JP2001210373A - Electrochemical element and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochemical element, especially a primary battery and secondary battery and its manufacturing method wherein the element can be actuated at a high capacity and a high current, that has a long life and superior reliability, and that can be manufactured inexpensively by using a heat polymerizable composition for high polymer solid electrolyte, which is superior in impregnation properties, curing properties and preservation stability, and provide the electrochemical element, especially an electric double layer capacitor and its manufacturing method wherein the element has a high output voltage, a large output current, a good workability, a long life and a superior reliability, and that can be manufactured inexpensively by using the heat polymerizable composition for high polymer solid electrolyte, which is superior in impregnation properties, curing properties and preservation stability. SOLUTION: By selecting kind and/or composition about materials such as solvent in the heat polymerizable composition, heat polymerizable compounds, electrolyte salt or the like, and by controlling the viscosity, the impregnation property is made to improve. Further, by using polymerization inhibitors of high polymerization inhibition, the storage stability is improved, and in addition, by selecting specific heat polymerization initiator and heat polymerizable compounds, curing properties are improved. By letting these thermosetting compounds impregnate and cure promptly in an element case, the primary battery, secondary battery and electric double layer capacitor having properties for the purposes can be easily obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for injecting a thermopolymerizable composition containing a polymerizable compound and an electrolyte salt in a liquid state before polymerization into an electrochemical element case in which constituent members are housed, and easily after injection. The present invention relates to an electrochemical device, particularly a battery or an electric double layer capacitor, which is obtained by curing to obtain a polymer solid electrolyte and / or a polymer gel electrolyte, and a method for producing the same.

[0002]

2. Description of the Related Art In the field of downsizing and all-solidification in the field of ionics, all-solid primary batteries, secondary batteries, and electric Practical application of multilayer capacitors has been desired, and some polymer solid electrolytes have begun to be used in Li-ion batteries.

That is, in a battery using a conventional electrolyte solution, there is a problem in long-term reliability because liquid leakage to the outside of the battery or elution of an electrode material easily occurs. Even in flexible sheet batteries that are expected recently,
When an electrolyte solution is used, there is a problem of an increase in internal impedance or an internal short circuit due to skewing or withering of the electrolyte solution in the battery container.

In recent years, electric double layer capacitors in which a carbon material having a large specific surface area is used as a polarizable electrode and an ion conductive solution is disposed between the polarizable electrodes have been widely used for a memory backup power supply and the like. Even in such electric double layer capacitors, current electrolyte solutions are liable to leak to the outside of the capacitor when used for a long time or when a high voltage is applied, and there is a problem in long-term use and reliability. There is.

On the other hand, batteries and electric double layer capacitors using a solid polymer electrolyte have no problems such as liquid leakage and elution of electrode materials, and can be processed into various shapes and are easily sealed. However, the ionic conductivity of polymer solid electrolytes generally studied is 10 ⁻⁴ to 1 at room temperature.
Although improved to about 0 ⁻⁵ S / cm, it is still at least two orders of magnitude lower than solution-based ion conductive materials. The same applies to a polymer solid electrolyte into which an oligooxyethylene chain has been attracting attention in recent years (for example, JP-A-4-211412). Further, when the temperature is lowered to 0 ° C. or lower, there is a problem that the ionic conductivity generally extremely decreases. As a method for incorporating a polymer solid electrolyte into a battery or an electric double layer capacitor, a so-called casting method has been performed in which a solution of the polymer solid electrolyte is applied and stretched on a substrate such as an electrode, and then the solvent is removed by drying. However, this method requires a complicated processing operation and does not have sufficient adhesion to the electrodes.

In view of the above, a curing method in which an electrolyte and a polymerizable compound are used as the main components of a polymer solid electrolyte, and these are charged in a liquid or gel state into a battery or capacitor structure, and then cured to form a composite. Is being considered.

As a method of curing such a polymerizable composition, a method of curing with an active ray has been actively studied and developed. Particularly, a solid polymer electrolyte using an ultraviolet photopolymerization initiator which is economically advantageous. Is being considered. However, with light irradiation, it is difficult to simultaneously compositely integrate each element of the positive electrode, the negative electrode, and / or the separator with the polymerizable composition for a solid polymer electrolyte due to the structure of the battery. In particular, it is difficult to integrate a positive electrode, a solid polymer electrolyte, and a negative electrode into a laminated type or a wound type because each element is not light-transmitting. In order to avoid curing failure due to impermeability of the actinic ray, it is conceivable to composite each element of the positive electrode and the negative electrode with the polymerizable composition for a solid polymer electrolyte, and then perform lamination, etc. Used to compensate for the problem that the polymerizable composition inside the electrode is not sufficiently cured due to being shielded by the material and the polymerization occurs unevenly in the depth direction of the electrode, or to compensate for the mechanical strength and the gap between the electrodes. When a separator is interposed, there is a problem that it is difficult to cure uniformly to the back side of the separator. Furthermore, there was a problem that the atmosphere in which the polymerizable composition was in contact easily was susceptible to oxygen inhibition, leading to poor curing.

[0008] For this reason, each element of the positive electrode, the negative electrode and / or the separator and the solid polymer electrolyte can be simultaneously combined and integrated with the curing, and the method of thermosetting which can reduce the internal impedance of the battery is also available. Proposed. For example, JP-A-11-121035 discloses a lithium-based solid electrolyte characterized by forming an electrolyte layer by heating after injecting a non-aqueous electrolyte containing a thermal polymerization initiator and a polymerizable compound into a battery case under reduced pressure. A method for manufacturing a secondary battery has been proposed. In this method, it is difficult to perform the photo-curing method using actinic rays. Superior in manufacturing. However, non-aqueous electrolytes containing these polymerizable compounds tend to have higher viscosities than ordinary electrolytes, and have a problem in operability that makes it difficult to inject into a battery component. Electrode materials used in electrochemical devices are oxidation-reduction materials, which often inhibit the deactivation of various thermal polymerization initiators and the polymerizability of polymerizable compounds. However, there remains a problem that the residual functional group adversely affects device performance. The present inventors
No. 10-147989 proposes a thermopolymerizable composition for a solid polymer electrolyte which can be easily cured in an electrochemical device by using a specific thermopolymerization initiator and has good electrochemical stability. However, demands on thermal stability are increasing. When a polymer solid electrolyte is formed by thermosetting, the mixture is thermally unstable because a thermal polymerization initiator is used, and the mixture containing the liquid polymerizable compound is being injected into the electrochemical element component. Gelation and solidification occur in
Difficulty in work etc.

[0009] The thermal polymerization initiator is often determined by the desired curing temperature. Therefore, for example, when the electrolyte contains a low-boiling solvent, the use of an initiator having a high radical generation temperature is restricted in order to avoid a change in solution composition due to volatilization of the solvent. As a result, polymerization accelerators are used in combination to cure at room temperature to medium temperature.These polymerization accelerators and their decomposition products have characteristics such as current physical properties such as ionic conductivity of polymer solid electrolyte and cycle life. Causes deterioration. When the composition is cured only by heating without using a polymerization accelerator, the curing rate depends on the thermal decomposition rate of the thermal polymerization initiator, so that it takes time to cure at a low temperature. It is also common practice to increase the amount of radicals generated by increasing the amount of polymerization initiator to perform efficient curing.However, since unreacted initiators and decomposition products increase, current characteristics such as ionic conductivity and cycle characteristics, etc. Has a problem of adversely affecting the electrochemical properties of the Therefore, a polymerizable compound-containing electrolytic solution, that is, a thermopolymerizable composition that can be easily injected into an electrochemical element, can be cured after the injection, and does not adversely affect the constituent materials of the electrochemical element has been strongly desired.

[0010]

SUMMARY OF THE INVENTION In the present invention, a thermal polymerization initiator having a high initiation efficiency at low and intermediate temperatures and a stability of a polymerizable compound-containing electrolytic solution without inhibiting the initiation ability, that is, an increase in viscosity and / or gelation A polymerization inhibitor that can extend the time for polymerization, a polymerizable compound with good curability, and by controlling these to an appropriate composition by combining them with an electrolytic solution, have excellent ion conductivity and curability at room temperature and low temperature. ,
An object of the present invention is to provide a method for producing an electrochemical device using a thermopolymerizable composition having practical use, which has low viscosity, long viscosity increase time, and excellent storage stability so that it can be easily injected into the electrochemical device. And

Further, the present invention provides a polymer solid electrolyte having high ionic conductivity and good stability, comprising a polymer having a crosslinked and / or side chain group obtained from the thermopolymerizable composition inside a battery and an electrolyte. An object of the present invention is to provide a primary battery and a secondary battery which can be operated at a high capacity and a high current, have a long service life, have excellent reliability and can be manufactured at low cost.

Further, the present invention relates to an electric capacitor which uses the above-mentioned polymer solid electrolyte inside a capacitor, has a high output voltage, a large take-out current, has good workability, has a long life, has excellent reliability and can be manufactured at low cost. It is an object to provide a multilayer capacitor.

[0013]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the following general formula (1)
It has been found that a compound having a specific structure represented by the formula (1) has a polymerization inhibitory effect and improves the storage stability of the thermopolymerizable composition.

[0014]

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Further, the above compound is a specific organic peroxide represented by the general formula (2), a thermal polymerization initiator, and a specific structure represented by the general formulas (3) and (4). By mixing a polymerizable compound having a molecular weight in an appropriate composition ratio and further mixing it with an appropriate amount of an electrolyte, it is easy to penetrate into the constituent materials in the electrochemical element, has excellent storage stability, and has excellent curing characteristics. Finding that a polymerizable composition can be obtained, that a polymer solid electrolyte is produced even in the electrode or in a material to which actinic rays cannot reach, and that the obtained polymer solid electrolyte has good adhesion to the electrode. Make sure you have
The present invention has been completed.

[0016]

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(The symbols in the formulas are the same as in claims 5, 6, and 9.) That is, the present invention relates to an electrochemical device obtained by polymerizing the following thermopolymerizable composition, in particular, a battery, an electric double layer capacitor, And a method for producing them.

1) 25 containing a polymerizable compound and an electrolyte salt
A thermopolymerizable composition having a viscosity at 30 ° C. of less than 30 mPa · s is injected into an electrochemical element case containing components other than the electrolyte material, and then cured by heating to produce an electrochemical element. 2) The time required for the viscosity at 25 ° C. containing the polymerizable compound and the electrolyte salt to increase to 50 mPa · s or more, which is 1 minute, comprising:
An electrochemical element characterized by producing an electrochemical element by injecting a thermopolymerizable composition that is longer than a time into an electrochemical element case containing each constituent material other than an electrolyte material, and then curing by heating. 3) The production of the electrochemical element according to 1) or 2) above, wherein the time required for the thermopolymerizable composition to be cured by heating at 100 ° C. or less is 20 hours or less. Method 4) At least one thermopolymerizable compound having a polymerizable functional group which becomes a polymer having a crosslinked and / or side chain structure by polymerizing the thermopolymerizable composition, at least one electrolyte salt, at least one Is a thermopolymerizable composition containing a polymerization initiator, at least one polymerization inhibitor, and at least one organic solvent, wherein the polymerization inhibitor is a compound having a vinyl group in the molecule. Wherein wherein the 1)
5) The method for producing an electrochemical device according to any one of 5) to 5), wherein the polymerization inhibitor is represented by the following general formula (1):

[0019]

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Wherein A represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, Ar represents a phenyl group which may have a substituent, and a represents 0 or 1 It is an integer, and the two Ars may be the same or different. ]
The method for producing an electrochemical device according to 4), wherein the polymerization initiator is a compound having a structure represented by the following formula: 6) wherein the polymerization initiator is represented by the following general formula (2):

[0021]

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[In the formula, X represents a linear, branched or cyclic alkyl or alkoxy group which may have a substituent, and Y represents a linear, branched or cyclic substituent. Represents an alkyl group which may be possessed, and m and n are independently 0 or 1, except for a combination of (m, n) = (0, 1). The method for producing an electrochemical device according to the above 4), wherein the amount of active oxygen of the organic peroxide is 1 to 1 with respect to the thermopolymerizable composition. 8) The method for producing an electrochemical device according to 6) above, wherein the organic peroxide is a diacyl peroxide containing no benzene ring, and a peroxydicarbonate containing no benzene ring. Wherein the polymerizable compound is selected from the group consisting of peroxyesters containing no benzene ring, 9) wherein the polymerizable compound is represented by the following general formula (3) and / or General formula (4)

[0023]

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[Wherein, R¹And R^ThreeIs a hydrogen atom or al
Represents a kill group;^TwoAnd R^FiveIs an oxyalkylene,
Fluorocarbon, oxyfluorocarbon or carb
A divalent group containing a nate group;^FourIs 10 or more carbon atoms
Represents the following divalent group. R^Two, R ^FourAnd R^FiveIs a heteroatom
Which may be linear, branched or cyclic
It may have this structure. x is 0 or 1 to 10
Indicates an integer. However, two or more of the above general formulas in the same molecule
Contains a polymerizable functional group represented by (3) or (4)
In the case, R in each polymerizable functional group¹, R^Two, R^Three,
R^Four, R^FiveAnd x may be the same or different. ]
Having any one of the polymerizable functional groups represented by
Including a polymerizable compound having an average molecular weight of 10,000 or less
According to any one of 1) to 8) above,
10) A method for producing an electrochemical element, 10) wherein the thermopolymerizable composition is a carbonate or an aliphatic
Esters, ethers, lactones, sulfoxides
, At least one organic solvent selected from amides
According to any one of 1) to 9) above,
11) The method for producing an electrochemical device, 11) wherein the content of the organic solvent is
Be in the range of 300% by mass or more and 1500% by mass or less
The method for producing an electrochemical device according to the above item 10), wherein
12) The electrolyte salt is an alkali metal salt, a quaternary ammonium salt.
Salts, quaternary phosphonium salts, transition metal salts, protonic acids
Before being characterized by at least one kind selected from
The production of the electrochemical device according to any one of 1) to 11)
13) At least one electrolyte salt is LiPF₆, LiB
F_Four, LiAsF₆, And LiN (R-SO_Two)_Two(Where
R represents a perfluoroalkyl group having 1 to 10 carbon atoms.
Express. ) Is a compound selected from
14) The method for producing an electrochemical device according to the above item 12), 14) a viscosity at 25 ° C containing a polymerizable compound and an electrolyte salt.
Is less than 30 mPa · s.
In an electrochemical element case that contains components other than materials
Electrification produced by injecting and curing by heating
15) Viscosity at 25 ° C containing polymerizable compound and electrolyte salt
However, the time required to increase the viscosity to 50 mPa · s or more is 1
The thermopolymerizable composition for longer than the time is applied to each component other than the electrolyte material.
After pouring into the electrochemical element case containing the component,
An electrochemical element manufactured by curing by heat. 16) The method according to any one of 1) to 13) above.
Or 17) the electrochemical element case is wound or laminated.
Case containing a negative / positive electrode stack via a separator
According to the above 14) or 15),
18) The electrochemical element case is wound or laminated.
Collect the polarizable electrode / polarizable electrode laminate via the separator
14) or characterized in that the
15) The electric double layer capacitor according to 15), 19) the negative electrode active material is lithium, a lithium alloy, or lithium.
Carbon material capable of storing and releasing ions, absorbing lithium ions
Storage and release of inorganic compounds and lithium ions
At least one selected from conductive polymers
20) The battery as described in 17) above, wherein the cathode active material is a conductive polymer, a metal oxide, or a metal sulfate.
At least one material selected from oxides and carbon materials
21) The battery according to 17), wherein the polarizable electrode material is a conductive polymer, a metal oxide,
Use at least one material selected from carbon materials
The electric double layer capacitor according to the above 18), and 22) the above 18), wherein the polarizable electrode material is activated carbon.
Electric double layer capacitor.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [1] Thermopolymerizable composition The thermopolymerizable composition of the present invention basically comprises (a) a thermopolymerizable compound, (b) a polymerization initiator, and (c) a polymerization inhibitor. And (d) an electrolyte salt. Further, it may contain (e) an organic solvent and (f) inorganic fine particles.

The thermopolymerizable composition of the present invention is low in viscosity, has little change in viscosity over time, and is sufficiently hardened in the electrochemical element so that it can be easily impregnated into each constituent material of the electrochemical element. There is a feature. To lower the viscosity, the molecular weight of the thermopolymerizable compound and the mixing ratio with the organic solvent were optimized. To suppress the change in viscosity, a polymerization inhibitor having an excellent inhibitory ability was used without inhibiting the curing, and the amount added was optimized. For the curability, a polymerization initiator or a polymerizable compound having excellent curing initiation ability was used, and the amount added and the curing conditions were optimized.

In particular, in the present invention, by using the specific polymerization inhibitor (c) represented by the formula (1), even if an initiator having excellent curability is used, the storage stability can be maintained in a low viscosity state. An excellent thermopolymerizable composition can be obtained. Further, equation (2)
A specific polymerization initiator (b) having a good polymerization initiation ability represented by
By combining with (c), a thermopolymerizable composition having low viscosity, good curability, good storage stability and excellent practicality can be obtained.

That is, the polymerization initiator represented by the formula (2)
The use of (b) causes a problem that the storage stability of the thermopolymerizable composition is inferior and accidental curing of the thermopolymerizable composition is likely to occur. When a specific polymerization inhibitor represented by the formula (1) is added thereto, the storage stability is specifically improved. The polymerization inhibitor represented by the formula (1) is a compound having a double bond of a styrene skeleton, and a growth radical gradually generated by decomposition of the polymerization initiator during storage of the thermopolymerizable composition under certain conditions. It has a function of adding a species to a double bond in the present polymerization inhibitor. Since the polymerization inhibitor to which the radical is added is stable for a long time, accidental polymerization of the thermopolymerizable composition can be prevented.

When the specific compound having a polymerizable functional group represented by the formula (3) and / or (4) is a thermopolymerizable compound (a), the curing properties of the thermopolymerizable composition are further increased, preferable. By using this specific thermopolymerizable compound (a), the obtained cured product is excellent in current characteristics and cycle characteristics and forms an electrochemically stable polymer solid electrolyte. Even more surprisingly, in a composition containing an organic solvent, even when the organic solvent exceeds 300% by mass of the polymerizable compound, the composition has good curability, high ionic conductivity, excellent film formability, film strength and electrochemical properties. Good mechanical properties.

Hereinafter, the components of the thermopolymerizable composition of the present invention will be described in detail. (a) Thermopolymerizable compound (a-1) Structure of thermopolymerizable compound The thermopolymerizable compound (a) used in the present invention is not particularly limited, but is represented by the following general formula (3) and / or general formula (4)

[0031]

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[Wherein R¹And R^ThreeIs a hydrogen atom or al
Represents a kill group;^TwoAnd R^FiveIs an oxyalkylene,
Fluorocarbon, oxyfluorocarbon or carb
A divalent group containing a nate group;^FourIs 10 or more carbon atoms
Represents the following divalent group. R^Two, R ^FourAnd R^FiveIs a heteroatom
Which may be linear, branched or cyclic
It may have this structure. x is 0 or 1 to 10
Indicates an integer. However, two or more of the above general formulas in the same molecule
Contains a polymerizable functional group represented by (3) or (4)
In the case, R in each polymerizable functional group¹, R^Two, R^Three,
R^Four, R^FiveAnd x may be the same or different. ]
Having any one of the polymerizable functional groups represented by
Polymerizable compounds having an average molecular weight of 10,000 or less are preferred.
No.

The polymerizable compound having any one of the functional groups represented by the general formulas (3) and / or (4) contains a (meth) acrylate structure and an oxyalkylene, fluorocarbon, oxyfluorocarbon and / or carbonate group. Consisting of parts. The (meth) acrylate structure forms a crosslink or a main chain by a polymerization reaction. The portion containing oxyalkylene, fluorocarbon, oxyfluorocarbon and carbonate groups is crosslinked and / or
Alternatively, a side chain structure is formed. In the side chain structure and the like, the hetero atom promotes ionization of the electrolyte salt to improve the ionic conductivity of the solid electrolyte, and also promotes curability by radical polymerization. As a result, it was found that even with a small amount of the thermal polymerization initiator added, the residual double bond was very small, and the curing was completely advanced.

It is particularly preferable to include the structure of the formula (4). When the thermopolymerizable compound has a polymerizable functional group represented by the general formula (4), a polymer obtained by polymerizing the compound contains a urethane group, has a high dielectric constant, and is used as a polymer solid electrolyte. The preferred feature is that the ionic conductivity in the case is increased. Furthermore, the thermopolymerizable compound having the structure of the formula (4) is preferable because it has good polymerizability, has a large film strength when formed into a thin film, and has a large amount of electrolyte solution. The oxyalkylene contained in R ^{2 of the} formula (3) or R ⁵ of the formula (4) is not particularly limited.

[0035]

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An oxyalkylene chain having a structure represented by the following formula: In the above formula, R ⁶ is a hydrogen atom or an alkyl side chain having 10 or less carbon atoms. The alkyl side chain is preferably a methyl group. The number of repetitions s is an integer in the range of 1 to 1000, preferably 1 to 50. R ⁶ may be different for each repeating unit.

R ^{2 of the} general formula (3) or the general formula (4)
The fluorocarbon contained in R ⁵ of above is not particularly limited, but is preferably one in which hydrogen bonded to carbon in an alkylene chain having 20 or less carbon atoms has been replaced with fluorine.
The skeleton of the carbon chain may have any of linear, branched and cyclic structures. The oxyfluorocarbon contained in R ² of the general formula (3) or R ⁵ of the general formula (4) is not particularly limited.

[0038]

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An oxyfluorocarbon chain having a structure represented by the following formula: In the formula, R ⁷ is a fluorine atom or a fluorocarbon side chain having 10 or less carbon atoms. The fluorocarbon side chain is preferably a perfluoromethyl group. The number of repetitions t is an integer in the range of 1 to 1000, preferably 1 to 50. R ⁷ may be different for each repeating unit.

R ^{2 of the} general formula (3) or the general formula (4)
The carbonate group contained in R ⁵ is not particularly limited, but is preferably represented by the following formula:

[0041]

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Is a poly or oligo carbonate chain represented by In the formula, R ⁸ represents a linear, branched, and / or cyclic divalent group having 1 to 10 carbon atoms which may contain a hetero atom, u is an integer of 1 to 10, Is 2
It is an integer of ~ 1000. If u exceeds 10 in the above general formula, the number of carbonate groups in the polymer compound decreases, the dielectric constant decreases, and the electrolyte salt becomes difficult to dissociate. Preferred u is 1 to 5. In the above general formula, R ⁸
If the number of carbon atoms is too large, the number of carbonate groups in the polymer compound decreases, the dielectric constant decreases, and the electrolyte salt is difficult to dissociate. Further, the hydrophobicity of the polymer compound increases, and the compatibility with various polar solvents decreases, which is not preferable. The carbon number of R ⁸ is preferably 1 to 6, more preferably 1 to 4. The number of repetitions w is in the range of 2 to 1000, preferably 3 to 100, and more preferably 5 to 50. In addition, in any of the above cases, R ^{2 of} the general formula (3) or R ⁵ of the general formula (4) may include any of a linear, branched, or cyclic structure. Heteroatoms may be included as long as they do not violate the above problem.

R ⁴ in the general formula (4) is preferably-(CH ₂ ) _p (CH (CH ₃ )) _q- . In the formula, p and q are each 0 or an integer of 1 to 5. However, when p = q = 0, x = 0. (O
R ⁴ ) When _x is 2 or more in x, —CH ₂ — and —CH
(CH ₃₎ - it may be irregularly arranged without continuous respectively.

(A-2) Molecular Weight of Thermopolymerizable Compound The lower the molecular weight of the thermopolymerizable compound used in the thermopolymerizable composition of the present invention, the lower the viscosity of the composition becomes, This is preferable because it can be easily injected into the device. However, if it is too small, the side chain in the polymer after polymerization, the amount of heteroatom-containing groups such as oxyalkylene in the crosslinked chain will decrease, the polarity of the polymer will decrease, and the compatibility with the electrolyte salt will decrease. And is not preferred. In the case of a polyfunctional polymerizable compound having two or more functional groups, if the molecular weight is too small, the crosslinked chains of the polymer after polymerization become short, the crosslink density increases, and the impregnating property and holding power of the solvent or the electrolytic solution are increased. , The glass transition point of the polymer increases, and the performance of the electrochemical element at low temperatures decreases, which is not preferable.

The preferred molecular weight of the thermopolymerizable compound is from 150 to 10,000 as a weight average molecular weight. Here, when divided into a monofunctional polymerizable compound and a polyfunctional polymerizable compound, the preferable mass average molecular weight of the monofunctional polymerizable compound is 150 or more and 1000 or less, more preferably 15 or less.
It is 0 or more and 800 or less. Preferred mass average molecular weight of the polyfunctional polymerizable compound is 300 or more and 10,000 or less,
More preferably, it is 500 or more and 7000 or less.

(A-3) Use Form of Thermopolymerizable Compound The thermopolymerizable compound used in the present invention is polymerized by heating in the presence of the above-mentioned polymerization initiator to form a solid polymer electrolyte. In the case of a thermopolymerizable compound having a polymerizable functional group represented by the general formulas (3) and / or (4), each may be used alone or in combination of two or more. Further, at least one polymerizable compound having a polymerizable functional group represented by the general formula (3) and / or (4) may be used in combination with another polymerizable compound.

Here, a polymer obtained by polymerizing a compound having only one functional group represented by the general formula (3) or (4) does not have a crosslinked structure and has insufficient film strength. For,
When used as an electrolyte membrane in a thin film, a short circuit may occur. In addition, when an electrolytic solution or a solvent is added, the holding power of the electrolytic solution or the solvent is poor. Therefore, it is copolymerized with a polymerizable compound having two or more functional groups represented by the general formulas (3) and / or (4) and crosslinked, or is represented by the general formulas (3) and / or (4). It is preferable to use together with a polymer obtained from a polymerizable compound having two or more functional groups. When these polymers are used as a thin film, the number of functional groups represented by the general formula (3) or (4) contained in one molecule is more preferably three or more in consideration of the strength.

The other polymerizable compound copolymerizable with the polymerizable compound having a polymerizable functional group represented by the general formula (3) and / or (4) is not particularly limited. For example, alkyl (meth) acrylates such as methyl methacrylate and n-butyl acrylate; various urethane acrylates; acrylamide, methacrylamide, N,
(Meth) acrylamide such as N-dimethylacrylamide, N, N-dimethylmethacrylamide, vinylene carbonate, (meth) acryloyl carbonate, N-vinylpyrrolidone, acryloylmorpholine, methacryloylmorpholine, N, N-dimethylaminopropyl (meth) acrylamide Styrene compounds such as styrene and α-methylstyrene; N-vinylamide compounds such as N-vinylacetamide and N-vinylformamide; and alkyl vinyl ethers such as ethyl vinyl ether. Among these, (meth) acrylic acid ester and urethane (meth) acrylate are preferable, and urethane (meth) acrylate is more preferable from the viewpoint of polymerizability.

(B) Thermal Polymerization Initiator The thermal polymerization initiator is largely classified into a system that generates a radical by causing homolysis by heat and a binary system that generates a radical by causing a one-electron transfer reaction between two substances. being classified. As the former, peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile,
The latter includes redox initiators. In the present invention, general formula (2)

[0050]

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[In the formula, X represents a linear, branched or cyclic alkyl group or an alkoxy group which may have a substituent, and Y represents a linear, branched or cyclic substituent. Represents an alkyl group which may be possessed, and m and n are independently 0 or 1, except for the combination of (m, n) = (0, 1). It is preferable to use an organic peroxide represented by the following formula: Azo compounds, for example, azobisdiphenylmethane, 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobis (2-methylpropionate)
For example, gas is generated with the generation of radicals. In the case of compounding a solid electrolyte on the electrode and / or inside the electrode,
This gas is not preferable because it causes problems such as a change in the battery shape such as peeling of the electrode material from the current collector and electrode expansion, and an increase in the current characteristics and interfacial resistance and a deterioration in the cycle characteristics.

Further, peroxides having a benzene ring, for example, benzoin compounds such as benzoin isobutyl ether, acetophenone compounds such as diethoxyacetophenone, and benzophenone compounds such as benzophenone and methyl benzoylbenzoate are thermally decomposed. There is a problem in electrochemical stability because the product contains a phenyl group,
The cycle characteristics of the battery deteriorate quickly. In general, a peroxide having a benzene ring has a high temperature at which the amount of active oxygen is reduced by half, easily causes deterioration and decomposition of the electrolyte, solvent and polymer, and volatilization of the solvent. This is not preferable because problems are likely to occur.

On the other hand, the polymerization initiator represented by the above general formula (2) has a good polymerization initiating ability, the reaction proceeds efficiently even in a very small amount, and the reaction proceeds from room temperature to medium temperature (80 ° C.). ° C
) Can cure the thermopolymerizable composition. As a result, there are very few residual double bonds and good curing properties.
A thermopolymerizable composition suitable for the purpose of obtaining a polymer solid electrolyte is obtained. Further, the thermopolymerizable composition using the present polymerization initiator generates little gas at the time of curing, and the product after curing is electrochemically stable. Therefore, the solid polymer electrolyte obtained from this thermopolymerizable composition does not cause electrochemical problems such as deterioration of current characteristics and deterioration of cycle characteristics. It was confirmed that the internal impedance did not increase, such as separation of the molecular solid electrolyte.

The organic peroxide as a polymerization initiator represented by the general formula (2) is diacyl peroxide, peroxydicarbonate or peroxyester, and preferably 3,5,5-trimethylhexa. Noyl peroxide, lauroyl peroxide, stearoyl peroxide, octanoyl peroxide, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2 -Ethoxyethyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-methoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, 1,1,
3,3-tetramethylbutylperoxyneodecanate, 1-cyclohexyl-1-methylethylperoxyneodecanate, t-hexylperoxyneodecanate, t-butylperoxyneodecanate, t-hexylperoxy Pivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1
-Methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate and the like. More preferably, diacyl peroxide, peroxyester, specifically,
3,5,5-trimethylhexanoyl peroxide,
Lauroyl peroxide, stearoyl peroxide, octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxyneodecanate, 1-cyclohexyl-1-methylethylperoxyneodecanate, t-hexylperoxyneone Decanate, t-butylperoxyneodecane, t-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylper Oxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate and the like are exemplified. These organic peroxides may be used alone or in any combination in the present invention, and may be used in combination of two or more.

When it is desired to cure the polymerizable compound and / or the polymerizable composition, the temperature may be reduced from room temperature due to the problem of thermal stability of the polymer solid electrolyte and the problem of adhesion to the composite with various constituent materials such as electrodes. Curing at medium temperatures is desirable. When curing at room temperature to medium temperature is desired, it is possible to use an initiator and a reducing promoter together or to decompose the initiator only by heat. However, rather than exhibiting activity in combination with the accelerator, cleavage occurs alone at room temperature,
Alternatively, those which decompose only upon heating to generate free radicals and exhibit activity are preferred. In the case of curing only with heat, it is only necessary to optimally select the thermal decomposition rate of the initiator,
It is also preferred to combine these initiators. In the polymerizable composition of the present invention, the amount of active oxygen defined by the following formula,
That is, active oxygen (—O
The value obtained by dividing the atomic weight of-) by the molecular weight of the organic peroxide and the mass% of the organic peroxide in the polymerizable composition is 1 ppm to 1000 ppm, and particularly preferably 10 to 500 ppm. .

Active oxygen content (% by mass) = (amount of organic peroxide / amount of polymerizable composition) × (16 × number of peroxide bonds / molecular weight of organic peroxide)

When the amount of active oxygen is too small, the reaction does not proceed sufficiently. On the other hand, when the amount of active oxygen is excessive, the amount of the terminator due to the initiator is large, the molecular weight is easily reduced, and the problem of insufficient film strength is caused. It adversely affects electrochemical characteristics such as deterioration of characteristics and cycle characteristics.

(C) Polymerization Inhibitor The polymerization inhibitor used in the thermopolymerizable composition of the present invention is a compound having a structure represented by the following general formula (1) containing a vinyl group in the molecule.

[0059]

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In the formula, A represents a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, Ar represents a phenyl group which may have a substituent, and a represents 0 or 1 It is an integer, and the two Ars may be the same or different. In the general formula (1), examples of the linear, branched, and cyclic alkylene groups represented by A include groups represented by the following formulas.

[0061]

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In the general formula (1), examples of the substituent for Ar include an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; a dialkylamino group; a nitro group; And a cyano group. Examples of the phenyl group which may have a substituent include a phenyl group and 2-phenyl
Methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4,6-trimethoxyphenyl group,
Examples include a 2,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 4-dimethylaminophenyl group, and a 4-fluorophenyl group. The polymerization inhibitor used in the present invention exhibits the following functions at the start of polymerization of the present thermopolymerizable composition.

First, the present polymerization inhibitor (c) rapidly adds or chain-transfers a primary radical or a growing radical generated by decomposition of a thermal polymerization initiator at the start of polymerization to a vinyl group of the present polymerization inhibitor. Is temporarily stopped and stabilized. Next, the radical generation reaction is restarted by transferring the radical generated in the double bond of the vinyl group to the polymerizable functional group of another polymerizable compound in the thermopolymerizable composition, and the polymerization reaction proceeds. Generally, the polymerization inhibitor mainly reduces the reaction rate of radical polymerization, and the effect of the inhibitor is determined by the reactivity with the first primary radical or growing radical and the reactivity of restart, so that the same compound can be used to form a polymerizable composition. It acts as an inhibitor depending on the type and composition of the substance. However, the present polymerization inhibitor containing a vinyl group
(c) functions as an inhibitor in the present thermopolymerizable composition. As a specific example of the compound having such a function, in the general formula (1), A is

[0064]

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Wherein a is 1 (Nofmer MSD manufactured by NOF) and A is

[0066]

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Wherein a is 1 and A is

[0068]

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Then, a compound wherein a is 1 and the like are mentioned. These polymerization inhibitors vary depending on the type and composition of the other components (polymerization initiator, polymerizable compound, organic solvent, etc.) of the thermopolymerizable composition, but are generally about 1 ppm to about 1% by mass, preferably about 1% by mass. It is used at an addition amount of 10 ppm to about 1% by mass.

(D) Electrolyte salt The type of electrolyte salt used in the present invention is not particularly limited.
Instead, use an electrolyte containing ions as carriers.
I just need. And the dissociation constant in the polymer solid electrolyte is large.
Preferably, LiCF_ThreeSO_Three, NaCF_ThreeS
O_Three, KCF_ThreeSO_ThreeSuch as trifluoromethanesulfonic acid
Alkali metal salt of LiN (CF_ThreeSO_Two)_Two, LiN
(CF_ThreeCF_TwoSO_Two)_TwoSuch as perfluoroalkane sulfo
Alkali metal salt of acid imide; LiPF₆, NaPF₆,
KPF₆Alkali metal salts of hexafluorophosphoric acid such as L;
iCLO_Four, NaClO_FourSuch as alkali metal perchlorates
Salt; LiBF _Four, NaBF_FourTetrafluoroborate such as;
LiSCN, LiAsF₆, LiI, NaI, NaAs
F₆, KI and the like. A
As ammonium salt, tetraethylammonium perchlorate
Quaternary ammonium salts of perchloric acid such as_TwoH_Five)_Four
NBF_FourQuaternary ammonium tetrafluoroborate
Salt; (C_TwoH_Five)_FourNPF₆Quaternary ammonium salts, such as
(CH_Three)_FourP ・ BF_Four, (C_TwoH _Five)_FourP ・ BF_FourSuch as 4
Grade phosphonium salts and the like. In these electrolytes
Then, from the solubility in an organic solvent and the ionic conductivity, Li
PF₆, LiBF_Four, LiAsF₆, Perfluoroalkane
Alkali metal salts of sulfonic acid imides and quaternary ammonium
Salts are preferred. Curing the thermopolymerizable composition of the present invention
Components and Electrolysis in Polymer Solid Electrolyte Obtained by Electrolysis
The compounding ratio of the electrolyte salt is 0.1 to
50% by mass is preferable, and 1 to 30% by mass is more preferable.
No. If the electrolyte salt is present in a proportion of 50% by mass or more,
ON movement is greatly inhibited, at a ratio of 0.1 mass% or less.
Indicates that the ion conductivity is low due to the shortage of the absolute amount of ions.
It becomes.

(E) Organic Solvent It is preferable that the polymer solid electrolyte of the present invention contains an organic solvent as a solvent, since the ionic conductivity of the polymer solid electrolyte is further improved. As the organic solvent that can be used, the compatibility with the thermopolymerizable compound (a) used in the thermopolymerizable composition for obtaining the polymer solid electrolyte of the present invention is good, the dielectric constant is large, and the thermopolymerizable composition of the present invention is large. Electrolyte salt used for materials
Compounds having high solubility (d), a boiling point of 70 ° C. or higher, and a wide electrochemical stability range are suitable. Further, an organic solvent having a low water content (a non-aqueous organic solvent) is more preferable.

Examples of such a solvent include oligoethers such as triethylene glycol methyl ether and tetraethylene glycol dimethyl ether; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and vinylene carbonate; Aliphatic esters such as methyl propionate and methyl formate; aromatic nitriles such as benzonitrile and tolunitrile; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; lactones such as γ-butyrolactone; sulfur such as sulfolane Compounds: N-methylpyrrolidone, N-vinylpyrrolidone, phosphates and the like. Of these, carbonates, aliphatic esters, and ethers are preferred, and carbonates are more preferred. These may be used alone or as a mixed solvent of two or more kinds.

The higher the content of the organic solvent, the higher the ionic conductivity of the solid polymer electrolyte. For this reason, it is generally desirable to increase the content, but on the other hand, if the content is excessive, curability, film formability, mechanical strength of the film and the like are impaired. A polymerizable composition comprising a polymerizable compound having a polymerizable functional group represented by formula (3) and / or (4), which is a preferred embodiment of the present invention, and an organic peroxide represented by formula (2). Is characterized by good curability even when the content of the organic solvent is increased, and excellent in film forming property and film mechanical strength. As a result, the composition can contain the organic solvent in an amount of about 200% by mass or more based on the weight of the thermopolymerizable compound used in the solid polymer electrolyte. From the viewpoints of current characteristics such as ionic conductivity, viscosity, and the like, it is more preferable that the solvent is contained in the range of about 300% by mass or more and about 1500% by mass or less based on the thermopolymerizable compound.

(F) Inorganic Fine Particles The constituent components of the polymer solid electrolyte produced by the thermopolymerizable composition of the present invention have been described above, but other components may be added unless the object of the present invention is impaired. Is also possible.
For example, it can be used as a composite electrolyte to which various inorganic fine particles are added, and thereby, not only the strength and the uniformity of the film thickness are improved, but also fine pores are generated between the inorganic fine particles and the polymer. When a solvent is added, the free electrolyte is dispersed in the pores in the composite electrolyte, and the ionic conductivity and the mobility can be increased without impairing the strength improving effect. Further, by adding the inorganic fine particles, the viscosity of the polymerizable composition increases, and even when the compatibility between the polymer and the solvent is insufficient, the effect of suppressing the separation between the polymer and the solvent appears.

As the inorganic fine particles to be used, those which are non-electroconductive and electrochemically stable are selected. Further, it is more preferable that the material has ion conductivity. Specific examples thereof include fine particles made of an ion-conductive or non-conductive ceramic such as α, β, or γ-alumina or silica. The inorganic fine particles preferably have a secondary particle structure in which primary particles are aggregated, from the viewpoint of improving the strength of the composite polymer electrolyte and increasing the amount of retained electrolyte. Specific examples of the inorganic fine particles having such a structure include ultrafine silica particles and ultrafine alumina particles such as Aerosil (manufactured by Nippon Aerosil Co., Ltd.). From the viewpoint of stability and composite efficiency, alumina ultrafine particles are more preferable. For the purpose of increasing the amount of the electrolyte-containing liquid in the electrolyte and increasing the ionic conductivity and mobility, the specific surface area of the filler is preferably as large as possible.
It is preferably at least about 5 m ² / g, more preferably at least about 50 m ² / g. The size of such inorganic fine particles is not particularly limited as long as it can be mixed with the polymerizable composition,
The average particle size is preferably about 0.01 μm to about 100 μm,
More preferably, about 0.01 μm to about 20 μm. In addition, various shapes such as a sphere, an egg, a cube, a rectangular parallelepiped, a cylinder or a rod can be used. If the added amount of the inorganic fine particles is too large, there arise problems that the strength and ionic conductivity of the composite electrolyte are reduced and that the film is difficult to be formed. Therefore, the addition amount is preferably about 50% by weight or less, more preferably about 0.1 to about 30% by weight based on the composite electrolyte.

(G) Mixing Order In preparing the thermopolymerizable composition of the present invention, the order of addition of the thermopolymerization initiator and the like is not particularly limited, but preferred examples include the following methods. All or a part of the polymerization inhibitor (c) represented by the general formula (1) can be added to any of a polymerizable compound, a solvent, an electrolytic solution, and a polymerizable composition prepared therefrom. However, the polymerization inhibitor (c) is preferably added to a solvent, an electrolytic solution or a polymerizable composition from the viewpoint of solubility. The thermal polymerization initiator (b) represented by the general formula (2) can also be added to any of the polymerizable compound, the solvent, the electrolytic solution, and the polymerizable composition prepared therefrom. However, from the viewpoint of storage stability and solubility, it is preferable to add them all to the last polymerizable composition mixed.

(H) Physical properties of the heat-polymerizable composition after compounding The physical properties of the heat-polymerizable composition obtained as described above are shown below. The viscosity is a low-viscosity liquid of less than 30 mPa · s at 25 ° C. so as to easily impregnate the porous material used for the electrochemical element. Further, the pressure is preferably 15 mPa · s or less at 25 ° C. In order to prevent the viscosity from increasing or hardening during the impregnation, it is necessary to suppress the increase in viscosity after the addition of the initiator as much as possible.
The time for thickening to 15 mPa · s or more is more preferably 3 hours or more. Curing properties include
100 considering the heat resistance of other constituent materials of the electrochemical element
It needs to be cured by heating at a temperature of ℃ or less. The curing time in that case is within 20 hours in consideration of the productivity of the electrochemical element. More preferable curing conditions are 90 ° C. or less and 15 hours or less.

[2] Solid Polymer Electrolyte and Method for Producing the Same (Polymerization of Thermopolymerizable Composition) The use of the thermopolymerizable composition of the present invention is mainly carried out by directly injecting into an electrochemical element case and then heating and curing. This is useful for a method for forming a solid polymer electrolyte at the same time as assembling the device. As preferable curing conditions of the thermopolymerizable composition, a desired polymerization temperature, a type and curability of the polymerizable compound, a thermopolymerization initiator is selected according to the boiling point of the solvent, and the amount of active oxygen of the initiator is reduced by half. Can be determined with reference to the temperature required for the half-life (half-life temperature). The curing temperature and the curing speed may be determined based on the half-life and activation energy of the thermal polymerization initiator. For example, in terms of the temperature required for a 10-hour half-life, the temperature is from room temperature to 100 ° C. or lower, and is further 40 ° C. to 7 ° C.
0 ° C. or lower is preferred. Further, two or more kinds of thermal polymerization initiators having different active oxygen amounts, activation energies and different half-lives may be arbitrarily used in combination. For the purpose of the invention, it is preferable to select an initiator and curing conditions that are most suitable for the curing reaction as a solid polymer electrolyte based on these indices.

For example, a polymerization inhibitor represented by the general formula (1) and a thermal polymerization initiator represented by the general formula (2) are combined with a urethane bond represented by the general formula (4) and containing an oxyalkylene group. When combined with a thermopolymerizable composition for a solid polymer electrolyte (JP-A-6-187822) comprising a (meth) acrylate monomer and an electrolyte, the composition was cured by heating at 60 ° C for 60 minutes. The ionic conductivity after curing is as high as 10 ^-4 S / cm (room temperature) even when no solvent is added, and when a solvent is further added, the ion conductivity is 10 ^-3 S / cm even at room temperature or lower.
It has been found that the above is improved. In addition, when applied to devices such as batteries and electric double layer capacitors, the solidification of the device can be easily achieved by heating and curing the thermopolymerizable composition previously introduced into the device after sealing the device.

The solid polymer electrolyte of the present invention can be used as a composite electrolyte by, for example, combining it with various porous polymer films to improve the strength, uniformity of the film thickness and prevent short circuit between electrodes. It is. However, depending on the type of polymer used, the shape of the film, and the composite ratio, the ion conductivity of the separator after absorbing the electrolytic solution may be lowered or the stability may be deteriorated. Therefore, it is necessary to select a suitable one. As the film to be used, a reticulated polyolefin sheet such as a polypropylene nonwoven fabric or a polyethylene net is used. As the separator, for example, polyethylene,
A woven fabric such as polypropylene, a nonwoven fabric, a nonwoven fabric such as a glass fiber or a ceramic fiber, a polymer solid electrolyte membrane, or a composite thereof is used. It is more preferable to use a polymer solid electrolyte membrane or a composite thereof as a separator because the polymer solid electrolyte and the polymer solid electrolyte of the present invention have good adhesion and adhesion. The mode of use of the polymer solid electrolyte of the present invention will be more specifically described below in connection with a battery and an electric double layer capacitor.

[3] Battery and Manufacturing Method Thereof FIG. 1 is a schematic sectional view of an example of a thin film battery as the battery of the present invention. In the figure, 1 is a positive electrode, 2 is a polymer solid electrolyte or a separator containing a polymer solid electrolyte, 3 is a negative electrode, 4 is a current collector, 5 is a laminate package, and 6 is an insulating resin sealant. In the configuration 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 1, a high voltage, A high capacity battery is obtained. Among such electrode active materials, cobalt oxide, manganese oxide,
Metal oxides such as vanadium oxide, nickel oxide, and molybdenum oxide, and metal sulfides such as molybdenum sulfide, titanium sulfide, and vanadium sulfide are preferable, and manganese oxide, nickel oxide, and cobalt oxide are preferable in terms of high capacity and high voltage. .

In this case, the method for producing the metal oxide or metal sulfide is not particularly limited.
2, 574 (1954),
It is manufactured by a general electrolytic method or a heating method. When these are used in a lithium battery as an electrode active material,
During the production of the battery, it is preferable to use the Li element in a state of being inserted (composite) into the metal oxide or metal sulfide in the form of, for example, Li _x CoO ₂ or Li _x MnO ₂ . The method of inserting the Li element in this way is not particularly limited. For example, a method of electrochemically inserting Li ions, and a method disclosed in U.S. Pat.
As described in JP-A-357,215, it can be carried out by mixing a salt such as Li ₂ CO ₃ and a metal oxide and subjecting the mixture to a heat treatment.

Further, a conductive polymer is preferred 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 its derivatives, polyselenophene and its derivatives, polyparaphenylenevinylene, polythienylenevinylene, polyfurylenevinylene,
Examples thereof include polyarylenevinylenes such as polynaphthenylenevinylene, polyselenophenevinylene, and polypyridinediylvinylene, and derivatives thereof. Among them, a polyaniline derivative, a polythienylene derivative, a polyparaphenylenevinylene derivative, and a polythienylenevinylene derivative that are soluble in an organic solvent are more preferable.

As the negative electrode active material used for the negative electrode 3 of the battery of the present invention, a low oxidation-reduction potential using an alkali metal ion such as the aforementioned alkali metal, alkali metal alloy, carbon material, metal oxide or metal chalcogenide as a carrier is used. It is preferable to use such a battery because a high-voltage, high-capacity battery can be obtained. Among such negative electrode active materials, lithium metal or lithium alloys such as lithium / aluminum metal, lithium / lead alloy, and lithium / antimony alloy are particularly preferable because they have the lowest redox potential. In addition, when a carbon material absorbs lithium ions, it is particularly preferable in that it has a low oxidation-reduction potential and is stable and safe. Materials that can store and release lithium ions include inorganic compounds such as tin oxide, natural graphite, artificial graphite,
Gas-phase graphite, petroleum coke, coal coke, pitch-based carbon, polyacene, fullerenes such as C60 and C70, and the like. It is preferable that the current collector 4 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.

An example of the method for manufacturing the battery of the present invention will be described. A lithium cobaltate positive electrode 1 coated and molded on an aluminum foil current collector and a natural graphite negative electrode 3 coated and molded on a copper foil current collector are laminated so as not to contact each other via a separator 2 made of a polyethylene microporous film. And put it in a battery case made of aluminum laminate. Next, the thermopolymerizable composition of the present invention is injected over about 1 hour,
By heating for 0 minutes to cure and solidify the thermopolymerizable composition, a solid Li-ion battery including a solid polymer electrolyte uniformly adhered to the electrode is obtained. Thereafter, the opening of the aluminum laminate battery case is sealed together with the current collector with a polyolefin thermoplastic sealing agent. The battery case may be made of a metal such as SUS, polypropylene, an aluminum laminate heat-sealing resin, polyimide, an ethylene-vinyl alcohol copolymer, or a ceramic material such as conductive or insulating glass. It is not limited to the one made of a material, and the shape may be a cylindrical shape, a box shape, a sheet shape, or any other shape.

[4] Electric Double Layer Capacitor and Manufacturing Method Thereof Next, the electric double layer capacitor of the present invention will be described.
According to the present invention, by using the thermopolymerizable composition of the present invention, there is provided a solid-state electric double layer capacitor having a high output voltage, a large take-out current, or excellent workability, life, and reliability. . FIG. 2 shows a schematic sectional view of an example of the electric double layer capacitor of the present invention. This example is a thin cell having a size of about 1 cm × 1 cm and a thickness of about 0.5 mm. Reference numeral 7 denotes a current collector, and a pair of polarizable electrodes 6 are arranged inside the current collector. A polymer solid electrolyte membrane or a polymer solid electrolyte containing separator 8 is provided. Reference numeral 9 denotes an aluminum laminate exterior body, and reference numeral 10 denotes an insulating resin sealant.

The polarizable electrode 6 may be an electrode made of a polarizable material such as a carbon material, and is not particularly limited as long as the specific surface area is large. The larger the specific surface area, the larger the capacity of the electric double layer, which is preferable. For example, carbon blacks such as furnace black, thermal black (including acetylene black) and channel black, activated carbon such as coconut charcoal, natural graphite, artificial graphite, so-called pyrolytic graphite produced by a gas phase method, polyacene and C60. , C70.

The current collector 7 is electron conductive and electrochemically corrosion resistant.
Use a material with a large specific surface area
Is preferred. For example, various metals and their sintered bodies,
Conductive polymers, carbon sheets, etc.
You. The shape of the electric double layer capacitor is as shown in FIG.
In addition to a simple sheet type, a coin type or a polarizable electrode,
A sheet-shaped laminate of a polymer solid electrolyte is wound into a cylindrical shape,
Put into a cylindrical tubular capacitor structure, seal
It may be a formed cylindrical type or the like. Electric double layer of the present invention
Types of electrolyte used for capacitors are particularly limited
Instead of a compound containing ions that you want to use as charge carriers
Things may be used. However, solutions in solid polymer electrolytes
Large separation constant, easy to form polarizable electrode and electric double layer
It is desirable to contain ions. Such a compound
The (CH_Three)_FourNBF_Four, (CH_ThreeCH_Two)_FourNCLO_Four
Quaternary ammonium salts such as AgClO_FourTransition metals such as
Salt, (CH_Three)_FourPBF_FourQuaternary phosphonium salts such as Li
CF_ThreeSO_Three, LiPF₆, LiClO_Four, LiI, LiB
F_Four, LiSCN, LiAsF₆, Li (CF _ThreeS
O_Two)_Two, NaCF_ThreeSO_Three, NaPF₆, NaClO_Four, N
aI, NaBF_Four, NaAsF₆, KCF_ThreeSO_Three, KPF
₆Metal salts such as KI and KI, paratoluenesulfonic acid
And organic acids and salts thereof, hydrochloric acid, inorganic acids such as sulfuric acid and the like.
Can be Among these, the output voltage is high and the dissociation constant is large.
Quaternary ammonium salt, quaternary phosphonic acid
Palladium salts and alkali metal salts are preferred. Quaternary ammonium
In the salt, (CH_ThreeCH_Two) (CH_ThreeCH_TwoCH_TwoCH_Two)
_ThreeNBF_FourReplacement of ammonium ion on nitrogen, such as
Those with different groups have different solubility in solid polymer electrolytes.
Alternatively, it is preferable because the dissociation constant is large.

Next, an example of a method for manufacturing the electric double layer capacitor of the present invention will be described. Two polarizable activated carbon electrodes 6 coated and formed on an aluminum foil current collector are laminated so as not to be in contact with each other via a separator 2 made of a polyethylene microporous film, and placed in an aluminum laminate electric double layer capacitor case. Next, the thermopolymerizable composition of the present invention is injected over about 2 hours, and heated at 60 ° C. for 30 minutes to harden and solidify the thermopolymerizable composition, thereby obtaining a highly adhered and uniformly adhered electrode. A solid state electric double layer capacitor containing a molecular solid electrolyte is obtained. Thereafter, the opening of the aluminum laminated electric double layer capacitor case is sealed together with the current collector with a polyolefin thermoplastic sealing agent. The electric double layer capacitor case is SU
Metals such as S, polypropylene, aluminum laminated heat-sealing resin, polyimide, ethylene-vinyl alcohol copolymer, or ceramic materials such as conductive or insulating glass may be used, but in particular limited to those made of these materials However, the shape may be cylindrical, box, sheet, or any other shape. The viscosity can be measured by a rotational viscometer according to the method described in JIS K7117, and the rotational viscometer can measure at various shear rates by changing the rotational speed. In addition, a long-term continuous measurement can be performed while keeping the rotation speed constant, and the change with time in the viscosity can be tracked. For the measurement, a Tokimec B-type viscometer was used as an apparatus.
Based on SZ 8809, it was used after being calibrated with a standard solution for viscometer calibration. The measurement was performed at 25 ° C. in an argon atmosphere.

[0090]

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

Example 1 Synthesis of Thermopolymerizable Compound (Compound 3) According to the following reaction formula, glycerin ester compound 1 and isocyanate group-containing methacrylate compound 2 were reacted. A thermopolymerizable compound (Compound 3) was obtained.

[0092]

Embedded image That is, Compound 1 (KOH value 34.0 mg / g, p / q =
7/3) A mixture of (50.0 g) and dimethyl carbonate (20 g) having a low water content was azeotroped under reduced pressure at 80 ° C. and a degree of vacuum of 3 mmHg. (50 g) was obtained. The water content of Compound 1 was measured by the Karl Fischer method.
It was 0 ppm. Next, this low water content compound 1 (50
g) and Compound 2 (4.6 g) were dissolved in well-purified tetrahydrofuran (THF) (100 ml) in a nitrogen atmosphere, and then dibutyltin dilaurate (0.44 g) was added. Thereafter, the mixture was reacted at 15 ° C. for about 25 hours to obtain a colorless viscous liquid. ¹ H-NMR, ¹³ C-NM
From R, compound 1 and compound 2 reacted one to three, and it was found from the infrared absorption spectrum that the absorption of the isocyanate group disappeared, urethane bonds were formed, and compound 3 was formed. The viscosity of this compound 3 is 2300 mPa · s (25
° C).

Example 2: Synthesis of thermopolymerizable compound (compound 5) According to the following reaction formula, compound 4 which is a polyether monool was reacted with compound 2, and the thermopolymerizable compound (compound 5) was obtained by the following procedure. 5) was obtained.

[0094]

Embedded image Compound 4 (average molecular weight 550, m / n = 7/3) (57.0
g) and dimethyl carbonate (20 g) having a low water content were azeotroped at 80 ° C. under a vacuum of 3 mmHg under reduced pressure, and water was distilled off together with the dimethyl carbonate to obtain Compound 4 (55 g) having a low water content. . The water content of Compound 4 measured by the Karl Fischer method was 35 ppm.
Next, the low moisture compound 4 (55.0 g) and the compound 2
(15.5 g) in THF (10
0 ml), then dibutyltin dilaurate (0.
66 g) was added. Thereafter, the mixture was reacted at 15 ° C. for about 25 hours to obtain a colorless viscous liquid. ¹ H-NM
From R and ¹³ C-NMR, it was found that Compound 4 and Compound 2 reacted one-to-one, and the absorption of the isocyanate group disappeared from the infrared absorption spectrum, urethane bonds were formed, and Compound 5 was formed. . The viscosity of this compound 5 is 130 mPa
S (25 ° C.).

Example 3 Synthesis of Compound 6

[0096]

Embedded image According to the above formula, excess phosgene gas is blown into 1,3-propanediol under nitrogen at a temperature of 10 ° C. or less in a conventional manner, and
After reacting for an hour, compound 6 was synthesized. Identification is GC-MS
(Gas chromatography-mass spectroscopy).

Example 4: Oligomerization of Compound 6 (Synthesis of Compound 7)

[0098]

Embedded image According to the above formula, compound 6 synthesized in Example 19 and 1,3-propanediol in a conventional manner were combined with pyridine in the presence of pyridine for 25 minutes.
After reacting in dichloromethane at 6 ° C. or lower for 6 hours, excess water is added, the remaining chloroformate terminals are hydroxylated, and oligocarbonates having hydroxyl groups at both terminals (compound 7)
Was synthesized. GPC analysis (gel permeation chromatogra
phy), the weight average molecular weight (Mw) and the average number of repetitions z were as follows. Mw: ~ 800, z: ~ 7.

Example 5: Synthesis of polymerizable compound 8

[0100]

Embedded image Compound 7 (average molecular weight 800) (40.0 g) and Compound 2 (1
5.5 g) in THF (200 g)
ml) and then dissolved in dibutyltin dilaurate (0.44 ml).
g) was added. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a colorless product. Its ¹ H-NMR,
From the results of IR and elemental analysis, Compound 7 and Compound 2 showed 1
Reaction with pair 2 causes the isocyanate group of compound 2 to disappear,
It was found that a urethane bond was formed, and that compound 8 was formed. The viscosity of this polymerizable compound 8 is 6000
mPa · s (25 ° C.).

Example 6: Synthesis of polymerizable compound 9

[0102]

Embedded image A colorless product was obtained by reacting compound 7 (average molecular weight 500) (40.0 g) with commercially available acrylic acid (15.0 g) according to a conventional method in the presence of a tosylic acid dehydration catalyst as described above. From the result of ¹ H-NMR, IR and elemental analysis of this product, it was found that the polymerizable compound 9 was formed. The viscosity of this polymerizable compound 9 is 220 mPa · s (2
5 ° C.).

Example 7: Preparation of thermopolymerizable composition A Compound 3 (0.2 g), compound 5 (0.8 g), 8.0 g of diethyl carbonate (DEC), ethylene carbonate (E)
C) 2.0 g, 1.00 g of LiPF ₆ and polymerization inhibitor 2,4-
2.4 mg of diphenyl-4-methyl-1-pentene (trade name: NOFMER MSD, manufactured by NOF Corporation) was mixed to obtain a thermopolymerizable composition for a solid polymer electrolyte. The viscosity of this thermopolymerizable composition was 4.3 mPa · s (25 ° C.).
This thermopolymerizable composition was placed in an argon atmosphere at 25 ° C. for 60 hours.
The viscosity when stored for 4.3 days is 4.3 mPa · s (25 ° C)
Had not changed at all. 5 g of t-hexyl peroxypivalate (trade name: perhexyl PV, manufactured by NOF Corporation) as a thermal polymerization initiator was added to 1 g of the thermally polymerizable composition.
g (5000 ppm) was mixed well in an argon atmosphere. This composition was sandwiched between two calcium fluoride plates (diameter: 2 mm, thickness: 1 mm) under an argon atmosphere to prepare a cell for measuring an infrared absorption spectrum. At this time, in order to secure a clearance, a 5 μm-thick polyimide film frame was used. Next, this cell was set on a hot stage with temperature control (Mettler, hot stage FP82 type), and an FT-IR apparatus (JASCO Corporation, Baroar 3)
Using a mold, the infrared absorption spectrum was measured while heating the cell, and the remaining double bond was quantified from the peak area near 1630 cm ^-1 corresponding to the unsaturated bond. Result 6
After heating at 0 ° C for 60 minutes, the remaining double bond is 0.1% of the quantitation limit.
It was as follows. After adding the initiator, the thermopolymerizable composition was left at 25 ° C. under an argon atmosphere. After 6 hours, the viscosity suddenly increased and the viscosity became 50 mPa · s or more,
The entire composition lost its fluidity and solidified. This thermopolymerizable composition was arranged at intervals of 200 μm using spacers.
After pouring between two SUS plates, the mixture was heated and cured in a closed container at 60 ° C. for 60 minutes to form a polymer solid electrolyte. 2 of this cured product
When the ionic conductivity at 5 ° C. and -10 ° C. was measured by the impedance method, they were 5.3 × 10 ⁻³ and 1.5 × 10 ⁻³ S, respectively.
/ Cm.

Example 8: Preparation of thermopolymerizable composition B Compound 8 (1.0 g), 7.4 g of DEC, 1.8 g of EC, 0.1 g of LiPF ₆ , and 2.7 g of LiBETI (Li · N (O ₂ SCF ₂ CF ₃ ) ₂ )
And polymerization inhibitor NOFMER MSD (manufactured by NOF CORPORATION) 39
The resulting mixture was mixed to obtain a thermopolymerizable composition for a solid polymer electrolyte. The viscosity of this thermopolymerizable composition is 6.3 mPa · s (2
5 ° C.). This thermopolymerizable composition has a viscosity of 6.4 mP when stored in an argon atmosphere at 25 ° C. for 60 days.
a · s (25 ° C.) was hardly changed. To 1 g of this thermopolymerizable composition, 5 mg (5000 ppm) of perhexyl PV (manufactured by NOF Corporation) as a thermal polymerization initiator was mixed well in an argon atmosphere. This composition was treated with a calcium fluoride plate (diameter 2 mm,
1 mm thick) sandwiched between two sheets to produce a cell for measuring the infrared absorption spectrum, and measuring the infrared absorption spectrum while heating the cell. From the peak area corresponding to the unsaturated bond near 1630 cm ⁻¹ , the residual Double bond quantification was performed. As a result, after heating at 60 ° C. for 120 minutes, the residual double bonds
0.1% or less. After adding this initiator to the thermopolymerizable composition, the composition was allowed to stand at 25 ° C. in an argon atmosphere.
After a lapse of time, the viscosity suddenly increased, the viscosity became 50 mPa · s or more, and the entire composition lost its fluidity and solidified. Two SUs having this thermopolymerizable composition arranged at intervals of 200 μm
After injection using a spacer between S plates, 60 ° C in a closed container
It was cured by heating for 120 minutes to obtain a solid polymer electrolyte. When the ionic conductivity of the cured product at 25 ° C. and −10 ° C. was measured by an impedance method, it was 4.8 × 10 ⁻³ ,
Was ^{3 S / cm - 1.2 × 10} .

Example 9: Preparation of thermopolymerizable composition C Compound 9 (1.0 g), DEC 6.0 g, EC 1.5 g, 0.05 g
LiPF ₆ of a mixture of LiBETI and polymerization inhibitor Nofiner MSD (NOF (Ltd.)) 2.8 mg of 2.3g, to obtain a polymer solid electrolyte for thermal composition. The viscosity of this thermopolymerizable composition was 6.0 mPa · s (25 ° C.).
This thermopolymerizable composition was placed in an argon atmosphere at 25 ° C. for 60 hours.
The viscosity when stored for 6.0 days is 6.0 mPa · s (25 ° C)
Had not changed at all. 5 g of t-butyl peroxyneodecanate (trade name: Perbutyl ND, manufactured by NOF Corporation) as a thermal polymerization initiator was added to 1 g of the thermally polymerizable composition.
g (5000 ppm) was mixed well in an argon atmosphere. This composition was sandwiched between two calcium fluoride plates (diameter 2 mm, thickness 1 mm) under an argon atmosphere in the same manner as in Example 7 to prepare a cell for measuring an infrared absorption spectrum. The absorption spectrum was measured, and the remaining double bond was quantified from the peak area corresponding to the unsaturated bond near 1630 cm ^-1 . As a result, after heating at 60 ° C. for 150 minutes,
The remaining double bonds were less than 0.1% of the limit of quantification. After adding this initiator to the thermopolymerizable composition, the composition was added under an argon atmosphere at 25 ° C.
When the composition was left at 30 ° C., the viscosity rapidly increased after 30 hours, and the viscosity became 50 mPa · s or more, and the entire composition lost its fluidity and solidified. This thermopolymerizable composition was injected using a spacer between two SUS plates arranged at intervals of 200 μm using a spacer, and then heated and cured in a closed vessel at 60 ° C. for 150 minutes to form a solid polymer electrolyte. The ionic conductivity of the cured product at 25 ° C. and −10 ° C. was measured by an impedance method and found to be 4.3 × 10 ⁻³ and 1.0 × 10 ⁻³ S / cm, respectively.

Example 10: Preparation of thermopolymerizable composition D Compound 3 (0.1 g), compound 5 (0.8 g), DEC 8.0 g,
EC 2.0 g, 1.00 g LiPF ₆ , aluminum oxide C as inorganic fine particles (secondary particle average particle size about 0.2 μm,
Japan Aerosil Co., Ltd., specific surface area about 100m ² / g)
0.10 g and polymerization inhibitor NOFMER MSD (Nippon Oil & Fats Co., Ltd.)
Was mixed to obtain a thermopolymerizable composition for a solid polymer electrolyte. The viscosity of this thermopolymerizable composition is 10.0 mP
a · s (25 ° C.). When this thermopolymerizable composition was stored in an argon atmosphere at 25 ° C. for 60 days, the viscosity was almost unchanged at 10.5 mPa · s (25 ° C.). 1 g of this thermopolymerizable composition was added with t-
Hexyl peroxyneodecanate (Perhexyl N
D, manufactured by NOF Corporation, 5 mg (5000 ppm) was mixed well in an argon atmosphere. This composition was treated with a calcium fluoride plate (diameter 2 mm, 1 mm) in an argon atmosphere in the same manner as in Example 7.
(mm thickness) sandwiched between two sheets to produce a cell for measuring the infrared absorption spectrum, and measuring the infrared absorption spectrum while heating the cell. From the peak area corresponding to the unsaturated bond around 1630 cm ⁻¹ , the remaining Double bond quantification was performed. As a result, after heating at 60 ° C. for 60 minutes, the residual double bond was found to have a quantitative limit of 0.1%.
% Or less. After adding the initiator to the thermopolymerizable composition,
When left at 25 ° C. in an argon atmosphere, the viscosity suddenly increased after 30 hours, and the viscosity became 50 mPa · s or more, and the entire composition lost its fluidity and solidified. Two sheets of SUS having this thermopolymerizable composition arranged at an interval of 200 μm
After injecting using a spacer between plates, 60 ° C 6
The mixture was cured by heating for 0 minutes to obtain a solid polymer electrolyte. When the ionic conductivity of the cured product at 25 ° C. and −10 ° C. was measured by an impedance method, they were 5.8 × 10 ⁻³ and 1.5 ×, respectively.
It was 10 ^-3 S / cm.

Example 11 Preparation of Thermopolymerizable Composition E Compound 5 (0.7 g) and tripropylene glycol (TPGD)
A: 0.3 g of DEC, 6.0 g of DEC, 1.5 g of EC, 0.05
g of LiPF ₆ , 2.3 g of LiBETI and 2.2 mg of polymerization inhibitor NOFMER MSD (manufactured by NOF CORPORATION),
A thermopolymerizable composition for a solid polymer electrolyte was obtained. The viscosity of this thermopolymerizable composition was 4.1 mPa · s (25 ° C.). The viscosity when this thermopolymerizable composition is stored at 25 ° C. for 60 days in an argon atmosphere is 4.1 mPa · s (25 mPa · s).
° C). 1 g of this thermopolymerizable composition
Then, 5 mg (5000 ppm) of bis (4-t-butylcyclohexyl) peroxydicarbonate (trade name: Parloyl TCP, manufactured by NOF Corporation) was thoroughly mixed in an argon atmosphere as a thermal polymerization initiator. This composition was treated with a calcium fluoride plate (diameter 2 m) in an argon atmosphere in the same manner as in Example 7.
m, 1 mm thick) sandwiched between two sheets to produce a cell for measuring an infrared absorption spectrum, and measuring the infrared absorption spectrum while heating the cell. From the peak area corresponding to the unsaturated bond near 1630 cm ⁻¹ , The remaining double bond was quantified. As a result, after heating at 60 ° C. for 100 minutes, the residual double bond became 0.1% or less of the limit of quantification. After adding this initiator, the thermopolymerizable composition was left at 25 ° C. under an argon atmosphere,
After 6 hours, the viscosity suddenly increased and the viscosity became 50 mPa · s or more, and the entire composition lost its fluidity and solidified. Two sheets of this S were placed at a distance of 200 μm.
After injection using a spacer between US plates, 60
The mixture was cured by heating at 100 ° C. for 100 minutes to obtain a solid polymer electrolyte. The ionic conductivity of the cured product at 25 ° C. and −10 ° C. was measured by an impedance method.
0 ^-3 and 1.2 × 10 ^-3 S / cm.

Comparative Example 1 Preparation of Thermopolymerizable Composition F Compound 3 (2.0 g) and diethyl carbonate (DEC)
8.0 g, 2.0 g of ethylene carbonate (EC), 1.00 g of LiPF ₆ and 4.8 mg of polymerization inhibitor NOFMER MSD (manufactured by NOF CORPORATION) were mixed to obtain a thermopolymerizable composition for a solid polymer electrolyte. The viscosity of this thermopolymerizable composition is 15.
It was 5 mPa · s (25 ° C.). The viscosity when this thermopolymerizable composition was stored at 25 ° C. for 60 days in an argon atmosphere was almost unchanged at 16.8 mPa · s (25 ° C.). 5 mg (50 g) of perhexyl PV (manufactured by NOF Corporation) as a thermal polymerization initiator was added to 1 g of the thermally polymerizable composition.
00 ppm) was mixed well in an argon atmosphere. This composition was sandwiched between two calcium fluoride plates (diameter 2 mm, thickness 1 mm) under an argon atmosphere in the same manner as in Example 7 to prepare a cell for measuring an infrared absorption spectrum. The absorption spectrum was measured, and the remaining double bond was quantified from the peak area corresponding to the unsaturated bond near 1630 cm ^-1 . As a result, after heating at 60 ° C. for 80 minutes, the residual double bond became 0.1% or less of the quantification limit. After adding the initiator, the thermopolymerizable composition was left at 25 ° C. under an argon atmosphere. After 3 hours, the viscosity suddenly increased to 50 m.
Pa · s or more, the fluidity of the entire composition was lost, and the composition was solidified. This thermopolymerizable composition was injected between two SUS plates arranged at intervals of 200 μm using a spacer, and then heated and cured in a closed container at 60 ° C. for 100 minutes to form a polymer solid electrolyte. The ionic conductivity of the cured product at 25 ° C. and −10 ° C. was measured by an impedance method, and was 2.8 × 10 ⁻³ and 0.8 × 10 ⁻³ S / cm, respectively.

Comparative Example 2 Preparation of Thermopolymerizable Composition G Compound 8 (1.0 g), 7.4 g of DEC, 1.8 g of EC, 0.1 g of LiPF ₆ , and 2.7 g of LiBETI (Li · N (O ₂ SCF ₂ CF ₃ ) ₂ )
And polymerization inhibitor NOFMER MSD (manufactured by NOF Corporation) 10
The resulting mixture was mixed to obtain a thermopolymerizable composition for a solid polymer electrolyte. The viscosity of this thermopolymerizable composition is 6.3 mPa · s (2
5 ° C.). This thermopolymerizable composition is gelled on agar after storage at 25 ° C. for 35 days in an argon atmosphere,
The viscosity could not be measured. Perhexyl PV (manufactured by NOF Corporation) was used as a thermal polymerization initiator in 1 g of the thermopolymerizable composition.
5 mg (5000 ppm) was mixed well in an argon atmosphere. This composition was sandwiched between two calcium fluoride plates (diameter 2 mm, thickness 1 mm) under an argon atmosphere in the same manner as in Example 7 to prepare a cell for measuring an infrared absorption spectrum. Measure the absorption spectrum, and measure 1630 cm ^-1
The remaining double bond was quantified from the peak area corresponding to the nearby unsaturated bond. As a result, after heating at 60 ° C. for 60 minutes,
The remaining double bonds were less than 0.1% of the limit of quantification. After adding this initiator to the thermopolymerizable composition, the composition was added under an argon atmosphere at 25 ° C.
When left at ℃, the viscosity suddenly increased after 30 minutes, the viscosity became 50 mPa · s or more, the fluidity of the entire composition was lost, and the composition was solidified. This thermopolymerizable composition was injected using a spacer between two SUS plates arranged at intervals of 200 μm using a spacer, and then heated and cured in a closed container at 60 ° C. for 60 minutes to form a solid polymer electrolyte. The ionic conductivity of the cured product at 25 ° C. and −10 ° C. was measured by an impedance method and found to be 5.0 × 10 ⁻³ and 1.2 × 10 ⁻³ S / cm, respectively.

Comparative Example 3 Preparation of Thermopolymerizable Composition H Compound 5 (0.7 g), TPGDA (manufactured by NOF Corporation) 0.3 g, DE
C 6.0 g, EC 1.5 g, 0.05 g LiPF ₆ , 2.3 g Li
BETI and 5.5 mg of polymerization inhibitor NOFMER MSD (manufactured by NOF Corporation) were mixed to obtain a thermopolymerizable composition for a solid polymer electrolyte. The viscosity of this thermopolymerizable composition was 4.1.
mPa · s (25 ° C.). The viscosity when this thermopolymerizable composition was stored in an argon atmosphere at 25 ° C. for 60 days was 4.1 mPa · s (25 ° C.), which was not changed at all. 5 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP, manufactured by NOF CORPORATION) as a thermal polymerization initiator was added to 1 g of the thermopolymerizable composition.
g (5000 ppm) was mixed well in an argon atmosphere. This composition was sandwiched between two calcium fluoride plates (diameter 2 mm, thickness 1 mm) under an argon atmosphere in the same manner as in Example 7 to prepare a cell for measuring an infrared absorption spectrum.
Measure the infrared absorption spectrum while heating at 0 ° C.
The remaining double bond was quantified from the peak area corresponding to the unsaturated bond in the vicinity of cm ^-1 , but hardening did not occur, and after 30 hours, about 10% of the initial double bond remained.

Example 12: Preparation of thermopolymerizable composition I Compound 5 (0.7 g) and tripropylene glycol (TPGD)
A: 0.3 g of Nippon Yushi, 9.2 g of PC (propylene carbonate), 3.0 g of TEMA.BF ₄ (triethylmethylammonium.tetrafluoroborate), and 3.0 mg of polymerization inhibitor NOFMER MSD (Nippon Yushi Co., Ltd.) The mixture was mixed to obtain a thermopolymerizable composition for a solid polymer electrolyte. The viscosity of this thermopolymerizable composition was 4.5 mPa · s (25 ° C.). This thermopolymerizable composition was placed in an argon atmosphere at 25
The viscosity when stored at 60 ° C for 60 days is 4.6 mPa · s
(25 ° C.) and hardly changed. To 1 g of this thermopolymerizable composition, 5 mg (5000 ppm) of perhexyl PV (manufactured by NOF Corporation) as a thermopolymerization initiator was well mixed in an argon atmosphere. This composition was sandwiched between two calcium fluoride plates (diameter 2 mm, thickness 1 mm) under an argon atmosphere in the same manner as in Example 7 to prepare a cell for measuring an infrared absorption spectrum. Measure the absorption spectrum,
The remaining double bond was quantified from the peak area near 1630 cm ^-1 corresponding to the unsaturated bond. As a result, 60 ° C 60
After heating for a minute, the residual double bond became 0.1% or less of the limit of quantification. After the addition of the initiator, the thermopolymerizable composition was left at 25 ° C. under an argon atmosphere. After 5 hours, the viscosity suddenly increased and the viscosity became 50 mPa · s or more. did. This thermopolymerizable composition is
After injection using a spacer between two SUS plates arranged at an interval of 00 μm, the mixture was heated and cured in a closed container at 60 ° C. for 100 minutes to form a polymer solid electrolyte. 25 ° C of this cured product,
When the ionic conductivity at -10 ° C was measured by the impedance method, they were 12.0 × 10 ^-3 and 3.0 × 10 ^-3 S / c, respectively.
m.

Example 13 Production of Lithium Cobaltate Positive Electrode 11 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, pulverization was performed to obtain a LiCoO ₂ powder. This LiCoO ₂ powder, acetylene black, and polyvinylidene fluoride were mixed at a mass ratio of 8: 1: 1, and an excess N-methylpyrrolidone solution was added to obtain a gel composition. About 2
It was applied on a 5 μm aluminum foil to a thickness of about 75 μm and press-molded to obtain a lithium cobaltate positive electrode sheet. This sheet was cut into a 38 mm square to obtain a positive electrode for a battery.

Example 14: Production of graphite negative electrode MCMB graphite manufactured by Osaka Gas Co., Ltd., vapor-phase graphite fiber manufactured by Showa Denko KK (average fiber diameter: 0.3 μm, average fiber length: 2.0 μm)
An excess N-methylpyrrolidone solution was added to a mixture of polyvinylidene fluoride at a mass ratio of 8.6: 0.4: 1.0 to obtain a gel composition. About 2
Applying pressure molding to a thickness of about 85 μm on a copper foil of 0 μm,
A graphite negative electrode sheet was obtained. This sheet was cut into a 40 mm square to obtain a negative electrode for a battery.

Example 15: Manufacture of an all-solid Li-ion secondary battery In a argon atmosphere glove box, the sheet-like graphite negative electrode (40 mm square) manufactured in Example 14 was used.
Initiator-added thermopolymerizable composition prepared in Example 7 using the lithium cobaltate positive electrode (38 mm square) manufactured by the above method and a polyethylene microporous film separator (42 mm square, 25 μm, opening ratio: about 60%, Asahi Kasei hypopore) A was allowed to stand for about 1 hour to be impregnated, and then the positive electrode and the negative electrode were bonded together with a microporous film interposed therebetween. At this time, the porous film is connected to the positive and negative edges (4
Side) and stuck slightly out of each side. This was stored in a bag (exterior body) made of a three-layer laminate of PP / Al / PET so that the lead wire portion came out of the opening side, and the inside of the bag was pressed using a 1.1 mm thick glass plate from both sides. Gas was expelled, and the opening was sealed by heating and fusion with the lead wire. Further, while pressurizing with a glass plate, the entire battery is placed in a 60 ° C.
By heating for a minute, the thermopolymerizable composition in the battery was cured to obtain a thin all-solid Li-ion battery as shown in FIG. The battery was operated at 25 ° C and -10 ° C with an operating voltage of 2.75.
When the battery was charged and discharged at a current of 7 mA with a voltage of 4.1 V, the maximum discharge capacities were 35.0 mAh and 28.0 mAh. At that time, the charge / discharge coulomb efficiency was almost 100%, and no reaction current derived from an uncured product or a decomposition product of the initiator was observed. Also,
Operating voltage 2.75 to 4.1 V at 25 ° C, charging 7 mA, discharging 28
When charge / discharge was repeated at mA, the maximum discharge capacity was 3
At 1.5 mAh, no extreme decrease in capacity was observed even after 250 cycles, and 25.2 mAh, 80% of the maximum capacity.
Had been maintained.

Examples 16 to 19: Production of all-solid Li-ion secondary batteries Except that thermopolymerizable compositions B, C, D, and E were used instead of thermopolymerizable composition A used in Example 15, A thin all-solid Li-ion battery was manufactured in the same manner as in Example 15, and Example 1 was used.
The same characteristic evaluation as that of No. 5 was performed. The characteristics in Examples 15 to 19 were as shown in Table 1.

[0116]

[Table 1]

Comparative Example 4 Production of All-Solid-State Li-Ion Secondary Battery Example 1 was repeated except that the thermopolymerizable composition F prepared in Comparative Example 1 was used instead of the thermopolymerizable composition A used in Example 15. 1
In the same manner as in Example 5, a thin all-solid Li-ion battery was manufactured.
The battery was operated at 25 ° C. and −10 ° C. with an operating voltage of 2.75-4.
When the battery was charged and discharged at 1 V and a current of 7 mA, the maximum discharge capacity was as low as 24.0 mAh and 8.0 mAh. Due to the high viscosity, it is presumed that the standing time of 1 hour is due to insufficient impregnation of the polymerizable composition into the electrode and the separator. When charging and discharging were repeated at an operating voltage of 2.75 to 4.1 V, charging 7 mA and discharging 28 mA at 25 ° C., the maximum discharging capacity was 18.0 mAh, and the capacity at 250 cycles was 5.4 m.
Ah and decreased to 30% of the maximum capacity.

Comparative Example 5 Production of All-Solid-State Li-Ion Secondary Battery The procedure of Example 15 was repeated except that the thermopolymerizable composition G prepared in Comparative Example 2 was used instead of the thermopolymerizable composition A used in Example 15. 1
In the same manner as in Example 5, a thin all-solid Li-ion battery was manufactured.
At this time, a part of the thermopolymerizable composition F was solidified while impregnating the electrode and the separator with the thermopolymerizable composition F. This battery is
Operating temperature 2.75 ~ 4.1V, current 7mA at ℃ and -10 ℃
The maximum discharge capacity was 20.0 mAh,
The capacity was as low as 9.5 mAh. It is presumed that impregnation was insufficient due to solidification of a part of the polymerizable composition during impregnation. In addition, operating voltage 2.75 ~ 4.1V at 25 ° C, charging 7m
A, when charging and discharging were repeated at a discharge of 28 mA, the maximum discharge capacity was 15.0 mAh, and the capacity at 250 cycles was 3.8 mAh, which was 25% of the maximum capacity.

Example 20: Manufacture of activated carbon electrode Steam-activated activated carbon of phenol resin fired product (specific surface area 2
010 m ² / g, average particle size 8 μm, pore volume 0.7 ml
/ G), a vapor-phase graphite fiber manufactured by Showa Denko KK (average fiber diameter: 0.3 μm, average fiber length: 2.0 μm, heat-treated at 2700 ° C), and a mixture of polyvinylidene fluoride in a mass ratio of 8.6: 0.4: 1.0. Was added with an excess N-methylpyrrolidone solution to obtain a gel composition. This composition was applied on an aluminum foil of about 25 μm in a thickness of about 150 μm and pressed to obtain an activated carbon electrode sheet. This sheet was cut into 40 mm squares, and 10
After vacuum drying at 0 ° C. for 10 hours, an activated carbon electrode for an electric double layer capacitor (224.0 mg) was obtained.

Example 21: Production of all-solid-state electric double layer capacitor In an argon atmosphere glove box, the activated carbon electrode (224.0 mg, 40 mm square) 2 produced in Example 20 was used.
A sheet of Teflon microporous film separator (42 mm square, 25 μm, manufactured by Mitsui Fluorochemicals) was allowed to stand in the thermopolymerizable composition I prepared in Example 12 for 1 hour to be impregnated. Were bonded together with a microporous film separator therebetween. At this time, the two electrodes were bonded so that the separator slightly protruded from the edges (four sides) of the two electrodes. This is called PP / Al
/ PET is stored in a bag (outer body) made of three-layer laminate so that the lead wire portion comes out from the opening side, and the inside gas is expelled while applying pressure from both sides using a 1.1 mm thick glass plate. The opening was sealed by heating and fusing together with the lead wire. Further, while pressing with a glass plate, the entire battery is placed in a thermostat at 60 ° C. and heated for 120 minutes to cure the thermopolymerizable composition in the battery, thereby obtaining a thin all-solid electric double layer capacitor as shown in FIG. Was. This capacitor is operated at 25 ° C., -10 ° C. and operating voltage 0-2.5.
When charging and discharging were performed at V and a current of 7 mA, the maximum capacities were 8.8 F and 7.2 F, respectively. 25 ° C,
When charging / discharging was performed at 14 mA, the maximum capacity was 8.7 F
Then, even after the charge and discharge were repeated 200 times, the capacity hardly changed.

[0121]

The thermopolymerizable composition for a solid polymer electrolyte of the present invention can easily impregnate porous materials used in an electrochemical device by controlling the viscosity, and fully exhibit the properties of each material. It is excellent in stability without being solidified during the impregnation work because a polymerization inhibitor having a high polymerization inhibitory effect is used. In addition, after impregnation, a thermopolymerizable initiator having a high polymerization initiation ability and a thermopolymerizable compound having a very good polymerizability are used, so that the all-solid-state electrochemical element is quickly cured, and the electrolyte is solidified. It can be easily manufactured. further,
The electrochemical stability is wide, and good characteristics such as current characteristics and cycle characteristics of the electrochemical device can be exhibited.

Since the battery of the present invention uses the above thermopolymerizable composition, it can be easily solidified and thinned. Furthermore, since each element of the positive electrode and / or the negative electrode and / or the separator and the polymer solid electrolyte can be easily compounded, it can be operated with high capacity and high current, and has a long life and excellent reliability. Therefore, the battery of the present invention can be operated 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 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.

The electric double layer capacitor of the present invention has a high output voltage, a large take-out current, good workability, a long life and excellent reliability by using the above thermopolymerizable composition. Furthermore, the electric double layer capacitor of the present invention has a higher voltage, higher capacity,
It is an all-solid-state electric double layer capacitor that can be operated at high current or has good cyclability, and is excellent in safety and reliability. For this reason, it can be used not only as a backup power source but also as a power source for various electric products in combination with a small battery. Moreover, it is excellent in workability such as thinning, and can be used for applications other than the conventional solid type electric double layer capacitor.

[0124]

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a thin all-solid-state battery showing one embodiment of the battery according to the present invention.

FIG. 2 is a schematic cross-sectional view showing one embodiment of a thin all-solid-state electric double layer capacitor according to the present invention.

[0125]

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Porous separator 3 Negative electrode 4 Current collector 5 Heat-fused polymer film 6 Element case 7 Polymer solid electrolyte 8 Polarized electrode 9 Porous separator 10-minute polar electrode 11 Current collector 12 Heat-fused polymer film 13 Device case 14 Polymer solid electrolyte

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5G301 CD01 CE10 5H029 AJ02 AJ03 AJ05 AJ12 AK02 AK03 AK05 AK06 AK16 AL01 AL06 AL07 AL12 AL16 AM00 AM16 BJ04 BJ12 BJ14 CJ02 CJ28 DJ02 DJ04 DJ08 DJ09 EJ12 HJ01 HJ02

Claims (22)

[Claims] 1. A thermopolymerizable composition containing a polymerizable compound and an electrolyte salt and having a viscosity at 25 ° C. of less than 30 mPa · s is injected into an electrochemical element case containing components other than the electrolyte material. And then curing by heating to produce an electrochemical element. 2. A thermopolymerizable composition containing a polymerizable compound and an electrolyte salt and having a viscosity at 25.degree. A method for producing an electrochemical element, comprising: pouring the constituent material into an electrochemical element case, and curing the composition by heating to produce the electrochemical element. 3. The method for producing an electrochemical device according to claim 1, wherein the time required for the thermopolymerizable composition to be cured by heating at 100 ° C. or lower is within 20 hours. 4. At least one thermopolymerizable compound having a polymerizable functional group which becomes a polymer having a crosslinked and / or side chain structure by polymerizing the thermopolymerizable composition, at least one electrolyte salt, A kind of polymerization initiator,
4. A thermopolymerizable composition containing at least one polymerization inhibitor and at least one organic solvent, wherein the polymerization inhibitor is a compound having a vinyl group in a molecule. 3. The method for producing an electrochemical device according to claim 1. 5. The method according to claim 1, wherein the polymerization inhibitor is represented by the following general formula (1). Wherein A represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, Ar represents a phenyl group which may have a substituent, and a is an integer of 0 or 1. ,
The two Ars may be the same or different. 5. The method for producing an electrochemical device according to claim 4, wherein the compound has a structure represented by the following formula: 6. The polymerization initiator according to the following general formula (2): [Wherein, X represents a linear, branched or cyclic alkyl or alkoxy group which may have a substituent;
Represents a linear, branched or cyclic alkyl group which may have a substituent, and m and n are independently 0 or 1, but a combination of (m, n) = (0, 1) Is excluded. ]
The method for producing an electrochemical device according to claim 4, wherein the method is an organic peroxide represented by the following formula: 7. The method for producing an electrochemical device according to claim 6, wherein the amount of active oxygen of the organic peroxide is 1 to 1000 ppm based on the thermopolymerizable composition. 8. The method according to claim 1, wherein the organic peroxide is selected from the group consisting of diacyl peroxides containing no benzene ring, peroxydicarbonates containing no benzene ring, and peroxyesters containing no benzene ring. The method for producing an electrochemical device according to claim 6, wherein 9. The polymerizable compound represented by the following general formula (3):
/ Or general formula (4)[Wherein, R¹And R^ThreeRepresents a hydrogen atom or an alkyl group
Then R^TwoAnd R^FiveIs oxyalkylene, fluorocarbon
Containing oxyfluorocarbon or carbonate groups
A divalent group;^FourIs a divalent group having 10 or less carbon atoms
Represents R^Two, R ^FourAnd R^FiveContains a heteroatom
Having a linear, branched or cyclic structure.
You may do it. x represents 0 or an integer of 1 to 10
You. However, a plurality of the above general formulas (3) and
When the polymerizable functional group represented by (4) is contained,
R in each polymerizable functional group¹, R^Two, R^Three, R^Four, R^Fiveas well as
x may be the same or different. ]
It has at least one polymerizable functional group and has a weight average molecular weight of 1
000 or less.
An electrochemical device according to any one of claims 1 to 8, wherein
Manufacturing method. 10. The thermo-polymerizable composition contains at least one organic solvent selected from carbonates, aliphatic esters, ethers, lactones, sulfoxides and amides. 10. The method for producing an electrochemical device according to any one of 1 to 9. 11. The method according to claim 10, wherein the content of the organic solvent is in the range of 300% by mass or more and 1500% by mass or less based on the thermopolymerizable compound. 12. The method according to claim 1, wherein the electrolyte salt is at least one selected from an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, a transition metal salt, and a protonic acid. 3. The method for producing an electrochemical device according to claim 1. 13. The method according to claim 13, wherein the at least one electrolyte salt is LiP
F₆, LiBF_Four, LiAsF ₆, And LiN (R-S
O_Two)_Two(Wherein R is a perfluorinated compound having 1 to 10 carbon atoms)
Represents a loalkyl group. ) Is a compound selected from
The electrochemical device according to claim 12, wherein
Construction method. 14. A polymer containing a polymerizable compound and an electrolyte salt at 25 ° C.
An electrochemical element manufactured by injecting a thermopolymerizable composition having a viscosity of less than 30 mPa · s into an electrochemical element case containing components other than the electrolyte material, and then curing the composition by heating. 15. A polymer containing a polymerizable compound and an electrolyte salt at 25 ° C.
The time required to increase the viscosity at 50 mPa · s or more at 50 mPa · s or more is 1 hour or more. After the thermopolymerizable composition is injected into the electrochemical element case containing each component material other than the electrolyte material, heating is performed. An electrochemical element manufactured by curing with 16. A battery or an electric double layer capacitor obtained by the method according to claim 1. 17. The case according to claim 14, wherein the electrochemical element case is a case in which a negative electrode / positive electrode stack is accommodated with a wound or laminated separator interposed therebetween.
The battery according to 1. 18. The electrochemical element case according to claim 1, wherein said case is a case in which a polarizable electrode / a polarizable electrode laminate is interposed via a wound or laminated separator.
16. The electric double layer capacitor according to 4 or 15. 19. The negative electrode active material is lithium, lithium alloy,
18. The battery according to claim 17, wherein at least one material selected from a carbon material capable of storing and releasing lithium ions, an inorganic compound capable of storing and releasing lithium ions, and a conductive polymer capable of storing and releasing lithium ions is used. 20. The battery according to claim 17, wherein the positive electrode active material uses at least one material selected from a conductive polymer, a metal oxide, a metal sulfide, and a carbon material. 21. The electric double layer capacitor according to claim 18, wherein the polarizable electrode material uses at least one material selected from a conductive polymer, a metal oxide and a carbon material. 22. The polarizable electrode material is activated carbon.
9. The electric double layer capacitor according to 8.