ₃ composite was about 300 μm transparent. Obtained as a free standing film. 2 of this film
The ionic conductivity measured at 5 ° C. by the impedance method was 2 × 10 ⁻³ S / cm.

Example 15 Instead of the propylene carbonate used in Example 14,
ACOA (350) / ACAC (4) was prepared in the same manner as in Example 14 except that tetraglyme (TG) was used.
00) Copolymer / TG / LiCF ₃ SO ₃ composite
Obtained as a transparent free standing film of 50 μm. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 7 × 10 ⁻⁴ S / cm.

Example 16 Instead of the propylene carbonate used in Example 14,
ACOA (350) / AC was obtained in the same manner as in Example 14 except that diethyl carbonate (DEC) was used.
The AC (400) copolymer / DEC / LiCF ₃ SO ₃ composite was obtained as a transparent free standing film of about 250 μm.
The ionic conductivity of this film measured at 25 ° C. by an impedance method was 3 × 10 ⁻³ S / cm.

Example 17 0.1 mol of hexamethylene diisocyanate (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 are sufficiently purified in a nitrogen atmosphere in tetrahydrofuran (THF) 10
After dissolving in 0 ml, 0.66 g of dibutyltin dilaurate was added. Thereafter, the mixture was reacted at 60 ° C. for about 1 hour to obtain a colorless viscous liquid product. 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. Further, as a result of measuring the product by gel filtration chromatography (GPC), the average molecular weight of the obtained product in terms of polyethylene glycol was about 750. 75 g of this compound obtained in the same manner as above and 0.1 mol (15.5 g) of methacryloyloxyethyl isocyanate (MOI)
After dissolving in 100 ml of well-purified THF in a nitrogen atmosphere, 0.66 g of dibutyltin dilaurate was added. Then, by reacting at 50 ℃ for about 3 hours,
The product was obtained as a colorless viscous liquid. Part ¹ H-NM
From the results of R, IR and elemental analysis, it was found that the isocyanate group of the MOI had disappeared and the urethane bond had increased. 2.69 g of this monomer was added to 10 m of THF.
and 0.14 g of LiCF ₃ SO ₃ was added and mixed well to prepare a polymerizable monomer mixture. Then
This mixture was applied on a glass plate under an argon atmosphere, and then heated at 100 ° C. for 1 hour to polymerize. As a result, a polymer solid electrolyte was obtained as a transparent free-standing film having a thickness of about 100 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 18 0.1 mol of hexamethylene diisocyanate (16.
8 g), 0.2 mol (80 g) of polyethylene glycol having an average molecular weight of 400 was dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and 0.66 g of dibutyltin dilaurate was added. Thereafter, the mixture was reacted at 60 ° C. for about 1 hour to obtain a white solid product. From the results of ¹ H-NMR and IR, it was found that the isocyanate group of hexamethylene diisocyanate disappeared and a urethane bond was formed. Further, as a result of measuring the product by gel filtration chromatography (GPC), the average molecular weight of the obtained product in terms of polyethylene glycol was about 1,000. This compound 5
0 g and acryloyloxyethyl isocyanate (AO
I) After dissolving 0.1 mol (14.1 g) in 100 ml of well-purified THF in a nitrogen atmosphere, 0.66 g
Of dibutyltin dilaurate was added. Then 50
The reaction was carried out at a temperature of about 3 hours to obtain a product as a white solid. From the results of ¹ H-NMR, IR and elemental analysis, it was found that the isocyanate group of AOI had disappeared and urethane bonds had increased.

Example 19 2.69 g of the monomer obtained in Example 17, 0.74 g of the monomer obtained in Example 18, and propylene carbonate (P
C) 1.8 g, 1.8 g of ethylene carbonate (EC)
And 0.28 g of LiCF ₃ SO ₃ were mixed well in an argon atmosphere to obtain a polymerizable monomer mixture as a viscous liquid. This mixture was applied on a glass plate under an argon atmosphere, and then heated at 100 ° C. for 1 hour to polymerize. As a result, a plasticized polymer solid electrolyte was obtained as a transparent free-standing film having a thickness of about 300 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, 1 × 1
It was 0 ^-3 S / cm.

Example 20 Preparation of a polymerizable monomer mixture MCOA (550) 2.10 synthesized in Examples 5 and 6
g, 0.51 g of ACAC (600), 1.3 g of propylene carbonate (PC), and ethylene carbonate (E
C) 1.3 g of LiBF _{4 and} 0.56 g of LiBF ₄ were mixed well in an argon atmosphere, and
A polymerizable monomer mixture of (600) / PC / EC / LiBF ₄ mixture was obtained as a viscous liquid. This polymerizable monomer mixture was coated on a glass plate under an argon atmosphere, and then heated at 100 ° C. for 1 hour.
0) / ACAC (600) copolymer / PC / EC / Li
The BF ₄ composite was obtained as a transparent free standing film of about 300 μm. The ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method, and was 3 × 10 ⁻³ and 1 × 10 ⁻³ S / cm, respectively.

Example 21 Production of Cobalt Oxide Positive electrode 22 g of Li ₂ CO ₃ and 24 g of Co ₃ O ₄ were mixed well,
After heating at 800 ° C. for 24 hours in an oxygen atmosphere, the mixture was pulverized to obtain a Li ₂ CoO ₂ powder. This Li ₂ CoO
_{The two} powders and the polymerizable monomer mixture prepared in Example 20 were mixed in an argon atmosphere at a weight ratio of 7: 3, and applied on a stainless steel foil to a thickness of 1 × 1 cm and a thickness of about 200 μm. Furthermore, by heating and polymerizing at about 100 ° C. for 1 hour, a cobalt oxide / polymer solid electrolyte composite positive electrode (65 m
g) was obtained.

Example 22 Production of Polymer Solid Electrolyte Secondary Battery In an argon atmosphere glove box, a 75 μm-thick lithium foil was cut into 1 × 1 cm (5.3 mg), and about 1 mm on each end thereof was 10 μm polyimide. On film,
Coated as a spacer. Next, the polymerizable monomer mixture (15 mg) prepared in Example 20 was applied on a lithium foil, and the cobalt oxide positive electrode produced in Example 21 was adhered thereto. After sealing with a resin, a lithium / cobalt oxide solid secondary battery having the configuration shown in FIG. 2 was obtained. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.3 V and a current of 0.1 mA, the maximum discharge capacity was 4.0 mAh and the capacity was 50%.
The cycle life before decreasing to 200 was 200 times.

Example 23 Production of Polyaniline Positive Electrode A aniline 0.5 M, HBF ₄ 1.5 M aqueous solution was used as a polymerization solution, and a graphite foil was used as a counter electrode, and 1 × 1
Approximately 100 μm on a 1 cm constant current method
m to a thickness of m. Next, after washing with methanol, it was vacuum dried at 80 ° C. for 24 hours. Next, this film (15 mg) was transferred into a glove box in an argon atmosphere, and was impregnated with the polymerizable monomer mixture prepared in Example 20, and polymerized at 100 ° C. for 1 hour to obtain a polyaniline / polymer solid electrolyte composite positive electrode. (45 mg) was obtained.

Example 24 Production of Polymer Solid Electrolyte Secondary Battery In the same manner as in Example 22 except that the polyaniline cathode produced in Example 23 was used instead of the cobalt oxide cathode,
A lithium / polyaniline solid secondary battery was obtained. When the 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 500 times.

Example 25 Production of Gas-phase Graphite Negative Electrode A gas-phase graphite fiber manufactured by Showa Denko (average fiber diameter 0.3 μm, average fiber length 2.0 μm, 10 g of a 2700 ° C. heat-treated product) and 200 ml of a 2.5 M butyllithium-containing hexane solution were mixed and stirred at room temperature for 8 hours. Subsequently, it was washed with hexane and dried to obtain a graphite fiber into which lithium ions had been preliminarily inserted. The C / Li atomic ratio was 12/1 as determined by elemental analysis. 6 g of the lithium-containing fiber thus obtained and 4 g of the polymerizable monomer mixture prepared in Example 20 were mixed at a weight ratio of 6: 4 under an argon atmosphere, and a portion thereof was taken to 1 × 1 cm on a stainless steel foil. , About 150 μm thick. Further, at about 100 ° C., 1
The mixture was heated and polymerized for a period of time to obtain a vapor phase graphite / polymer solid electrolyte composite negative electrode (21 mg).

Example 26 Production of polymer solid electrolyte secondary battery In the same manner as in Example 22 except that the vapor phase graphite negative electrode produced in Example 25 was used instead of the lithium foil, vapor phase graphite / oxidation was carried out. 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 was reduced to 50% was 300 times. there were.

Example 27 Synthesis of Polyaniline Soluble in Organic Solvent A thermometer, a stirrer, and a condenser were attached to a 1-liter four-necked flask, and a 1N aqueous HCl solution was added to a 500-mL flask.
Then, 20.3 g of aniline was dissolved while bubbling nitrogen through. Then, with stirring and nitrogen bubbling.
5 g of ammonium persulfate was added over about 30 minutes while remaining solid. The reaction temperature was kept at about 22 ° C. After the addition, the mixture was further reacted for 22 hours, followed by filtration, and the residue was washed with 500 ml of distilled water. The product was then transferred to a beaker and stirred with 500 ml of 5% aqueous ammonia for about 1 hour.
Filtration, washing with distilled water, and drying under reduced pressure gave about 16 g of undoped polyaniline powder. Then 300m
hydrazine monohydrate, 150 ml
And the above-mentioned undoped polyaniline powder was added over about 1 hour at room temperature with nitrogen flow under stirring. After stirring at room temperature for about 10 hours under a nitrogen flow, the mixture was filtered in a nitrogen atmosphere and dried under reduced pressure. Further, by washing with purified THF and purified ether under a nitrogen atmosphere and drying under reduced pressure, about 14 g of reduced polyaniline powder was obtained. The elemental analysis value of the reduced polyaniline powder is 98% in total of carbon, hydrogen and nitrogen, and the elemental ratio of carbon / hydrogen / nitrogen is 6.00 / 4.95 / 1.01, which is almost in agreement with the theoretical value. did. This powder was dissolved in purified N-methylpyrrolidone (NMP) under an argon atmosphere to a concentration of about 5% by weight. The number average molecular weight of polyaniline determined by GPC measurement of this solution was about 20,000 in terms of polystyrene.

Example 28 Preparation of Polyaniline Positive Electrode The polymerizable monomer mixture prepared in Example 20 was prepared in Example 27 in a glove box under an argon atmosphere.
The polyaniline and the polymerizable monomer mixture were mixed in a wt% polyaniline / NMP solution so that the weight ratio of the mixture was 1: 1. This mixture was mixed with 50 μm polyimide film 3
It was applied to a portion surrounded by a polyimide film on a 15 × 15 mm, 100 μm thick stainless steel foil attached to the four ends with a width of mm. Then 60 ° C, 80 ° C, 10
By heating at 0 ° C. for 1 hour each, drying and polymerization were performed to obtain a polyaniline positive electrode (68 mg).

Example 29 Production of Polymer Solid Electrolyte Secondary Battery In an argon atmosphere glove box, a 25 μm-thick lithium foil was cut into 12 × 12 mm (2.6 mg).
About 2 mm square of the end was covered with a 10 μm polyimide film as a spacer. Next, the polymerizable monomer mixture prepared in Example 20 was applied on a lithium foil,
Further, the polyaniline positive electrode produced in Example 28 was adhered, heated at 100 ° C. for 1 hour, and then sealed at the battery end with an epoxy resin to obtain a lithium / polyaniline solid secondary battery having the structure shown in FIG. This battery is operated at an operating voltage of 2.0 to 2.0
When charge and discharge were repeated at 4.0 V and a current of 0.1 mA,
The maximum discharge capacity was 1.5 mAh, and the cycle life until the capacity was reduced to 50% was 200 times.

Example 30 Preparation of poly-o-anisidine positive electrode Instead of the aniline used in Example 27, 27.0 g of o-anisidine was used.
Except that anisidine was used, 18 g of reduced poly-o-anisidine powder was synthesized and treated in the same manner as in Example 27. The elemental analysis value of the reduced poly-o-anisidine powder was 98% in total of carbon, hydrogen and nitrogen, and the elemental ratio of carbon / hydrogen / nitrogen was 7.00 / 6.91 /
1.03 almost coincided with the theoretical value. This powder was added to purified N-methylpyrrolidone (NMP) for about 8 under an argon atmosphere.
It dissolved to a concentration of wt%. The number average molecular weight of poly-o-anisidine determined from 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 28, except that an 8 wt% poly-o-anisidine / NMP solution was used instead of the 5 wt% polyaniline / NMP solution used in 8. .

Example 31 Production of Solid Electrolyte Secondary Battery The polyaniline cathode prepared in Example 30 was used instead of the polyaniline positive electrode.
A lithium / poly-o-anisidine solid secondary battery was obtained in the same manner as in Example 29 except that the o-anisidine positive electrode (62 mg) was used. This battery was operated at an operating voltage of 1.8 to 3.
When charging and discharging were repeated at 8 V and a current of 0.1 mA, the maximum discharge capacity was 1.1 mAh and the cycle life until the capacity was reduced to 50% was 210 times.

Example 32 Production of polymer solid electrolyte secondary battery In the same manner as in Example 29 except that the vapor phase graphite negative electrode produced in Example 25 was used instead of the lithium foil, vapor phase graphite / polyaniline was used. A solid secondary battery was obtained. When this battery was repeatedly charged and discharged at an operating voltage of 1.5 to 3.8 V and a battery of 0.1 mA, the maximum discharge capacity was 1.5 mAh and the capacity was 5
The cycle life before decreasing to 0% was 300 times.

Example 33 Preparation of Polymerizable Monomer Mixture MCOA (550) 2.10 Synthesized in Examples 5 and 6
g, ACAC (600) 0.51 g, propylene carbonate (PC) 1.6 g, ethylene carbonate (E
C) 1.6 g and 0.90 g of ethyltributylammonium perchlorate (EBAP) are mixed well in an argon atmosphere, and then MCOA (550) / ACAC (600)
A polymerizable monomer mixture consisting of / PC / EC / EBAP was obtained as a viscous liquid. This polymerizable monomer mixture was applied on a glass plate under an argon atmosphere, and then heated at 100 ° C. for 1 hour to polymerize, resulting in MCOA (550) / A
CAC (600) copolymer (one of the (M) ACE polymers) / PC / EC / EBAP complex is about 30
Obtained as a 0 μm transparent free-standing film. When the ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method, it was 3.0 × 10 3 each.
^-3 , 1.0 × 10 ^-3 S / cm.

Example 34 Production of Activated Carbon Electrode The coconut palm activated carbon and the polymerizable monomer mixture prepared in Example 33 were mixed in an argon atmosphere at a weight ratio of 1: 1.
Approximately 150μ in size of 1cm x 1cm on stainless steel foil
m. Further, the mixture was heated at about 100 ° C. for 1 hour for polymerization to obtain an activated carbon / polymer solid electrolyte composite electrode (13 mg).

Example 35 Production of Solid Electric Double-Layer Capacitor In an argon atmosphere glove box, about 1 mm × 1 cm of the activated carbon electrode (13 mg) produced in Example 34 was used as a spacer with a polyimide film having a thickness of 10 μm as a spacer. Coated. Next, the polymerizable monomer mixture (15 mg) prepared in Example 33 was applied on the electrode, and another electrode was bonded thereto, heated at 100 ° C. for 1 hour, and then sealed at the capacitor end with epoxy resin. Then, a solid electric double layer capacitor as shown in FIG. 3 was manufactured. This capacitor is operated at an operating voltage of 0 to 2.5 V and a current of 0.1 m.
When charging and discharging were performed at A, the maximum capacity was 200 mF. In addition, even if charging and discharging were repeated 50 times under these conditions, the capacity hardly changed.

Example 36 Production of Solid Electric Double Layer Capacitor Instead of the salt EBAP used for the polymerizable monomer mixture produced in Example 33, lithium perchlorate (LiC
A polymerizable monomer mixture was prepared using 0.3 g of (10 ₄ ). A solid electric double layer capacitor was manufactured in the same manner as in Example 35 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 50 mF. In addition, even if charging and discharging were repeated 50 times under these conditions, the capacity hardly changed.

Example 37 Production of Acetylene Black Electrode Acetylene black and the polymerizable monomer mixture produced in Example 33 were mixed in an argon atmosphere at a weight ratio of 6: 4, and the mixture was 1 cm × 1 cm on a stainless steel foil. , About 1
It was applied to a thickness of 50 μm. Furthermore, by heating and polymerizing at about 100 ° C. for 1 hour, an acetylene black / polymer solid electrolyte composite electrode (14 mg) was obtained. Example 38 Production of Solid Electric Double Layer Capacitor The acetylene black electrode (14 m) produced in Example 37
A solid electric double layer capacitor was manufactured in the same manner as in Example 35 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 50 mF. In addition, even if charging and discharging were repeated 50 times under these conditions, the capacity hardly changed.

[0110]

The polymer solid electrolyte of the present invention is composed of a composite of a polymer having an oxyalkyl group in a side chain bonded by a urethane bond and at least one electrolyte, and has a good film 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 a side chain, a polyaniline polymer or other conductive polymer soluble in an organic solvent, a metal oxide, a metal sulfide or a carbon material An electrode containing an electrode active material or a polarizable material and a method of manufacturing the same,
It can provide an electrode with high electrochemical activity and flexibility,
In particular, a thin electrode can be provided, and is useful as an electrode used for various batteries or electric double layer capacitors and the like and a method for producing the same.

Further, the battery of the present invention is a battery which can operate at a high capacity and a high current as an all solid type, or has excellent cyclability, and is excellent in safety and reliability. It can be used as a power supply for electric products such as a backup power supply, a large power supply for electric vehicles, and a load leveling. Further, since it can be easily thinned, it can be used as a paper battery for an identification card or the like. Furthermore, the electric double layer capacitor of the present invention has a high voltage, a high capacity,
It is an electric double layer capacitor which can be operated at a high current or has good cycleability, and is excellent in safety and reliability, and can be an all solid electric double layer capacitor having such characteristics. For this reason, it can be used not only as a backup power supply but also as a power supply for various electric products in combination with a small battery. Further, it is excellent in workability such as thinning, and can be expected for uses other than the use of the conventional solid type electric double layer capacitor.

[Brief description of the drawings]

FIG. 1 is a graph showing temperature characteristics of ionic conductivity of a polymer solid electrolyte film measured in Example 13.

FIG. 2 is a schematic cross-sectional view of one embodiment of a thin solid-state battery shown as an example of the battery according to the present invention.

FIG. 3 is a schematic sectional view of an embodiment of the solid-state electric double layer capacitor of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Polymer solid electrolyte 3 Negative electrode 4 Current collector 5 Spacer 6 Insulating resin sealing agent 7 Polarizing electrode 8 Current collector 9 Polymer solid electrolyte membrane 10 Spacer 11 Insulating resin sealing agent 12 Lead wire

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI H01G 4/06 H01G 4/06 9/025 H01M 10/40 B H01M 10/40 H01G 9/00 301G (31) Priority claim number Japanese Patent Application No. 6-133839 (32) Priority Date May 24, 1994 (May 24, 1994) (33) Priority Country Japan (JP) (72) Inventor Miyuki Ueda Onodai, Midori-ku, Chiba City, Chiba Prefecture 1-1-1 Showa Denko KK Research Institute (72) Inventor Jun Noguchi 1-1-1 Onodai, Midori-ku, Chiba-shi, Chiba Prefecture Showa Denko KK Research Institute (56) References JP-A-5-205515 ( JP, A) JP-A-5-25353 (JP, A) Polymer, Voi. 29 (12), p2271-2276 (1988) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 220/34 C08L 33/14 C08L 71/02 G02F 1/15 H01B 1/06 H01G 4 / 06 H01G 9/025 H01M 10/40 CA, REGISTRY (STN)

Claims (29)

(57) [Claims] 1. General formula (1) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) (wherein R ¹ represents hydrogen or a methyl group, and R ² represents an oxyalkylene group. Represents an organic chain containing at least one or more linear, branched, or cyclic structures, and contains one or more elements other than carbon, hydrogen, and oxygen.
More than one may be included. Copolymers and side to represented by 2-acryloyloxyethyl carbamates or 2-methacryloyloxy obtained from at least one compound selected from oxyethyl carbamate ester polymer and / or said compound copolymerizable components) chain
A polymer solid electrolyte comprising a composite containing at least one kind of electrolyte at a ratio of 1 to 2 to 100 ether oxygen atoms . 2. General formula (2) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO (R ³ O) _n R ⁴ (2) (wherein R ¹ represents hydrogen or a methyl group; R ³ is-
(CH ₂ ) ₂ — or —CH (CH ₃ ) CH ₂ —, wherein R ⁴ is an alkyl group having 1 to 10 carbon atoms;
_{CONH (CH 2) 2 OCOCH =} CH 2 or -CO
NH (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ ,
n represents one or more numbers. 2-methacryloyloxyethylcarbamic acid ω-alkyl oligooxyalkyl ester, 2-acryloyloxyethylcarbamic acid ω-alkyl oligooxyalkyl ester represented by
2-methacryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid 2-acryloyloxyethyl carbamoyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligo Oxyalkyl ester or general formula (3) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO ｛(R ⁶ O) _m CONHR ⁵ NHCOOO｝ _k (R ³ O) _n R ⁴ (3) Wherein R ¹ represents hydrogen or a methyl group, and R ³ and R ⁶ are each independently — (CH ₂ ) ₂ — or —CH
(CH ₃ ) CH ₂ —, wherein R ⁴ has 1 to 10 carbon atoms
Range alkyl group, -CONH (CH _{2) 2} OCOC
H = CH ₂ or —CONH (CH ₂ ) ₂ OCOC (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 1 or more. A) a polymer obtained from at least one compound selected from the group consisting of: and / or a copolymer containing the compound as a copolymer component and 1 to 100 ether oxygen atoms in the side chain.
Battery, which comprises using at least including one electrolyte consisting of a complex polymer solid electrolyte of the interleaf. 3. The battery according to claim 1, wherein the electrolyte of the polymer solid electrolyte is at least one compound selected from an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, and a transition metal salt. 4. The battery according to claim 1, wherein a plasticizer is added to the solid polymer electrolyte. 5. The lithium battery according to claim 1, wherein the negative electrode is an electrode containing lithium or a lithium alloy. 6. The method according to claim 1, wherein the negative electrode comprises an electrode containing a carbon material capable of inserting and extracting lithium ions.
The lithium ion battery according to the item. 7. The positive electrode comprises an electrode containing an organic solvent-soluble aniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material.
The battery according to claim 1. 8. A compound represented by the general formula (1): CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) (wherein symbols have the same meanings as in claim 1). -Acryloyloxyethylcarbamate or at least one compound selected from 2-methacryloyloxyethylcarbamate and a side chain
A polymerizable monomer mixture containing at least one electrolyte at a ratio of 1 to 2 to 100 ether oxygen atoms , or a polymerizable monomer mixture obtained by adding a plasticizer to the mixture. A method for producing a battery, comprising a step of placing the polymerizable monomer mixture in a structure for use or disposing the polymerizable monomer mixture on a support. 9. General formula (2) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO (R ³ O) _n R ⁴ (2) (wherein symbols have the same meanings as in claim 2) 2-methacryloyloxyethyl carbamic acid ω-alkyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid ω-alkyl oligooxyalkyl ester, 2-methacryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligo Oxyalkyl esters, 2-acryloyloxyethylcarbamic acid 2-acryloyloxyethylcarbamoyl oligooxyalkyl ester, 2-acryloyloxyethylcarbamic acid 2-methacryloyloxyethylcarbamoyl oligooxyalkyl ester, or general formula (3) ^{_{H 2 = C (R 1)}} COO (CH 2) 2 NHCOO {(R 6 O) m CONHR 5 NHCOO} k (R 3 O) n R 4 (3) ( symbols in the formulas have the same meaning as in claim 2 the expressed. compound represented by) at least one compound and ether side chain selected from
A polymerizable monomer mixture containing at least one electrolyte in a ratio of 1 to 2 to 100 oxygen atoms , or a polymerizable monomer mixture to which a plasticizer is added, is placed in the battery structure, or A method for producing a battery, comprising a step of disposing on a support and polymerizing such a polymerizable monomer mixture. 10. A compound represented by the general formula (1): CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) (wherein the symbols have the same meanings as in claim 1). -Acryloyloxyethylcarbamate or a polymer obtained from at least one compound selected from 2-methacryloyloxyethylcarbamate and / or a copolymer containing the compound as a copolymer component and an electrode active material or a polarizable material An electrode comprising: 11. General formula (2) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO (R ³ O) _n R ⁴ (2) (wherein symbols have the same meanings as in claim 2) 2-methacryloyloxyethyl carbamic acid ω-alkyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid ω-alkyl oligooxyalkyl ester, 2-methacryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligo Oxyalkyl ester, 2-acryloyloxyethylcarbamic acid 2-acryloyloxyethylcarbamoyl oligooxyalkyl ester, 2-acryloyloxyethylcarbamic acid 2-methacryloyloxyethylcarbamoyl oligooxyalkyl ester, or general formula (3) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO ｛(R ⁶ O) _m CONHR ⁵ NHCOOO｝ _k (R ³ O) _n R ⁴ (3) (The symbols in the formula are the same as those in claim 2) A polymer obtained from at least one compound selected from the group consisting of a compound represented by the formula: and / or a copolymer containing the compound as a copolymer component, and an electrode active material or a polarizable material. Electrode. 12. The method according to claim 10, wherein the electrode active material or the polarizable material is an organic solvent-soluble aniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material. electrode. 13. A compound represented by the general formula (1): CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) wherein the symbols have the same meanings as in claim 1. -Acryloyloxyethylcarbamate or at least one compound selected from 2-methacryloyloxyethylcarbamate and a polymerizable monomer mixture containing an electrode active material or a polarizable material, or a polymerizable mixture obtained by adding a plasticizer to the mixture. A method for producing an electrode, comprising a step of polymerizing a monomer mixture. 14. The general formula (2): CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO (R ³ O) _n R ⁴ (2) (wherein the symbols have the same meanings as in claim 2) 2-methacryloyloxyethyl carbamic acid ω-alkyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid ω-alkyl oligooxyalkyl ester, 2-methacryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligo Oxyalkyl ester, 2-acryloyloxyethyl carbamic acid 2-acryloyloxyethyl carbamoyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligooxyalkyl ester, or general formula (3) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO ｛(R ⁶ O) _m CONHR ⁵ NHCOOO｝ _k (R ³ O) _n R ⁴ (3) (the symbols in the formula are the same as those in claim 2) A process of polymerizing a polymerizable monomer mixture containing at least one compound selected from the group consisting of a 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 producing an electrode, comprising: 15. The method according to claim 13, wherein the electrode active material or the polarizable material is an organic solvent-soluble aniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material. Manufacturing method of electrode. 16. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the ion conductive substance is represented by the general formula (1): CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) (wherein, 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 be any of a linear, branched, or cyclic structure. May be composed of an element other than carbon, hydrogen and oxygen.
More than one may be included. Copolymers and side to represented by 2-acryloyloxyethyl carbamates or 2-methacryloyloxy obtained from at least one compound selected from oxyethyl carbamate ester polymer and / or said compound copolymerizable components) chain
An electric double layer capacitor comprising a polymer solid electrolyte comprising a composite containing at least one kind of electrolyte per 2 to 100 ether oxygen atoms . 17. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the ion conductive substance is represented by the following general formula (2): CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO (R ³ O) _n R ⁴ (2) (wherein, R ¹ represents hydrogen or a methyl group, and R ³ represents —
(CH ₂ ) ₂ — or —CH (CH ₃ ) CH ₂ —, wherein R ⁴ is an alkyl group having 1 to 10 carbon atoms;
_{CONH (CH 2) 2 OCOCH =} CH 2 or -CO
NH (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ ,
n represents one or more numbers. 2-methacryloyloxyethylcarbamic acid ω-alkyl oligooxyalkyl ester, 2-acryloyloxyethylcarbamic acid ω-alkyl oligooxyalkyl ester represented by
2-methacryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid 2-acryloyloxyethyl carbamoyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligo Oxyalkyl ester or general formula (3) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO ｛(R ⁶ O) _m CONHR ⁵ NHCOOO｝ _k (R ³ O) _n R ⁴ (3) Wherein R ¹ represents hydrogen or a methyl group, and R ³ and R ⁶ are each independently — (CH ₂ ) ₂ — or —CH
(CH ₃ ) CH ₂ —, wherein R ⁴ has 1 to 10 carbon atoms
Range alkyl group, -CONH (CH _{2) 2} OCOC
H = CH ₂ or —CONH (CH ₂ ) ₂ OCOC (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 1 or more. A) a polymer obtained from at least one compound selected from the group consisting of: and / or a copolymer containing the compound as a copolymer component and 1 to 100 ether oxygen atoms in the side chain.
Electric double layer capacitor, which is a solid polymer electrolyte comprising a complex comprising at least one electrolyte of the interleaf. 18. The electric power according to claim 16, wherein the electrolyte of the polymer solid electrolyte is at least one compound selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts and transition metal salts. Double layer capacitor. 19. The electric double layer capacitor according to claim 16, wherein a plasticizer is added to the solid polymer electrolyte. 20. In an electric double layer capacitor having a polarizable electrode arranged via an ion conductive substance, the polarizable electrode is made of a carbon material and a general formula (1) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) (The symbols in the formula have the same meanings as in claim 1.) At least one compound selected from 2-acryloyloxyethylcarbamate or 2-methacryloyloxyethylcarbamate An electric double layer capacitor comprising a composite containing a polymer obtained from the above and / or a copolymer containing the compound as a copolymer component. 21. In an electric double layer capacitor having a polarizable electrode arranged via an ion conductive substance, the polarizable electrode is made of a carbon material and a general formula (2) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO (R ³ O) _n R ⁴ (2) (wherein the symbols have the same meaning as in claim 2) 2-methacryloyloxyethylcarbamic acid ω-alkyl oligooxyalkyl ester represented by the formula: Acryloyloxyethyl carbamic acid ω-alkyl oligooxyalkyl ester, 2-methacryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid 2-acryloyloxyethyl carbamoyl oligooxyalkyl ester, 2 -Acryloyloxyethyl cal Bamidic acid 2-methacryloyloxyethylcarbamoyl oligooxyalkyl ester or the general formula (3): CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO ｛(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), and a polymer obtained from at least one compound selected from the group consisting of: An electric double-layer capacitor comprising a composite comprising: 22. An electric double layer capacitor in which a polarizable electrode is arranged via an ion-conductive substance, wherein the polarizable electrode is represented by the general formula (1): CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) At least one compound selected from 2-acryloyloxyethylcarbamate or 2-methacryloyloxyethylcarbamate represented by (the symbols in the formula have the same meanings as in claim 1) and a carbon material An electric double layer capacitor characterized by being a polarizable electrode produced by polymerizing a polymerizable monomer mixture containing: 23. In an electric double layer capacitor having a polarizable electrode arranged via an ion conductive substance, the polarizable electrode is formed by a general formula (2) CH ₂ ＝ C (R ¹ ) COO (CH ₂ ) ₂ NHCOO ( R ³ O) _n R ⁴ (2) (wherein the symbols have the same meaning as in claim 2) 2-methacryloyloxyethylcarbamic acid ω-alkyl oligooxyalkyl ester, 2-acryloyloxyethyl Carbamic acid ω-alkyl oligooxyalkyl alkyl ester, 2-methacryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid 2-acryloyloxyethyl carbamoyl oligooxyalkyl ester, 2-acryloyloxy Ethyl carbamic acid 2 -Methacryloyloxyethylcarbamoyl oligooxyalkyl ester, or the general formula (3): CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO ｛(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 meaning as in claim 2), and a polymerizable monomer mixture containing a carbon material and at least one compound selected from the group consisting of: An electric double layer capacitor characterized by being a polarized electrode. 24. General formula (1) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) (wherein the symbols have the same meanings as in claim 1). At least one compound selected from -acryloyloxyethylcarbamate or 2-methacryloyloxyethylcarbamate and a side chain
A polymerizable monomer mixture containing at least one kind of electrolyte at a ratio of 1 to 2 to 100 ether oxygen atoms , or a polymerizable monomer mixture to which a plasticizer has been added. Put in the multilayer capacitor structure,
Alternatively, a method for producing an electric double layer capacitor, comprising a step of disposing on a support and polymerizing such a polymerizable monomer mixture. 25. General formula (2) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOO (R ³ O) _n R ⁴ (2) (wherein the symbols have the same meanings as in claim 2) 2-methacryloyloxyethyl carbamic acid ω-alkyl oligooxyalkyl ester, 2-acryloyloxyethyl carbamic acid ω-alkyl oligooxyalkyl ester, 2-methacryloyloxyethyl carbamic acid 2-methacryloyloxyethyl carbamoyl oligo An oxyalkyl ester, 2-acryloyloxyethylcarbamic acid 2-acryloyloxyethylcarbamoyl oligooxyalkyl ester, 2-acryloyloxyethylcarbamic acid 2-methacryloyloxyethylcarbamoyl oligooxyalkyl ester, or a compound represented by the general formula (3) ^{_{CH 2 = C (R 1)}} COO (CH 2) 2 NHCOO {(R 6 O) m CONHR 5 NHCOO} k (R 3 O) n R 4 (3) ( symbols in the formulas have the same meaning as in claim 2 the expressed. compound represented by) at least one compound and ether side chain selected from
A polymerizable monomer mixture containing at least one electrolyte in a ratio of 1 to 2 to 100 oxygen atoms , or a polymerizable monomer mixture to which a plasticizer is added, is placed in the structure for forming an electric double layer capacitor. A method for producing an electric double layer capacitor, comprising a step of putting or disposing on a support and polymerizing such a polymerizable monomer mixture. 26. A carbon material and represented by the general formula (1) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) (the symbols in the formula represent the same meaning as in claim 1). A polymer obtained from at least one compound selected from 2-acryloyloxyethylcarbamate or 2-methacryloyloxyethylcarbamate, and / or a composite containing the compound as a copolymer component At least one selected from 2-acryloyloxyethylcarbamate or 2-methacryloyloxyethylcarbamate represented by the general formula (1) between a pair of polarizable electrodes consisting of: Of the compound and side chain
A polymerizable monomer mixture containing at least one electrolyte in a ratio of 1 to 2 to 100 ether oxygen atoms ,
Alternatively, a method for producing an electric double layer capacitor, comprising a step of injecting a polymerizable monomer mixture to which a plasticizer is added, and polymerizing the polymerizable monomer mixture. 27. General formula (1) CH ₂ ＣC (R ¹ ) COO (CH ₂ ) ₂ NHCOOR ² (1) wherein R ¹ represents hydrogen or a methyl group, and R ² represents an oxyalkylene group Represents an organic chain containing at least one or more linear, branched, or cyclic structures, and contains one or more elements other than carbon, hydrogen, and oxygen.
More than one may be included. Copolymers and side to represented by 2-acryloyloxyethyl carbamates or 2-methacryloyloxy obtained from at least one compound selected from oxyethyl carbamate ester polymer and / or said compound copolymerizable components) chain
A solid polymer electrolyte comprising a composite containing at least one kind of electrolyte at a ratio of 1 to 2 to 100 ether oxygen atoms . 28. The solid polymer electrolyte according to claim 27, wherein the electrolyte is at least one compound selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts. 29. The polymer solid electrolyte according to claim 27, wherein a plasticizer is added.