JPH107759A - Monomer compound for solid polyelectrolyte, solid polyelectrolyte, and their use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a solid polyelectrolyte which exhibits high strengths in thin-film formation, has a high ion conductivity at room temp. and at high temps., and is excellent in processibility by combining specific compds. to form a monomer compsn. having urethane bonds and contg. an oxyalkylene deriv. and polymerizing the compsn. SOLUTION: This monomer compd. for a solid polyelectrolyte is a mixture contg. or a reaction product obtd. from the following two compds.: a compd. represented by the formula (wherein R<1> is H or an alkyl; R<2> is a divalent org. chain provided when v is 1, then R<2> is dispensable; x and y are each an integer of 0-5; and z is 0 or 1-10 provided when x=0 and y=0, then z=0) and a compd. repersented by the formula: R<3> (-NCO)k (wherein R<3> is an at least monovalent org. group provided it may be linear, branched, or cyclic and may contain one or more atoms other than carbon, hydrogen, and oxygen; and k is an integer of 1 or higher).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a monomer composition having a urethane bond and containing an oxyalkylene derivative, a novel polymer using the same, and a high ionic conductivity using a composite comprising an electrolyte. Polymer solid electrolyte, electrode using the polymer solid electrolyte and manufacturing method thereof, battery using the polymer solid electrolyte or the electrode and manufacturing method thereof, and electric double layer capacitor using the polymer solid electrolyte and the same It relates to a manufacturing method.

[0002]

2. Description of the Related Art In the field of downsizing and all-solidification in the field of ionics, all-solid primary and secondary batteries and solid-state batteries using solid electrolytes are used as new ion conductors instead of conventional electrolyte solutions. Applications to multilayer capacitors are being actively pursued. 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 polyelectrolytes include the British Polymer Journal (B
r. 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 a metal oxide such as MnO ₂ or MoS ₂ or a metal sulfide as a positive electrode. For example, "Journal of Electrochemical Society (J. Electrochem. Soc.), 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 attracted 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 disposed therebetween for use as a memory backup power supply or the like. . 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, with current electric double-layer capacitors using an electrolyte solution, when the battery is used for a long period of time or abnormalities such as when a high voltage is applied, liquid leakage to the outside of the capacitor is likely to occur. There is a problem with sex. 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 the use of a polyphosphazene-based polymer as an ion-conductive substance for batteries and electric double-layer capacitors. The use of a conductive material has the advantages that the output voltage is higher than that of an inorganic ion conductive material, that the material can be processed into various shapes, and that sealing is simple. However, in this case, the ionic conductivity of the solid polymer electrolyte is 10 ⁻⁴ to 10 ⁻⁶ S / c.
m was not sufficient, and there was a drawback that the takeout current was 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 with a polarizable electrode into a capacitor,
There is also a problem that it is difficult to uniformly composite the carbon material with the carbon material having a large specific surface area due to the mixture of the solids.

[0008] In order to solve these problems, the present inventors have proposed an ionic conductivity using a polymer comprising a (meth) acrylate monomer mixture containing an oxyalkylene group having a urethane bond and a composite comprising an electrolyte. (JP-A-6-187822).
The ionic conductivity of this polymer solid electrolyte is 10 ⁻⁴ S / cm (room temperature) ^without adding a plasticizer, which is a high level.
Further addition of a plasticizer, it becomes room temperature or from 10 ^{@ 3} S / cm or higher even at low temperatures, also improved to the extent that the film quality is also obtained as a free standing film. In addition, this monomer has good polymerizability, and has an advantage in processing when applied to batteries and electric double layer capacitors. However,
The film strength was insufficient, and there was a problem in the film strength particularly when a plasticizer was added to make a thin film.

[0009] The solid polymer electrolyte layer in the battery and the capacitor is responsible only for ion transfer. The thinner the polymer electrolyte layer, the smaller the volume of the whole battery and the capacitor, and the higher the energy density of the battery and the capacitor. Further, when the polymer solid electrolyte layer is thinned, the electric resistance of the battery and the capacitor can be reduced, the takeout current and the charging current can be increased, and the power density of the battery can be improved. Further, corrosion of ions, particularly alkali metal ions, hardly occurs, and the cycle life is improved. Accordingly, there has been a demand for a polymer solid electrolyte having high ionic conductivity which has as good a film strength as possible and which can be made into a thin film.

[0010]

SUMMARY OF THE INVENTION The present invention provides a polymer solid electrolyte which has good strength even when formed into a thin film of about several tens of micrometers, has high ionic conductivity at room temperature and low temperature, and has excellent workability. The purpose is to provide. Another object of the present invention is to develop a primary battery and a secondary battery which can be easily formed into a thin film, can be operated at a high capacity and a high current, and have excellent reliability by using the polymer solid electrolyte. And Also,
An object of the present invention is to provide an electrode having high electrochemical activity and flexibility, and a secondary battery using the same and having good cycleability. Another object of the present invention is to provide an electrode which is used in an electric double layer capacitor, has good polarizability, has good strength when formed into a film, and has good contact with a solid electrolyte. 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.

[0011]

Means for Solving the Problems The present inventors diligently studied to solve the above-mentioned problems, and found that the object can be achieved by further increasing the urethane bonds in the monomer for a solid polymer electrolyte. In the description of the present specification, the expression “oxyalkyl” includes oligooxyalkylene and polyoxyalkylene each containing at least one oxyalkylene group. Furthermore, they have found that the use of this solid polymer electrolyte in a battery improves the problems of the above-described ionic conductivity, membrane strength, workability, and the like. Furthermore, the present inventors use a polarizable material used as a polarizable electrode of an electric double layer capacitor, a carbon material as described below, and a polymer into which an oxyalkyl side chain having a urethane bond is introduced. Accordingly, a polarizable electrode suitable for the capacitor can be obtained without impairing the polarization characteristics of the 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. Furthermore, the present inventors use the above-mentioned polymer solid electrolyte to provide a high output voltage, a large take-out current, workability,
That an electric double layer capacitor with excellent reliability can be obtained,
In particular, they have found that an all-solid-state electric double layer capacitor can be used, and have completed the present invention.

That is, the present invention has achieved the above object by developing the following. 1) In formula _{(1) {CH 2 = C} (R 1) CO [O (CH 2) x (CH (CH 3)) y] z} v R 2 O H ... (1) [ In the formula, R ¹ Represents hydrogen or an alkyl group. R ² is 2
It is an organic chain having a valency or higher, but may not be present when v is 1. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. Where x = 0 and y = 0
In the case of, z = 0. Also, (CH ₂ ) and (CH (CH
₃ )) may be arranged irregularly. However, a plurality of R ¹ in the same molecule and the values of x, y, and z are independent and need not be the same. And a general formula (2) R ³ (—NCO) _k (2) wherein R ³ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. k represents an integer of 1 or more. ] A monomer compound for a solid polymer electrolyte comprising a mixed composition or a reaction product composition thereof. 2) mixing the composition formula ^{(3) {HO- (R 4} O) n -} m R 5 ... (3) [ wherein, R ⁴ are each _{- (CH 2) 2 -,} - CH
(CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) —
And n and m represent an integer of 1 or more. R ⁵ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. ] The monomer compound for a solid polymer electrolyte according to the above 1), which comprises a compound represented by the following formula:

3) General formula (1) {CH ₂ ＣC (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z } _v R ² OH (1) , R ¹ represents hydrogen or an alkyl group. R ² is 2
It is an organic chain having a valency or higher, but may not be present when v is 1. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. Where x = 0 and y = 0
In the case of, z = 0. Also, (CH ₂ ) and (CH (CH
₃ )) may be arranged irregularly. However, a plurality of R ¹ in the same molecule and the values of x, y, and z are independent and need not be the same. And a general formula (2) R ³ (—NCO) _k (2) wherein R ³ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. k represents an integer of 1 or more. A polymer obtained from at least one of a mixed composition containing the compound represented by the formula or a reaction product composition thereof, and / or a copolymer containing the composition or the reaction product composition thereof as a copolymer component, and at least A solid polymer electrolyte composed of a composite containing one type of electrolyte. 4) mixing the composition formula ^{(3) {HO- (R 4} O) n -} m R 5 ... (3) [ wherein, R ⁴ are each _{- (CH 2) 2 -,} - CH
(CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) —
And n and m represent an integer of 1 or more. R ⁵ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. ] The solid polymer electrolyte according to the above item 3), comprising a compound represented by the following formula:

5) The electrolyte according to 3) or 4) above, wherein the electrolyte is at least one selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts.
The solid polymer electrolyte according to the above. 6) The polymer solid electrolyte according to any one of 3) to 5) above, wherein a plasticizer is added to the polymer solid electrolyte containing the electrolyte. 7) A battery using the polymer solid electrolyte according to any one of 2) to 6). 8) The battery according to the above item 7), wherein the negative electrode of the battery is an electrode containing lithium, a lithium alloy, or a carbon material capable of inserting and extracting lithium ions. 9) The battery according to 7) or 8) above, wherein the positive electrode of the battery is an electrode containing a conductive polymer, a metal oxide, a metal sulfide, or a carbon material.

10) General formula (1) {CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z } _v R ² OH (1) , R ¹ represents hydrogen or an alkyl group. R ² is 2
It is an organic chain having a valency or higher, but may not be present when v is 1. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. Where x = 0 and y = 0
In the case of, z = 0. Also, (CH ₂ ) and (CH (CH
₃ )) may be arranged irregularly. However, a plurality of R ¹ in the same molecule and the values of x, y, and z are independent and need not be the same. And a general formula (2) R ³ (—NCO) _k (2) wherein R ³ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. k represents an integer of 1 or more. ] A polymerizable monomer composition containing at least one of a mixed composition or a reaction product composition thereof, and a polymerization obtained by adding a plasticizer thereto A method for producing a battery, comprising: introducing a polymerizable monomer composition into a structure for battery configuration or disposing the polymerizable monomer composition on a support, and polymerizing the polymerizable monomer composition. 11) mixture composition formula ^{(3) {HO- (R 4} O) n -} m R 5 ... (3) [ wherein, R ⁴ are each _{- (CH 2) 2 -,} - CH
(CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) —
And n and m represent an integer of 1 or more. R ⁵ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. ] The method for producing a battery according to the above item 10), comprising a compound represented by the following formula: 12) In an electric double-layer capacitor having a polarizable electrode disposed via an ion-conductive substance, the ion-conductive substance is the solid polymer electrolyte described in any of 2) to 6) above. Double layer capacitor.

13) General formula (1) {CH ₂ ＣC (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z ｝ _v R ² OH (1) , R ¹ represents hydrogen or an alkyl group. R ² is 2
It is an organic chain having a valency or higher, but may not be present when v is 1. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. Where x = 0 and y = 0
In the case of, z = 0. Also, (CH ₂ ) and (CH (CH
₃ )) may be arranged irregularly. However, a plurality of R ¹ in the same molecule and the values of x, y, and z are independent and need not be the same. And a general formula (2) R ³ (—NCO) _k (2) wherein R ³ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. k represents an integer of 1 or more. ] A polymerizable monomer composition containing at least one of a mixed composition or a reaction product composition thereof, and a polymerization obtained by adding a plasticizer thereto A method for producing an electric double-layer capacitor, comprising: introducing a water-soluble monomer composition into a structure for forming an electric double-layer capacitor or disposing the same on a support, and polymerizing the polymerizable monomer composition. 14) mixture composition formula ^{(3) {HO- (R 4} O) n -} m R 5 ... (3) [ wherein, R ⁴ are each _{- (CH 2) 2 -,} - CH
(CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) —
And n and m represent an integer of 1 or more. R ⁵ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. ] The method for producing an electric double layer capacitor according to the above item 13), comprising a compound represented by the following formula:

Hereinafter, the present invention will be described in detail. The monomer used for the polymer solid electrolyte of the present invention is a mixed composition containing the compound represented by the general formula (1) and the compound represented by the general formula (2) or a reaction product composition thereof. Preferably, the mixed composition further contains a compound represented by the general formula (3). Here, the reaction product composition is a reaction between an —OH group in the compound represented by the general formula (1) or (3) and a —NCO group in the compound represented by the general formula (2). It is a mixture of compounds produced by

The compound represented by the general formula (1) (hereinafter referred to as "compound (A)") which is a raw material of the monomer compound for a polymer solid electrolyte of the present invention includes hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and the like. Hydroxyalkyl acrylates such as hydroxyhexyl acrylate, ω-hydroxy-polyoxyethyl methacrylate, ω-hydroxy-polyoxypropyl methacrylate, ω-hydroxy-polyoxyethyl acrylate, ω-hydroxy-polyoxypropyl acrylate, ω-hydroxy-
Poly-co-oxyethyl-oxypropyl methacrylate, ω-hydroxy-poly-co-oxyethyl-oxypropyl acrylate, a reaction product of glycidyl (meth) acrylate represented by the following formula and (meth) acrylic acid

Embedded image [Wherein, R ⁶ and R ⁷ each represent hydrogen or a methyl group. ] And the like.

Among them, ω-hydroxy-polyoxyethyl methacrylate, ω-hydroxy-polyoxypropyl methacrylate, ω-hydroxy-polyoxyethyl acrylate having a molecular weight of about 200 to 1,000,
ω-hydroxy-polyoxypropyl acrylate, ω
-Hydroxy-poly-co-oxyethyl-oxypropyl methacrylate and ω-hydroxy-poly-co-oxyethyl-oxypropyl acrylate are preferred because many oxyalkylene chains can be introduced into the resulting polymer. Further, the larger v in the general formula (1), the higher the crosslink density in the solid polymer electrolyte and the better the film quality.
If it is too large, the ionic conductivity will decrease. Therefore, a preferable value of v is 1 to 6.

As the organic (poly) isocyanate, which is a compound represented by the general formula (2) (hereinafter referred to as "compound (B)"), which is a raw material of the monomer compound for a polymer solid electrolyte of the present invention, various compounds can be mentioned. However, for example, monoisocyanates such as propyl isocyanate, hexyl isocyanate, and benzyl isocyanate, diisocyanates such as diphenylmethane diisocyanate, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate, triisocyanates, and oligomers thereof. No. Of these, aliphatic isocyanates such as propyl isocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate are particularly preferred. Further, as the amount of isocyanate in the compound (B) increases, the crosslink density in the polymer solid electrolyte increases and the film quality improves, but when too large, the ionic conductivity decreases. Therefore, a preferable value of k is 1 to 6.

The compound represented by the general formula (3) (hereinafter referred to as "compound (C)") which can be used as a raw material of the monomer compound for a polymer solid electrolyte of the present invention includes monomethyl polyethylene glycol, monoethyl polypropylene glycol, Monoalkyl polyalkylene glycol such as mono-methyl-co-ethylene glycol-propylene glycol, alkylene glycol such as polyethylene glycol, polypropylene glycol, poly-co-ethylene glycol-propylene glycol, and trihydric alcohol such as glycerin are subjected to addition polymerization of alkylene oxide. Tetraol, such as oxyalkylenetriol and pentaerythritol, to which alkylene oxide has been added and polymerized, and α-D-glucopyranose has alkylene oxide. Addition polymerization was penta, hexaols like obtained by addition polymerization of alkylene oxide to mannitol and the like, can be used instead to obtain the functionality of the target composition, the number of hydroxy.
The molecular weight of these compounds is 350-20,000
Are preferred, and 500 to 10,000 are particularly preferred. The value of m in the general formula (3) is preferably from 1 to 6.

Elements other than carbon, hydrogen and oxygen contained in R ³ in the general formula (2) or R ⁵ in the general formula (3) include nitrogen, sulfur, phosphorus, fluorine, silicon and the like. Is raised.

The polymer in the polymer solid electrolyte of the present invention comprises:
It is obtained by polymerizing a mixed composition of compound (A) and compound (B) or a reaction product composition thereof, or a mixed composition further containing compound (C) or a reaction product composition thereof as a monomer. These compounds (A) to
The reaction (C) can be carried out by a general urethane-forming reaction of a hydroxyl group and an isocyanate group, that is, 20 to
Heat at 100 ° C. for several hours. In order to shorten the reaction time or lower the heating temperature, an Sn catalyst such as dibutyltin dilaurate or an amine catalyst may be used.

When the amounts of the compound (A) and the compound (B) are large, the amount of polymerized and crosslinked components of the polymer increases, and the membrane strength of the polymer solid electrolyte becomes good. And the ionic conductivity decreases. Further, since the compound (C) has a function of improving the thermal kinetic properties of the polymer and the solubility of the electrolyte, the ionic conductivity of the polymer solid electrolyte is improved when the amount of the compound is large. Therefore, as the compounding amount of each compound, the compound (A) is 1 to 60% by weight,
The compound (B) is 1 to 60% by weight, and the compound (C) is 5 to 9% by weight.
A range of 8% by weight is preferred. The polymer used in the polymer solid electrolyte of the present invention belongs to the category even if it is a homopolymer of the composition of the compound (A) and the compound (B) or the composition of the compounds (A) to (C). It may be a copolymer of two or more compositions or a copolymer of at least one of the compositions and another polymerizable compound.

Other polymerizable compounds copolymerizable with the composition of the compound (A) and the compound (B) or the composition of the compounds (A) to (C) are not particularly limited. For example, N-
Compounds having at least one unit represented by the following general formula (4) in one molecule such as methacryloylcarbamic acid ω-methyl oligooxyethyl ester, methacryloyloxyethyl carbamic acid ω-methyl oligooxyethyl ester The compound is referred to as a urethane (meth) acrylate having an oxyalkylene chain.) CH ₂ ＣC (R ⁸ ) CO [O (CH ₂ ) _p (CH (CH ₃ ) _q ] _r NHCOOR ⁹ − (4) , R ⁸ represents hydrogen or a methyl group, and R ⁹ represents a divalent organic group containing an oxyalkylene group, which may have any of a linear, branched, or cyclic structure; One or more elements other than hydrogen and oxygen may be contained, p and q each represent an integer of 0 or 1 to 5, and r represents a numerical value of 0 or 1 to 10, provided that p If 0 and q = 0 is r = 0. Also the (CH ₂₎ (C
H (CH ₃ )) may be arranged irregularly. However, the values of R ⁸ , R ⁹ and p, q, and r in a plurality of units represented by the above general formula (4) in the same molecule are independent of each other and need not be the same. ], (Meth) acrylic esters having an oxyalkylene chain such as methacrylic acid ω-methyl oligooxyethyl ester, methyl (meth) acrylate, alkyl (meth) acrylates such as n-butyl acrylate, acrylamide, methacrylamide,
(Meth) acrylamide compounds such as N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, acryloylmorpholine, methacryloylmorpholine, N, N-dimethylaminopropyl (meth) acrylamide, and styrene such as styrene and α-methylstyrene N-vinyl amide compounds such as N-vinyl acetamide and N-vinyl formamide; and alkyl vinyl ethers such as ethyl vinyl ether. Of these, urethane (meth) acrylate having an oxyalkylene chain, (meth) acryl ester having an oxyalkylene chain, and (meth) acrylamide-based compound are preferably used. Among these, urethane (meth) acrylates having an oxyalkylene chain are particularly preferable in view of the fact that more urethane groups and oxyalkylene groups can be introduced into the polymer.

For the polymerization and copolymerization, a general method utilizing the polymerizability of an acryloyl group or a methacryloyl group in the monomer compound can be employed. That is, a radical thermal polymerization catalyst such as azobisisobutyronitrile and benzoyl peroxide, benzophenone and 2,2-dimethoxy- are added to these monomers alone or a mixture of these monomers and the above-mentioned copolymerizable polymerizable compound. Radical ultraviolet polymerization catalysts such as benzophenone and benzyl methyl ketal, aminophenyl ketones, β-
Radical visible light polymerization catalyst such as diketones, CF ₃ CO
Radical polymerization, cationic polymerization or anionic polymerization can be performed using a cationic polymerization catalyst such as a protonic acid such as OH, a Lewis acid such as BF ₃ or AlCl ₃ , or an anionic polymerization catalyst such as butyllithium, sodium naphthalene, or lithium alkoxide. it can. Further, when the total content of the compounds (A) to (C) exceeds 20% by weight with respect to the total monomer weight, it is only necessary to raise the temperature to 70 ° C. or more under anoxic condition. Polymerization can be performed.

It is also possible to polymerize such a polymerizable monomer mixture after forming it into a film or the like. A polymer obtained from at least one of the compositions (compound (C) may be omitted, the same applies hereinafter) composed of compounds (A) to (C) and / or a copolymer containing the compound as a copolymer component, When the polymerizable solid electrolyte is used as a polymer of the present invention, it is particularly advantageous to polymerize the polymerizable monomer mixture after forming the film. That is, compound (A)
(C) and at least one electrolyte such as an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt or a transition metal salt. A compound and / or 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, the film is polymerized by, for example, heating and / or irradiation of electromagnetic waves such as light to form a film-like polymer. This is a great advantage in application.

When a solvent is used in the polymerization, any solvent may be used as long as it does not inhibit the polymerization, for example, tetrahydrofuran, acetonitrile, toluene, etc., depending on the type of monomer and the presence or absence of a polymerization catalyst. it can. As the temperature for polymerization, compounds (A) to
Depending on the type of the composition comprising (C), the temperature may be any temperature at which polymerization occurs, and usually, it may be carried out in the range of 0 ° C to 200 ° C. In the case of polymerizing by electromagnetic wave irradiation, depending on the type of the composition comprising the compounds (A) to (C), for example, the polymer is polymerized by irradiating ultraviolet light, visible light, γ-ray, electron beam or the like of several mW or more. be able to.

The polymer used for the solid polymer electrolyte of the present invention is a polymer obtained from at least one of the compositions comprising the compounds (A) to (C) and / or a copolymer containing the compound as a copolymer component. And another polymer. For example, a polymer obtained from at least one of the compositions consisting of the compounds (A) to (C) and / or a copolymer containing the compound as a copolymer component, polyethylene oxide, polyacrylonitrile, polybutadiene, polymethacryl (or A mixture with a polymer such as acrylate), polystyrene, polyphosphazenes, polysiloxane or polysilane may be used for the solid polymer electrolyte of the present invention. In this case, compounds (A) to (C)
It is desirable that the amount of the copolymer having the composition comprising as a copolymer component be 50% by weight or more based on the total amount of the polymer used for the solid polymer electrolyte. When the structural unit derived from the composition consisting of the compounds (A) to (C) is in the above-specified amount range, the polymer can sufficiently exhibit membrane strength, and the ionic conductivity of the polymer solid electrolyte can be improved. The degree is also large.

It is preferable to add a low molecular compound as a plasticizer to the solid polymer electrolyte of the present invention since the ionic conductivity of the solid polymer electrolyte is further improved. As the plasticizer that can be used, a compound having good compatibility with the composition monomer used for the polymer solid electrolyte of the present invention, a large dielectric constant, a boiling point of 70 ° C. or higher, and a wide electrochemical stability range is suitable. ing. 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, dimethyl carbonate, diethyl carbonate, vinylene carbonate, (meth) acryloyl carbonate, and benzo. Aromatic nitriles such as nitrile and tolunitrile; sulfur compounds such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone, and sulfolane; and phosphate esters. Among them, oligoethers and carbonates are preferable,
Carbonates are particularly preferred.

Although the ionic conductivity of the solid polymer electrolyte increases as the amount of the plasticizer added increases, the mechanical strength of the solid polymer electrolyte decreases when the amount is too large. The preferred addition amount is 6 times or less the weight of the composition monomer used for the polymer solid electrolyte of the present invention. Further, a composition comprising compounds (A) to (C) using a polymerizable compound such as vinylene carbonate, (meth) acryloyl carbonate, or N-vinylpyrrolidone as a plasticizer in combination with a non-polymerizable plasticizer. By copolymerizing with, without reducing the mechanical strength,
It is preferable because the amount of the plasticizer added can be increased to improve the ionic conductivity.

The composite ratio of the electrolyte in the solid polymer electrolyte of the present invention is preferably in the range of 0.1 to 50% by weight,
0% by weight is particularly preferred. If the amount of the electrolyte used for the composite is too large, the movement of ions is greatly inhibited. 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 an electric charge may be used. (CH ₃ )
₄ quaternary ammonium salts NBF _4, etc., (CH _{3) 4} PB
A quaternary phosphonium salt such as F _4, a transition metal salt such as AgClO ₄ , or a protic acid such as hydrochloric acid, perchloric acid, or borofluoric acid is recommended.

As the negative electrode active material used in the battery of the present invention, an alkali metal, an alkali metal alloy,
The use of a material having a low oxidation-reduction potential using an alkali metal ion such as a carbon material as a carrier and a mixture thereof are preferable because a high-voltage and high-capacity battery can be obtained. Therefore, when such a negative electrode is used in a battery using an alkali metal ion as a carrier, an alkali metal salt is required as an electrolyte in the solid polymer electrolyte. As the kind of the alkali metal salt, for example, LiCF ₃ S
O ₃ , LiPF ₆ , LiClO ₄ , LiI, LiBF
_{4, LiSCN, LiAsF 6, NaCF} 3 SO 3, Na
PF ₆ , NaClO ₄ , NaI, NaBF ₄ , NaAs
F ₆ , KCF ₃ SO ₃ , KPF ₆ , KI and the like can be mentioned. 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 the 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 contain ions which are large and easily form a polarizable electrode and an electric double layer. Such compounds include (CH ₃ ) ₄
Quaternary ammonium salts such as NBF ₄ , (CH ₃ CH ₂ ) ₄ ClO ₄ , transition metal salts such as AgClO ₄ , (CH ₃ ) ₄
Quaternary phosphonium salts such as PBF ₄ , LiCF ₃ SO ₃ ,
LiPF ₆ , LiClO ₄ , LiI, LiBF ₄ , Li
SCN, LiAsF ₆ , NaCF ₃ SO ₃ , NaPF
₆ , NaClO ₄ , NaI, NaBF ₄ , NaAsF
₆ , alkali metal salts such as KCF 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 in that the output voltage can be increased and the dissociation constant is large. 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 , have a large solubility or dissociation constant in the solid polymer electrolyte. preferable.

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. In addition, the carbon material is particularly preferable because 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, a high oxidation-reduction potential electrode active material (positive electrode active material) such as a metal oxide, a metal sulfide, a conductive polymer or a carbon material, or a mixture thereof is used for the positive electrode. This is preferable because a high-voltage, high-capacity battery can be obtained. Among such electrode active materials, metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, molybdenum oxide, molybdenum sulfide, and sulfide Metal sulfides such as titanium 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. The method for producing the metal oxide or metal sulfide in this case is not particularly limited, and for example, "Electrochemistry, Vol. 22,
574, 1954 "by a general electrolytic method or a heating method. Further, when these are used in a lithium battery as an electrode active material, for example, Li _x CoO ₂ or Li _x MnO ₂
It is preferable to use the Li element inserted (composite) into the metal oxide or metal sulfide in such a form. As described above, the method of inserting the Li element is not particularly limited. For example, a method of electrochemically inserting Li ions and a method of US Pat.
Li ₂ CO ₃ , as described in US Pat.
Can be carried out by mixing and heat-treating such a salt with a metal oxide.

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

Examples of the carbon material include natural graphite, artificial graphite, vapor-grown graphite, petroleum coke, coal coke, fluorinated graphite, pitch-based carbon, and polyacene. Further, 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 positive electrode active material in the electrode or battery of the present invention is advantageous because molding can be performed by solution coating, and is extremely advantageous in the case of producing a thin film battery. Examples of the aniline-based polymer include polyaniline, poly-o-toluidine, poly-m-
Toluidine, poly-o-anisidine, poly-m-anisidine, polyxylidines, poly-2,5-dimethoxyaniline, poly-2,6-dimethoxyaniline, poly-
2,5-diethoxyaniline, poly-2,6-diethoxyaniline, poly-o-ethoxyaniline, poly-m-
Examples thereof include ethoxyaniline and a copolymer thereof, but are not particularly limited thereto, and may be 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-based polymers include, for example, polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-anisidine, poly-m-anisidine, and polyxylidines.

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 comprises, for example, a composition comprising the compounds (A) to (C), and optionally further adding another polymerizable compound and / or a plasticizer to the electrode active material (the positive electrode active material). Material or negative electrode active material). In that case, the ratio of each component to be mixed is
It is 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 can be performed by the same polymerization method as in the case of obtaining a polymer from the composition comprising the compounds (A) to (C). For example, the polymerization can be performed by heating and / or irradiation with electromagnetic waves. it can. As in the case of the electrode active material, for example, an organic solvent-soluble aniline-based polymer,
When a polymerizable monomer / electrode active material mixture having a high fluidity is provided, the mixture is applied to a current collector or another support such as glass to form a film, and then molded, and then polymerized. To produce an electrode.

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 the 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 an end of the electrode via a spacer having an appropriate thickness, and the resultant structure is placed in the structure. Next, compounds (A) to
It was prepared by mixing the composition comprising (C) and at least one electrolyte selected from the above-mentioned electrolytes such as alkali metal salts, and optionally adding and mixing other polymerizable compounds and / or plasticizers. After injecting the polymerizable monomer mixture, for example, polymerization by heating and / or irradiation with electromagnetic waves is performed, and a polymer obtained from the composition comprising the compounds (A) to (C) and / or a copolymerization component of the compound is obtained. By polymerizing in the same manner as the polymerization method in the case of obtaining a copolymer to be, or, further, if necessary after the polymerization, by sealing with a polyolefin resin, an insulating resin such as an epoxy resin, the electrode and A battery with good contact with the electrolyte is obtained.

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. It is not limited to what is, and its shape is
It may be cylindrical, box-shaped, sheet-shaped or any other shape. As described above, by polymerizing a mixture obtained by mixing a monomer mixture containing the composition comprising the compounds (A) to (C) with at least one electrolyte, the compounds (A) to (C) are polymerized. When a method for producing a polymer solid electrolyte comprising a polymer obtained from a composition comprising and / or a copolymer containing the compound as a copolymer component and at least one electrolyte is used to produce a thin film battery Especially useful for:

FIG. 1 is a schematic sectional view of an example of a thin-film solid-state secondary battery as an example of the battery of the present invention thus manufactured. In the figure, 1 is a positive electrode, 2 is a solid polymer electrolyte, 3
Denotes an anode, 4 denotes a current collector, 5 denotes an insulating resin film serving as a spacer, and 6 denotes an insulating resin sealant. In the case of manufacturing a wound type battery, the above-described positive electrode and negative electrode are pasted together through a previously prepared polymer solid electrolyte sheet, wound, and inserted into a battery structure, and then the polymerizable monomer is further added. 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. 2 is a schematic sectional view of an example of the solid electric double layer capacitor of the present invention. This example is 1cm in size
A thin cell having a size of about 1 mm and a thickness of about 0.5 mm, 8 is a current collector, and a pair of polarizable electrodes 7 is disposed inside the current collector, and a solid polymer electrolyte membrane 9 is disposed therebetween. Have been. 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.

It is preferable that the current collector 8 be made of a material having electron conductivity, electrochemical corrosion resistance, and as large a specific surface area 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 any electrode made of a polarizable material such as a carbon material usually used for an electric double layer capacitor. However, it is preferable that the carbon material is combined with the polymer solid electrolyte of the present invention. The carbon material as the polarizable material is not particularly limited as long as it has a large specific surface area. For example, carbon blacks such as furnace black, thermal black (including acetylene black), and channel black; activated carbon such as coconut charcoal; natural graphite; artificial graphite; so-called pyrolytic graphite produced by a gas phase method; mention may be made of _60, C _70.

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 a composition comprising the compounds (A) to (C) and at least one electrolyte, the composition comprises the compounds (A) to (C). The method for producing a composite containing a polymer obtained from the composition and / or a copolymer containing the compound as a copolymer component and at least one electrolyte is particularly suitable for producing the solid electric double layer capacitor of the present invention. Useful. Preferably used in the solid electric double layer capacitor of the present invention,
When manufacturing a polarizable electrode including a polymer obtained from at least one of polarizable materials such as a carbon material and / or a copolymer having the compound as a copolymer component, first, for example, the compounds (A) to (A) are used. The composition comprising (C) is mixed with a polarizable material, if necessary, with the addition of 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 capacitor. After forming the polymerizable monomer / polarizable material mixture thus obtained on a support, for example, a current collector, the compound (A) may be polymerized by heating and / or irradiation with electromagnetic waves. A polarizable electrode is produced by polymerizing by a method similar to the polymerization method for obtaining a polymer obtained from the composition comprising (C) to (C) and / or a copolymer containing the compound as a copolymer component. 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 put in a structure for forming a capacitor so as not to contact 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,
It is put in the above-mentioned structure, and then, between the two polarizable electrodes, a composition comprising the compounds (A) to (C) and an electrolyte are mixed, and in some cases, another polymerizable compound and / or After injecting a polymerizable monomer mixture prepared by adding and mixing a plasticizer, by polymerizing in the same manner as described above, or further, if necessary after polymerization, a polyolefin resin, an insulating resin such as an epoxy resin, or the like. By sealing, an electric double layer capacitor in which the electrode and the electrolyte are in good contact is obtained. When preparing such a polymerizable monomer mixture, the ratio of each component to be mixed is determined to be appropriate for the intended capacitor. By this method, a particularly thin all-solid-state electric double layer capacitor can be manufactured. The structure for forming the capacitor or the support may be a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. It is not limited to, and its shape is
It may be cylindrical, box-shaped, sheet-shaped or any other shape.

As the shape of the electric double layer capacitor, in addition to the sheet type as shown in FIG. 2, a coin type or a sheet-like laminate of a polarizable electrode and a solid polymer electrolyte is wound into a cylindrical shape, and a cylindrical tubular shape is obtained. Put in the structure for capacitor construction,
It may be a cylindrical type or the like manufactured by sealing. In the case of manufacturing a wound capacitor, the above-mentioned polarizable electrode is bonded through a polymer solid electrolyte sheet prepared in advance, wound, and inserted into the capacitor structure, and then the polymerizable monomer mixture is further added. Is injected and polymerized.

[0048]

The solid polymer electrolyte of the present invention is, as described above,
Easy film formation from the polymerizable monomer mixture that is the raw material,
A highly ion-conductive solid electrolyte consisting of a comb-type polymer or a network-like polymer with an oxyalkyl group having a urethane bond that can be compounded introduced into the side chain, with good film strength and excellent thin film processability. I have. The battery of the present invention is a highly reliable battery that can be easily processed into a thin film by using the polymer solid electrolyte as an ion conductive material, does not cause a short circuit even in a thin film, has a large take-out current, and has high reliability. In particular, an all-solid-state battery can be used. Also,
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 processed into a thin film by using the polymer solid electrolyte as an ion conductive material. The battery is easy to use, does not cause a short circuit even in the case of a thin film, has a large take-out current, and has high reliability. In particular, it can be an all solid-state battery.

Further, the positive electrode of the present invention is preferably prepared by using the compound (A)
To (C) and / or a copolymer containing the compound as a copolymer component and an organic solvent-soluble aniline polymer or other conductive polymer;
A battery comprising an electrode containing an active material such as a metal oxide, a metal sulfide or a carbon material, and using the polymer solid electrolyte as an electrolyte, is easy to process such as thinning, and short-circuiting even in a thin film. There is no fear, the take-out current is large, the capacity is high, and the battery is highly reliable. In particular, an all-solid-state battery can be used. 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-like polymer or a network-like polymer in which an oxyalkyl group having a urethane bond is 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,
Good contact between the polarizable electrode and the solid polymer electrolyte, which is an ion-conductive substance, has no short circuit even in a thin film.
Provided is an electric double layer capacitor having a high output voltage and a large take-out current and having high reliability, and particularly an all-solid-state electric double layer capacitor.

[0051]

The present invention will be described more specifically with reference to representative examples. These are merely examples for explanation, and the present invention is not limited to these. Example 1 <Preparation of Monomer Composition 1> In a nitrogen atmosphere, 16.8 g (0.1 mol) of hexamethylene diisocyanate (HMDI) and 0.05 g of dibutyltin dilaurate are dissolved in 500 cc of purified THF and stirred at 50 ° C. This solution has an average molecular weight of 60
0 dehydrated polyethylene glycol (PEG600)
A solution of 30 g (0.05 mol) dissolved in 100 cc of purified THF was added over about 1 hour. Thereafter, the reaction was carried out at 50 ° C. for 2 hours to obtain a reaction product of HMDI / PEG600 (2/1). The solution was then cooled to 10 ° C. and 11.6 g of dehydrated 2-hydroxyethyl acrylate (abbreviated as HEA, MEHQ 100 ppm additive) in dry air.
0.05 g of dibutyltin dilaurate was added, stirred for 20 hours, reacted, and then THF was distilled off to obtain HEA / HMDI / PE as a monomer composition 1.
The G600 (2/2/1) reaction was obtained as a viscous liquid.

<Preparation and Evaluation of Monomer Composition 1-Based Polymer Solid Electrolyte> 1.50 g of monomer composition 1, 2.00 g of ethylene carbonate (EC), and propylene carbonate (P
C) 1.00 g, LiClO ₄ 0.30 g, Irgacure 50
0 (manufactured by Ciba-Geigy) in an argon atmosphere, and thoroughly mixed to obtain a monomer composition 1 / EC / PC / LiClO.
_Four photopolymerizable mixed solutions were obtained. Aluminized PET film (30 μm) is applied to this photopolymerizable solution under an argon atmosphere.
After coating with a coater to a thickness of 30 μm on alumina, a polymer solid electrolyte layer was formed by irradiating a mercury lamp for 10 seconds, and then a polypropylene film (30 μm) was formed on the polymer solid electrolyte layer. Are stacked,
After irradiating with a mercury lamp for further 10 minutes, the polymer composition 1 / EC / PC / L, which is a kind of the monomer composition 1-based polymer solid electrolyte, is peeled off from the upper and lower films.
iClO ₄ was obtained as a transparent free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, 1 × 10 ⁻³ , 2
× 10 ^-4 S / cm.

Example 2 A polymer composition 1 / EC / TG / was prepared in exactly the same manner as in Example 1 except that tetraglyme (TG) was used instead of propylene carbonate.
LiClO ₄ was obtained as a transparent free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, 8 × 10 ⁻⁴ ,
It was 1 × 10 ⁻⁴ S / cm.

Example 3 A polymer composition 1 / E was prepared in the same manner as in Example 1 except that diethyl carbonate (DEC) was used instead of propylene carbonate.
C / DEC / LiClO ₄ was obtained as a transparent free-standing film of about 30 μm. The ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method and found to be 8 × 10 ⁻⁴ and 1 × 10 ⁻⁴ S / cm.

Example 4 <Preparation of Monomer Composition 2> In a nitrogen atmosphere, 8.4 g (0.05 mol) of hexamethylene diisocyanate (HMDI) and 0.02 g of dibutyltin dilaurate were dissolved in 300 cc of purified THF. Stir. This solution has an average molecular weight of 55
27.5 g (0.05 mol) of dehydrated polyethylene glycol methyl ether (MPEG550) in 200 cc of purified T
The solution dissolved in HF was added over about 1 hour. Thereafter, by reacting at 50 ° C. for 2 hours, HMDI / MP
A reaction product of EG550 (1/1) was obtained. The solution was then cooled to 10 ° C. and dried in dry air with dehydrated 2-hydroxyethyl acrylate (abbreviated HEA, MEHQ1
5.8g, dibutyltin dilaurate
0.02 g was added and reacted by stirring for 20 hours.
By distilling off HF, a monomer composition 2 was obtained.
The HEA / HMDI / MPEG550 (1/1/1) reaction was obtained as a viscous liquid.

<Preparation and Evaluation of Monomer Composition (1 + 2) -Based Polymer Solid Electrolyte> Monomer composition 1 0.70 g, monomer composition 2 0.80 g, ethylene carbonate (EC) 2.0
0g, Propylene carbonate (PC) 1.00g, LiPF
₆ 0.35g, Irgacure 500 (Ciba-Geigy)
0.02 g was mixed well in an argon atmosphere, and (monomer composition 1 + monomer composition 2) / EC / PC / LiPF ₆
A photopolymerizable mixed solution was obtained. This photopolymerizable solution was coated on an alumina-deposited PET film (30 μm) in an argon atmosphere to a thickness of 30 μm using a coater.
After irradiating the mercury lamp for 10 seconds to form a polymer solid electrolyte layer, a polypropylene film (30 μm) is laminated on the polymer solid electrolyte layer, and after further irradiating the mercury lamp for 10 minutes, the upper and lower layers are irradiated. The polymer composition (1 + 2) / E, which is a kind of the monomer composition (1 + 2) -based solid polymer electrolyte, is peeled off from the film of (1).
C / PC / LiPF ₆ was obtained as a transparent free standing film of about 30 μm. The ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method.
× 10 ⁻³ and 5 × 10 ⁻⁴ S / cm.

Example 5 <Preparation of Monomer Composition 3> 8.5 g (0.1 mol) of n-propyl isocyanate (NPI) and 0.02 g of dibutyltin dilaurate were dissolved in 300 cc of purified THF in a dry air atmosphere. Cool to 0 ° C and stir. To this solution was added a solution prepared by dissolving 38.0 g (0.10 mol) of dehydrated polypropylene glycol methacrylate having an average molecular weight of 380 (PPGMA380, MEHQ 800 ppm additive) in 200 cc of purified THF over about 30 minutes. Thereafter, the mixture was stirred for 20 hours, and then THF was distilled off to obtain a PPGMA380 / NPI (1/1) reactant as a monomer composition 3 as a viscous liquid.

<Preparation of Monomer Composition 4> 16.8 g of hexamethylene diisocyanate (HMDI) in a nitrogen atmosphere
(0.1 mol) and 0.05 g of dibutyltin dilaurate are dissolved in 500 cc of purified THF and stirred at 50 ° C. Dehydrated polyethylene glycol having an average molecular weight of 600 (P
A solution of 30 g (0.05 mol) of EG600 in 100 cc of purified THF was added over about 1 hour. Thereafter, the mixture was reacted at 50 ° C. for 2 hours to obtain HMDI / PEG600.
A reaction product of (2/1) was obtained. The solution was then cooled to 10 ° C. and dried in dry air with a dehydrated polypropylene glycol methacrylate (PPGMA having an average molecular weight of 380).
380, MEHQ 800ppm additive) 38.0g (0.10mo
l), 0.05 g of dibutyltin dilaurate was added, and 20
The mixture was stirred for a period of time to react, and then THF was distilled off to obtain PPGMA380 / H as a monomer composition 4.
The MDI / PEG600 (2/2/1) reaction was obtained as a viscous liquid.

<Preparation and Evaluation of Monomer Composition (3 + 4) -Based Polymer Solid Electrolyte> Monomer composition 3 0.70 g, monomer composition 4 0.80 g, ethylene carbonate (EC) 2.0
0g, Propylene carbonate (PC) 1.00g, LiPF
₆ 0.35g, Irgacure 500 (Ciba-Geigy)
0.02 g was mixed well in an argon atmosphere, and (monomer composition 3 + monomer composition 4) / EC / PC / LiPF ₆
A photopolymerizable mixed solution was obtained. This photopolymerizable mixed solution was mixed with an alumina-deposited PET film (30 μm) under an argon atmosphere.
m) was coated on a 30 μm-thick alumina using a coater, and irradiated with a mercury lamp for 10 seconds to form a polymer solid electrolyte layer. 30 μm), irradiate with a mercury lamp for further 10 minutes, and peel off from the upper and lower films to obtain the monomer composition (3+
4) A polymer composition (3) which is a kind of solid polymer solid electrolyte
+4) / EC / PC / LiPF ₆ was obtained as a transparent free-standing film of about 30 μm. 25 ° C of this film, -2
When the ionic conductivity at 0 ° C. was measured by the impedance method, it was 2 × 10 ⁻³ and 7 × 10 ⁻⁴ S / cm.

Example 6 Instead of LiPF ₆ , NaC
Except for using 0.40 g of F ₃ SO ₃ ,
The solid polymer electrolyte was obtained as a transparent free-standing film of about 30 μm. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 3 × 10 ⁻³ S / cm.

Example 7 In place of LiPF ₆ , 0.50 g
In the same manner as in Example 5 except that tetraethylammonium tetrafluoroborate was used, a solid polymer electrolyte was obtained as a transparent free-standing film of about 40 μm. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 2 × 10 ⁻³ S / cm.

Example 8 CH ₃ (OCH ₂ CH ₂ ) _m OH + CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ NCO (Compound 1) (Compound 2) → CH ₃ (OCH ₂ CH ₂ ) _m OCONHCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (Compound 3)

<Synthesis of Compound 3> According to the above formula, 55 g of Compound 1 (average molecular weight Mn = 550) and 15.5 g of Compound 2 were dissolved in 100 ml of well-purified THF in a nitrogen atmosphere.
0.66 g of dibutyltin dilaurate are added. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a colorless viscous liquid. From the results of ¹ H-NMR, IR, and elemental analysis, compound 1 and compound 2 reacted one-to-one, the isocyanate group of compound 2 disappeared, and a urethane bond was formed. It turned out that it was generating.

<(Compound 3 + Monomer Composition 4) Preparation and Evaluation of Copolymer-Based Solid Polymer Electrolyte>
Monomer composition 4 0.80 g, ethylene carbonate (E
C) 2.00 g, propylene carbonate (PC) 1.00 g,
0.35 g of LiPF _{6 and} 0.02 g of Irgacure 500 (manufactured by Ciba-Geigy) are mixed well in an argon atmosphere, and (compound 3 + monomer composition 4) / EC / PC / LiPF ₆
A photopolymerizable mixed solution was obtained. This photopolymerizable mixed solution was mixed with an alumina-deposited PET film (30 μm) under an argon atmosphere.
m) was coated on a 30 μm-thick alumina using a coater, and irradiated with a mercury lamp for 10 seconds to form a polymer solid electrolyte layer. (Compound 3 + monomer composition 4), which is a kind of (compound 3 + monomer composition 4) copolymer type polymer solid electrolyte, by irradiating with a mercury lamp for further 10 minutes and peeling off from the upper and lower layer films. 4) Copolymer / EC / PC / L
iPF ₆ was obtained as a transparent free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, 2 × 10 ⁻³ , 8
× 10 ^-4 S / cm.

[Embodiment 9]

Embedded image <Preparation of Monomer Composition 5> Compound 6 was synthesized from compound 4 and compound 5 according to the method described in JP-A-8-62838. In a nitrogen atmosphere, 16.8 g (0.1 mol) of hexamethylene diisocyanate (HMDI) and 0.05 g of dibutyltin dilaurate are dissolved in 500 cc of purified THF.
Stir at 50 ° C. To this solution was added dehydrated polypropylene glycol having an average molecular weight of 425 (PPG425) 21.
A solution of 5 g (0.05 mol) dissolved in 100 cc of purified THF is
The addition took about 1 hour. Thereafter, the reaction was performed at 50 ° C. for 2 hours to obtain a reaction product of HMDI / PPG425 (2/1). The solution was then cooled to 10 ° C. and dried in dry air to give 21.4 g of compound 6 (HQ 1000 ppm additive).
(0.10 mol) and 0.05 g of dibutyltin dilaurate were added thereto, and the mixture was stirred and reacted for 20 hours. Then, THF was distilled off to obtain a compound 6 / H as a monomer composition 5.
The MDI / PPG425 (2/2/1) reaction was obtained as a viscous liquid.

<Preparation and Evaluation of Monomer Composition 5-Based Polymer Solid Electrolyte> Monomer composition 5 1.50 g, ethylene carbonate (EC) 2.00 g, propylene carbonate (P
C) 1.00 g, LiPF ₆ 0.35 g, Irgacure 500
0.02 g (manufactured by Ciba-Geigy) was mixed well in an argon atmosphere to obtain a monomeric composition 5 / EC / PC / LiPF ₆ photopolymerizable mixed solution. This photopolymerizable mixed solution is subjected to alumina deposition PET film (30 μm) under an argon atmosphere.
After coating with a coater to a thickness of 30 μm on alumina, a polymer solid electrolyte layer was formed by irradiating a mercury lamp for 10 seconds, and then a polypropylene film (30 μm) was formed on the polymer solid electrolyte layer. Are stacked,
The polymer composition 5 / EC / PC / L, which is a kind of the monomer composition 5 type polymer solid electrolyte, is peeled off from the upper and lower layers after irradiating with a mercury lamp for 10 minutes.
iPF ₆ was obtained as a transparent free-standing film of about 20 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, 1 × 10 ⁻³ , 1
× 10 ^-4 S / cm.

Example 10 NK ester M-230G
(Shin-Nakamura Chemical Co., Ltd.) 0.70g, monomer composition 4
0.80 g, ethylene carbonate (EC) 2.00 g, propylene carbonate (PC) 1.00 g, LiPF ₆ 0.35 g,
0.02 g of Irgacure 500 (manufactured by Ciba Geigy) was mixed well in an argon atmosphere to obtain a (M-230G + monomer composition 4) / EC / PC / LiPF ₆ photopolymerizable mixed solution. This photopolymerizable mixed solution is placed under an argon atmosphere,
After applying a 30 μm-thick film onto alumina of an alumina-deposited PET film (30 μm) using a coater, a mercury lamp is irradiated for 10 seconds to form a polymer solid electrolyte layer. A polypropylene film (30 μm) is laminated from above, irradiated with a mercury lamp for further 10 minutes, and then peeled off from the upper and lower films to form a kind of monomer composition 4 type polymer solid electrolyte (M-230G + polymer composition) Product 4) / EC / PC
/ LiPF ₆ as a transparent free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, it was 1.5 × 1
0 ^-3 and 8 × 10 ^-4 S / cm.

Example 11 <Preparation and Evaluation of Monomer Composition (3 + 4) -Based Polymer Solid Electrolyte> Monomer Composition 30 0.70 g, Monomer Composition 4
0.80 g, ethylene carbonate (EC) 2.00 g, propylene carbonate (PC) 1.00 g, LiPF ₆ 0.35 g,
0.003 g of AIBN is mixed well in an argon atmosphere,
(Monomer composition 3 + monomer composition 4) / EC / PC
/ LiPF ₆ thermopolymerizable mixed solution was obtained. After applying this thermopolymerizable mixed solution to a thickness of 100 μm using a coater in a 10 μm × 10 cm frame of polyimide 100 μm on a glass substrate under an argon atmosphere, further cover the glass plate,
By heating at 80 ° C. for 30 minutes, the polymer composition (3 + 4) / EC / PC / LiPF ₆ , which is a kind of the monomer composition (3 + 4) -based solid polymer electrolyte, is converted to about 100 μm.
As a transparent free-standing film. 25 of this film
When the ionic conductivity at -20 ° C. and -20 ° C. was measured by an impedance method, they were 1.5 × 10 ⁻³ and 7 × 10 ⁻⁴ S / cm.

Example 12 <Production of Lithium Cobaltate Cathode> 11 g of Li ₂ CO ₃
And 24 g of Co ₃ O ₄ are mixed well, and the mixture is
After heating at 0 ° C. for 24 hours, pulverization is performed to obtain LiCoO.
_Two powders were obtained. The LiCoO ₂ powder, acetylene black, and polyvinylidene fluoride were mixed at a weight ratio of 8: 1: 1, and an excess N-pyrrolidone solution was added to obtain a gel composition. This composition was placed on an aluminum foil of about 25 μm in a thickness of 1
It was applied and molded to a size of cm × 1 cm and a thickness of about 200 μm. Furthermore, by heating and vacuum drying at about 100 ° C. for 24 hours, a lithium cobaltate positive electrode (80 mg) was obtained.

Example 13 <Production of Li secondary battery> A 75 μm-thick lithium foil was cut into 1 cm × 1 cm (5.3 mg) in an argon atmosphere glove box, and about 1 mm on each end thereof was filled with 5 μm polyimide. The film was coated as a spacer. Next, an electrolytic solution (1.5 mol / l LiPF ₆ / (PC + E
C (weight ratio 1: 2))) and a thin film of the polymer solid electrolyte film (12 mm × 12 mm) prepared in Example 5
On a lithium foil, and further impregnated the lithium cobaltate positive electrode (10 mm × 10 mm) produced in Example 12 with an electrolyte solution (1.5 mol / l LiPF ₆ / (PC + EC (weight ratio 1: 2))). Then, the battery ends were sealed with an epoxy resin to obtain a lithium / cobalt oxide secondary battery. FIG. 1 shows a cross-sectional view of the obtained battery. This battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.3 mA. The maximum discharge capacity was 7.0 mAh and the capacity was 50%.
The cycle life until it decreased to 110 was 110.

Example 14 <Production of Graphite Negative Electrode> MCMB graphite (manufactured by Osaka Gas), vapor phase graphite fiber (manufactured by Showa Denko KK; average fiber diameter: 0.3 μm,
An excess N-pyrrolidone solution was added to a mixture (average fiber length: 2.0 μm, heat treated at 2700 ° C.) and polyvinylidene fluoride (weight ratio: 8.6: 0.4: 1.0) to obtain a gel composition.
This composition was placed on a copper foil of about 15 μm in a size of 1 cm × 1 cm, about 25 cm.
It was applied and molded to a thickness of 0 μm. Further, by heating and vacuum drying at about 100 ° C. for 24 hours, a graphite negative electrode (30 m
g) was obtained.

[Example 15] <Production of Li-ion secondary battery> An electrolyte (1.5 mol / l Li-ion)
PF ₆ / (PC + EC (weight ratio 1: 2))), except that a material impregnated with graphite /
A lithium cobaltate-based Li-ion secondary battery was obtained. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.3 mA, the maximum discharge capacity was 6.9 mAh and the capacity was 50%.
The cycle life before decreasing to 270 was 270 times.

Example 16 <Manufacture of Solid Lithium Secondary Battery> In an argon atmosphere glove box, a lithium foil having a thickness of 75 μm was 1 cm × 1.
C. (5.3 mg), and about 1 mm square of the end was covered with a polyimide film of 5 .mu.m as a spacer. Next, the thermopolymerizable mixed solution prepared in Example 11 was thinly applied on a lithium foil, the solid polymer electrolyte film prepared in Example 5 was laminated thereon, and the cobalt acid solution prepared in Example 12 was further applied. Lithium positive electrode (10mm × 10m
m) impregnated with the polymerizable mixed solution prepared in Example 11 was adhered thereto, heated at 80 ° C. for 30 minutes to polymerize the polymerizable mixed solution, and then sealed at the battery end with an epoxy resin.
A lithium / cobalt acid solid lithium secondary battery was obtained.
When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 6.8 mAh and the capacity was 5
The cycle life before decreasing to 0% was 230 times.

Example 17 <Production of Solid Li-Ion Secondary Battery> Example 15 was repeated except that the graphite negative electrode produced in Example 14 was impregnated with the polymerizable mixed solution prepared in Example 11. In the same way as
A graphite / lithium cobaltate-based solid Li-ion secondary battery was obtained. When the battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 6.8 mAh, and the cycle life until the capacity was reduced to 50% was 410 times.

Example 18 <Production of Activated Carbon Electrode> An excess N-pyrrolidone solution was added to a mixture of coconut palm activated carbon and polyvinylidene fluoride at a weight ratio of 9.0: 1.0 to obtain a gel composition. . This composition was placed on a stainless steel foil in a size of 1 cm × 1 cm in a size of about 150 mm.
It was applied to a thickness of μm. After vacuum drying at about 100 ° C. for 10 hours, an activated carbon electrode (14 mg) was obtained.

Example 19 <Production of Solid Electric Double Layer Capacitor> In an argon atmosphere glove box, about 1 mm × 1 cm of the activated carbon electrode (14 mg) produced in Example 18 was applied with a thickness of 5 mm on each side.
Two electrodes coated with a μm polyimide film and impregnated with the polymerizable mixed solution prepared in Example 11 were prepared. Next, the polymer solid electrolyte film (1
2 mm x 12 mm) was bonded to one electrode, and the other electrode was bonded. After heating at 100 ° C for 1 hour, the end of the capacitor was sealed with epoxy resin. A multilayer capacitor was manufactured. 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 450 mF. In addition, even if charging and discharging were repeated 50 times under these conditions, the capacity hardly changed.

From the above results, the polymer solid electrolyte of the present invention has good thin film strength, high ionic conductivity, and shows good physical properties when applied to batteries and solid electric double layer capacitors. You can see that.

[0078]

The polymer solid electrolyte of the present invention comprises a complex of a polymer having an oxyalkyl group bonded by a urethane bond in a side chain and / or a crosslinking group and at least one electrolyte, and has a membrane strength. Is easily obtained as a good thin film, and has characteristics 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. In addition, the battery of the present invention is a battery that can operate at high capacity and high current as an all solid type, or has good cyclability, and is excellent in safety and reliability. It can be used as a power supply for electric appliances, electric vehicles, and large power supplies for road leveling. Further, since it can be easily thinned, it can be used as a paper battery for an identification card or the like.

Further, the electric double layer capacitor of the present invention
Compared with conventional all solid type capacitors, it can operate at high voltage, high capacity, high current, or has good cycleability,
It is an electric double layer capacitor with excellent safety and reliability.
An all-solid-state electric double layer capacitor having such characteristics can be obtained. Therefore, not only the backup power supply,
It can be used as a power source for various electrical products when used with small batteries. 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. Further, by using the method for producing a battery of the present invention, the battery of the present invention can be efficiently produced, and by using the method for producing a capacitor of the present invention, the capacitor of the present invention can be produced efficiently. be able to.

[Brief description of the drawings]

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

FIG. 2 is a schematic sectional view of an embodiment of the solid 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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location H01M 10/40 H01G 9/02 331G

Claims (14)

[Claims] 1. General formula (1) {CH ₂ ＣC (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z ｝ _v R ² OH (1) , R ¹ represents hydrogen or an alkyl group. R ² is 2
It is an organic chain having a valency or higher, but may not be present when v is 1. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. Where x = 0 and y = 0
In the case of, z = 0. Also, (CH ₂ ) and (CH (CH
₃ )) may be arranged irregularly. However, a plurality of R ¹ in the same molecule and the values of x, y, and z are independent and need not be the same. And a general formula (2) R ³ (—NCO) _k (2) wherein R ³ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. k represents an integer of 1 or more. ] A monomer compound for a solid polymer electrolyte comprising a mixed composition or a reaction product composition thereof. 2. A mixture composition formula ^{(3) {HO- (R 4} O) n -} m R 5 ... (3) [ wherein, R ⁴ are each _{- (CH 2) 2 -,} - CH
(CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) —
And n and m represent an integer of 1 or more. R ⁵ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. The monomer compound for a solid polymer electrolyte according to claim 1, wherein the compound is a compound represented by the following formula: 3. General formula (1) {CH ₂ ＣC (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z ｝ _v R ² OH (1) , R ¹ represents hydrogen or an alkyl group. R ² is 2
It is an organic chain having a valency or higher, but may not be present when v is 1. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. Where x = 0 and y = 0
In the case of, z = 0. Also, (CH ₂ ) and (CH (CH
₃ )) may be arranged irregularly. However, a plurality of R ¹ in the same molecule and the values of x, y, and z are independent and need not be the same. And a general formula (2) R ³ (—NCO) _k (2) wherein R ³ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. k represents an integer of 1 or more. A polymer obtained from at least one of a mixed composition containing the compound represented by the formula or a reaction product composition thereof, and / or a copolymer containing the composition or the reaction product composition thereof as a copolymer component, and at least A solid polymer electrolyte composed of a composite containing one type of electrolyte. 4. The mixture composition formula ^{(3) {HO- (R 4} O) n -} m R 5 ... (3) [ wherein, R ⁴ are each _{- (CH 2) 2 -,} - CH
(CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) —
And n and m represent an integer of 1 or more. R ⁵ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. 4. The polymer solid electrolyte according to claim 3, wherein the compound is represented by the following formula: 5. The solid polymer electrolyte according to claim 3, wherein the electrolyte is at least one selected from an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, and a transition metal salt. 6. The solid polymer electrolyte according to claim 3, wherein a plasticizer is added to the solid polymer electrolyte containing the electrolyte. 7. A battery using the polymer solid electrolyte according to claim 2. 8. The battery according to claim 7, wherein the negative electrode of the battery is an electrode containing lithium, a lithium alloy, or a carbon material capable of inserting and extracting lithium ions. 9. The battery according to claim 7, wherein the positive electrode of the battery comprises an electrode containing a conductive polymer, a metal oxide, a metal sulfide, or a carbon material. 10. General formula (1) {CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z ｝ _v R ² OH (1) , R ¹ represents hydrogen or an alkyl group. R ² is 2
It is an organic chain having a valency or higher, but may not be present when v is 1. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. Where x = 0 and y = 0
In the case of, z = 0. Also, (CH ₂ ) and (CH (CH
₃ )) may be arranged irregularly. However, a plurality of R ¹ in the same molecule and the values of x, y, and z are independent and need not be the same. And a general formula (2) R ³ (—NCO) _k (2) wherein R ³ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. k represents an integer of 1 or more. ] A polymerizable monomer composition containing at least one of a mixed composition or a reaction product composition thereof, and a polymerization obtained by adding a plasticizer thereto A method for producing a battery, comprising: introducing a polymerizable monomer composition into a structure for battery configuration or disposing the polymerizable monomer composition on a support, and polymerizing the polymerizable monomer composition. 11. A mixed composition represented by the following general formula (3): ｛HO— (R ⁴ O) _n −｝ _m R ⁵ (3) wherein R ⁴ is — (CH ₂ ) ₂ —, CH
(CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) —
And n and m represent an integer of 1 or more. R ⁵ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. 11. The method for producing a battery according to claim 10, comprising a compound represented by the formula: 12. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, wherein the ion conductive material is the solid polymer electrolyte according to any one of claims 2 to 6. Electric double layer capacitor. 13. The general formula (1) {CH ₂ ＣC (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z ｝ _v R ² OH (1) , R ¹ represents hydrogen or an alkyl group. R ² is 2
It is an organic chain having a valency or higher, but may not be present when v is 1. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. Where x = 0 and y = 0
In the case of, z = 0. Also, (CH ₂ ) and (CH (CH
₃ )) may be arranged irregularly. However, a plurality of R ¹ in the same molecule and the values of x, y, and z are independent and need not be the same. And a general formula (2) R ³ (—NCO) _k (2) wherein R ³ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. k represents an integer of 1 or more. ] A polymerizable monomer composition containing at least one of a mixed composition or a reaction product composition thereof, and a polymerization obtained by adding a plasticizer thereto A method for producing an electric double-layer capacitor, comprising: introducing a water-soluble monomer composition into a structure for forming an electric double-layer capacitor or disposing the same on a support, and polymerizing the polymerizable monomer composition. 14. A mixture composition formula ^{(3) {HO- (R 4} O) n -} m R 5 ... (3) [ wherein, R ⁴ are each _{- (CH 2) 2 -,} - CH
(CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) —
And n and m represent an integer of 1 or more. R ⁵ represents a monovalent or higher valent organic group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. The method for producing an electric double layer capacitor according to claim 13, wherein the compound is represented by the following formula: