JP2001123040A - Resin composition for polymeric solid electrolyte, polymeric electrolyte and polymer cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polymeric solid electrolytes having good membrane strength, high ionic conductivity, and excellent processability. SOLUTION: Compositions for polymeric solid electrolyte resins comprise (A) a polyfunctional (meth)acrylate having a urethane bond in the molecule, (C) a plasticizer, and an electrolyte.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition for a solid polymer electrolyte containing a (meth) acrylate having a specific structure, a photopolymerization initiator, a plasticizer and an electrolyte, a solid polymer electrolyte, and a polymer battery. .

Conventionally, electrolytes constituting electrochemical devices such as batteries, capacitors and sensors have been used in the form of solutions or pastes in view of ion conductivity, but there is a risk of damage to equipment due to liquid leakage. In addition, since a separator impregnated with an electrolytic solution is required, problems have been pointed out that there is a limit in miniaturization and thinning of the device. On the other hand, a product using a solid electrolyte does not have such a problem and can be easily made thin. Further, the solid electrolyte is excellent in heat resistance, and is advantageous in a process of manufacturing a product such as a battery.

[0003] In particular, those using a solid electrolyte containing a polymer as a main component have the advantages that the flexibility of the battery is increased and that it can be processed into various shapes as compared with inorganic materials. However, those studied so far have a problem that the extraction current is small because the ionic conductivity of the solid polymer electrolyte is low. For example, a method of adding a specific alkali metal salt to a mixture of an epichlorohydrin-based rubber and a low-molecular-weight polyethylene glycol derivative to apply it to a polymer solid electrolyte (Japanese Patent Laid-Open No. 2-235957) or crosslinking by a polymerization reaction of polyethylene glycol diacrylate. Although a method (Japanese Patent Application Laid-Open No. 62-285954) has been proposed, there is a problem that the film has no strength and a support is required, and the film strength, ionic conductivity, and adhesion to the electrode are required. Further improvement is desired in such balances.

Further, in recent years, electric double layer capacitors in which a carbon material having a large specific surface area, such as activated carbon or carbon black, is used as a polarizable electrode and an ion-conductive solution is arranged between them, as a memory backup power supply or the like, have been frequently used. . For example, Japanese Patent Application Laid-Open No. 63-244570 discloses a capacitor using Rb ₂ Cu ₃ I ₃ Cl ₇ having high electric conductivity as an inorganic solid electrolyte.
Also, "Functional Materials", February 1989, p. 33, describes a capacitor using a carbon-based polarizable electrode and an organic electrolyte. However, with current electric double layer capacitors that use an electrolyte solution, in the event of abnormalities such as prolonged use or when a high voltage is applied, liquid leakage to the outside of the capacitor is likely to occur. There is a problem with sex. On the other hand, there is a problem that the decomposition voltage of the conventional inorganic ion conductive material is low and the output voltage is low.

[0005] The solid polymer electrolyte layer in a battery and a capacitor only performs ion transfer. The thinner the layer, the smaller the volume of the whole battery and the capacitor, and the higher the energy density of the battery and the capacitor. Further, when the polymer solid electrolyte layer is thinned, the electric resistance of the battery and the capacitor can be reduced, the take-out current and the charging current can be increased, and the power density of the battery can be improved. Further, corrosion of ions, particularly alkali metal ions, hardly occurs, and the cycle life is improved. Therefore,
There has been a demand for a solid polymer electrolyte having high ionic conductivity, which has as good a film strength as possible and can be made into a thin film.

[0006]

The present invention has a strength that does not require a support even when a thin film having a thickness of about several tens of μm is obtained, has high ionic conductivity at room temperature and low temperature, and has excellent workability. It is an object of the present invention to provide a resin composition for a solid polymer electrolyte.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have found that a composition containing a specific (meth) acrylate and a composition containing a plasticizer and an electrolyte can be used. I found that I could achieve my purpose. Furthermore, by using a polymer solid electrolyte obtained by curing this composition for a battery, the ionic conductivity,
The inventors have found that problems such as film strength and workability can be improved, and have completed the present invention. That is, the present invention provides (1) a resin composition for a polymer solid electrolyte, comprising: a polyfunctional (meth) acrylate (A) having a urethane bond in a molecule; a plasticizer (C); and an electrolyte. (2) The resin composition for a solid electrolyte according to the above (1), wherein the number of (meth) acryl groups in the polyfunctional (meth) acrylate (A) is 3 or more per molecule; (3) a photopolymerization initiator ( (3) The resin composition for a solid polymer electrolyte according to the above (1) or (2), which contains B), (4) the photopolymerization initiator (B) having a wavelength of 350 to 4
(3) the resin composition for a solid polymer electrolyte according to (3), wherein the maximum molar extinction coefficient at 50 nm is 50 or more; (5) the electrolyte is an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, or a transition metal salt; The resin composition for a solid polymer electrolyte according to any one of (1) to (4), which is at least one selected from the group consisting of: (6) The resin composition according to any one of (1) to (5). (7) the polymer solid electrolyte according to (6), which is a sheet-shaped polymer solid electrolyte comprising a cured product of the resin composition for a polymer solid electrolyte;
(6) A polymer battery having the solid polymer electrolyte according to (7).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for a solid polymer electrolyte of the present invention is characterized by containing a polyfunctional (meth) acrylate (A) having a urethane bond in a molecule, a plasticizer (C) and an electrolyte. And In particular, the (meth) of the polyfunctional (meth) acrylate (A) having a urethane bond in the molecule
When the number of acryl groups is 3 or more in one molecule, improvement in film strength, impartation of flexibility, and rapid curing are preferably achieved.

The polyfunctional (meth) acrylate (A) having a urethane bond in the molecule of the present invention includes, for example, a reaction product of a polyol, an organic isocyanate and a monohydroxyl group-containing (meth) acrylate, or a reaction product of an organic isocyanate and a monohydroxyl group. Reaction products of contained (meth) acrylates.

The polyol compound includes, for example, alkyl polyol, polyester polyol, polyether polyol, acrylic polyol, polybutadiene polyol, polycarbonate polyol, polysiloxane polyol, phenolic polyol and / or flame-retardant polyol.

As the alkyl polyol, for example,
1,4-butanediol, 1,6-hexanediol,
1,8-octanediol, neopentyl glycol,
Cyclohexanedimethanol, trimethylolpropane, pentaerythritol and the like can be mentioned.

Examples of the polyester polyol include a condensation type polyester polyol, an addition-polymerized polyester polyol, and a polycarbonate polyol. As specific examples of the condensation type polyester polyol,
For example, a diol compound, adipic acid, isophthalic acid,
It is obtained by a condensation reaction with an organic polybasic acid such as terephthalic acid, sebacic acid or dimer acid, and has a molecular weight of 100 to 10
000 is preferred. Examples of the diol compound include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and 3-methyl-
1,5-pentanediol, 1,9-nonanediol,
Examples thereof include 1,4-siloxanehexanedimethanol, dimer acid diol, and polyethylene glycol.

The addition-polymerized polyester polyol includes, for example, polycaprolactone, and has a molecular weight of 1
00 to 100,000 is preferred. Polycarbonate polyol is synthesized by direct phosgenation of polyol, transesterification with diphenyl carbonate, and the like, and preferably has a molecular weight of 100 to 100,000.

Examples of the polyether polyol include PEG (polyethylene glycol), PPG (polypropylene glycol) and PTG (polytetramethylene glycol) polyols. The PEG-based polyol is obtained by subjecting ethylene oxide to addition polymerization using a compound having active hydrogen as a reaction initiator, and preferably has a molecular weight of 100 to 100,000. The PPG-based polyol is obtained by subjecting propylene oxide to addition polymerization using a compound having active hydrogen as a reaction initiator, and preferably has a molecular weight of 100 to 100,000. The PTG-based polyol is synthesized by cationic polymerization of tetrahydrofuran, and preferably has a molecular weight of 100 to 100,000.

Examples of polyether polyols other than the above-mentioned polyether polyols include an ethylene oxide adduct or a propylene oxide adduct of bisphenol A, and preferably have a molecular weight of 100 to 100,000.

Other polyols are copolymers of (meth) acrylic polyol, which is a copolymer of hydroxyl group-containing (meth) acrylate and other (meth) acrylate, and butadiene, and have a hydroxyl group at the terminal. Polybutadiene polyol which is a homo- or copolymer having, a polycarbonate polyol having a carbonate group in the structure, a phenolic polyol containing a phenol molecule in the molecule, a polysiloxane polyol having a silicon atom in the molecule, an epoxy polyol, a phosphorus atom, a halogen atom And the like, and the molecular weight is preferably 100 to 100,000. These polyol compounds can be used alone or in combination of two or more.

As the organic isocyanate compound, 2,
4- and / or 2,6-tolylene diisocyanate,
4,4'-diphenylmethane diisocyanate (MD
I) Polymerit MDI, 1,5-naphthylene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, hydrogenated MDI and the like. Can be These polyisocyanate compounds can be used alone or in combination of two or more.

Examples of the monohydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. Compounds having two or more (meth) acryl groups in the molecule, for example, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethylene oxide or propylene oxide modified products thereof Are preferred.

As a method for producing a reaction product of the polyol, organic isocyanate and monohydroxyl group-containing (meth) acrylate of the present invention, first, a polyol compound is reacted with an organic isocyanate compound to obtain a prepolymer. The isocyanate group of the organic isocyanate compound is 1.1 to 2.
Preferably, one equivalent is reacted. The prepolymerization reaction temperature is usually from room temperature to 100 ° C, preferably from 50 to 90 ° C.
It is.

It is preferable to react 0.9 to 1.5 equivalents of the hydroxyl group of the monohydroxyl group-containing (meth) acrylate with respect to 1 equivalent of the isocyanate group of the terminal isocyanate urethane prepolymer thus obtained.
Particularly preferably, it is 1.0 to 1.1 equivalent. The reaction temperature of the acrylate reaction is usually from room temperature to 100 ° C, preferably from 50 to 90 ° C. In order to prevent gelation due to radical polymerization during this reaction, usually 50 to 2000 ppm
It is preferable to add a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, P-methoxyphenol and P-benzoquinone. The reaction between the hydroxyl group and the isocyanate group proceeds without a catalyst. For example, a catalyst such as triethylamine, dibutyltin laurate, or dibutyltin diacetate may be added. Note that organic solvents and photopolymerizable monomers may be added during this reaction.

Next, a method for preparing a reaction product of the organic isocyanate and the monohydroxyl group-containing (meth) acrylate is as follows.
Preferably, 1.5 equivalents are reacted, particularly preferably 1.0 to 1.1 equivalents. The reaction temperature of the acrylate reaction is usually from room temperature to 100 ° C, preferably from 50 to 90 ° C.
° C. In order to prevent gelation due to radical polymerization during this reaction, it is usually preferable to add 50 to 2000 ppm of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, P-methoxyphenol, and P-benzoquinone. The reaction between the hydroxyl group and the isocyanate group proceeds without a catalyst. For example, a catalyst such as triethylamine, dibutyltin laurate, or dibutyltin diacetate may be added. Note that organic solvents and photopolymerizable monomers may be added during this reaction.

Specific examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; ethyl acetate;
Esters such as butyl acetate; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycol derivatives such as butyl cellosolve acetate, carbitol acetate, diethylene bricol dimethyl ether and propylene glycol monomethyl ether acetate. Alicyclic hydrocarbons such as cyclohexanone and cyclohexane, and petroleum solvents such as petroleum ether and petroleum naphtha; One or more of these organic solvents may be added.

In the present invention, a reactive monomer (D) other than the polyfunctional (meth) acrylate (A) having a urethane bond in the molecule, a reactive oligomer (E) and the like can be used in combination. The amount of the reactive monomer (D) and oligomer (E) to be used is preferably 0 to 100 parts by weight with respect to 100 parts by weight of the component (A).

Examples of the reactive monomer (D) include carbitol (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane polyoxyethyl tri (meth) acrylate and the like can be mentioned.

Examples of the reactive oligomer (E) include polyester poly (meth) acrylate, epoxy (meth) acrylate and the like.

Examples of the polyester poly (meth) acrylate include a reaction product of a polyester polyol composed of a polyhydric alcohol and a polybasic acid or an anhydride thereof and (meth) acrylic acid. Examples of the polyhydric alcohol include ethylene glycol, neopentyl glycol, polyethylene glycol, and trimethylolpropane.Examples of the polybasic acid include succinic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, And trimellitic acid.

As the epoxy (meth) acrylate,
For example, a reaction product of an aliphatic polyglycidyl ether and (meth) acrylic acid can be mentioned. Examples of the aliphatic polyglycidyl ether include glycerin diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether.

In the present invention, a photopolymerization initiator (B) can be used. As the photopolymerization initiator (B), all known photopolymerization initiators can be used.
Those having a maximum molar extinction coefficient of not less than 50 between 450 μm can be preferably used. By using this photopolymerization initiator (B), the resin composition of the present invention becomes an ultraviolet-curable resin composition. When the photopolymerization initiator (B) is used, its amount is preferably from 0.5 to 70 parts by weight, particularly preferably from 1 to 30 parts by weight, per 100 parts by weight of the component (A).

As the photopolymerization initiator (B), for example, 2-
Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (Irgacure 369, manufactured by Ciba Specialty Chemicals), 2,4-diethylthioxanthone, 2-isopropylthioxanthone, Michler's ketone, 4,4 '-Bis (diethylamino) benzophenone, bisacylphosphine oxide and the like can be mentioned. Particularly preferred are phosphorus-based compounds such as bisacylphosphine oxide. Examples of the bisacylphosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Can be

These photopolymerization initiators (B) include other photopolymerization initiators such as 1-hydroxy-2-cyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, methylphenylglyoxylate, It can also be used in combination with 2-diethoxyacetophenone and the like.

In the present invention, a plasticizer (C) is used. It is preferable to add a low-molecular compound as a plasticizer (C) to the composition of the present invention, since the ionic conductivity of the solid polymer electrolyte obtained by curing is further improved. The amount of the plasticizer (C) added is 50 to 15 parts by weight per 100 parts by weight of the component (A).
00 parts by weight is preferred, and 100 to 1000 parts by weight is particularly preferred. The ionic conductivity of the solid polymer electrolyte increases as the amount added increases, but the mechanical strength of the solid polymer electrolyte decreases when the amount is too large.

The plasticizer (C) that can be used includes (A)
Good compatibility with components, high dielectric constant, boiling point of 70
A compound having a temperature of not less than ° C and a wide electrochemical stability range is suitable. Examples of such a plasticizer (C) include oligoethers such as triethylene glycol methyl ether and tetraethylene glycol dimethyl ether, and carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate, and (meth) acryloyl carbonate. And aromatic nitriles such as benzonitrile and tolunitrile, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, sulfolane, phosphate esters and the like. Of these, oligoethers and carbonates are preferred, and carbonates are particularly preferred.

In the present invention, an electrolyte is used. The proportion of the electrolyte in the composition of the present invention is preferably in the range of 0.1 to 50% by weight, particularly preferably 1 to 30% by weight. If the amount of the electrolyte is too large, the movement of ions is greatly hindered. On the other hand, if the amount is too small, the absolute amount of ions becomes insufficient and the ionic conductivity decreases.

The electrolyte used in the present invention is particularly limited.
It is not specified, but I
Can be obtained by using an electrolyte containing
It is desirable that the dissociation constant in the polymer solid electrolyte is large.
And alkali metal salts, (CH _Three)_Four NBF₆Class 4 Ann
Monium salt, (CH_Three)_Four PBF₆Quaternary phosphonium such as
Salt, AgClO_FourTransition metal salts such as
Acids, protic acids such as borofluoric acid are recommended, for example
Alkali metal salts, quaternary ammonium salts, quaternary phosphoni
Palladium salts or transition metal salts are preferred.

As the alkali metal salt, for example, LiCF
₃ SO ₃ , LiPF ₆ , LiClO ₄ , LiI, LiB
F ₄ , LiSCN, LiAsF ₆ , NaCF ₃ SO ₃ , Na
PF ₆ , NaClO ₄ , NaI, NaBF ₄ , NaAsF
₆ , KCF ₃ SO ₃ , KPF ₆ , KI and the like.

The resin composition for a solid polymer electrolyte of the present invention is prepared by mixing the (meth) acrylate (A), the photopolymerization initiator (B), the plasticizer (C), and the electrolyte, It can be obtained by adding the water-soluble monomer (D), the oligomer (E), the other polymer (F) and / or the solvent, and mixing them uniformly. When a solvent is used, any solvent may be used as long as it does not inhibit polymerization, and for example, tetrahydrofuran, toluene and the like can be used.

In the present invention, the polymer (F) which can be used in some cases is, for example, polyethylene glycol, polyacrylonitrile, polybutadiene, poly (meth) acrylates, polystyrene, polyphosphazenes, polysiloxane or polysilane. . The amount of the polymer (F) used is (A) component 1
It is preferable to use 0 to 100 parts by weight with respect to 00 parts by weight.

The solid polymer electrolyte of the present invention comprises a cured product of the above resin composition for a solid polymer electrolyte. This cured product is obtained by irradiating the above resin composition for a polymer solid electrolyte with an electromagnetic wave (energy ray) such as ultraviolet rays to polymerize the resin composition. In particular, it is preferable that the resin composition for a polymer solid electrolyte be formed into a sheet (film) shape or the like and then polymerized by irradiating an electromagnetic wave such as an electron beam or ultraviolet light to form a sheet-shaped polymer. The degree of freedom is increased, which is a great advantage in application. When a sheet-shaped polymer solid electrolyte is produced, the above resin composition for a polymer solid electrolyte is usually applied to a support by a roll coater, a dip coater, various coaters such as a curtain coater or the like, and then electromagnetic waves such as ultraviolet rays are applied. May be applied to cure the resin composition. As the support, for example, aluminum-deposited PET
Films and the like. In order to more reliably cure the surface, another support may be laminated on the surface of the cured film of the resin composition, and further irradiated with electromagnetic waves such as ultraviolet rays. Other supports include, for example, polypropylene films and the like. The support is usually used after being removed.

The polymer battery of the present invention has a structure in which the above solid polymer electrolyte is sandwiched between a negative electrode active material and a positive electrode active material. This polymer battery is preferably in the form of a sheet. For this purpose, the polymer solid electrolyte, the negative electrode active material, and the positive electrode active material are all in the form of a sheet.

The negative electrode active material used in the battery is described below.
So, alkali metal, alkali metal alloy, carbon material
Redox using such alkali metal ions as carriers
By using those of the original potential and a mixture thereof,
This is preferable because a high-voltage, high-capacity battery can be obtained. Follow
Using such a negative electrode, the carrier
In solid polymer electrolytes when used in batteries
As a quality, an alkali metal salt is required. This arca
Examples of the type of the remetal salt include, for example, LiCF_ThreeSO_Three, L
iPF₆, LiClO_Four, LiI, LiBF_Four, LiSC
N, LiAsF₆, NaCF_ThreeSO_Three, NaPF₆, NaC
10_Four , NaI, NaBF_Four, NaAsF ₆, KCF_ThreeS
O_Three, KPF₆, KI and the like. In this
Alkali metal or alkali metal alloy as negative electrode active material
When using lithium or lithium as the negative electrode active material,
High voltage, high capacity when using a titanium alloy, and
It is most preferable because it can be thinned. In this case,
As a kind of the alkali metal salt, for example, a lithium salt is preferable.
New In the case of a carbon material negative electrode, an alkali metal salt is used.
Quaternary ammonium salts, quaternary phosphonium salts,
Transition metal salts and various protonic acids can be used.

In the construction of the battery, by using an electrode active material having a low oxidation-reduction potential (negative electrode active material) using an alkali metal ion such as an alkali metal, an alkali metal alloy or a carbon material as a carrier, a high voltage, This is preferable because a 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. When the carbon material also absorbs Li ions, it is particularly preferable in that it has a low oxidation-reduction potential and is stable and safe. The carbon material of Li ions can occluding and releasing, natural graphite, artificial graphite, vapor grown graphite, petroleum coke, coal coke, pitch carbon, polyacene, C _60, C _{7 0} fullerenes such as and the like.

In the construction of the battery, a metal oxide is provided on the positive electrode,
It is preferable to use a high oxidation-reduction potential electrode active material (a positive electrode active material) such as a metal sulfide, a conductive polymer, or a carbon material, or a mixture thereof, since a high-voltage, high-capacity battery can be obtained. Among such electrode active materials, metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, molybdenum oxide, molybdenum sulfide, and sulfide Metal sulfides such as titanium and vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide and the like are particularly preferable in terms of high capacity and high voltage.
When these are used for a lithium battery as an electrode active material, for example, Li _x CoO ₂ or Li _x M
It is preferable to use the Li element in a state of being inserted (composite) into the metal oxide or metal sulfide in the form of nO ₂ or the like. Such a method of inserting an Li element and a method disclosed in US Pat.
As described in JP-A No. 215, a material for a positive electrode can be prepared by a method of mixing a salt such as Li ₂ CO ₃ and a metal oxide and performing a heat treatment.

Also, in terms of being flexible and easy to form a thin film,
It is preferable to use a conductive polymer for the positive electrode. Examples of the conductive polymer include polyaniline, polyacetylene 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 Derivatives, polyarylenevinylenes such as polyparaphenylenevinylene, polythienylenevinylene, polyfurylenevinylene, polynaphthenylenevinylene, polyselenophenvinylene, polypyridinediylvinylene, and derivatives thereof, and the like can be given. Among them, a polymer of an aniline derivative soluble in an organic solvent is particularly preferable. The conductive polymer used as an electrode active material in these batteries or electrodes is manufactured according to a chemical or electrochemical method described later or other known methods.

Examples of the carbon material that can be used for the positive electrode include natural graphite, artificial graphite, vapor-grown graphite, petroleum coke, coal coke, fluorinated graphite, bitch carbon, and polyacene. Further, as the carbon material used as the electrode active material in the battery or the electrode of the present invention, a commercially available carbon material can be used, or it is manufactured according to a known method. The use of an organic solvent-soluble aniline-based polymer as the positive electrode active material in the electrode or battery of the present invention is advantageous because molding can be carried out by solution coating, and is extremely advantageous in producing a thin film battery. As the aniline-based polymer, for example, polyaniline,
Poly-o-toluidine, poly-m-toluidine, poly-
o-anisidine, poly-m-anisidine, polyxylidines, poly-2,5-dimethoxyaniline, poly-2,
6-dimethoxyaniline, poly-2,5-diethoxyaniline, poly-2,6-diethoxyaniline, poly-o
Examples thereof include -ethoxyaniline, poly-m-ethoxyaniline, and copolymers thereof, but are not particularly limited thereto, and may be any polymer having a repeating unit derived from an aniline derivative. In addition, the introduction amount of the side chain of the organic solvent-soluble aniline-based polymer is more convenient in terms of solubility as the amount is larger, but the more the amount introduced, the lower the capacity per weight of the positive electrode decreases. Appears. Therefore, preferred aniline polymers include, for example, polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-anisidine, poly-m-anisidine, and polyxylysines.

The polymer battery of the present invention is obtained, for example, by bonding a sheet-shaped negative electrode and a sheet-shaped positive electrode to the sheet-shaped polymer electrolyte of the present invention. The sheet-shaped negative electrode or the positive electrode is formed by, for example, forming a positive electrode active material or a negative electrode active material into a sheet, impregnating the resin composition for a polymer solid electrolyte of the present invention, and then irradiating an electromagnetic wave such as an electron beam or ultraviolet light. And cured.

[0046]

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.

Synthesis Example 1 (Synthesis example of polyfunctional (meth) acrylate (A) having urethane bond) In a round bottom flask equipped with a stirrer and a condenser, a polyester polyol (P-1010, manufactured by Kuraray Co., Ltd.) 1020 g of a hydroxyl value (110 mg KOH / g) and 348 g of tolylene diisocyanate were charged and reacted at 85 ° C. for 15 hours until the isocyanate group concentration became 6.14%. Then, pentaerythritol triacrylate 6
13 g and methoxyphenol 1.0 g were charged at 85 ° C.
For 10 hours. When the isocyanate group became 0.3%, the reaction was stopped to obtain a polyfunctional (meth) acrylate (A-1) having a urethane bond. Its weight-average molecular weight measured by GPC method was 3,500.

Synthesis Example 1 (Synthesis example of polyfunctional (meth) acrylate (A) having a urethane bond) In a round bottom flask equipped with a stirrer and a condenser, 168 g of hexamethylene diisocyanate, 613 g of pentaerythritol triacrylate, 613 g of methoxyphenol 0.
g, and reacted at 85 ° C. for 10 hours. When the isocyanate group became 0.3%, the reaction was stopped, and a polyfunctional (meth) acrylate having a urethane bond (A-2) was prepared.
I got Its weight-average molecular weight measured by GPC was 1500.

Example 1 1.5 g of the polyfunctional (meth) acrylate (A-1) having a urethane bond obtained in Synthesis Example 1, 2.00 g of ethylene carbonate (EC), and propylene carbonate (PC)
1.00 g, LiClO ₄ 0.30 g, bis (2,6
-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (photopolymerization initiator) 0.0
5 g were mixed well in an argon atmosphere to obtain an electrolyte mixture. This mixed solution is subjected to aluminum deposition PE in an argon atmosphere.
After coating to a thickness of 30 μm on a T film (30 μm) aluminum using a coater, 200 mJ / cm using a high pressure mercury lamp.
^{(2) After} irradiation, a polymer solid electrolyte was formed, a polypropylene film (30 μm) was laminated on the polymer solid electrolyte layer, and further 300 mJ / cm.
⁽²⁾ After irradiation with a high-pressure mercury lamp, the polymer solid electrolyte was obtained as a transparent free-standing film of about 30 μm by peeling off from the upper and lower layer films. 25 ° C, -20 of this film
The measured ionic conductivity at 1 ° C was 1 × 10 ⁻³ s
/ Cm (25 ° C), 4 × 10 ^-4 s / cm (-20 ° C)
Met.

Example 2 1.5 g of the polyfunctional (meth) acrylate (A-2) having a urethane bond obtained in Synthesis Example 2, 2.00 g of ethylene carbonate, 1.00 g of propylene carbonate, Li
0.35 g of PF _{6 and} 0.05 g of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (photopolymerization initiator) are mixed well in an argon atmosphere,
An electrolyte mixture was obtained. This mixture is placed under an argon atmosphere.
After coating to a thickness of 30 μm on an aluminum-deposited PET film (30 μm) aluminum using a coater, 2
After irradiation with 00 mJ / cm ² to form a polymer solid electrolyte, a polypropylene film (30 μm) was laminated on the polymer solid electrolyte layer,
After irradiation with a high-pressure mercury lamp of 00 mJ / cm ² , the polymer solid electrolyte was obtained as a transparent free-standing film of about 30 μm by peeling off the upper and lower films. When the ionic conductivity at 25 ° C. and −20 ° C. of this film was measured,
1 × 10 ⁻³ s / cm (25 ° C.), 3 × 10 ⁻⁴ s / cm
(−20 ° C.).

From the above results, it can be seen that the polymer solid electrolyte obtained by curing the resin composition of the present invention has a strength that can be peeled from the support, has a good thin film strength, and has a high ionic conductivity. It is clear that you are doing.

[0052]

The resin composition for a solid polymer electrolyte of the present invention comprises a specific (meth) acrylate (A), a photopolymerization initiator (B), a plasticizer (C) and an electrolyte. Excellent workability, easy to obtain a thin film with good film strength, the polymer solid electrolyte obtained by curing this resin composition,
It has good film strength and high ionic conductivity.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 5/49 C08K 5/49 5H029 C08L 33/14 C08L 33/14 H01B 1/06 H01B 1/06 A H01G 9/038 H01M 6/18 E 9/028 10/40 B H01M 6/18 C08F 2/50 10/40 290/06 // C08F 2/50 299/06 290/06 H01G 9/00 301D 299/06 9/02 331G F-term (reference) 4J002 CK031 CK041 CK051 DD017 DD087 DE177 DE197 DG037 DH007 DK007 DM007 ED036 EE038 EH038 EL066 EN098 EP016 ET006 EU026 EU238 EV186 EV257 EV306 EV308 EW046 EW128 EY017 FD0SA FD117 Q14 SA1415 SA1415 SA64 SA77 TA05 TA08 TA09 TA10 UA01 UA03 WA10 4J027 AG03 AG04 AG06 AG09 AG10 AG13 AG14 AG15 AG23 AG24 AG27 AG33 CB04 CC04 CD00 5G301 CA30 CD01 5H024 AA02 AA09 AA11 CC12 FF22 FF23 5H029 AJ14 AJ15 AM16

Claims (8)

[Claims] 1. A resin composition for a solid polymer electrolyte, comprising a polyfunctional (meth) acrylate (A) having a urethane bond in a molecule, a plasticizer (C) and an electrolyte. 2. The resin composition for a solid electrolyte according to claim 1, wherein the polyfunctional (meth) acrylate (A) has three or more (meth) acrylic groups in one molecule. 3. The resin composition for a solid polymer electrolyte according to claim 1, further comprising a photopolymerization initiator (B). 4. A photopolymerization initiator (B) having a wavelength of 350 to 45.
The resin composition for a polymer solid electrolyte according to claim 3, wherein the maximum molar extinction coefficient at 0 nm is 50 or more. 5. The polymer solid according to claim 1, wherein the electrolyte is at least one selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts. A resin composition for an electrolyte. 6. A solid polymer electrolyte comprising a cured product of the resin composition for a solid polymer electrolyte according to any one of claims 1 to 5. 7. The polymer solid electrolyte according to claim 6, which is in the form of a sheet. 8. A polymer battery comprising the polymer solid electrolyte according to claim 6.