JPH11171912A - Polymerizable composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful for a solid polyelectrolyte, good in polymerizability and excellent in handleability by including a plolymerizable compound and a specified polymerization initiator therein. SOLUTION: This composition is obtained by including (A) one or more polymerizable compounds, (B) one or more polymerization initiators comprising a compound having the ability to decompose with an acid and initiate the polymerization, as necessary, (C) one or more electrolytic salts having a free acid, etc. A quaternary boric salt-based initiator or the like represented by formula I [R<1> to R<4> are each a (substituent group-containing)alkyl, a heterocyclic ring or the like; Z<4> is a quaternary ammonium cation, a metal cation or the like] is preferred as the component B. The component A preferably has a polymerizable functional group represented by formula II or formula III [R<5> and R<7> are each H or an alkyl; R<6> and R<9> are each a bivalent group containing oxyalkylene or the like and/or a carbonate; R<8> is a <=10C bivalent (heteroatom- containing) group of a linear, a branched or a cyclic structure; (x) is 0 or 1-10] or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymer solid electrolyte having good processability, which is polymerized using an initiator which is easily decomposed by an acid, particularly a quaternary boron salt-based initiator having a high ability. The present invention relates to a method for producing the same, and a polymerizable composition for obtaining the solid polymer electrolyte. Further, the present invention relates to an electrode, a battery, an electric double layer capacitor using the polymerizable composition and / or the polymer solid 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, solid electrolytes are used as all-solid primary batteries, secondary batteries, and electric double layers as new ion conductors that replace conventional electrolyte solutions. It is widely applied to electrochemical devices such as capacitors. Current electrochemical devices using an electrolyte solution have a problem in long-term reliability because liquid leakage to the outside of the component or elution of the electrode material is likely to occur. On the other hand, a product using a solid electrolyte does not have such a problem, and it is easy to reduce the thickness. Further, the solid electrolyte is excellent in heat resistance, and is advantageous in a process of manufacturing a product such as a battery. In particular, those using a solid electrolyte containing a polymer compound as a main component have the advantage that the flexibility of the battery is increased and that the battery can be processed into various shapes as compared with inorganic substances. However, those studied so far have had a problem that the extraction current is small because the ionic conductivity of the solid polymer electrolyte is low.

Recently, LiCoO ₂ , LiNiO ₂ , Li
Many lithium secondary batteries use inorganic oxides such as MnO ₂ and MoS ₂ and inorganic chalcogenides for the positive electrode and lithium, lithium alloys, carbon materials capable of inserting and extracting lithium ions, and inorganic or polymer compounds for the negative electrode. Has been studied. For example, "Journal of Electrochemical Society (J. Electrochem. Soc.)
138 (No. 3, page 665, 1991), a battery using MnO ₂ or NiO ₂ as a positive electrode is reported. These have attracted attention because of their high capacity per weight or volume. In addition, there have been many reports on batteries using a conductive polymer as an electrode active material. For example, a lithium secondary battery using a polyaniline as a positive electrode and a lithium alloy as a negative electrode is described in “27th Battery Symposium,
A05L and 3A06L, 1986, Bridgestone and Seiko have already marketed coin-type batteries for backup power. In addition, polyaniline has attracted attention as a positive electrode active material having high capacity and excellent flexibility. Furthermore, in recent years, a carbon material having a large specific surface area such as activated carbon or carbon black has been used as a polarizable electrode for a memory backup power supply or the like.
In the meantime, electric double layer capacitors in which an electrolyte solution is arranged have been frequently used. For example, "Functional Materials 1989 2
In the monthly issue, p. 33, a capacitor using a carbon-based polarizable electrode and an organic electrolyte is described in "173rd Electrochemical Society Meeting Atlanta Georgia, 5th.
Monthly, No. 18, 1988 "describes an electric double layer capacitor using a sulfuric acid aqueous solution. Japanese Patent Application Laid-Open No. 63-244570 discloses an electric double layer capacitor using Rb ₂ Cu ₃ I ₃ Cl ₇ having high electric conductivity as an inorganic solid electrolyte.

However, current batteries and electric double-layer capacitors using an electrolyte solution are liable to leak out of the capacitor when the battery is used for a long period of time or when an abnormality such as high voltage is applied. Have problems with long-term use and reliability. On the other hand, conventional batteries and electric double layer capacitors using an inorganic ion conductive material have a problem that the decomposition voltage of the ion conductive material is low and the output voltage is low. The ionic conductivity of the polymer solid electrolyte generally studied is 10 ⁻⁴ to 10 ⁻⁵ S / at room temperature.
Although improved to the order of centimeters, it is still at least two orders of magnitude lower than liquid ion-conductive materials. Also, 0
When the temperature is lower than or equal to ° C., the ionic conductivity is further extremely reduced. Furthermore, when these solid electrolytes are incorporated into devices such as batteries and electric double-layer capacitors, or when these solid electrolytes are thinly incorporated into batteries and electric double-layer capacitors, composites with electrodes and securing of contact properties are required. Processing technology was difficult and there was a problem with the manufacturing method.

[0005] To solve these problems, (meth)
Improvement of ion conductivity has been achieved by using a polymer solid electrolyte obtained by polymerizing a composition comprising an acrylate monomer or a prepolymer / electrolyte salt / organic solvent (US Pat. No. 4,792,504). Also, in order to improve the contact with the electrode when applied to an electrochemical device, a liquid composition consisting of a prepolymer / electrolyte salt / organic solvent is applied onto the electrode, then polymerized with actinic light and adhered to the electrode. There is also a study of solidification in a state of being made (US Patent No. 4,830,939). However, these systems also have insufficient film strength to be used as separators for batteries and the like, and there is room for improvement in industrial handling. Further, when polymerization is performed by heating or actinic rays using a usual initiator and applied to a battery or an electric double layer capacitor, problems such as poor polymerization and a short pot life remain.

[0006] Conventionally, polymerization by actinic light is performed by curing a coating film.
It is widely used in printing and semiconductor resists. Especially the curing method is energy saving, global environmental problem,
The field of application is also actively researched and developed from the viewpoint of economy. Curing of printing ink (for example, see JP-A-1-229)
No. 084, JP-A-2-22370), an ink containing an ultraviolet polymerization initiator is being studied. However, a polymerizable composition containing a pigment, a dye having a high ultraviolet shielding effect, and the like has a problem in that ultraviolet light is transmitted, and there is a problem that only the surface of the polymerizable composition is cured and the inside is not cured. In addition, many of the colored substances generally have an absorption in the ultraviolet region, and when the colored substance is thick, poor curing inside has been a problem.

[0007] When polymerization by actinic light is applied to a battery or an electric double layer capacitor, for example, a polymerizable composition for a polymer solid electrolyte is introduced into a package or an electrode to provide an economically advantageous activity. Even when the photopolymerization initiator is used for curing, a general polymerization initiator has a problem that the active light is blocked by the package material and the electrode material, and the polymerization of the polymerizable composition inside is insufficient. For such polymerization of the actinic ray-shielding portion, it is natural to consider using a general thermal polymerization initiator to carry out heat polymerization.However, since a high temperature is required and the polymerization rate is slow, the constituent materials are required. Polymerization may be insufficient due to the volatilization or deterioration of the polymer or the influence of a polymerization inhibitor present in a constituent material such as oxygen or a metal. On the other hand, when a thermal polymerization initiator having a high initiating ability and a low decomposition half-life temperature is used, the pot life of the composition is shortened. Occurs.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymerizable composition useful for a solid polymer electrolyte, having good polymerizability and excellent handleability. The present invention also provides
An object of the present invention is to provide a polymer solid electrolyte having high ionic conductivity, stability and good processability, and a method for producing the same. Another object of the present invention is to provide a battery electrode and an electric double layer capacitor electrode which are composited with a polymer solid electrolyte, have excellent workability, can operate at a high capacity and a high current, and have a long life. Still another object of the present invention is to provide a primary battery and a secondary battery that can be operated at high capacity and high current, have a long life, have excellent reliability, and can be manufactured at low cost. Another object of the present invention is to provide an electric double layer capacitor which has a high output voltage, a large take-out current, good workability, a long service life, excellent reliability and low cost.

[0009]

Means for Solving the Problems The present inventors have focused on the fact that free acids such as HF and HCl are present in electrolyte salts used in electrochemical devices such as batteries and electric double layer capacitors, and are usually stable. However, by focusing on an initiator that can be easily decomposed by the free acid and adding the acid-decomposable initiator to the polymerizable composition for a solid polymer electrolyte, the pot life is usually long, and It has been found that a polymerizable composition having good polymerizability and good polymerizability can be obtained in an electrode or a battery. In particular, it has been found that a compound having a quaternary boron anion represented by the general formula (1) as an initiator has a high ability to initiate by acid decomposition and is suitable for the polymerizable composition for a polymer solid electrolyte.

Embedded image [Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an allyl optionally having a substituent. Group, an aralkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a silyl group which may have a substituent, a heterocyclic group, Or a halogen atom, and Z ⁺ represents a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a phosphonium cation, a sulfonium cation, an oxosulfonium cation, an iodonium cation, or a metal cation. ]

The present inventors further have the general formula (2) or the general formula (3)

Embedded image

Embedded image [Wherein, R ⁵ and R ⁷ represent hydrogen or an alkyl group;
⁶ , R ⁹ represents a divalent group containing oxyalkylene, fluorocarbon, oxyfluorocarbon, and / or carbonate, and R ⁸ represents a divalent group having 10 or less carbon atoms.
The divalent group may contain a hetero atom, and may be linear,
Any of a branched structure and a cyclic structure may be used. x shows 0 or the numerical value of 1-10. However, the values of R ^{5 to} R ⁹ and x in a plurality of polymerizable functional groups represented by the above general formula (2) or (3) in the same molecule are independent of each other and are the same. No need. A polymerizable compound having a polymerizable functional group represented by the formula
It has been found that, in a polymerizable composition combined with a graded boron anion-based initiator, the residual double bond is small even with a small amount of the initiator added, and the polymerization proceeds completely.

Furthermore, the present inventors have found that a polymer solid electrolyte containing a polymer having a crosslinked and / or side chain group obtained from the polymerizable composition has high ionic conductivity and good stability. . Furthermore, the present inventors have found that a primary battery, a secondary battery and an electric double layer capacitor using the polymer solid electrolyte for the inside of an electrode and a separator layer have good workability, can operate at a high capacity and a high current, and have a long life. And excellent in reliability.

That is, in the present invention, the above object has been achieved by developing the following. 1) A polymerizable composition for a solid polymer electrolyte comprising at least one type of polymerizable compound and at least one type of polymerization initiator, wherein the at least one type of polymerization initiator is capable of being decomposed by an acid to initiate polymerization. A polymerizable composition for a solid polymer electrolyte, comprising: 2) The polymerizable composition for a solid polymer electrolyte as described in 1) above, further comprising an electrolyte salt having a free acid. 3) at least one polymerization initiator represented by the above general formula (1)
The polymerizable composition for a solid polymer electrolyte according to the above 1) or 2), which is a quaternary boron salt-based initiator represented by the following formula:

4) The polymerization for a solid polymer electrolyte according to any one of 1) to 3) above, wherein at least one polymerizable compound has a polymerizable functional group represented by the general formula (2). Composition. 5) The polymerizable composition for a solid polymer electrolyte according to any one of 1) to 3) above, wherein at least one polymerizable compound has a polymerizable functional group represented by the general formula (3). 6) The above 1) to 5) containing at least one organic solvent.
The polymerizable composition for a solid polymer electrolyte according to any one of the above. 7) The polymerizable composition for a solid polymer electrolyte according to any one of 1) to 6) above, comprising an inorganic filler having a size of 0.01 to 100 µm. 8) The polymer solid electrolyte according to any one of 1) to 7) above, which comprises at least one electrolyte salt selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, transition metal salts, and protonic acids. Polymerizable composition.

9) The quaternary boron salt-based initiator in the polymerizable composition for a solid polymer electrolyte according to any one of the above 3) to 8) is decomposed by an acid and / or heat to prepare the polymerizable composition. Polymer solid electrolyte obtained by polymerization. 10) A solid polymer electrolyte obtained by polymerizing the polymerizable composition for a solid polymer electrolyte according to any one of 1) to 8) above with a polymerization initiator decomposed by an acid released from an electrolyte salt. 11) A polymer solid electrolyte characterized by decomposing a polymerization initiator in the polymerizable composition for a polymer solid electrolyte according to any one of 1) to 8) with an acid and polymerizing the polymerizable composition. Manufacturing method. 12) Decomposing the quaternary boron salt-based initiator in the polymerizable composition for a solid polymer electrolyte according to any one of the above 3) to 8) with an acid and / or heating to polymerize the polymerizable composition. A method for producing a solid polymer electrolyte, comprising:

13) An electrode for a battery, comprising a polymer obtained from at least one of the polymerizable compositions for a solid polymer electrolyte according to any one of the above 3) to 8), and an electrode active material. 14) A mixture containing at least one polymerizable composition for a solid polymer electrolyte according to any one of the above 3) to 8) and an electrode active material is prepared, and after molding the mixture, 4% of the polymerizable composition A method for producing an electrode for a battery, comprising decomposing a graded boron salt-based initiator by an acid and / or heating to polymerize the polymerizable composition. 15) An electrode for an electric double layer capacitor, comprising a polymer obtained from at least one of the polymerizable compositions for a solid polymer electrolyte according to any one of the above 3) to 8), and a polarizable material. 16) A mixture containing at least one polymerizable composition for a solid polymer electrolyte according to any of the above 3) to 8) and a polarizable material is prepared, and after molding the mixture, 4 A method for producing an electrode for an electric double layer capacitor, comprising decomposing a graded boron salt-based initiator by an acid and / or heating to polymerize the polymerizable composition.

17) A battery using the polymer solid electrolyte described in 9) or 10) above. 18) A battery using the electrode according to 13 above. 19) The battery according to the above 17), wherein the negative electrode of the battery uses at least one material selected from lithium, a lithium alloy, a carbon material capable of inserting and extracting lithium ions, an inorganic oxide, an inorganic chalcogenide, and a conductive polymer. Or the battery according to 18). 20) The battery according to any one of 17) to 19), wherein the positive electrode of the battery is made of a conductive polymer, an inorganic oxide, an inorganic chalcogenide, and / or a carbon material. 21) An electric double layer capacitor using the polymer solid electrolyte described in 9) or 10) above. 22) An electric double layer capacitor using the electrode described in 15) above.

23) At least one kind of the polymerizable composition for a solid polymer electrolyte according to any one of the above 1) to 8) is placed in a structure for battery construction or placed on a support, and the polymerizable composition is provided. A method for producing a battery, comprising decomposing a polymerization initiator therein with an acid and polymerizing the polymerizable composition. 24) At least one kind of the polymerizable composition for a solid polymer electrolyte according to any one of the above 3) to 8) is placed in a structure for battery construction or placed on a support, and 4 A method for producing a battery, comprising decomposing a graded boron salt-based initiator by an acid and / or heating to polymerize the polymerizable composition. 25) The polymerizable composition according to any one of 1) to 8) above, wherein at least one kind of the polymerizable composition for a solid polymer electrolyte is placed in a structure for forming an electric double layer capacitor or disposed on a support. A method for producing an electric double layer capacitor, comprising decomposing a polymerization initiator therein with an acid and polymerizing the polymerizable composition. 26) The polymerizable composition according to any one of 3) to 8) above, wherein at least one kind of the polymerizable composition for a solid polymer electrolyte is placed in a structure for forming an electric double layer capacitor or placed on a support, and A method for producing an electric double layer capacitor, comprising decomposing a quaternary boron salt-based initiator therein by an acid and / or heating to polymerize the polymerizable composition.

27) A fluorinated electrolyte salt having a free acid or an electrolytic solution in which a fluorinated electrolyte salt having a free acid is dissolved is disposed on a support, and then at least one polymerizable compound and at least one kind of the General formula (1)
By adding a polymerizable composition containing a quaternary boron salt-based initiator represented by
A method for producing a polymer solid electrolyte, comprising decomposing a graded boron salt-based initiator with a free acid and polymerizing the polymerizable composition. 28) An electrolyte solution in which a fluorinated electrolyte salt having a free acid or a fluorinated electrolyte salt having a free acid is previously dissolved is placed in a structure for forming a battery or placed on a support, and then at least one kind of a polymerizable compound and By adding a polymerizable composition containing at least one quaternary boron salt-based initiator represented by the general formula (1) and not containing an electrolyte salt and bringing them into contact with each other, the quaternary boron salt-based initiator is converted into a free acid Wherein the polymerizable composition is polymerized. 29) A fluorine-based electrolyte salt having a free acid or an electrolyte solution in which a fluorine-based electrolyte salt having a free acid is dissolved is placed in a structure for forming an electric double layer capacitor or placed on a support, and then at least one type of polymerization is performed. A quaternary boron salt-based initiator by adding and contacting a polymerizable composition containing a conductive compound and at least one quaternary boron salt-based initiator represented by the general formula (1), but not containing an electrolyte salt. Is decomposed with a free acid to polymerize the polymerizable composition.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [1] Polymerizable Composition for Polymer Solid Electrolyte (1-a) Initiator The initiator used for the polymerizable composition for a polymer solid electrolyte of the present invention is preferably one that is decomposed by an acid and generates a radical. As such an initiator, the following general formula (1)
The boron salt-based initiator represented by

Embedded image [Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an allyl optionally having a substituent. Group, an aralkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a silyl group which may have a substituent, a heterocyclic group, Or a halogen atom, and Z ⁺ represents a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a phosphonium cation, a sulfonium cation, an oxosulfonium cation, an iodonium cation, or a metal ion. ]

Specific examples of the anion moiety of the quaternary boron salt-based initiator include n-butyltriphenyl borate,
-Octyl triphenyl borate, n-dodecyl triphenyl borate, sec-butyl triphenyl borate, t-butyl triphenyl borate, benzyl triphenyl borate, n-butyl trianisyl borate, n
-Octyl trianisyl borate, n-dodecyl trianisyl borate, n-butyl tri (4-tolyl) borate, n-butyl tri (2-tolyl) borate, n-butyl tri (4-t-butylphenyl) borate, n-butyl tri ( 4-fluoro-2-methylphenyl) borate, n-butyl tri (4-fluorophenyl) borate, n-butyl trinaphthyl borate, triphenylsilyl triphenyl borate, diphenylmethyl silyl triphenyl borate, dimethylphenyl silyl triphenyl borate, Examples include trimethylsilyl triphenyl borate, tetra-n-butyl borate, di-n-butyl diphenyl borate, tetrabenzyl borate and the like.

Specific examples of the cation moiety of the quaternary boron salt-based initiator represented by the general formula (1) include tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, tetraoctylammonium, methyl Quinolinium, ethylquinolium, methylpyridinium, ethylpyridinium, tetramethylphosphonium, tetra-n-butylphosphonium, trimethylsulfonium, triphenylsulfonium, trimethylsulfoxonium, diphenyliodonium, di (4
-T-butylphenyl) iodonium, lithium, sodium and the like. These anion part and cation part can be used in the present invention in any combination. The present invention is not limited to these examples,
These quaternary boron salt-based initiators may be used in combination of two or more. The preferable addition amount of these quaternary boron salt-based initiators is 10 to 10 in the polymerizable composition.
0000 ppm, particularly preferably 10 to 10000 ppm, more preferably 10 to 1000 ppm.

Since the above quaternary boron salt-based initiator can be decomposed by heating to generate radicals, the polymerizable composition of the present invention can be naturally polymerized by heating.
In the present invention, other actinic rays and / or thermal polymerization initiators may be used in combination. Examples of the actinic ray polymerization initiator include a compound having a structure represented by the general formula (4). Ar-CO-X (4) [wherein, Ar represents an aryl group which may have a substituent, and X represents an alkyl group, a hydroxy-substituted alkyl group, a halogen-substituted alkyl group, an alkoxy-substituted alkyl group, a morpholino-substituted alkyl. Group, an amino-substituted alkyl group, a benzyl group, a hydroxy-substituted benzyl group, an alkoxy-substituted benzyl group, an alkoxycarbonyl group, an aryl group which may have a substituent, or a phosphinoyl group having a substituent. Specific examples of the general formula (4) include benzoin-based compounds such as benzoin isobutyl ether, benzoin isopropyl ether, benzoin ethyl ether, and benzyldimethyl ketal, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1. -ON,
1- (4-isopropylphenyl) -2-hydroxy-
2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-t-butyl-trichloroacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-
Acetophenone-based compounds such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, glyoxyester-based compounds such as methylphenylglyoxylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Acylphosphine oxide compounds such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, hydroxybenzophenone,
Benzophenone compounds such as phenylbenzophenone and acrylated benzophenone are exemplified.

The thermal polymerization initiator includes a system that causes homolysis by heat to generate radicals, and a system between the two substances.
It is broadly classified into a binary system that generates a radical by causing an electron transfer reaction. Examples of the former include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile, and examples of the latter include a redox initiator. For example, general formula (5) X—C (＝ O) —O—O— (C ＝ O) _m — (O) _n —Y (5) [wherein, X is an alkyl which may have a substituent. Y is a group, an alkoxy group, or an alkyl group which may have a substituent, and may have any of a linear, branched, or cyclic structure. However, X and Y are each independent,
It doesn't have to be the same. In the formula, m and n are each 0 or 1, except for the combination of (m, n) = (0, 1). Azobisdiphenylmethane, 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobis (2-methylpropionate)
Peroxides having a benzene ring, such as azo compounds such as benzoin isobutyl ether, benzoin compounds such as diethoxyacetophenone, benzophenone compounds such as benzophenone and methyl benzoylbenzoate. Among them, the polymerization initiator represented by the above (5) has excellent electrochemical stability affecting cycle characteristics and the like, does not generate gas, and can be said to be a particularly preferable thermal polymerization initiator. Examples of the organic peroxide represented by the general formula (5) include diacyl peroxide, peroxydicarbonate, and peroxyester. Specifically, 3,5,5-trimethylhexanoyl 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-methoxybutyl peroxydicarbonate, di (3
-Methyl-3-methoxybutyl) peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanate, 1-cyclohexyl-1-methylethylperoxyneodecanate, t-hexylperoxyneone Decanate, t-butyl peroxy neodecane, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1 -Cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate and the like.

The amount of the thermal polymerization initiator to be added is defined as active oxygen content defined by the following formula: active oxygen content (% by weight) = (amount of organic peroxide / amount of polymerizable composition) × (16) × number of peroxide bonds / organic peroxide molecular weight) That is, active oxygen (—O
The value obtained by dividing the atomic weight of-) by the molecular weight of the organic peroxide and the weight% of the organic peroxide in the polymerizable composition is 1 to 1000 ppm, and 10 to 500 ppm.
Is particularly preferable, and 10 to 150 ppm is more preferable. If the amount of active oxygen is too small, the reaction does not proceed sufficiently. If the amount of active oxygen is excessive, the amount of the terminator due to the initiator is large, and the molecular weight tends to be low, and the electrochemical properties such as the problem of insufficient film strength and the deterioration of current characteristics and cycle characteristics are adversely affected.

(1-b) Polymerization Inhibitor A polymerization inhibitor can be added to the polymerizable composition of the present invention for the purpose of preventing polymerization during storage.
Specific examples of the polymerization inhibitor that can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone,
Examples include alkyl-substituted hydroquinone, catechol, t-butyl catechol, phenothiazine and the like.

(1-c) Polymerizable compound In general, as the polymer in the polymer solid electrolyte, those which are non-electroconductive, can dissolve various electrolyte salts, and can absorb and hold various organic polar solvents are used. . Such polymers include polyalkylene oxides, polyalkyl imines, polyacrylonitriles, polycarbonates, poly (meth) acrylates, polyphosphazenes,
Examples include polar thermoplastic polymers and heteropolymers having hetero atoms, such as polyvinylidene fluoride, polyurethane, polyamide, polyester, and polysiloxane. In particular, since the crosslinked polymer is a viscoelastic body and has good strength, it is suitable for the polymer solid electrolyte of the present invention. The cross-linking represented here includes not only a cross-linked chain formed by a covalent bond, but also a cross-linked side chain which is cross-linked by an ionic bond or a hydrogen bond, and a cross-linked chain which is physically cross-linked through various additives. In. Among the above polymers, polyalkylene oxide, polyurethane, oxyalkylene such as polycarbonate,
Those containing a urethane or carbonate structure in the molecular structure are preferable because they have good compatibility with various polar solvents and good electrochemical stability. Further, from the viewpoint of stability, those having a fluorocarbon group such as polyvinylidene fluoride in the molecular structure are also preferable. These oxyalkylene, urethane, carbonate and fluorocarbon groups may be contained in the same polymer. The number of repetitions of these groups may be in the range of 1 to 1000, and preferably in the range of 5 to 100. Therefore, the polymer used in the polymer solid electrolyte of the present invention includes, among the above-mentioned polymers, a compound represented by the general formula (2):
Or (3)

Embedded image

Embedded image [Wherein, R ⁵ and R ⁷ represent hydrogen or an alkyl group;
⁶ , R ⁹ represents a divalent group containing oxyalkylene, fluorocarbon, oxyfluorocarbon, and / or carbonate, and R ⁸ represents a divalent group having 10 or less carbon atoms.
The divalent group may contain a hetero atom, and may be linear,
Any of a branched structure and a cyclic structure may be used. x shows 0 or the numerical value of 1-10. However, the values of R ^{5 to} R ⁹ and x in a plurality of polymerizable functional groups represented by the above general formula (2) or (3) in the same molecule are independent of each other and are the same. No need. The polymer obtained by curing at least one type of polymerizable compound having a polymerizable functional group represented by the formula (1) is easy to form a film, has a good film strength, and has a good compatibility with an electrode used in various electrochemical devices. Composite is easy and preferable. Therefore, in the polymerizable composition for a solid polymer electrolyte of the present invention, the polymerizable compound is preferable.

In the polymerizable compound having a functional group represented by the general formula (2) or (3) having oxyalkylene, urethane, fluorocarbon, oxyfluorocarbon, or carbonate used in the polymerizable composition of the present invention. The number of repeating oxyalkylene, fluorocarbon, oxyfluorocarbon, and carbonate groups, for example, R ⁶ , R ⁹ in the general formula (2) or (3)
The number of repeating oxyalkylene, fluorocarbon, oxyfluorocarbon, and carbonate groups contained therein is preferably in the range of 1 to 1,000, and particularly preferably in the range of 1 to 50.

The method for synthesizing the polymerizable compound having a group represented by the general formula (2) is not particularly limited. For example, an acid chloride and an oligooxyalkyleneol having a hydroxyl group at a terminal can be prepared as follows. Can be easily obtained by reacting

Embedded image [However, wherein R ⁵ is the same as the general formula (2), R ¹⁰
Represents a hydrogen atom or an alkyl group having 10 or less carbon atoms,
R ¹¹ represents an alkyl group having 10 or less carbon atoms;
000, preferably an integer in the range of 1 to 50. ]

The method for synthesizing the polymerizable compound having a group represented by the general formula (3) is not particularly limited.

Embedded image Wherein R ⁷ , R ⁸ , and x are the same as those in the general formula (3). Can be easily obtained by reacting an isocyanate compound represented by the formula [1] with an oligooxyalkyleneol having a hydroxyl group at a terminal.

As a specific method, the compound having one functional group represented by the general formula (3) is, for example, a methacryloyl isocyanate compound (hereinafter abbreviated as MI) or an acryloyl isocyanate compound (hereinafter AI).
Abbreviated as kind. ) And a monoalkylalkylene glycol in a 1: 1 molar ratio as in the following reaction.

Embedded image [Where, R ⁷ is the same as the general formula (3), R ¹⁰ represents a hydrogen atom or having 10 or less of the alkyl group carbon, R ¹¹
Represents an alkyl group having 10 or less carbon atoms, and j represents 1 to 100.
0, preferably an integer in the range of 1 to 50. ]

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

Compounds having five functional groups represented by the general formula (3) include, for example, MIs and / or AIs and pentaol obtained by addition polymerization of α-D-glucopyranose with oligoalkylene glycol. Can be easily obtained by reacting with a 5: 1 molar ratio. Also,
The compound having six functional groups represented by the general formula (3)
For example, it can be easily obtained by reacting MIs and / or AIs with hexaol obtained by addition polymerization of mannitol with an oligoalkylene glycol at a molar ratio of 6: 1.

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

The polymer which is preferable as a component of the polymer solid electrolyte of the present invention is represented by the general formula (2) or (3):
Or a copolymer of two or more compounds belonging to the category, or a copolymer of at least one of the compounds and another polymerizable compound. It may be united. Accordingly, the polymerizable composition for a solid polymer electrolyte of the present invention can contain the following polymerizable compounds. The other polymerizable compound copolymerizable with the compound having a functional group represented by the general formula (2) or (3) is not particularly limited. For example, acrylamide, methacrylamide, N, N-dimethylmethacrylamide, vinylene carbonate, N-vinylpyrrolidone, acryloylmorpholine, methacryloylmorpholine, (meth) acrylamide compounds such as N, N-dimethylaminopropyl (meth) acrylamide, styrene , Styrene compounds such as α-methylstyrene, N
N such as vinylacetamide and N-vinylformamide
-Vinyl amide compounds and alkyl vinyl ethers such as ethyl vinyl ether.

(1-d) Solvent The presence of an organic compound as a solvent in the solid polymer electrolyte of the present invention is preferable because the ionic conductivity of the solid polymer electrolyte is further improved. Therefore, from that point, it is preferable to add a solvent to the polymerizable composition for a solid polymer electrolyte of the present invention. As a solvent that can be used, the compatibility with the polymerizable compound used in the polymerizable composition for a solid polymer electrolyte of the present invention is good, the dielectric constant is large, the boiling point is 70 ° C. or more, and the electrochemical stability range is Broad compounds are suitable. Examples of such a solvent include triethylene glycol dimethyl ether, oligoethers such as tetraethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate,
Carbonates such as diethyl carbonate, vinylene carbonate, (meth) acryloyl carbonate, aromatic nitriles such as benzonitrile and tolunitrile, dimethylformamide, dimethylsulfoxide, sulfur compounds such as N-methylpyrrolidone, N-vinylpyrrolidone and sulfolane, phosphorus Acid esters and the like. Of these, oligoethers and carbonates are preferred, and carbonates are particularly preferred. Although the ionic conductivity of the polymer solid electrolyte increases as the amount of the solvent added increases, the mechanical strength of the polymer solid electrolyte decreases when the amount is too large. A preferable addition amount is 12 times or less, particularly preferably 8 times or less, the weight of the polymerizable compound in the polymerizable composition for a solid polymer electrolyte of the present invention.

(1-e) Electrolyte Salt In the case where the polymerizable composition of the present invention is polymerized to form a solid polymer electrolyte, an electrolyte salt serving as a carrier for ion transfer is previously mixed with the polymerizable composition to form a composite. Alternatively, the composite may be formed by post-addition such as impregnation after polymerization.
The amount of the electrolyte salt complexed in the solid polymer electrolyte of the present invention is preferably from 0.1 to 50% by weight, particularly preferably from 1 to 30% by weight, based on the weight of the solid polymer electrolyte. When the electrolyte salt used for the composite is present in a ratio of 50% by weight or more,
On the other hand, when the ratio is 0.1% by weight or less, the absolute amount of ions becomes insufficient and the ion conductivity decreases. The type of the electrolyte salt used for the composite is not particularly limited, and an electrolyte salt containing an ion to be used as a carrier with a charge may be used. However, it is preferable that the dissociation constant in the solid polymer electrolyte is large, and LiCF _{3 is used.}
SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiPF ₆ , Li
ClO ₄ , LiI, LiBF ₄ , LiSCN, LiAs
F ₆ , NaCF ₃ SO ₃ , NaPF ₆ , NaClO ₄ ,
NaI, NaBF ₄ , NaAsF ₆ , KCF ₃ SO ₃ ,
Alkali metal salts such as KPF ₆ and KI, (CH ₃ ) ₄ NB
A quaternary ammonium salt such as F _{4, a} quaternary phosphonium salt such as (CH ₃ ) ₄ PBF ₄ , a transition metal salt such as AgClO ₄ , or a protic acid such as hydrochloric acid, perchloric acid, and borofluoric acid are recommended. When the polymerization initiator is decomposed with an acid to initiate a polymerization reaction, it is desirable to use an electrolyte salt containing a free acid.

As the negative electrode active material used in the battery of the present invention, an alkali metal, an alkali metal alloy,
A material having a low oxidation-reduction potential using an alkali metal ion such as a carbon material as a carrier is preferable because a high-voltage and high-capacity battery can be obtained. Therefore, an alkali metal salt is required as an electrolyte salt in a polymer solid electrolyte when the negative electrode is used in a battery using an alkali metal ion as a carrier. As the kind of the alkali metal salt, for example, LiCF ₃ SO ₃ , LiPF ₆ , LiClO ₄ ,
LiBF ₄ , LiSCN, LiAsF ₆ , LiN (CF
₃ SO ₂ ) ₂ , NaCF ₃ SO ₃ , LiI, NaPF
₆ , NaClO ₄ , NaI, NaBF ₄ , NaAsF
₆ , KCF ₃ SO ₃ , KPF ₆ , KI and the like. Among the negative electrodes, the case where lithium is used as the alkali metal is most preferable because the obtained battery has a high voltage, a high capacity, and can be formed into a thin film. In the case of a carbon material negative electrode, not only alkali metal ions but also quaternary ammonium salts, quaternary phosphonium salts, transition metal salts, and various protonic acids can be used.

In the case of an electric double layer capacitor, the type of electrolyte salt used for the composite is not particularly limited, and a compound containing an ion to be used as a charge carrier may be used. It is desirable to contain ions which are large and easily form a polarizable electrode and an electric double layer. Such compounds include (CH ₃ ) ₄ N
Quaternary ammonium salts such as BF ₄ , (CH ₃ CH ₂ ) ₄ NClO ₄ , transition metal salts such as AgClO ₄ , (CH ₃ ) ₄
Quaternary phosphonium salts such as PBF ₄ , LiCF ₃ SO ₃ ,
LiPF ₆ , LiClO ₄ , LiI, LiBF ₄ , Li
SCN, LiAsF ₆ , LiN (CF ₃ SO ₂ ) ₂ , N
aCF ₃ SO ₃ , NaPF ₆ , NaClO ₄ , NaI,
NaBF ₄ , NaAsF ₆ , KCF ₃ SO ₃ , KPF
₆ , alkali metal salts such as KI, organic acids and salts thereof such as paratoluenesulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. Among them, quaternary ammonium salts, quaternary phosphonium salts, and alkali metal salts are preferable in that the output voltage can be increased and the dissociation constant is large. Among the quaternary ammonium salts, (CH ₃ CH ₂ ) (CH ₃ CH ₂ CH ₂ C
Those having different substituents on the nitrogen of the ammonium ion, such as H ₂ ) ₃ NBF ₄ , are preferable in view of their high solubility in polymer solid electrolytes or large dissociation constants.

(1-f) Filler The solid polymer electrolyte of the present invention can be used as a composite electrolyte to which various fillers are added. This not only improves strength and film thickness uniformity, but also results in the formation of fine pores between the filler and the polymer. Particularly when a solvent is added, a free electrolyte solution is contained in the pores of the composite electrolyte. Ionic conductivity and mobility can also be increased without impairing the strength increase. Therefore, in that respect, it is preferable to include a filler in the polymerizable composition for a solid polymer electrolyte of the present invention. Examples of the filler include fillers made of various non-electroconductive polymers such as polystyrene / divinylbenzene copolymer gel, polyethylene and polypropylene, and non-electroconductive inorganic oxides such as α, β, γ-alumina, silica, magnesia and hydrotalcite. Fillers. Of these, inorganic oxide fillers are preferred in terms of composite efficiency and stability, and alumina, magnesia, and hydrotalcite are particularly preferred. Further to increase the holding amount of the electrolyte-containing solution of the solid polymer electrolyte complexed with fillers, ionic conductivity, for the purpose of increasing the mobility, it is preferable specific surface area of the filler is as large as possible, 5 m ² with the BET method / g or more, preferably 50 m ²
/ g or more is more preferable.

From the viewpoint of improving the uniformity of the thickness of the composite electrolyte, it is preferable to use a filler having a uniform size, such as spacer beads for liquid crystal. Examples include liquid crystal spacers such as polymer beads represented by divinylbenzene copolymer beads (Sekisui Fine Chemical, SP series), and polymer beads are particularly preferable in terms of stability and ease of compounding. The size of the filler having such various shapes is not particularly limited as long as it can be mixed with the polymerizable composition, but the size is 0.01 μm to 100 μm.
Is particularly preferable, and 0.01 μm to 20 μm is particularly preferable.
In addition, the shape is spherical, oval, cubic, rectangular,
Various shapes such as a cylinder or a rod can be used. Conversely, if the amount of the filler is too large, the strength or ionic conductivity of the composite electrolyte is reduced, or the fluidity of the mixture when mixed with the polymerizable compound-containing material and / or the electrolyte-containing solution is impaired, and the There is a problem that it is difficult to perform compounding and molding. Therefore, the amount of addition is preferably 50 wt% or less based on the composite electrolyte, and 0.1 to 30 wt%.
Is particularly preferred.

[2] Solid Polymer Electrolyte The solid polymer electrolyte of the present invention can be obtained by curing the polymerizable composition for a solid polymer electrolyte of the present invention. When the polymerizable composition contains an electrolyte salt, it can be directly obtained by directly decomposing and polymerizing the initiator with an acid and / or heating. When the polymerizable composition does not contain an electrolyte salt, by transferring the electrolyte salt, the initiator is decomposed by the free acid contained in the electrolyte salt to cause a polymerization reaction, the polymerizable Obtained directly by curing the composition. Further, when the polymerizable composition does not contain an electrolyte salt, the initiator is decomposed by heat to cause a polymerization reaction, and after the polymerizable composition is cured, the electrolyte salt is obtained by transferring the electrolyte salt. It is also possible.

(2-a) Components of Polymer Solid Electrolyte Preferred polymers used in the polymer solid electrolyte of the present invention are:
As described above, even if it is a homopolymer of a compound having a functional group represented by the general formula (2) or (3), or a copolymer of two or more kinds belonging to the category, Alternatively, it may be a copolymer of at least one of the compounds and another polymerizable compound. Further, a polymer obtained from at least one compound having a functional group represented by the general formula (2) or (3) and / or a copolymer containing the compound as a copolymer component and another polymer And a mixture thereof. For example, a polymer obtained from at least one compound having a functional group represented by the general formula (2) or (3) and / or a copolymer containing the compound as a copolymer component, polyethylene oxide, A mixture of a polymer such as polypropylene oxide, polyacrylonitrile, polybutadiene, polymethacrylic acid (or acrylic) ester, polystyrene, polyphosphazene, polysiloxane or polysilane, polyvinylidene fluoride, or polytetrafluoroethylene is used as the polymer solid of the present invention. It may be used for an electrolyte. When a copolymer and / or a mixture is used, the amount of the structural unit derived from the compound having a functional group represented by the general formula (2) or (3) may be different from that of the other copolymer component or polymer mixture component. Although it depends on the type, in consideration of ionic conductivity and membrane strength, heat resistance, and current characteristics when used in a solid polymer electrolyte, it is preferable that the content be 40% by weight or more based on the total amount of the copolymer or the polymer mixture. , More preferably 60% by weight or more. In addition, the electrolyte salt which is an essential component of the polymer solid electrolyte of the present invention, the solvent and the filler which are optional components are as described in the section of [1] Polymerizable composition for polymer solid electrolyte. .

(2-b) Method for Producing Polymer Solid Electrolyte The polymer solid electrolyte of the present invention can be obtained by curing the polymerizable composition for a polymer solid electrolyte of the present invention as described above. The polymerization of the compound can be carried out by decomposing the polymerization initiator with an acid and / or heat by utilizing the polymerizability of the functional group of the compound.
For example, the polymerization of the compound having a functional group represented by the general formula (2) or (3) can be performed by utilizing the polymerizability of an acryloyl group or a methacryloyl group that is a functional group. Further, a polymer obtained from at least one of the compounds having a functional group represented by the general formula (2) or (3) and / or a copolymer containing the compound as a copolymer component of the present invention When used for such a polymer of a solid polymer electrolyte, it is advantageous to polymerize the polymerizable compound after film formation. That is, a compound having a functional group represented by the general formula (2) or (3) and at least one polymerization initiator represented by the general formula (1), and in some cases, at least one electrolyte salt. In some cases, at least one inorganic filler and / or at least one organic solvent are mixed, and in some cases, a polymerizable composition to which another polymerizable compound is added is prepared, and the polymerizable composition is added in the presence of an acid. If necessary, the mixture is polymerized by heating. In particular, after the polymerizable composition is formed into a shape such as a film, for example, by adding an acid and / or heating,
By polymerizing to form a film-like polymer, the degree of freedom in the processing surface is widened, which is a great advantage in application.

The acid used in the polymerization is not particularly limited, and may be any acid capable of releasing protons, such as various organic acids such as carboxylic acid, hydrogen chloride and hydrogen fluoride, and inorganic acids. It is sufficient that the amount is 1 ppm or more based on the polymerizable composition. Further, in the case of performing heating, depending on the type of the polymerizable compound and the polymerization initiator, the temperature may be any temperature at which polymerization occurs.
In the case of further adding another actinic ray initiator and further polymerizing by irradiating actinic rays, depending on the type of the polymerizable compound, for example, it is irradiated with ultraviolet light or γ-ray of several mW or more, γ-ray, electron beam or the like. It can be polymerized.

[3] Battery (3-a) Negative Electrode In the configuration of the battery of the present invention, an alkali metal ion such as an alkali metal, an alkali metal alloy, a carbon material, an inorganic oxide, or a conductive polymer is used as a carrier for the negative electrode. It is preferable to use a low oxidation-reduction potential electrode active material (negative electrode active material) because a high-voltage, high-capacity battery can be obtained. Among such electrode active materials, lithium metal or lithium alloys such as lithium / aluminum alloy, lithium / lead alloy, and lithium / antimony alloy are particularly preferable because they have the lowest redox potential. In addition, carbon materials, inorganic oxides, and conductive polymers are particularly preferable in that they have a low oxidation-reduction potential when they occlude Li ions, and are stable and safe. Examples of carbon materials capable of inserting and extracting Li ions include natural graphite, artificial graphite, vapor-grown graphite, petroleum coke, coal coke, pitch-based carbon, polyacene, C ₆₀ ,
Fullerenes such as C ₇₀ and the like. Examples of the inorganic oxide capable of inserting and extracting Li ions include tin oxide and its composite oxide, indium oxide and its composite oxide, and the like. Examples of the conductive polymer capable of inserting and extracting Li ions include polyacetylene, polyparaphenylene, polythienylene, polypyridine, polypyrimidine, and derivatives thereof.

(3-b) Positive Electrode In the configuration of the battery of the present invention, the positive electrode has a high oxidation-reduction potential electrode active material such as metal oxide, metal sulfide, conductive polymer or carbon material (positive electrode active material). Is preferable because a high-voltage, high-capacity battery can be obtained. Among such electrode active materials, metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, and molybdenum oxide, molybdenum sulfide, and sulfide Titanium,
Metal sulfides such as vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide and the like are particularly preferable in terms of high capacity and high voltage. The method for producing the metal oxide or metal sulfide in this case is not particularly limited, and for example, a general electrolytic method or a general electrolytic method described in “Electrochemistry, Vol. 22, pp. 574, 1954”. It is manufactured by a heating method. When these are used for a lithium battery as an electrode active material, for example, Li _x CoO
Preferably, Li is used in a state of being inserted (composite) into a metal oxide or metal sulfide in the form of Li ₂ or Li _x MnO ₂ . The method for inserting the Li element in this way is not particularly limited. For example, a method for electrochemically inserting Li ions or a salt such as Li ₂ CO ₃ as described in US Pat. No. 4,357,215. And a metal oxide, followed by heat treatment.

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

(3-c) Method for Producing Battery Electrode In the present invention, by combining the above-described negative electrode and positive electrode active materials with the polymer solid electrolyte of the present invention, the processability is excellent, and the battery operates with high capacity and high current. As a result, a long-life battery electrode free of liquid seepage can be obtained. For the production method, for example, the following method is preferable because the mixing and adhesion of the electrode active material and the solid polymer electrolyte are good and the processing is easy.
First, after the liquid polymerizable composition of the present invention is mixed with an electrode active material with an appropriate composition, and optionally mixed with a conductive auxiliary or a binder, it is applied to a substrate such as a current collector or pressed. And the like to form into an electrode shape. Next, the polymerizable composition is polymerized by adding an acid or heating, and cured as an electrode.

(3-d) Method of Manufacturing Battery The method of manufacturing the battery of the present invention will be described with reference to examples.
Positive and negative electrodes are put into the structure for battery construction via the polymer solid electrolyte membrane obtained by polymerizing the polymerizable composition of the present invention so as not to come into contact with each other. Next, after injecting the electrolytic solution or the polymerizable composition of the present invention (adding an initiator), the battery is sealed with an insulating resin such as a polyolefin resin or an epoxy resin to obtain a target battery. When the polymerizable composition is injected, the battery is completely solidified with the solid polymer electrolyte of the present invention by polymerizing with an acid or heating.

The battery of the present invention can also be manufactured by the following method. The positive electrode and the negative electrode are impregnated with the electrolyte solution (without initiator) or the electrolyte salt-added polymerizable composition (without initiator), and a spacer is disposed on one of the electrodes. After applying the composition (with initiator) to a uniform thickness, the polymer is polymerized by the free acid in the electrolyte solution or the polymerizable composition impregnated in the electrode and / or by heating to form a uniform coating on the electrode. A polymer solid electrolyte membrane having a large thickness is formed. Then, the other electrode is attached to the solid polymer electrolyte membrane, placed in a battery structure, and sealed with an insulating resin such as a polyolefin resin or an epoxy resin to obtain a target battery.
When the polymerizable composition is impregnated in the electrode, the battery is further solidified with the solid polymer electrolyte of the present invention by further adding an acid and / or polymerizing by heating. Electrolyte salt-added polymerizable composition (without initiator) or electrolyte salt-free polymerizable composition (with initiator added) by this method
Is stable and has a long pot life, so that it is easy to impregnate and coat the inside of the electrode and is very advantageous in terms of process.

The battery of the present invention can also be manufactured by the following method. Laminate the positive and negative electrodes so that they do not contact each other via a suitable spacer such as a porous separator,
Put it inside the battery structure. Then inject the electrolyte,
After performing general degassing or the like by preliminary charging or the like, excess electrolyte is extracted, and the pressure is further reduced, and the solvent in the electrolyte is distilled off to some extent, and the next injection of the polymerizable composition is facilitated. Next, the polymerizable composition without the electrolyte salt of the present invention (initiator added) is injected under reduced pressure, and the free acid in the previously injected electrolyte and / or heating is applied to polymerize the polymerizable composition. . Then, the intended battery can be obtained by sealing the battery with an insulating resin such as a polyolefin resin or an epoxy resin. When the solvent is completely distilled off under reduced pressure, a battery completely solidified with the polymer solid electrolyte of the present invention can be obtained. Since the polymerizable composition without an electrolyte salt (addition of an initiator) in this method is stable and has a long pot life, it is easy to impregnate and apply in an electrode, and is very advantageous in terms of process. Further, the process is completely dry until the positive and negative electrodes are inserted into the battery structure through the spacer, which is advantageous because the process can be simplified in terms of atmosphere and the like.

The structure for the battery or the support may be made of metal such as SUS, polypropylene, aluminum laminated heat sealing resin, polyimide, Evar, or ceramic material such as conductive or insulating glass. It is not particularly limited to those made of these materials, and the shape may be cylindrical, box, sheet, or any other shape. As an example of the battery of the present invention,
FIG. 1 shows a schematic cross-sectional view of an example of a thin-film solid state secondary battery. In the figure, 1 is a positive electrode, 2 is a polymer solid electrolyte, 3 is a negative electrode, 4 is a current collector, and 5 is an insulating resin sealant. In addition to the sheet type as shown in FIG. 1, a coin type, or a sheet-shaped laminated body of a positive electrode, a solid polymer electrolyte, and a negative electrode is wound into a cylindrical shape to form a cylindrical tubular battery structure. It may be a cylindrical type or the like manufactured by putting in a body and sealing.

[4] Electric Double Layer Capacitor Next, the electric double layer capacitor of the present invention will be described.
In the electric double layer capacitor of the present invention, by using the polymer solid electrolyte obtained from the polymerizable composition of the present invention, the output voltage is high, the takeout current is large, or the processability, life, and reliability are excellent. An electric double layer capacitor is provided. FIG. 2 shows a schematic sectional view of an example of the electric double layer capacitor of the present invention. This example is 1cm in size
A thin cell having a size of about 1 cm and a thickness of about 0.5 mm, 7 is a current collector, and a pair of polarizable electrodes 6 is disposed inside the current collector, and a polymer solid electrolyte membrane 8 is disposed therebetween. Have been. 9 is an insulating resin sealant, and 10 is a lead wire.

(4-a) Current Collector The current collector 7 is preferably 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. (4-b) Polarizable electrode The polarizable electrode 6 may be any electrode made of a polarizable material such as a carbon material which is usually used for an electric double layer capacitor.
The carbon material as the polarizable material is not particularly limited as long as it has a large specific surface area. For example, carbon blacks such as furnace black, thermal black (including acetylene black), and channel black,
Activated carbon such as coconut charcoal, natural graphite, artificial graphite, so-called pyrolytic graphite produced by the gas phase method, polyacene and C ₆₀ , C
₇₀ can be mentioned.

(4-c) Method for Producing a Polarizable Electrode In the present invention, by combining the above-mentioned polarizable material and the solid polymer electrolyte of the present invention, it is excellent in workability, and can be operated with a high capacity and a high current. A long-life polarizable electrode for an electric double layer capacitor free of liquid seepage can be obtained. For the production method, for example, the following method is preferable because the mixing and adhesion of the polarizable material and the solid polymer electrolyte are good and the processing is easy. First, after the liquid polymerizable composition of the present invention is mixed with a polarizable material with an appropriate composition, and optionally mixed with a conductive auxiliary or a binder, the mixture is applied or pressed on a substrate such as a current collector. And the like to form into an electrode shape. Next, the polymerizable composition is polymerized by adding an acid or heating, and cured as an electrode.

(4-d) Method for Manufacturing Electric Double Layer Capacitor Next, a method for manufacturing the electric double layer capacitor of the present invention will be described with reference to examples. Two polarizable electrodes are placed in the structure for forming an electric double layer capacitor so as not to contact each other via the solid polymer electrolyte membrane of the present invention. Next, after injecting the electrolytic solution or the polymerizable composition of the present invention (addition of an initiator), the resultant is sealed with an insulating resin such as a polyolefin resin or an epoxy resin to obtain a desired electric double layer capacitor. When the polymerizable composition is injected, an electric double layer capacitor completely solidified with the polymer solid electrolyte of the present invention is obtained by polymerizing with an acid or heating.

The electric double layer capacitor of the present invention can also be manufactured by the following method. Two polarizable electrodes are impregnated with an electrolyte solution (without initiator) or an electrolyte salt-added polymerizable composition (without initiator), and a spacer is disposed on one of the electrodes to obtain an electrolyte salt of the present invention. After applying the added polymerizable composition (addition of an initiator) to a uniform thickness, the polymer is polymerized by free acid and / or heating in the electrolyte solution or the polymerizable composition impregnated in the electrode, and the electrode is heated. A polymer solid electrolyte membrane having a uniform thickness is formed thereon. Next, the other electrode is attached to a polymer solid electrolyte membrane, placed in a structure for forming an electric double layer capacitor, and sealed with an insulating resin such as a polyolefin resin or an epoxy resin to obtain a desired electric double layer capacitor. be able to. When the electrode is impregnated with the polymerizable composition, the electric double-layer capacitor completely solidified with the polymer solid electrolyte of the present invention is polymerized by further adding an acid and / or heating. can get. The polymerizable composition with electrolyte salt added (without initiator) and the polymerizable composition without electrolyte salt (with initiator added) are stable and have a long pot life in this method. It is very advantageous in terms of quality.

The electric double layer capacitor of the present invention can also be manufactured by the following method. The two polarizable electrodes are stuck together via a suitable spacer such as a porous separator so as not to contact with each other, and are placed in the structure for forming an electric double layer capacitor. Next, an electrolytic solution is injected, an excessive electrolytic solution is drawn out, and the pressure is further reduced, a solvent in the electrolytic solution is distilled off to some extent, and the next injection of the polymerizable composition is facilitated. Then, the polymerizable composition without the electrolyte salt of the present invention (initiator added) is injected under reduced pressure, and the free acid in the previously injected electrolyte and / or further heating is performed to polymerize the polymerizable composition. Let it. Then, the desired electric double layer capacitor can be obtained by sealing the electric double layer capacitor with an insulating resin such as polyolefin resin or epoxy resin. When the solvent is completely distilled off under reduced pressure, an electric double layer capacitor completely solidified with the solid polymer electrolyte of the present invention is obtained. Since the polymerizable composition without an electrolyte salt (addition of an initiator) in this method is stable and has a long pot life, it is easy to impregnate and apply in an electrode, and is very advantageous in terms of process. Further, the two polarizable electrodes are completely dry type until they are inserted into the structure for forming the electric double layer capacitor via the spacer, which is advantageous because the process such as atmosphere can be simplified.

The structure for forming the electric double layer capacitor or the support may be made of metal such as SUS, polypropylene, aluminum laminated heat sealing resin, polyimide, EVAL, or ceramic material such as conductive or insulating glass. It is sufficient that the material is not particularly limited to those made of these materials, and the shape is cylindrical,
The shape may be a box, a sheet, or any other shape. The shape of the electric double-layer capacitor is not limited to a sheet type as shown in FIG. It may be a cylindrical type or the like manufactured by sealing in a structure for structure.

[0060]

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]

Embedded image Polyethylene glycol dimethacrylate (Compound A:
Nippon Yushi Blenmer PDE600, n = 14) 1.2 g,
Aluminum oxide C particles heat-treated at 1000 ° C. (average crystal particle diameter 0.013 μm, manufactured by Japan Aerosil,
Specific surface area about 100m ² / g, water content 600ppm) 0.33g,
1.8 g of ethylene carbonate (EC), 4.2 g of ethyl methyl carbonate (EMC), 0.60 g of LiPF ₆ (battery grade manufactured by Hashimoto Kasei), and tetra n-butyl ammonium / n-butyl triphenyl borate (4B
AB3P, manufactured by Showa Denko) 0.005 g was mixed well in an argon atmosphere to obtain a polymerizable composition. The water content of this composition (Karl Fischer method) was 35 ppm. Immediately after this polymerizable composition was prepared, it was coated on a PET film in a closed container under EMC saturation under an argon atmosphere, and then allowed to stand for 30 minutes. The compound A polymer / aluminum oxide C impregnated with an EC / EMC electrolyte solution About 30 composite films
It was obtained as a μm freestanding film. 2 of this film
When the ion conductivity at 5 ° C. and −20 ° C. was measured by the impedance method, they were 2.5 × 10 ⁻³ and 0.7 × 10 ⁻³ S /, respectively.
cm.

[Examples 2, 3, 4] 4B as an initiator
A polymerizable composition was prepared in the same manner as in Example 2 except that a boron salt-based initiator (manufactured by Showa Denko) shown in Table 1 was used instead of AB3P, and a compound A polymer / aluminum oxide C composite was prepared. The film was obtained as a free standing film of about 30 μm. When the ionic conductivity of these films at 25 ° C. and −20 ° C. was measured by the impedance method, all values were almost the same as those in Example 1.

[Table 1]

Example 5 Example 1 was repeated except that 0.50 g of battery grade LiBF ₄ manufactured by Hashimoto Kasei was used instead of LiPF _6.
In the same manner as in the above, a polymerizable composition was obtained. The water content (Karl Fischer method) of this composition was 45 ppm. This polymerizable composition was coated on a PET film in the same manner as in Example 1 and then heated to 60 ° C. and left for 30 minutes.
A compound A polymer / KW2200 composite film impregnated with MC electrolyte was obtained as a free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, each was 1.5 ×
^{They were} 10 ⁻³ and 0.4 × 10 ⁻³ S / cm.

Example 6 Compound A (1.2 g, 1000 ° C.)
0.33 g of aluminum oxide C particles (average crystal particle diameter: 0.013 μm, manufactured by Nippon Aerosil Co., Ltd., specific surface area: about 100 m ² / g, water content: 600 ppm), 6.0 g of propylene carbonate (PC), tetraethylammonium tetrafluoroborate (TEAB) 1.00 g of high purity product manufactured by Hashimoto Kasei) and 0.005 g of 4BAB3P as an initiator were mixed well in an argon atmosphere to obtain a polymerizable composition.
The water content (Karl Fischer method) of this composition is 100
ppm. Immediately after the preparation of this polymerizable composition, the composition was coated on a PET film in an argon atmosphere in a closed container, and then applied to a PET film.
After standing at 30 ° C for 30 minutes, a compound A polymer / aluminum oxide C composite film impregnated with a PC-based electrolyte was obtained as a self-supporting film of about 30 µm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, it was 5.5 × 10 ⁻³ , 1.0, respectively.
× 10 ^-3 S / cm.

[Embodiment 7]

Embedded image Compound A 0.6 g, methoxypolyethylene glycol monomethacrylate (Compound B: Nippon Yushi Blenmer PM
E400, n = 9) 0.6 g, hydrotalcite particles heat-treated at 500 ° C. (KW2200, KW2200, average particle size about 1.0 μm, BET specific surface area 135 m ² / g, water content 1000 ppm) 0.33 g, EC 1.8 g, EMC 1.6
g, diethyl carbonate (DEC) 1.6 g, LiPF ₆
(Hashimoto Chemical Battery Grade) 0.60 g and 4BAB3P (manufactured by Showa Denko) 0.005 g as an initiator were mixed well in an argon atmosphere to obtain a polymerizable composition. The water content of this composition (Karl Fischer method) was 35 ppm. Immediately after this polymerizable composition was prepared, it was coated on a PET film in a sealed container under EMC saturation under an argon atmosphere and allowed to stand for 30 minutes. The compound A + B polymer / KW2200 impregnated with an EC / EMC / DEC electrolyte solution About 3 composite films
Obtained as a 0 μm freestanding film. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, they were 2.8 × 10 ⁻³ and 0.8 × 10 ⁻³ , respectively.
It was S / cm.

Example 8 A salt-free polymerizable composition was obtained in the same manner as in Example 1 except that LiPF ₆ was not used.
The water content of this composition (Karl Fischer method) is 10 pp
m. This salt-free polymerizable composition was previously placed in a sealed container under an EMC atmosphere and an argon atmosphere in a 1.2 M LiP solution.
F ₆ / EC + EMC (weight ratio 3: 7) was impregnated and applied to a polyethylene microporous film (Asahi Kasei hypopore, thickness 25 μm, opening ratio 55%) which absorbed liquid.
After standing for a minute, a compound A polymer / aluminum oxide C / hypore composite film impregnated with an EC / EMC electrolytic solution was obtained as a free-standing film of about 30 μm.
When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, each was 5.5 ×
It was 10 ^-4 and 2.8 × 10 ^-4 S / cm.

Example 9 A salt-free polymerizable composition was obtained in the same manner as in Example 6 except that TEAB was not used. The water content (Karl Fischer method) of this composition is 20 ppm
Met. This salt-free polymerizable composition was impregnated and coated on a polyethylene microporous film (Asahi Kasei Hypore, thickness 25 μm, opening ratio 55%) in which 1.2 M TEAB / PC was previously absorbed in a sealed container in an argon atmosphere. After standing at 60 ° C. for 30 minutes, a compound A polymer / aluminum oxide C / hypore composite film impregnated with a PC electrolyte was obtained as a self-supporting film having a thickness of about 30 μm. The ionic conductivity of this film measured at 25 ° C. and −20 ° C. by an impedance method was 1.0 × 10 ⁻³ and 2.1 × 10 ⁻⁴ S / cm, respectively.

Example 10 <Synthesis of Compound>

Embedded image 50.0 g of the compound (KOH value 34.0 mg / g, p / q = 7/3) and 4.6 g of the compound were thoroughly purified in a nitrogen atmosphere.
After dissolving in 0 ml, add 0.44 g of dibutyltin dilaurate. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a colorless product. From the results of ¹ H-NMR, IR, and elemental analysis, the compound and the compound reacted in a ratio of 1: 3, further, the isocyanate group of the compound disappeared, and a urethane bond was formed, and the compound was formed. I understand.

Example 11 1.0 g of compound, 500 ° C.
Particles (Kyowa Chemical, K
W2200, average particle size about 1.0 μm, BET specific surface area 135 m ² / g, water content 1000 ppm) 0.33 g, EC
1.8 g, EMC 4.2 g, LiPF ₆ (Hashimoto Chemicals battery grade) 0.60 g, and tetra-n-butylammonium / n-butyltriphenylborate (4BA
B3P, manufactured by Showa Denko KK) was mixed well in an argon atmosphere to obtain a polymerizable composition. The water content of this composition (Karl Fischer method) was 35 ppm. Immediately after this polymerizable composition was prepared, it was coated on a PET film in a sealed container under EMC saturation under an argon atmosphere, and then allowed to stand for 30 minutes. It was obtained as a free-standing film of about 30 μm. The ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method and found to be 5.0 × 10 ⁻³ and 1.2 × 10 ⁻³ S / cm, respectively.

[Examples 12, 13, 14] Polymerization was carried out in the same manner as in Example 11 except that a boron salt-based initiator (manufactured by Showa Denko) shown in Table 2 was used instead of 4BAB3P as an initiator. Preparation of water-soluble composition, compound polymer / KW
A 2200 composite film was obtained as a free standing film of about 30 μm. The ionic conductivities of these films at 25 ° C. and −20 ° C. were measured by an impedance method, and all showed almost the same values as in Example 11.

[Table 2]

Example 15 A polymerizable composition was obtained in the same manner as in Example 11 except that 0.50 g of battery grade LiBF ₄ manufactured by Hashimoto Kasei was used instead of LiPF ₆ . The water content (Karl Fischer method) of this composition was 45 ppm.
After coating this polymerizable composition on a PET film in the same manner as in Example 11, the composition was heated to 60 ° C. and left for 30 minutes.
C / Compound polymer impregnated with EMC electrolyte / KW22
00 composite film was obtained as a free standing film of about 30 μm. The ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method and found to be 4.1 × 10 ⁻³ and 0.8 × 10 ⁻³ S / cm, respectively.

Example 16 Compound 1.0 g, 1000
0.33 g of aluminum oxide C particles (average crystal particle diameter: 0.013 μm, manufactured by Nippon Aerosil Co., Ltd., specific surface area: about 100 m ² / g, water content: 600 ppm), 6.0 g of propylene carbonate (PC), tetraethylammonium tetrafluoroborate ( TEAB, Hashimoto Kasei's high-purity product) 1.00 g, and 4BAB3P as an initiator
0.005 g was mixed well in an argon atmosphere to obtain a polymerizable composition. The water content (Karl Fischer method) of this composition was 110 ppm. Immediately after this polymerizable composition was prepared, it was applied on a PET film in a closed container under EMC saturation under an argon atmosphere, and then left at 60 ° C. for 30 minutes. The compound polymer / aluminum oxide impregnated with a PC-based electrolyte solution The C composite film was obtained as a free standing film of about 30 μm. 25 ° C, -20 of this film
When the ionic conductivity at ° C was measured by an impedance method, they were 9.2 × 10 ⁻³ and 1.8 × 10 ⁻³ S / cm, respectively.

Example 17 <Synthesis of Compound> 55 g of the compound (average molecular weight: 550) and 15.5 g of the compound are dissolved in 100 ml of well-purified THF in a nitrogen atmosphere.
0.66 g of dibutyltin dilaurate was added. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a colorless viscous liquid. From the results of ¹ H-NMR, IR and elemental analysis, the compound and the compound reacted one-to-one,
It was found that the isocyanate group of the compound disappeared, urethane bonds were generated, and the compound was generated.

Example 18 0.5 g of compound, compound
0.5g, KW2200 particles heat-treated at 500 ° C (water content: 1000ppm) 0.33g, EC 1.8g, EMC 1.6g
, 1.6 g of diethyl carbonate (DEC), LiPF ₆
(Hashimoto Chemical Battery Grade) 0.60 g and 4BAB3P (manufactured by Showa Denko) 0.005 g as an initiator were mixed well in an argon atmosphere to obtain a polymerizable composition. The water content (Karl Fischer method) of this composition was 35 ppm. Immediately after preparing this polymerizable composition, an argon atmosphere, EMC
After being coated on a PET film in a closed container under saturation and allowed to stand for 30 minutes, a compound / polymer / KW2200 composite film impregnated with an EC / EMC / DEC electrolyte was obtained as a free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, it was 5.5 × 10 ⁻³ and 1.0 × 10 ³ , respectively.
^-3 S / cm.

Example 19 Compound: CH ₃ (OCH ₂ CH ₂ ) _s O
COC (CH ₃ ) = CH ₂ (Nippon Oil & Fat, Blemmer AE-400, M
w400) 0.3 g, compound 0.7 g, EC 1.8 g, EMC
1.6 g, DEC 1.6 g, LiPF ₆ (Hashimoto Kasei battery grade) 0.60 g, and 4BAB3P (manufactured by Showa Denko) 0.005 g as an initiator were mixed well in an argon atmosphere to obtain a polymerizable composition. The water content (Karl Fischer method) of this composition was 80 ppm. Immediately after preparing this polymerizable composition, PE was placed in a closed container under an argon atmosphere and EMC saturation.
After being applied on a T film and allowed to stand for 30 minutes, EC /
Compound + polymer impregnated with EMC / DEC electrolyte
A KW2200 composite film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method,
They were 3.8 × 10 ⁻³ and 0.6 × 10 ⁻³ S / cm, respectively.

Example 20 <Synthesis of Compound>

Embedded image The above formula 1,3-propanediol bischloroformate (compound) and 1,3-propanediol are allowed to react in dichloromethane at 25 ° C. or lower in the presence of pyridine for about 6 hours, and then excess water is added. The remaining chloroformate terminals were hydroxylated, and oligocarbonates (compounds) having hydroxyl groups at both ends were synthesized. The weight average molecular weight (Mw) determined by GPC analysis was 1200, and the average number of repetitions t was about 10.

[0077]

Embedded image 60.0 g of compound (average molecular weight 1200) and MOI 15.
After dissolving 5 g in 200 ml of well-purified THF in a nitrogen atmosphere, 0.44 g of dibutyltin dilaurate is added.
Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a colorless product. From the results of ¹ H-NMR, IR and elemental analysis, the compound and the MOI reacted one to two, the isocyanate group of the MOI disappeared, and a urethane bond was formed.
The compound was found to be formed.

Example 21 Compound 1.0 g, 1000
Aluminum oxide C (water content 60
0ppm) 0.33g, EC 1.8g, EMC 4.2g, LiPF
₆ (Hashimoto Kasei battery grade) 0.60 g and 4BAB3P (manufactured by Showa Denko) 0.005 g as an initiator were mixed well in an argon atmosphere to obtain a polymerizable composition. The water content of this composition (Karl Fischer method) was 25 ppm. Immediately after preparing this polymerizable composition, an argon atmosphere, EMC
After coating on a PET film in a closed container under saturation, the mixture was allowed to stand for 30 minutes. As a result, a compound polymer / aluminum oxide C composite film impregnated with an EC / EMC electrolyte was obtained as a self-supporting film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, it was 6.0 × 10 ⁻³ and 1.5 × 10 ³ , respectively.
^-3 S / cm.

Example 22 The procedure was performed except that 1.00 g of high-purity tetraethylammonium tetrafluoroborate (TEAB) manufactured by Hashimoto Kasei was used instead of LiPF ₆ , the solvent was EC, and 4.2 g of PC and 1.8 g of EC were used instead of EMC. A polymerizable composition was obtained in the same manner as in Example 21. The water content of this composition (Karl Fischer method) was 100 ppm. This polymerizable composition was applied and polymerized in the same manner as in Example 21 to obtain a compound polymer / aluminum oxide C composite film impregnated with a PC + EC electrolyte as a self-supporting film of about 30 μm. 25 ° C. of this solid electrolyte, −2
When the ionic conductivity at 0 ° C. was measured by an impedance method, they were 10.5 × 10 ⁻³ and 1.8 × 10 ⁻³ S / cm, respectively.

Example 23 A salt-free polymerizable composition was obtained in the same manner as in Example 11 except that LiPF ₆ was not used. The water content (Karl Fischer method) of this composition is 1
It was 0 ppm. This polymerizable composition is placed in an argon atmosphere,
1.2M LiPF ₆ in a closed container under EMC saturation
/ EC + EMC (weight ratio 3: 7) was impregnated and applied to a polyethylene microporous film (Asahi Kasei hypopore, thickness 25 μm, opening ratio 55%) which had been absorbed, and then allowed to stand for 30 minutes. Then, the EC / EMC electrolyte was impregnated. Compound polymer / KW2200 / Hipore composite film is about 30μ
m2 free standing film. 25 of this film
° C., ionic conductivity at -20 ° C. was measured by the impedance method, respectively, 7.5 × 10 ^-4 , 3.0 × 10 ^-4 S / cm
Met.

Example 24 A salt-free polymerizable composition was obtained in the same manner as in Example 21 except that LiPF ₆ was not used. The water content (Karl Fischer method) of this composition is 1
It was 5 ppm. This polymerizable composition is placed in an argon atmosphere,
1.2M LiPF ₆ in a closed container under EMC saturation
/ EC + EMC (weight ratio 3: 7) was impregnated and applied to a polyethylene microporous film (Asahi Kasei hypopore, thickness 25 μm, opening ratio 55%) which was absorbed and then allowed to stand for 30 minutes. The resulting compound polymer / aluminum oxide C / hypore composite film was obtained as a free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, they were 7.0 × 10 ⁻⁴ ,
It was 2.5 × 10 ⁻⁴ S / cm.

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

Example 26 <Production of Graphite Negative Electrode> MCMB graphite (manufactured by Osaka Gas), vapor phase graphite fiber (manufactured by Showa Denko KK: average fiber diameter: 0.3 μm)
An excess N-methylpyrrolidone solution was added to a mixture of polyvinylidene fluoride at a weight ratio of 8.6: 0.4: 1.0 to obtain a gel composition. This composition was coated on a copper foil of about 15 μm in a thickness of 10 mm ×
It was applied and molded to a thickness of 10 mm and a thickness of about 250 μm. further,
Heating and vacuum drying at about 100 ° C. for 24 hours gave a graphite negative electrode (35 mg).

[Example 27] <Production of Li-ion secondary battery> In the argon atmosphere glove box, the graphite negative electrode (10 m
m × 10 mm) in the electrolyte (1M LiPF ₆ / EC + E)
MC (3: 7)) impregnated with the compound A-based polymer solid electrolyte / aluminum oxide C composite film (12 mm × 12 mm) produced in Example 1 and further added with the cobalt produced in Example 25. Electrolyte (1M LiPF ₆ ) is applied to the lithium oxide positive electrode (10 mm × 10 mm).
/ EC + EMC (3: 7)) were bonded together, and the battery end was sealed with an epoxy resin to obtain a graphite / cobalt oxide Li-ion secondary battery. FIG. 1 shows a cross-sectional view of the obtained battery. This battery was charged at 60 ° C., 25 ° C., −1
When charging and discharging were performed at 0 ° C with an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA, the maximum discharge capacity was 7.2 mAh, 7.2 mAh, and 3.2 mAh, respectively.
Met. In addition, 60 ℃, operating voltage 2.75 ~ 4.1V, charging 0.
When charge and discharge were repeated at 5 mA and discharge at 3.0 mA, the maximum discharge capacity was 7.0 mAh, and the cycle life until the capacity was reduced to 50% was 305 times.

[Example 28] <Production of Li-ion secondary battery> Instead of compound A-based polymer solid electrolyte / aluminum oxide C composite film, compound A + B-based polymer solid electrolyte / KW2200 composite prepared in Example 7 was used. Example 2 except that a film was used
7, a Li-ion secondary battery having the cross-sectional view shown in FIG. When the battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 60 ° C., 25 ° C., and −10 ° C., the maximum discharge capacities were 7.2 mAh, 7.2 mAh, and 3.8 mAh, respectively. Also, 60 ° C, operating voltage 2.75 ~ 4.1V, charging 0.5mA,
When charging and discharging were repeated at 3.0 mA, the maximum discharging capacity was
At 7.0 mAh, the cycle life before the capacity was reduced to 50% was 275 times.

[Example 29] <Production of Li-ion secondary battery> Instead of the compound A-based polymer solid electrolyte / aluminum oxide C composite film, the compound A-based polymer solid electrolyte /
A Li-ion secondary battery having a cross-sectional view shown in FIG. 1 was manufactured in the same manner as in Example 27 except that the aluminum oxide C / hypore composite film was used. This battery was heated at 60 ° C,
When charging and discharging were performed at 25 ° C and -10 ° C with an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA, the maximum discharge capacity was 7.2 mAh and 7.
0 mAh and 2.8 mAh. Also, 60 ° C, operating voltage 2.75 ~
When charge and discharge were repeated at 4.1 V, charge 0.5 mA, and discharge 3.0 mA, the maximum discharge capacity was 6.8 mAh and the cycle life until the capacity was reduced to 50% was 380 times.

Example 30 <Production of All-Solid Li-Ion Secondary Battery> The graphite negative electrode (10 mm × 10 mm) / microporous film (hypore, 12 mm × 12 mm) produced in Example 26 was placed in an argon atmosphere glove box. / A laminate of the lithium cobaltate positive electrode (10 mm × 10 mm) manufactured in Example 25 is prepared, and the upper and lower sides are fixed with clips. This was impregnated with an electrolyte solution (1.2 M LiPF ₆ / EC + EMC (weight ratio 3: 7)), charged at a current of 0.5 mA to 3.7 V, and then discharged at a current of 0.5 mA to 2.75 V, and a secondary reaction initially generated The gas was removed. Then, after removing excess electrolyte, the layer was further dried under vacuum for about 1 hour to remove EMC in the electrolyte remaining in the laminate, so that LiPF ₆ and EC remained in the dried laminate. . Next, the laminate was moved under reduced pressure, and after injecting the salt-free compound A / aluminum oxide C-based polymerizable composition prepared in Example 8, the pressure was returned to normal pressure.
The end of the laminate was sealed with an epoxy resin. Further, at 60 ° C
For 30 minutes, and the polymerizable composition was cured by the action of free acid and heating to obtain a graphite / cobalt oxide-based all-solid Li-ion secondary battery shown in FIG. The battery was heated at 60 ° C. and 25
℃, -10 ℃ operating voltage 2.75 ~ 4.1V, current 0.5mA, when the maximum discharge capacity is 7.2mAh, 6.6mA respectively
h, 2.0 mAh. In addition, 60 ℃, operating voltage 2.75-4.1
When charge and discharge were repeated at V, charge 0.5 mA and discharge 1.5 mA, the maximum discharge capacity was 7.0 mAh and the cycle life until the capacity was reduced to 50% was 410 times.

Example 31 <Production of All-Solid Li-Ion Secondary Battery> Instead of the salt-free compound A / aluminum oxide C-based polymerizable composition prepared in Example 8, a salt containing no aluminum oxide C was added. A graphite / cobalt oxide-based all-solid Li-ion secondary battery shown in FIG. 1 was obtained in the same manner as in Example 30 except that an unadded compound A-based polymerizable composition was prepared and used. The battery was operated at 60 ° C., 25 ° C., -10 ° C. and operating voltage 2.75 to 4.1.
When charge and discharge were performed at V and a current of 0.5 mA, the maximum discharge capacities were 7.2 mAh, 6.6 mAh, and 2.4 mAh, respectively. Also, 60
When charge and discharge were repeated at a temperature of 2.degree. C., an operating voltage of 2.75 to 4.1 V, a charge of 0.5 mA, and a discharge of 1.5 mA, the maximum discharge capacity was 7.1 mAh, and the cycle life until the capacity was reduced to 50% was 380 times.

Example 32 <Production of Li-Ion Secondary Battery> The graphite negative electrode (10 m) produced in Example 26 was placed in an argon atmosphere glove box.
m × 10 mm) in the electrolyte (1M LiPF ₆ / EC + E)
MC (3: 7)), the composite polymer solid electrolyte / KW2200 composite film (12 mm × 12 mm) produced in Example 2 was bonded to the impregnated lithium ion, and the lithium cobaltate positive electrode produced in Example 25 (10mm
× 10mm) with electrolyte (1M LiPF ₆ / EC + EM)
C (3: 7)), the battery end is sealed with epoxy resin, and graphite / cobalt oxide Li
An ion secondary battery was obtained. FIG. 1 shows a cross-sectional view of the obtained battery. When the battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 60 ° C., 25 ° C., and −10 ° C., the maximum discharge capacities were 7.2 mAh, 7.2 mAh, and 5.6 mAh, respectively. In addition, 60 ° C, operating voltage 2.75 ~ 4.1V, charge 0.5mA, discharge 3.
Repeated charge and discharge at 0 mA, the maximum discharge capacity is 7.0 mAh
And the cycle life until the capacity is reduced to 50% is 35
It was 0 times.

[Example 33] <Production of Li-ion secondary battery> Instead of the compound polymer solid electrolyte / KW2200 composite film, Example 21 was used.
1 was manufactured in the same manner as in Example 32 except that the compound-based polymer solid electrolyte / aluminum oxide C composite film manufactured in the above was used. The battery was charged and discharged at 60 ° C., 25 ° C., −10 ° C. with an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA.
The maximum discharge capacities were 7.2 mAh, 7.2 mAh, and 4.8 mAh, respectively.
In addition, 60 ℃, operating voltage 2.75 ~ 4.1V, charge 0.5mA, discharge
Repeated charging and discharging at 3.0mA, the maximum discharge capacity is 7.2m
At Ah, the cycle life before capacity is reduced to 50% is 3
It was 80 times.

Example 34 <Production of Li-ion secondary battery> Instead of the compound-based polymer solid electrolyte / KW2200 composite film, Example 24 was used.
1 was manufactured in the same manner as in Example 32, except that the compound-based polymer solid electrolyte / aluminum oxide C / hypore composite film manufactured in the above was used. This battery was charged at 60 ° C., 25 ° C., −1
When charge and discharge were performed at 0 ° C with an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA, the maximum discharge capacities were 7.2 mAh, 7.2 mAh, and 4.2 mAh, respectively.
Met. In addition, 60 ℃, operating voltage 2.75 ~ 4.1V, charging 0.
When charge and discharge were repeated at 5 mA and 3.0 mA, the maximum discharge capacity was 6.8 mAh and the cycle life until the capacity was reduced to 50% was 300 times.

Example 35 <Production of Li-ion secondary battery> The graphite negative electrode (10 m
m × 10 mm) in the electrolyte (1.2 M LiPF ₆ / EC)
+ EMC (3: 7)), and then apply the salt-free compound / KW2200-based polymerizable composition prepared in Example 23 so as to have a thickness of 30 μm. Then, the container is sealed in an argon atmosphere under EMC saturation. For 30 minutes in a polymer electrolyte solid electrolyte impregnated with electrolyte / K
A W2200 composite film was formed directly on the graphite negative electrode.
Further, an electrolytic solution (1.2 M LiPF) was applied to the lithium cobaltate positive electrode (10 mm × 10 mm) produced in Example 25.
₆ / EC + EMC (3: 7)) were bonded together, and the battery end was sealed with an epoxy resin to obtain a graphite / cobalt oxide-based Li-ion secondary battery shown in FIG. This battery was operated at 60 ° C., 25 ° C., and −10 ° C. with an operating voltage of 2.75 to 4.
When charging and discharging were performed at 1 V and a current of 0.5 mA, the maximum discharge capacities were 7.2 mAh, 7.2 mAh, and 6.5 mAh, respectively. Also, 60
When charging and discharging were repeated at a temperature of 2.degree. C., an operating voltage of 2.75 to 4.1 V, a charge of 0.5 mA, and a discharge of 3.0 mA, the maximum discharge capacity was 7.2 mAh, and the cycle life until the capacity was reduced to 50% was 380 times.

[Example 36] <Production of Li-ion secondary battery> Instead of the salt-free compound / KW2200-based polymerizable composition prepared in Example 23, the salt-free compound / aluminum prepared in Example 24 was used. Except that the oxide C-based polymerizable composition was used, a graphite / cobalt oxide-based L shown in FIG.
An i-ion secondary battery was obtained. The battery was heated at 60 ° C. and 25
℃, -10 ℃ operating voltage 2.75 ~ 4.1V, 0.5mA current charge and discharge, the maximum discharge capacity is 7.2mAh, 7.2mA respectively
h, 6.1 mAh. In addition, 60 ℃, operating voltage 2.75-4.1
When charge and discharge were repeated at V, charge 0.5 mA and discharge 3.0 mA, the maximum discharge capacity was 7.2 mAh and the cycle life until the capacity was reduced to 50% was 420 times.

Example 37 <Production of All-Solid Li-Ion Secondary Battery> Graphite negative electrode (10 mm × 10 mm) / microporous film (hypore, 12 mm × 12 mm) produced in Example 26 in an argon atmosphere glove box. / A laminate of the lithium cobaltate positive electrode (10 mm × 10 mm) manufactured in Example 25 is prepared, and the upper and lower sides are fixed with clips. This was impregnated with an electrolyte solution (1.2 M LiPF ₆ / EC + EMC (weight ratio 3: 7)), charged at a current of 0.5 mA to 3.7 V, and then discharged at a current of 0.5 mA to 2.75 V, and a secondary reaction initially generated The gas was removed. Then, after removing excess electrolyte, the layer was further dried under vacuum for about 1 hour to remove EMC in the electrolyte remaining in the laminate, so that LiPF ₆ and EC remained in the dried laminate. . Next, this laminate was transferred under reduced pressure, and the salt-free compound prepared in Example 23 / KW22
After injecting the 00 type polymerizable composition, the pressure was returned to normal pressure, and the end of the laminate was sealed with an epoxy resin. Furthermore, the polymerizable composition was hardened by the action of free acid and heating at 60 ° C. for 30 minutes to obtain a graphite / cobalt oxide-based all-solid Li-ion secondary battery shown in FIG. This battery was used at 60 ° C, 25 ° C, -10
When the battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at ℃, the maximum discharge capacities were 7.2 mAh, 7.0 mAh, and 4.5 mAh, respectively. In addition, 60 ℃, operating voltage 2.75 ~ 4.1V, charging 0.5m
A. When charging and discharging were repeated at a discharge of 1.5 mA, the maximum discharge capacity was 7.2 mAh and the cycle life until the capacity was reduced to 50% was 430 times.

Example 38 <Production of All-Solid Li-Ion Secondary Battery> Instead of the salt-free compound / KW2200-based polymerizable composition prepared in Example 23, the salt-free compound prepared in Example 24 A graphite / cobalt oxide-based all-solid Li-ion secondary battery shown in FIG. 1 was obtained in the same manner as in Example 37 except that the / aluminum oxide C-based polymerizable composition was used. This battery is
Operating voltage 2.75 to 4.1V at 0 ° C, 25 ° C, -10 ° C, current 0.
When charging and discharging at 5 mA, the maximum discharge capacity was 7.2 m each
Ah, 7.2 mAh and 4.1 mAh. Also, 60 ° C, operating voltage
When charge and discharge were repeated at 2.75 to 4.1 V, charge 0.5 mA and discharge 1.5 mA, the maximum discharge capacity was 7.0 mAh and the cycle life until the capacity was reduced to 50% was 480 times.

Example 39 <Production of Activated Carbon Electrode> Excess N-methylpyrrolidone solution was added to a mixture of coconut palm activated carbon and polyvinylidene fluoride at a weight ratio of 9.0: 1.0 to obtain a gel composition. This composition was applied on a stainless steel foil in a size of 10 mm × 10 mm to a thickness of about 150 μm. After vacuum drying at about 100 ° C. for 10 hours, an activated carbon electrode (14.0 mg) was obtained.

Example 40 <Production of Electric Double Layer Capacitor> The activated carbon electrode (14) produced in Example 39 was placed in an argon atmosphere glove box.
mg) 10mm x 10mm in electrolyte (1M TEAB / P
Two electrodes impregnated with C) were prepared. Next, Example 6
Bonding the compound A-based polymer solid electrolyte / aluminum oxide C composite film (12 mm x 12 mm) manufactured in step 1 to one electrode, bonding the other electrode, and sealing the end of the capacitor with epoxy resin. As a result, an electric double layer capacitor as shown in FIG. 2 was manufactured. This capacitor is operated at 60 ° C. and 25 ° C. with an operating voltage of 0
When charging and discharging were performed at 2.5 V and a current of 0.2 mA,
The maximum capacities were 470 mF and 450 mF, respectively. The maximum capacity at 60 ° C. and 2.5 mA is 430 mF,
There was almost no change in the capacity even when charging and discharging were repeated 50 times.

Example 41 <Production of All Solid Electric Double Layer Capacitor> In an argon atmosphere glove box, activated carbon electrode (14 mg) produced in Example 39, 10 mm × 10 mm / microporous film (hypore, 12 mm × 12 mm). / A laminate of activated carbon electrode (14 mg) 10 mm × 10 mm manufactured in Example 39 was prepared, and the upper and lower sides were fixed with clips. This was impregnated with an electrolytic solution (1.0 M TEAB / acetonitrile (AN)). Then, after removing excess electrolyte, the layer was further dried under vacuum for about 1 hour to distill off AN in the electrolyte remaining in the laminate, so that TEAB remained in the dried laminate.
Next, the laminate was moved under reduced pressure, and after injecting the salt-free compound A-based polymerizable composition prepared in Example 31, the pressure was returned to normal pressure, and the end of the laminate was sealed with an epoxy resin. further,
The polymerizable composition was cured by the action of free acid and heating at 80 ° C. for 60 minutes to produce an all solid electric double layer capacitor as shown in FIG. This capacitor, 60 ℃,
When charging and discharging were performed at 25 ° C. at an operating voltage of 0 to 2.5 V and a current of 0.2 mA, the maximum capacities were 410 mF and 40 mF, respectively.
It was 0 mF. The maximum capacity at 60 ° C. and 1.0 mA was 380 mF, and there was almost no change in the capacity even when charging and discharging were repeated 50 times.

Example 42 <Production of Electric Double Layer Capacitor> In an argon atmosphere glove box, the activated carbon electrode (14
mg) 10mm x 10mm in electrolyte (1M TEAB / P
Two electrodes impregnated with C) were prepared. Next, Example 1
By bonding the compound polymer solid electrolyte / aluminum oxide composite film (12 mm x 12 mm) manufactured in Step 6 to one electrode, bonding another electrode, and sealing the capacitor end with epoxy resin. An electric double layer capacitor as shown in FIG. 2 was manufactured. This capacitor is operated at 60 ° C. and 25 ° C. with an operating voltage of 0
When charging and discharging were performed at 2.5 V and a current of 0.2 mA,
The maximum capacities were 470 mF and 470 mF, respectively. The maximum capacity at 60 ° C. and 2.5 mA is 450 mF,
There was almost no change in the capacity even when charging and discharging were repeated 50 times.

Example 43 <Production of All Solid Electric Double Layer Capacitor> In an argon atmosphere glove box, activated carbon electrode (14 mg) produced in Example 39, 10 mm × 10 mm / microporous film (hypore, 12 mm × 12 mm). / A laminate of activated carbon electrode (14 mg) 10 mm × 10 mm manufactured in Example 39 was prepared, and the upper and lower sides were fixed with clips. This was impregnated with an electrolytic solution (1.0 M TEAB / acetonitrile (AN)). Then, after removing excess electrolyte, the layer was further dried under vacuum for about 1 hour to distill off AN in the electrolyte remaining in the laminate, so that TEAB remained in the dried laminate.
Next, the laminate was moved under reduced pressure, and after injecting the salt-free compound / aluminum oxide C-based polymerizable composition prepared in Example 24, the pressure was returned to normal pressure, and the end of the laminate was sealed with an epoxy resin. did. Further, the polymerizable composition was left to stand at 80 ° C. for 60 minutes to cure the polymerizable composition by the action of free acid and heating.
An all-solid-state electric double layer capacitor as shown in FIG.
This capacitor was operated at an operating voltage of 0 to 2.degree.
When charge and discharge were performed at 5 V and a current of 0.2 mA, the maximum capacities were 460 mF and 430 mF, respectively. Also, 6
The maximum capacity at 0 ° C. and 1.0 mA was 430 mF, and there was almost no change in the capacity even when charging and discharging were repeated 50 times.

Example 44 <Production of Polymer Solid Electrolyte / Lithium Cobaltate Composite Positive> Under an argon atmosphere, a polymerizable composition which had not been prepared for a long time after preparation in Example 1 and LiCoO ₂ powder obtained in Example 25 And acetylene black in a weight ratio of 5: 4.5: 0.5 to obtain a gel composition. Immediately after mixing this composition, a 10 mm × 10 mm, about 200 μm
The mixture was left to stand at 60 ° C. for 30 minutes to obtain a compound A polymer polymer solid electrolyte / lithium cobaltate composite positive electrode (150 mg).

Example 45 <Preparation of Polymer Solid Electrolyte / Graphite Composite Negative Electrode> Under an argon atmosphere, a polymerizable composition which had not been prepared for a long time after preparation in Example 1, MCMB graphite (manufactured by Osaka Gas), gas phase method Graphite fiber (manufactured by Showa Denko KK: average fiber diameter 0.3 μm, average fiber length)
2.0μm, heat treated at 2700 ° C) at a weight ratio of 5: 4.8:
The mixture was mixed at 0.2 to obtain a gel composition. Immediately after mixing this composition, a 10 mm × 10 mm, about 25 μm
The resultant was coated and molded to a thickness of 0 μm and left at 60 ° C. for 30 minutes to obtain a compound A polymer solid polymer electrolyte / graphite composite negative electrode (68 mg).

Example 46 <Production of All-Solid Li-Ion Secondary Battery> The composite negative electrode (10 mm × 10 mm) / microporous film (hypore, 12 mm × 12 mm) produced in Example 45 was placed in an argon atmosphere glove box. / A laminate of the lithium cobaltate positive electrode (10 mm × 10 mm) manufactured in Example 44 is prepared, and the upper and lower sides are fixed with clips. This was impregnated with the salt-free compound A-based polymerizable composition prepared in Example 31, immediately charged to 2.5 V at a current of 2.5 mA to remove the initially generated side reaction gas, and the end of the laminate was epoxied. Sealed with resin. Furthermore, the polymerizable composition was hardened by the action of free acid and heating at 60 ° C. for 30 minutes to obtain a graphite / cobalt oxide-based all-solid Li-ion secondary battery shown in FIG.
The battery was operated at an operating voltage of 2.75 at 60 ° C., 25 ° C., and −10 ° C.
When charge and discharge were performed at ~ 4.1 V and a current of 0.5 mA, the maximum discharge capacities were 7.0 mAh, 6.3 mAh, and 1.5 mAh, respectively. Also, 6
When charge and discharge were repeated at 0 ° C., operating voltage 2.75 to 4.1 V, charge 0.5 mA, and discharge 1.5 mA, the maximum discharge capacity was 6.8 mAh, and the cycle life until the capacity was reduced to 50% was 430 times. .

Example 47 <Production of Polymer Solid Electrolyte / Lithium Cobaltate Composite Positive> Under an argon atmosphere, the polymerizable composition which had not been prepared for a long time after preparation in Example 11 and LiCoO ₂ obtained in Example 25 were used.
The powder and acetylene black were mixed at a weight ratio of 5: 4.5: 0.5 to obtain a gel composition. Immediately after mixing this composition, 10 mm × 10 mm, about 200 μm on an aluminum foil of about 25 μm.
m, and left for 30 minutes to obtain a compound polymer-based polymer solid electrolyte / lithium cobaltate composite positive electrode (150 mg).

Example 48 <Production of Polymer Solid Electrolyte / Graphite Composite Negative Electrode> Under an argon atmosphere, a polymerizable composition not prepared for a long time after preparation in Example 11, MCMB graphite (manufactured by Osaka Gas), gas phase method Graphite fiber (manufactured by Showa Denko KK: average fiber diameter, 0.3 μm, average fiber length, 2.0 μm, heat-treated at 2700 ° C.) weight ratio of 5: 4.8
: 0.2 to obtain a gel composition. Immediately after mixing this composition, a 10 mm × 10 mm, about 2
It was coated and molded to a thickness of 50 μm and left for 30 minutes to obtain a compound polymer-based polymer solid electrolyte / graphite composite negative electrode (68 mg).

Example 49 <Production of All-Solid Li-Ion Secondary Battery> Composite negative electrode (10 mm × 10 mm) / microporous film (hypore, 12 mm × 12 mm) produced in Example 48 in an argon atmosphere glove box. / A laminate of the lithium cobaltate positive electrode (10 mm × 10 mm) manufactured in Example 25 is prepared, and the upper and lower sides are fixed with clips. This was impregnated with the salt-free polymerizable composition prepared in Example 23, immediately charged to 3.7 V at a current of 2.5 mA, and then charged at a current of 2.5 mA.
Discharge to 2.75V to remove the initially generated side reaction gas,
The end of the laminate was sealed with an epoxy resin. Further, at 60 ° C
For 30 minutes, and the polymerizable composition was cured by the action of free acid and heating to obtain a graphite / cobalt oxide-based all-solid Li-ion secondary battery shown in FIG. The battery was heated at 60 ° C. and 25
℃, -10 ℃ operating voltage 2.75 ~ 4.1V, when the current was 0.5mA, the maximum discharge capacity is 7.2mAh, 6.8mA respectively
h, 4.0 mAh. In addition, 60 ℃, operating voltage 2.75-4.1
When charge and discharge were repeated at V, charge 0.5 mA and discharge 1.5 mA, the maximum discharge capacity was 7.2 mAh and the cycle life until the capacity was reduced to 50% was 510 times.

Example 50 <Production of Polymer Solid Electrolyte / Activated Carbon Composite Electrode> Under an argon atmosphere, the polymerizable composition, coconut activated carbon, and acetylene black which had not been prepared for a long time after preparation in Example 16 were mixed with 5.0.
: 4.5: 0.5 to obtain a gel composition. Immediately after mixing this composition, a 10 mm × 10 mm
About 150μm in thickness, 60 ℃, 30
After leaving the mixture for 2 minutes, a compound polymer-based polymer solid electrolyte / activated carbon composite electrode (28.0 mg) was obtained.

Example 51 <Production of All Solid Electric Double Layer Capacitor> In an argon atmosphere glove box, the composite electrode (28 mg) produced in Example 50, 10 mm × 10 mm / microporous film (hypore, 12 mm × 12 mm) / A composite body (28 mg) manufactured in Example 50 having a size of 10 mm × 10 mm is prepared, and upper and lower portions are fixed with clips. Next, the laminate was moved under reduced pressure, and after the compound / aluminum oxide C-based polymerizable composition prepared in Example 16 was injected, the pressure was returned to normal pressure, and the end of the laminate was sealed with an epoxy resin. further,
The polymerizable composition was cured by the action of free acid and heating at 80 ° C. for 60 minutes to produce an all solid electric double layer capacitor as shown in FIG. This capacitor, 60 ℃,
When charging and discharging were performed at 25 ° C. at an operating voltage of 0 to 2.5 V and a current of 0.2 mA, the maximum capacities were 460 mF and 40 mF, respectively.
It was 0 mF. Further, the maximum capacity at 60 ° C. and 1.0 mA was 430 mF, and the capacity hardly changed even if charging and discharging were repeated 50 times.

[0109]

According to the present invention, since an initiator which is usually stable and has a long pot life and which is easily decomposed by a free acid contained in an electrolyte salt or the like in an electrochemical element is contained, it is easy to handle and the electrode And when injected into an electrochemical element, a polymerizable composition having good polymerizability was obtained. Further, in the present invention, high ionic conductivity including a polymer having a crosslinked and / or side chain group obtained from the acid-polymerizable composition and an electrolyte, few residual double bonds and residual by-products, and stability. A polymer solid electrolyte suitable for various electrochemical devices, which was favorable and simple in production method, was obtained. Further, in the present invention, by combining the above-mentioned polymer solid electrolyte with various electrode active materials and polarizable materials, it is excellent in workability, can be operated at high capacity and high current, and has a long life without exuding liquid. And / or a composite electrode for an electric double layer capacitor was obtained. In addition, the battery and the electric double layer capacitor of the present invention obtained by using the above polymer solid electrolyte are easy to manufacture, can operate at high capacity and high current, or have good cyclability and temperature characteristics, It is a highly reliable battery and electric double-layer capacitor, and can be used as a main power supply for portable equipment, a power supply for electric appliances such as a backup power supply, a large power supply for electric vehicles and road leveling. Further, since it can be easily thinned, it can be used as a paper battery for an identification card or the like.

[Brief description of the drawings]

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

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

[Explanation of symbols]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01M 4/04 H01M 4/06 N 4/06 V 6/18 E 6/18 10/40 B 10/40 H01G 9/00 301G

Claims (29)

[Claims] A polymerizable composition for a solid polymer electrolyte comprising at least one kind of polymerizable compound and at least one kind of polymerization initiator. A polymerizable composition for a solid polymer electrolyte, comprising: 2. The polymerizable composition for a solid polymer electrolyte according to claim 1, further comprising an electrolyte salt having a free acid. 3. The polymerizable material for a solid polymer electrolyte according to claim 1, wherein the at least one polymerization initiator is a quaternary boron salt-based initiator represented by the following general formula (1). Composition. Embedded image [Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an allyl optionally having a substituent. Group, an aralkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a silyl group which may have a substituent, a heterocyclic group, Or a halogen atom, and Z ⁺ represents a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a phosphonium cation, a sulfonium cation, an oxosulfonium cation, an iodonium cation, or a metal cation. ] 4. The method according to claim 1, wherein the at least one polymerizable compound has the following general formula (2): [Wherein, R ⁵ represents hydrogen or an alkyl group; R ⁶ represents a divalent group containing oxyalkylene, fluorocarbon, oxyfluorocarbon, and / or carbonate;
⁸ represents a divalent group having 10 or less carbon atoms. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. However, R ⁵ and R ⁶ in a plurality of polymerizable functional groups represented by the general formula (2) in the same molecule are each independent and need not be the same. The polymerizable composition for a solid polymer electrolyte according to any one of claims 1 to 3, which has a polymerizable functional group represented by the following formula: 5. The method of claim 1, wherein the at least one polymerizable compound has the following general formula (3): [Wherein, R ⁷ represents hydrogen or an alkyl group, R ⁹ represents a divalent group containing oxyalkylene, fluorocarbon, oxyfluorocarbon, and / or carbonate;
⁸ represents a divalent group having 10 or less carbon atoms. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x is 0 or 1
The numerical value of 10 is shown. However, the values of R ^{7 to} R ⁹ and x in a plurality of polymerizable functional groups represented by the above general formula (3) in the same molecule are independent of each other and need not be the same. The polymerizable composition for a solid polymer electrolyte according to any one of claims 1 to 3, which has a polymerizable functional group represented by the following formula: 6. The polymerizable composition for a solid polymer electrolyte according to claim 1, comprising at least one organic solvent. 7. The polymerizable composition for a solid polymer electrolyte according to claim 1, further comprising an inorganic filler having a size of 0.01 to 100 μm. 8. An alkali metal salt, a quaternary ammonium salt,
A quaternary phosphonium salt, a transition metal salt, or at least one electrolyte salt selected from protonic acids.
8. The polymerizable composition for a solid polymer electrolyte according to any one of the above items 7. 9. A quaternary boron salt-based initiator in the polymerizable composition for a solid polymer electrolyte according to claim 3, which is decomposed by an acid and / or heat to polymerize the polymerizable composition. Polymer solid electrolyte obtained by performing 10. A polymer solid electrolyte obtained by polymerizing the polymerizable composition for a polymer solid electrolyte according to claim 1 by a polymerization initiator decomposed by an acid released from an electrolyte salt. . 11. A polymer obtained by decomposing a polymerization initiator in a polymerizable composition for a solid polymer electrolyte according to any one of claims 1 to 8 with an acid and polymerizing the polymerizable composition. A method for producing a solid electrolyte. 12. The quaternary boron salt-based initiator in the polymerizable composition for a solid polymer electrolyte according to any one of claims 3 to 8, which is decomposed by an acid and / or heat to polymerize the polymerizable composition. A method for producing a solid polymer electrolyte. 13. An electrode for a battery, comprising a polymer obtained from at least one of the polymerizable compositions for a solid polymer electrolyte according to any one of claims 3 to 8, and an electrode active material. 14. A mixture containing at least one polymerizable composition for a solid polymer electrolyte according to any one of claims 3 to 8 and an electrode active material is prepared, and after the mixture is molded, the mixture is mixed with the polymerizable composition. A method for producing a battery electrode, comprising decomposing the quaternary boron salt-based initiator by acid and / or heating to polymerize the polymerizable composition. 15. An electric double layer capacitor comprising a polymer obtained from at least one of the polymerizable compositions for a solid polymer electrolyte according to claim 3 and a polarizable material. electrode. 16. A mixture containing at least one polymerizable composition for a solid polymer electrolyte according to any one of claims 3 to 8 and a polarizable material, and after molding the mixture, the mixture is added to the polymerizable composition. A method for producing an electrode for an electric double layer capacitor, comprising decomposing the quaternary boron salt-based initiator by acid and / or heating to polymerize the polymerizable composition. 17. A battery comprising the polymer solid electrolyte according to claim 9 or 10. 18. A battery using the electrode according to claim 13. 19. A battery according to claim 19, wherein the negative electrode of the battery is lithium, a lithium alloy, or a carbon material capable of inserting and extracting lithium ions.
19. The battery according to claim 17, wherein at least one material selected from an inorganic oxide, an inorganic chalcogenide, and a conductive polymer is used. 20. The battery according to claim 17, wherein the positive electrode of the battery is made of a conductive polymer, an inorganic oxide, an inorganic chalcogenide and / or a carbon material. 21. An electric double layer capacitor using the polymer solid electrolyte according to claim 9 or 10. 22. An electric double-layer capacitor using the electrode according to claim 15. 23. At least one kind of the polymerizable composition for a solid polymer electrolyte according to any one of claims 1 to 8 is placed in a structure for battery construction or placed on a support, and A method for producing a battery, comprising decomposing a polymerization initiator of the above with an acid and polymerizing the polymerizable composition. 24. At least one kind of the polymerizable composition for a solid polymer electrolyte according to any one of claims 3 to 8 is placed in a structure for battery construction or placed on a support, and A method for producing a battery, comprising decomposing the quaternary boron salt-based initiator by acid and / or heating to polymerize the polymerizable composition. 25. The polymerizable composition for a solid polymer electrolyte according to any one of claims 1 to 8, which is placed in a structure for forming an electric double layer capacitor or placed on a support, and Decompose the polymerization initiator in the composition with an acid,
A method for producing an electric double layer capacitor, comprising polymerizing the polymerizable composition. 26. The polymerizable composition for a solid polymer electrolyte according to claim 3, wherein at least one of the polymerizable compositions is placed in a structure for forming an electric double layer capacitor, or disposed on a support, and A method for producing an electric double layer capacitor, comprising decomposing a quaternary boron salt-based initiator in a composition by an acid and / or heating to polymerize the polymerizable composition. 27. A fluorinated electrolyte salt having a free acid or an electrolytic solution in which a fluorinated electrolyte salt having a free acid is dissolved is disposed on a support, and then at least one polymerizable compound and at least one general A quaternary boron salt-based initiator represented by the formula (1) is added, and a polymerizable composition not containing an electrolyte salt is added thereto. A method for producing a solid polymer electrolyte, comprising polymerizing a polymerizable composition. Embedded image [Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an allyl optionally having a substituent. Group, an aralkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a silyl group which may have a substituent, a heterocyclic group, Or a halogen atom, and Z ⁺ represents a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a phosphonium cation, a sulfonium cation, an oxosulfonium cation, an iodonium cation, or a metal cation. ] 28. A fluorine-containing electrolyte salt having a free acid or an electrolyte solution in which a fluorine-containing electrolyte salt having a free acid is previously dissolved is placed in a structure for battery construction or placed on a support, and then at least one type of polymerization is carried out. A quaternary boron salt-based initiator containing a conductive compound and at least one quaternary boron salt-based initiator represented by the general formula (1), by adding a polymerizable composition containing no electrolyte salt and bringing the polymerizable composition into contact therewith. A method for producing a battery, comprising decomposing with a free acid to polymerize the polymerizable composition. 29. An electrolytic solution in which a fluorinated electrolyte salt having a free acid or a fluorinated electrolyte salt having a free acid is previously dissolved is placed in a structure for forming an electric double layer capacitor, or placed on a support, and then at least A polymerizable composition containing one kind of polymerizable compound and at least one kind of quaternary boron salt-based initiator represented by the general formula (1) and containing no electrolyte salt is added and brought into contact with the composition to form a quaternary boron salt-based initiator. A method for producing an electric double layer capacitor, comprising decomposing an initiator with a free acid and polymerizing the polymerizable composition.