JP2001028276A - Manufacture of polyelectrolyte and photoelectric transducer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for a polyelectrolyte, having high mechanical strength, high safety and a high photoelectric transducing function, and to provide a photoelectric transducer using it. SOLUTION: A polyelectrolyte is manufactured by oxidation-reduction type electrolyte impregnated a polymer matrix. The oxidation-reduction type electrolyte is made of halogen molecules and a halide, such as LiI having halogen ions as a pair ion, while the polymer matrix uses a cured substance of a polymerizable monomer solution. By this method, the polymer matrix can be easily manufactured in a short light irradiation time. Because the polyelectrolyte for a photoelectric transducer can be obtained by the simple method, i.e., the impregnation into the oxidation-reduction type electrolyte solution, time and energy can be saved. The obtained polyelectrolyte is superior in mechanical strength, stability and machinability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer electrolyte having high mechanical strength and stability and high photoelectric conversion ability, and a photoelectric conversion element using the same.

[0002]

2. Description of the Related Art In recent years, as a solar cell which can be manufactured at low cost, Gretzel et al. (M. Gratzel Nature, 1991, vol. 35)
3, p737) has been actively developed. This technology uses a titanium oxide porous thin film sensitized by a ruthenium complex as an electrode, and is capable of supporting a large amount of a ruthenium complex at low cost, thereby exhibiting high energy conversion efficiency. Since the electrolyte used in this wet solar cell is in a liquid state, there is also a problem such as liquid leakage. For this reason, there is an increasing need for a solid electrolyte having no problem such as liquid leakage as an electrolyte used in the photoelectric conversion element. As this solid electrolyte, for example, JP-A-9-27352 discloses
An electrolyte supported in a resin matrix is disclosed

[0003]

SUMMARY OF THE INVENTION However, Japanese Patent Application Laid-Open No. Hei 9-2
In the method described in JP-A-7352, since a halogen-based electrolyte, in particular, an iodine-based electrolyte is included in the curing system, nitrogen replacement is required at the time of curing, and there is a problem that the energy cost required for the curing is complicated and high. In addition, there is a problem that the conversion efficiency is lower than when a solution-based electrolyte is used.

[0004]

Means for Solving the Problems Accordingly, the present inventors have
As a result of various investigations, a solution-based electrolyte was obtained by impregnating a redox-based electrolyte in a solution, which was hardened with heat or energy rays such as light, radiation, and electron beams, and contained substantially no inorganic electrolyte. A polymer electrolyte having a photoelectric conversion efficiency equal to or higher than that of the polymer electrolyte can be manufactured. That is, the present invention

(1) A method for producing a polymer electrolyte characterized by impregnating a polymer matrix with an oxidation-reduction electrolyte, and (2) a method for producing a polymer electrolyte according to (1) for use in a photoelectric conversion element. (3) The method for producing a polymer electrolyte according to (1) or (2), wherein the redox electrolyte comprises a halogen compound having a halogen ion as a counter ion and a halogen molecule, and (4) the iodine compound is a halogen compound. (4) The method for producing a polymer electrolyte according to (4), wherein the halogen molecule is iodine. (5) Impregnation of the oxidation-reduction electrolyte is performed by immersing the solvent-containing polymer matrix in the oxidation-reduction electrolyte solution ( (1) The method for producing a polymer electrolyte according to any one of (4) to (4), (6) the polymer electrolyte according to (5), wherein the solvent of the redox electrolyte solution is a polar organic solvent. (7) The method for producing a polymer electrolyte according to any one of (1) to (6), wherein the polymer matrix is a solvent-containing polymer matrix, and (8) the solvent-containing polymer matrix is polymerizable. The method for producing a polymer electrolyte according to (7), which is a cured product of a monomer solution,

(9) The method for producing a polymer electrolyte according to (8), wherein the polymerizable monomer is a monomer having an acryloyl or methacryloyl group, and the polymerizable monomer according to (10) is a monomer having a vinyl ether group. (8) The polymer electrolyte and the production method according to (8), (11).
Any one of (8) to (10), wherein the polymerizable monomer has an ethylene oxide chain or a propylene oxide chain
(12) The method for producing a polymer electrolyte according to item (12), wherein the polymerizable monomer has an alkyl fluoride group (8) to (1).
(1) The polymer matrix according to any one of (8) to (12), wherein the polymer matrix is a polymer electrolyte and a production method, and (13) the polymerizable monomer has a quaternary nitrogen base. (14) The method for producing a polymer electrolyte according to any one of (8) to (13), wherein the polymerizable monomer is a mixture of a polyfunctional monomer and a monofunctional monomer, (15) (1) or (1)
4) A photoelectric conversion element having the polymer electrolyte according to any one of 4) and (16) a solvent-containing polymer matrix for a photoelectric conversion element substantially containing no electrolyte.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a polymer electrolyte according to the present invention is characterized in that a polymer matrix is impregnated with a redox electrolyte. The polymer electrolyte obtained by this method is suitable for a photoelectric conversion element used for a solar cell or the like.

The impregnation of the polymer matrix with the redox electrolyte can be carried out by a method of dipping the polymer matrix in a redox electrolyte solution or a method of applying the electrolyte solution on the matrix. The concentration of the redox electrolyte in the redox electrolyte solution is about 0.01% to 99% by weight, preferably about 0.1% to 95% by weight of the whole solution. The impregnation time is about 1 second to 100 hours, preferably about 1 minute to 20 hours, but these conditions are not particularly limited and can be changed according to the difficulty of impregnation.

The redox electrolyte solution is obtained by dissolving the above redox electrolyte in a solvent. The solvent is not limited as long as it can dissolve the electrolyte in an amount of 0.01% by weight to 500% by weight. For example, propylene carbonate, ethylene carbonate, acetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 3-methoxypro Pionitrile, γ-butyrolactone, dimethoxyethane, diethyl carbonate, diethyl ether, dimethyl sulfoxide, sulfolane, tetrahydrofuran, 2-
Organic solvents such as methyl tetrahydrofuran, 1,3-dioxolane, ethyl methyl carbonate, chloroethylene carbonate, trifluoromethyl propylene carbonate, methyl propyl carbonate, propylene glycol monomethyl ether, various ketones and esters, and water. Can be Among them, the boiling point is 50
The solvent is preferably a solvent having a relative dielectric constant of 10 ° C. or higher, for example, propylene carbonate (bp: 241.7).
° C, relative dielectric constant: 64.4), ethylene carbonate (b.
p .: 248 ° C, relative permittivity: 89.6), acetonitrile (bp: 81.8 ° C, relative permittivity: 38.0), and 3-methoxypropionitrile are preferred. These can be used alone or in combination of two or more.

[0010] The redox electrolyte solution further comprises:
1,2-dimethyl-3-propylimidazolium salt, t
By adding butylpyridine, methylfuran, benzene, ethyltrimethylammonium chloride, polyethylene glycol dimethyl ether, various crown ethers and the like, it is possible to improve the electrode characteristics of the polymer electrolyte. In addition, these properties can be improved by adding a surface plasticizer, a dispersant, a surfactant, and the like.

The impregnation of the oxidation-reduction electrolyte into the polymer matrix can be performed, for example, by dispersing the microcapsules enclosing the electrolyte in a solvent-containing monomer and curing the microcapsules, for example, by opening the microcapsules by heating. Can also be done.

The redox electrolyte used in the present invention is a halogen redox electrolyte composed of a halogen compound having a halogen ion as a counter ion and a halogen molecule, and a ferrocene-ferricyanate or ferrocene-ferricinium ion. Examples thereof include metal redox electrolytes such as metal complexes, and aromatic redox electrolytes such as alkylthiol-alkyl disulfide, viologen dyes, and hydroquinone-quinone. Halogen redox electrolytes are preferred.

[0013] Examples of the halogen molecule in the halogen redox electrolyte composed of a halogen compound and a halogen molecule include an iodine molecule and a bromine molecule, and an iodine molecule is preferable. Examples of the halogen compound having a halogen ion as a counter ion include, for example, LiI, NaI, K
Examples thereof include metal halide salts such as I, CsI and CaI2, and organic quaternary ammonium salts of halogens such as tetraalkylammonium iodide and pyridinium iodide. Salt compounds having iodine ion as a counter ion are preferable. Examples of the salt compound having iodine ion as a counter ion include lithium iodide, sodium iodide, and trimethylammonium iodide.
The ratio of iodine molecules to the whole redox electrolyte is
0.01 to 99% by mole, preferably 1 to
% By mole to 90% by mole. The ratio of the redox electrolyte to the entire polymer electrolyte is 0.01% by weight to 8%.
0% by weight, preferably 0.05% to 30% by weight
It is about.

The polymer matrix before impregnation with the redox electrolyte has a three-dimensional network structure, and does not substantially contain an electrolyte. “Substantially” means that no electrolyte other than the electrolyte derived from the raw material at the time of producing the polymer matrix is contained. This polymer matrix is usually obtained by curing a thermosetting resin or an energy ray-curable resin. More preferably, a solvent-containing polymer matrix obtained by dissolving these resins in a solvent and then curing the resin is used. The solvent content in the solvent-containing polymer matrix is from 1% to 99.9% by weight, preferably 10% by weight.
About 95% by weight. When a photoelectric conversion element is manufactured, a polymer matrix obtained by curing a resin on a porous film substrate of a metal oxide semiconductor represented by titanium oxide is more practical.

The resin for obtaining the polymer matrix includes, for example, an energy ray-curable resin and a thermosetting resin. Examples of the energy ray-curable resin include (meth) acrylates and vinyl ethers, and include a (meth) acrylate group or a monofunctional monomer having one vinyl group and two (meth) acrylate groups or two vinyl groups. Those obtained in combination with the above-mentioned bifunctional or higher polyfunctional monomer are preferred. The ratio of the polyfunctional monomer to the monofunctional monomer is 0.01% to
100%, preferably 0.5% to 30%. The viscosity of the resin liquid before curing is preferably low in order to facilitate the removal of air bubbles.

Preferred monofunctional monomers having one (meth) acrylate group include, for example, ethyl carbitol (meth) acrylate, methoxytriethylene glycol methacrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol ( (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate, tetrafurfuryl (meth) acrylate, morpholinyl ( Meth) acrylate, ethylene glycol ethyl carbonate (meth) acrylate, and the like. Bitoru (meth) acrylate,
Methoxytripropylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate,
Polyalkylene glycol (polymerization number: 2 to 50) such as hexaethylene glycol (meth) acrylate (meth) acrylate.

Preferred as the bifunctional or higher polyfunctional (meth) acrylate monomer having two or more (meth) acrylate groups are, for example, tetraethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, octaethylene. Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, hexapropylene glycol azi (meth) acrylate, octapropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified dipentaerythritol hexa (meth) acrylate EO-modified dipentaerythritol hexa (meth) acrylate, tetraethylene glycol di (meth) acrylate, octaethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, octapropylene glycol di (meth) ) Polyalkylene glycols such as acrylates (polymerization number is 2 to 5)
0) Poly (meth) acrylate.

As the basic skeleton of these monomers, those having a (C 2 -C 50) alkylene oxide skeleton such as ethylene oxide or propylene oxide in the main chain and side chains are preferable. In addition, as a combination, monofunctional monomers having one (meth) acrylate group include (C2-C48) alkoxypoly (C2-C4) such as ethyl carbitol acrylate, methoxytriethylene glycol acrylate, and methoxydipropylene glycol acrylate.
8) Using an alkylene glycol (polymerization number: 2 to 50) mono (meth) acrylate, tetraethylene glycol diacrylate or octa as a bifunctional or higher polyfunctional (meth) acrylate monomer having two or more (meth) acrylate groups. Ethylene glycol diacrylate,
It is preferable to use polyalkylene (C2-C3) glycol (polymerization number: 4 to 10) poly (meth) acrylate such as dipentaerythritol hexaacrylate and ethylene oxide-modified dipentaerythritol hexaacrylate.

Preferred monofunctional monomers having one vinyl ether group usable in the present invention include, for example, ethyl vinyl ether, propyl vinyl ether,
n-butyl vinyl ether, isobutyl vinyl ether, ethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, 2-ethylhexyl vinyl ether, t-butyl vinyl ether, t
-Amyl vinyl ether, cyclohexyl vinyl ether, n-octadecyl vinyl ether, dodecyl vinyl ether, propenyl ether propylene carbonate, aminopropyl vinyl ether, 2-dimethylaminoethyl vinyl ether and the like, and ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, ethylene Glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, 2-ethylhexyl vinyl ether, t-butyl vinyl ether, and propenyl ether propylene carbonate are particularly preferred. It is also possible to use vinyl ether-modified monomers or vinyl ether-modified oligomers.

The vinyl ether group which can be used in the present invention is 2
Preferred as the bifunctional monomer having two or more, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, tripropylene glycol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, Examples thereof include tetraethylene glycol divinyl ether, trimethylolpropane trivinyl ether, and 1,4-cyclohexane dimethanol divinyl ether. Ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, and trimethylolpropane trivinyl ether are particularly preferable. It is also possible to use vinyl ether-modified monomers or vinyl ether-modified oligomers.

As the basic skeleton of these monomers, those having a (C 2 -C 50) alkylene oxide skeleton such as ethylene oxide or propylene oxide in the main chain and side chains are preferable. As a combination, (C2-C48) alkoxypoly (C2-C4) such as ethyl carbitol vinyl ether, methoxytriethylene glycol vinyl ether, methoxydipropylene glycol vinyl ether or the like as a monofunctional monomer having one vinyl ether group.
8) Use of alkylene glycol (polymerization number: 2 to 50) monovinyl ether, and tetraethylene glycol divinyl ether, octaethylene glycol divinyl ether, trimethylolpropanetriene as a difunctional or higher polyfunctional vinyl ether monomer having two or more vinyl ether groups. Polyalkylene such as vinyl ether (C2
It is preferred to use -C3) glycol (polymerization number 4 to 10) polyvinyl ether.

In the present invention, a polymer matrix having a fluorinated alkyl group in the polymer skeleton can be used. Such a polymer matrix is obtained by homopolymerization of a monomer having a fluorinated alkyl group in the molecular skeleton and copolymerization of two or more types. The matrix can also be obtained by copolymerization of a monomer having an alkyl fluoride group in the molecular skeleton and a monomer not containing the alkyl fluoride group. In this case, the ratio of the monomer having the fluorinated alkyl group to the monomer not containing the fluorinated alkyl group is 0% to 100%,
1% to 95% is preferable, and 1% to 50% is particularly preferable.

Examples of the monomer having a fluorinated alkyl group in the molecular skeleton used in the present invention include, for example, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, 2,2,3,3,3-pentane Fluoropropyl (meth) acrylate, 2,2,3
3,4,4-heptafluorobutyl (meth) acrylate, 2,2,3,3-tetrafluorobutyl di (meth)
Acrylate, 2,2,3,3,4,4-hexafluorohexyldi (meth) acrylate, tetrafluoroethylene, trifluoroethylene, trifluoromethylethylene glycol (meth) acrylate, trifluoromethyldiethylene glycol (meth) acrylate, Trifluoromethyltetraethylene glycol (meth) acrylate, trifluoromethylethylene glycol di (meth) acrylate, trifluoromethyldiethylene glycol di (meth) acrylate, trifluoromethyltetraethylene glycol di (meth) acrylate,
1,2-difluoroethylene, trifluoroethyl vinyl ether, pentafluoropropyl vinyl ether,
Trifluoroethyl glycidyl ether, pentafluoropropyl glycidyl ether, tetrafluorobutyl glycidyl ether, trifluoromethyl ethylene glycol vinyl ether, trifluoromethyl diethylene glycol vinyl ether, trifluoromethyl tetraethylene glycol vinyl ether, trifluoromethyl ethylene glycol divinyl ether, trifluoromethyl Examples thereof include diethylene glycol divinyl ether, trifluoromethyltetraethylene glycol divinyl ether, tetrafluorobutyl diglycidyl ether, and hexafluoropentyl diglycidyl ether, and trifluoroethyl (meth) acrylate and pentafluoroethyl (meth) acrylate are preferable.

In the present invention, a polymer matrix having a quaternary nitrogen salt in the polymer skeleton can be used. Such a polymer matrix is obtained by homopolymerization of a monomer having a quaternary nitrogen salt in the molecular skeleton and copolymerization of two or more kinds. The matrix can also be obtained by copolymerization of a monomer having a quaternary nitrogen salt in the molecular skeleton and a monomer containing substantially no ionic species. In that case, the ratio of the monomer having a quaternary nitrogen salt in the molecular skeleton to the monomer substantially containing no ionic species is 0% to 100%, preferably 0.01% to 95%, and more preferably 1%. ~ 50% is particularly preferred.

The monomer having a quaternary nitrogen salt in the molecular skeleton used in the present invention is, for example, trimethylammonium iodideethyl (meth) acrylate, trimethylammonium iodideethylene glycol (meth) acrylate, trimethylammonium iodide diethylene glycol ( (Meth) acrylate, trimethylammonium iodide triethylene glycol (meth) acrylate, trimethylammonium iodide propylene glycol (meth) acrylate, trimethylammonium iodide dipropylene glycol (meth) acrylate, trimethylammonium iodide tripropylene glycol (meth) acrylate 1,2-dimethylimidazolium iodideethyl (meth) acrylate, 1,2-di Tyl imidazolium iodide ethylene glycol (meth) acrylate, 1,2-dimethyl imidazolium iodide diethylene glycol (meth) acrylate, 1,2-dimethyl imidazolium iodide triethylene glycol (meth) acrylate, 1,2-dimethyl imidazo Lium iodide propyl (meth) acrylate, 1,2-dimethyl imidazolium iodide propylene glycol (meth) acrylate, 1,2-dimethyl imidazolium iodide dipropylene glycol (meth) acrylate, dimethyl ammonium iodide di (meth) Acrylate, dimethyl ammonium iodide diethyl (meth) acrylate, dimethyl ammonium iodide dipropyl (meth) acrylate, dimethyl ammonium Yoda Lee blunder butyl (meth) acrylate, dimethyl ammonium iodide Lee blunder (polyalkyl) (meth) acrylate, 1
-Methylimidazolium iodidedi (meth) acrylate, 1-methylimidazolium iodidediethyl (meth) acrylate, 1-methylimidazolium iodidedipropyl (meth) acrylate, 1-methylimidazolium iodidedibutyl (meth) acrylate Acrylate, 2-methylimidazolium iodide di (meth) acrylate, 2-methylimidazolium iodidediethyl (meth) acrylate, 2-methylimidazolium iodidedipropyl (meth) acrylate, 2-methylimidazolium iodidedibutyl (Meth) acrylate, 3-methylimidazolium iodide di (meth)
Acrylate, 3-methylimidazolium iodidediethyl (meth) acrylate, 3-methylimidazolium iodidedipropyl (meth) acrylate, 3-methylimidazolium iodidedibutyl (meth) acrylate, N, N-dimethylallylammonium iodine Id,
N, N-dimethylallyldiethylammonium iodide,
N, N-dimethylallyldipropylammonium iodide, diallyl-N, N-dimethylammonium iodide,
Diallyl-N, N-dimethyldiethylammonium iodide, diallyl-N, N-dimethyldipropylammonium iodide, trimethylammonium fluorideethyl (meth) acrylate, trimethylammonium chlorideethyl (meth) acrylate, trimethylammonium bromideethyl (meth) A) acrylate, trimethylammonium perchlorate ethyl (meth) acrylate, trimethylammonium borateethyl (meth) acrylate, trimethylammonium tetrafluoroborateethyl (meth) acrylate, trimethylammonium hexafluorophosphate ethyl (meth) acrylate, trimethylammonium iodide ethyl Vinyl ether, trimethyl ammonium iodide ethylene glycol vinyl Ether, 1,2-dimethylimidazolium iodide ethyl vinyl ether and the like, and trimethyl ammonium iodide ethyl (meth) acrylate, trimethyl ammonium iodide ethylene glycol (meth) acrylate, trimethyl ammonium iodide diethylene glycol (meth)
Acrylate, 1,2-dimethylimidazolium iodideethyl (meth) acrylate, 1,2-dimethylimidazolium iodideethylene glycol (meth) acrylate, 1,2-dimethylimidazolium iodidediethylene glycol (meth) acrylate, dimethylammonium Iodide di (meth) acrylate, dimethyl ammonium iodide diethyl (meth) acrylate, 1-methylimidazolium iodide di (meth) acrylate, 1-methylimidazolium iodide diethyl (meth) acrylate, 2-methylimidazolium ioda Idodi (meth) acrylate, 2-methylimidazolium iodidediethyl (meth) acrylate, 3-methylimidazolium iodidedi (meth) acrylate, 3-meth Louis imidazolium iodide diethyl (meth) acrylate, N, N-dimethylallylammonium iodide, N, N-dimethylallyldiethylammonium iodide, diallyl-N, N-dimethylammonium iodide, diallyl-N, N-dimethyl Preferred are diethylammonium iodide, trimethylammonium iodide ethyl vinyl ether, trimethylammonium iodide ethylene glycol vinyl ether, 1,2-dimethylimidazolium iodideethyl vinyl ether, and the like. Trimethylammonium iodideethyl (meth) acrylate, trimethylammonium iodide Glycol (meth) acrylate, 1,2
-Dimethyl imidazolium iodide ethyl (meth) acrylate, 1,2-dimethyl imidazolium iodide ethylene glycol (meth) acrylate, dimethyl ammonium iodide di (meth) acrylate, 1-
Methyl imidazolium iodide di (meth) acrylate, 2-methyl imidazolium iodide di (meth) acrylate, 3-methyl imidazolium iodide di (meth) acrylate, N, N-dimethylallylammonium iodide, N, N -Dimethylallyl diethylammonium iodide, 1,2-dimethylimidazolium iodide ethyl vinyl ether and the like are particularly preferred.

In the present invention, when the energy ray-curable resin is cured using ultraviolet rays, a photopolymerization initiator or the like is usually used. The usage ratio of the photopolymerization initiator is preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, based on the total weight of the above-mentioned polymerizable monomers.

Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; acetophenone;
-Dimethoxy-2-phenylacetophenone, 2,2-
Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, N, N- Acetophenones such as dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-
Chloroanthraquinone, 2-amylanthraquinone, 2
Anthraquinones such as aminoanthraquinone, 2,4
Thioxanthones such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methylbenzophenone and 4,4′-dichloro Benzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, 4
Benzophenones such as -benzoyl-4'-methyldiphenylsulfide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio-phenyl] sulfide bishexafluorophosphate, bis [4- (di ( 4- (2-
Hydroxyethyl) phenyl) sulfonio-phenyl] sulfide bishexafluoroantimonate, etc., and these can be used alone or in combination of two or more.

Further, photosensitizers such as tertiary amines such as ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, pentyl 4-dimethylaminobenzoate, triethylamine and triethanolamine. Sensitizers can be used alone or in combination of two or more.

The thermosetting resin used in the production of the polymer matrix used in the present invention includes epoxy resins and melamine resins (for example, homopolymers of diallyl melamine, copolymers with other monomers, methylol melamine Cured products such as alkoxymelamine). Epoxy resins include copolymers of glycidyl ethers with amine-based curing agents and non-amine-based curing agents. As glycidyl ethers, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, phenylglycidyl ether, hydrogenated bisphenol A diglycidyl ether and the like, and diethylene glycol diglycidyl ether and dipropylene glycol are preferable.
As amine-based curing agents, for example, diaminoethylene,
Examples thereof include diaminoethylene glycol, diaminopropylene glycol, diaminodiethylene glycol, diaminodipropylene glycol, and the like, with diaminodiethylene glycol and diaminodipropylene glycol being preferred. As the non-amine curing agent, ethylene glycol,
Examples of carboxylic acid-based cross-linking agents such as glycerin, cresol, phthalic anhydride, pyromellitic anhydride, and maleic anhydride include terephthalic acid and acetone dicarboxylic acid.

The polymer matrix used in the present invention comprises:
Solvent-containing polymer matrices containing solvents are preferred. As the solvent, for example, propylene glycol, ethylene glycol, acetonitrile, ethylene glycol, propylene glycol, triethylene glycol,
3-methoxypropionitrile, γ-butyrolactone and the like can be mentioned. The content ratio is about 0.1% to 99.9% by weight, preferably 1% to 99% by weight, and particularly preferably 5% by weight of the total weight of the polymer matrix.
~ 95% by weight.

The production of the polymer matrix used in the present invention may be carried out, for example, as follows. That is, for example, in the case of a photoelectric conversion element, a monomer may be applied to a porous substrate for a photoelectric conversion element and then cured. As a method of applying the monomer to the porous substrate, a dip coating method, a spin coating method, a screen printing method, a transfer method, a doctor blade method, a curtain coating method, or the like can be used. Further, when the distance between the electrode and the counter electrode is small, it is also possible to use a capillary phenomenon or the like.

In order to produce a solvent-containing polymer matrix, for example, a monomer may be dissolved in the above-mentioned solvent and the solution may be cured. Is that the concentration of the monomer solution is about 0.1% to 99.9% by weight, preferably 1% to 99% by weight, particularly preferably 5% to 95% by weight of the total weight of the polymerizable monomer solution. % By weight.

As the curing method, it is possible to use heat or energy rays such as light, an electron beam, and radiation, but it is not limited thereto. The curing conditions are as follows: (1) In the case of photocuring, 1 mJ / cm2 to 100
50mJ / cm2 to 1000mJ / c in J / cm2
The range of m2 is preferred. The irradiation wavelength is 150 nm to 4
The range of ultraviolet light at 50 nm and 200-400 nm is preferred. The temperature at the time of irradiation is 0 ° C. to 300 ° C. and 10 ° C.
The range of -200 ° C is preferred. (2) In the case of thermal curing, the curing temperature is -50C to 300C, preferably in the range of 0C to 250C, and the heating time is 1 second to 100 hours, and may be about 10 seconds to 10 hours. preferable. (3) In the case of electron beam curing, the irradiation energy is 1 Gy to 1000 kGy.
, And preferably in the range of 100 Gy to 500 kGy. The thickness of the polymer electrolyte cured by these methods is preferably 1 μm to 10 cm, and preferably about 5 μm to 100 μm, but is not limited to these ranges.

Examples of the photoelectric conversion element of the present invention include dye-sensitized solar cells. As an example of a method for producing this cell, (1) a counter electrode substrate A obtained by depositing platinum on conductive glass, a photosensitizing dye (for example, a ruthenium complex dye, a rhodamine dye, an azo dye, a hydroquinone dye, etc.) ) -Supported porous substrate B of metal oxide semiconductor
Are bonded on two sides with a gap, (2) the curable resin composition is injected into the gap, and the resin composition is cured by heat or energy rays such as light, an electron beam, and radiation. , (3) dipping the device obtained in (2) in an electrolyte solution,
The method includes four steps of (4) connecting a conductor such as a lead wire to the porous substrate B and the counter electrode substrate A by impregnating the polymer with an electrolyte.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 9 g of ethyl carbitol acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.) and polyethylene glycol diacrylate (PEG-4 manufactured by Nippon Kayaku Co., Ltd.) were used as monomers.
00DA) 1 g and 1-hydroxy-cyclohexyl-
0.1 g of phenyl-ketone (Irgacure 184, manufactured by Nippon Ciba Geigy Co., Ltd.) was added to propylene carbonate 3
0 g to give a mixed solution. Next, a counter electrode substrate A in which platinum is deposited on conductive glass and a porous substrate B (a substrate in which porous titanium oxide is sintered on a transparent conductive glass electrode and a dye is supported) are provided with a gap of 50 μm. And glued together on two sides. Next, the mixed solution was injected into the gap and irradiated with 200 mJ / cm ² of ultraviolet light to obtain a solvent-containing polymer matrix. Next, this apparatus was immersed in a (0.3 M lithium iodide-0.03 M iodine) / propylene carbonate solution at room temperature for 15 hours, and the solvent-containing polymer matrix was impregnated with lithium iodide and iodine. A lead wire was attached to both electrodes as a molecular electrolyte to produce a photoelectric conversion element. AM
1.5 solar simulator (1000W / m ² )
Light was irradiated, and current and voltage characteristics were measured. Result 1cm
^The open voltage is 0.51 V and the short circuit current is 6.91 per ²
mA, and the fill factor (fill factor) is 0.3
6. The conversion efficiency was 1.15%.

Example 2 In Example 1, 30 g of propylene carbonate was added to 4 parts.
Except that the amount was changed to 0 g, the same treatment as in Example 1 was performed to produce a photoelectric conversion element according to the present invention. An AM1.5 solar simulator (1000 W /
m ² ) Light was irradiated to measure current and voltage characteristics. result,
The open voltage was 0.51 V, the short-circuit current was 8.34 mA, the fill factor (fill factor) was 0.37, and the conversion efficiency was 1.59% per 1 cm ² . In addition, lithium ions and iodine in the polymer electrolyte were quantified by an atomic absorption method and a potentiometric titration method. As a result, 0.16% by weight of lithium ion and 0.63% by weight of iodine were contained. These are 80% of the concentration in the impregnating solution.
As described above, it was shown that the polymer compound was efficiently doped with the redox electrolyte by the impregnation.

Example 3 In Example 2, 9 g of ethyl carbitol acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.) and polyethylene glycol diacrylate (Nippon Kayaku Co., Ltd.) were used.
1 g of PEG-400DA (manufactured by Kyoeisha Chemical Co., Ltd., EC-A) 9.5 g.
g, and 0.5 g of polyethylene glycol diacrylate (PEG-400DA, manufactured by Nippon Kayaku Co., Ltd.), and the same procedure as in Example 2 was carried out to prepare a photoelectric conversion element. The photoelectric conversion element was irradiated with AM1.5 solar simulator (1000 W / m ² ) light, and current and voltage characteristics were measured. As a result, the open circuit voltage was 0.1 cm / cm ² .
The short-circuit current was 56 V, the short-circuit current was 7.18 mA, the fill factor (fill factor) was 0.36, and the conversion efficiency was 1.44%.

Example 4 In Example 3, the impregnation solution (0.3 M lithium iodide-0.03 M iodine) / propylene carbonate solution was used (0.1 M lithium iodide-0.1 M iodine-0.6 M iodine).
Except for using 1,2-dimethyl-3-propylimidazolium iodide-1.0Mt-butylpyridine) / 3-methoxypropionitrile, the same procedure as in Example 3 was carried out to produce a photoelectric conversion element. This photoelectric conversion element has A
M1.5 solar simulator (1000W /
m ² ) Light was irradiated to measure current and voltage characteristics. result,
The open voltage was 0.67 V, the short circuit current was 7.25 mA, the fill factor (fill factor) was 0.64, and the conversion efficiency was 3.10% per 1 cm ² .

Example 5 In Example 2, 1 g of polyethylene glycol diacrylate (PEG-400DA manufactured by Nippon Kayaku Co., Ltd.) was used.
Was changed to 1 g of dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) in the same manner as in Example 2 to produce a photoelectric conversion element. An AM1.5 solar simulator (1
000 W / m ² ), and the current and voltage characteristics were measured. As a result, the open-circuit voltage was 0.52 V, the short-circuit current was 5.47 mA, the fill factor (fill factor) was 0.41, and the conversion efficiency was 1.10% per 1 cm ² .

Example 6 1 g of polyethylene glycol diacrylate (PEG-400DA manufactured by Nippon Kayaku Co., Ltd.)
Was changed to 1 g of Eo-modified dipentaerythritol hexaacrylate (DPHA-12Eo, manufactured by Nippon Kayaku Co., Ltd.) to produce a photoelectric conversion element. The photoelectric conversion element was irradiated with AM1.5 solar simulator (1000 W / m ² ) light, and current and voltage characteristics were measured. As a result, the open-circuit voltage was 0.54 V, the short-circuit current was 7.02 mA, the fill factor (fill factor) was 0.38, and the conversion efficiency was 1.41% per 1 cm ² .

Example 7 In Example 2, except that 9 g of ethyl carbitol acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.) was changed to 9 g of methoxytriethylene glycol acrylate (MTG-A manufactured by Kyoeisha Chemical Co., Ltd.) By performing the same processing as in Example 2, a photoelectric conversion element was manufactured. This photoelectric conversion element has A
M1.5 solar simulator (1000W /
m ² ) Light was irradiated to measure current and voltage characteristics. result,
The open-circuit voltage was 0.50 V, the short-circuit current was 8.10 mA, the fill factor (fill factor) was 0.39, and the conversion efficiency was 1.48% per 1 cm ² .

Example 8 9 g of ethyl carbitol acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.) and polyethylene glycol diacrylate (PEG-4 manufactured by Nippon Kayaku Co., Ltd.) were used as monomers.
00DA) 1 g and a polymerization initiator azobisisobutyronitrile 0.1 g were dissolved in propylene carbonate 30 g to prepare a mixed solution. Next, a counter electrode substrate A in which platinum is deposited on conductive glass and a porous substrate B (a substrate in which porous titanium oxide is sintered on a transparent conductive glass electrode and a dye is supported) are provided with a gap of 50 μm. And glued together on two sides.
Next, the mixed solution was injected into the gap,
The mixture was heated for a time to obtain a solvent-containing polymer matrix. next,
This device was placed under room temperature conditions (0.3 M lithium iodide-
0.03 M iodine) / immersion in propylene carbonate solution for 15 hours, impregnating lithium iodide and iodine in a solvent-containing polymer matrix to obtain a polymer electrolyte, attaching lead wires to both electrodes to obtain a photoelectric conversion element . AM1.5 solar simulator (1)
000 W / m ² ) and irradiated with light to measure current and voltage characteristics. As a result, the open-circuit voltage was 0.50 V, the short-circuit current was 6.50 mA, the fill factor (fill factor) was 0.36, and the conversion efficiency was 1.02% per 1 cm ² .

Example 9 In Example 1, 9 g of ethyl carbitol acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.) was mixed with 4.5 g of fluorinated alkylene ethyl acrylate (Biscoat 17F manufactured by Osaka Organic Chemical Co., Ltd.) and ethyl carbitol. Except that 4.5 g of tall acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.) and 30 g of propylene carbonate and 10 g of propylene glycol monomethyl ether were treated in the same manner as in Example 1 to obtain a photoelectric conversion element according to the present invention. Produced.
The photoelectric conversion element was irradiated with AM1.5 solar simulator (1000 W / m ² ) light, and current and voltage characteristics were measured. As a result, the open-circuit voltage was 0.70 / cm ^2.
V, the short-circuit current was 6.23 mA, the fill factor (fill factor) was 0.62, and the conversion efficiency was 2.67%.

Example 10 In Example 9, 4.5 alkylene ethyl acrylate (Viscoat 17F manufactured by Osaka Organic Chemical Co., Ltd.) was used.
g and 4.5 g of ethyl carbitol acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.), 1 g of fluorinated alkylene ethyl acrylate (Biscoat 17F manufactured by Osaka Organic Chemical Co., Ltd.) and ethyl carbitol acrylate (Kyoeisha Chemical Co., Ltd.) EC-A) A photoelectric conversion device according to the present invention was produced in the same manner as in Example 9, except that the amount was changed to 8 g. This photoelectric conversion element is irradiated with AM1.5 solar simulator (1000 W / m ² ) light,
The voltage characteristics were measured. As a result, the open-circuit voltage was 0.72 V, the short-circuit current was 6.12 mA, the fill factor (fill factor) was 0.59, and the conversion efficiency was 2.6 per cm ^2.
1%.

Example 11 The procedure of Example 1 was repeated except that ethyl carbitol acrylate was used.
9 g of Kyoeisha Chemical Co., Ltd. EC-A
9 g of ammonium ethyl acrylate iodonium salt
30 g of propylene carbonate
The same processing as in Example 1 except that the coal is 25 g
Thus, a photoelectric conversion element according to the present invention was produced. This photoelectric
AM1.5 solar simulator (10
00W / m ^Two) Irradiate light and measure current and voltage characteristics
Was. Result 1cm^TwoHit, open voltage is 0.69V, short
And the fill factor (curve
Factor) was 0.50, and the conversion efficiency was 2.26%.

Example 12 The procedure of Example 11 was repeated except that trimethylammonium ethyl alcohol was used.
9 g of acrylate iodonium salt was added to ethyl carbitol
8 g of acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.)
Trimethyl ammonium ethyl acrylate iodonium
Except that the salt was changed to 1 g.
Thus, a photoelectric conversion element according to the present invention was produced. This photoelectric change
AM1.5 solar simulator (100
0W / m ^Two) Light was irradiated, and current and voltage characteristics were measured.
Result 1cm^TwoContact, open voltage is 0.69V, short circuit voltage
Current is 7.00 mA and the fill factor (curve factor)
) And the conversion efficiency was 2.98%.

Example 13 In Example 1, 9 g of ethyl carbitol acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.) and polyethylene glycol diacrylate (PEG-4 manufactured by Nippon Kayaku Co., Ltd.) were used.
(00DA) 1 g of trimethylammonium ethyl acrylate iodonium salt, 8 g of ethyl carbitol acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.), and 1 g of dipentaerythritol hexaacrylate were treated in the same manner as in Example 1. Thus, a photoelectric conversion element according to the present invention was produced. The photoelectric conversion element was irradiated with AM1.5 solar simulator (1000 W / m ² ) light, and current and voltage characteristics were measured. As a result, the open-circuit voltage was 0.70 V, the short-circuit current was 6.81 mA, the fill factor (fill factor) was 0.62, and the conversion efficiency was 2.93% per cm ² .

Example 14 In Example 11, except that 9 g of trimethylammonium ethyl acrylate iodonium salt was changed to 9 g of 1,2-dimethylimidazolium-5-ethyl methacrylate iodonium salt and 30 g of propylene carbonate was changed to 25 g of triethylene glycol. In the same manner as in Example 11, a photoelectric conversion element according to the present invention was manufactured. The photoelectric conversion element was irradiated with AM1.5 solar simulator (1000 W / m ² ) light, and current and voltage characteristics were measured. As a result, the open circuit voltage was 0.1 cm / cm ² .
The short-circuit current was 65 V, the short-circuit current was 6.19 mA, the fill factor (fill factor) was 0.55, and the conversion efficiency was 2.23%.

Example 15 In Example 14, 9 g of 1,2-dimethylimidazolium-5-ethylmethacrylate iodonium salt was added.
4.5 g of 1,2-dimethylimidazolium-5-ethyl methacrylate iodonium salt and 4.5 g of ethyl carbitol acrylate (EC-A manufactured by Kyoeisha Chemical Co., Ltd.)
Except for that, the same processing as in Example 14 was carried out to produce a photoelectric conversion element according to the present invention. This photoelectric conversion element has A
M1.5 solar simulator (1000W /
m ² ) Light was irradiated to measure current and voltage characteristics. result,
The open voltage was 0.68 V, the short circuit current was 5.38 mA, the fill factor (fill factor) was 0.65, and the conversion efficiency was 2.38% per 1 cm ² .

Example 16 The procedure of Example 13 was repeated, except that 1 g of trimethylammonium ethyl acrylate iodonium salt was changed to 1 g of 1,2-dimethylimidazolium-5-ethyl methacrylate iodonium salt.
A photoelectric conversion device according to the present invention was produced. An AM1.5 solar simulator (1000 W
/ M ² ) Light was irradiated to measure current and voltage characteristics. As a result, the open-circuit voltage was 0.68 V, the short-circuit current was 5.87 mA, and the fill factor (fill factor) was 1 cm ^2.
Was 0.62 and the conversion efficiency was 2.51%.

Example 17 The procedure of Example 1 was repeated except that ethyl carbitol acrylate was used.
(EC-A manufactured by Kyoeisha Chemical Co., Ltd.) 9 g and polyethylene
Glycol diacrylate (PEG- manufactured by Nippon Kayaku Co., Ltd.)
400DA) 1 g of diethylene glycol divinyl ether
10 g, 1-hydroxy-cyclohexyl-
Phenyl-ketone (IRGA manufactured by Nippon Ciba Geigy Co., Ltd.)
Cure 184) 0.1 g (UVI-6990)
The same processing as in Example 1 except that the amount was 1 g,
A light-emitting photoelectric conversion device was manufactured. This photoelectric conversion element
AM1.5 solar simulator (1000W / m
^Two) Light was irradiated, and current and voltage characteristics were measured. Result 1
The open-circuit voltage is 0.68 V and the short-circuit current is 5.
72 mA, and the fill factor (fill factor) is 0.
64, and the conversion efficiency was 2.60%.

Comparative Example 1 The photoelectric conversion element used in Example 1 was a solution electrolyte as the polymer electrolyte. 50μ from substrate B carrying dye
The counter electrode substrate A was attached with a gap of m, and a (0.3 M lithium iodide-0.03 M iodine) / propylene carbonate solution was injected into the gap. Next, a lead wire was attached, and a photoelectric conversion element was manufactured. AM1.5 solar simulator (1000)
W / m ² ) Light was irradiated to measure current and voltage characteristics. As a result, the open-circuit voltage was 0.53 V, the short-circuit current was 7.97 mA, and the fill factor was 1 cm ^2.
Was 0.34, and the conversion efficiency was 1.44%.

Comparative Example 2 In Comparative Example 1, the electrolyte solution (0.3 M lithium iodide-0.03 M iodine) / propylene carbonate was used (0.1 M lithium iodide-0.1 M iodine-0.6 M iodine).
Except for using 1,2-dimethyl-3-propylimidazolium iodide) / 3-methoxypropionitrile, the same procedure as in Comparative Example 1 was carried out to produce a photoelectric conversion element according to the present invention. The photoelectric conversion element was irradiated with AM1.5 solar simulator (1000 W / m ² ) light, and current and voltage characteristics were measured. As a result, the open-circuit voltage was 0.62 V, the short-circuit current was 7.09 mA, the fill factor (fill factor) was 0.64, and the conversion efficiency was 2.77% per 1 cm ² .

Comparative Example 3 To 10 g of ethyl carbitol acrylate (EC-A, manufactured by Kyoeisha Chemical Co., Ltd.) was added 0.1 g of 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Geigy Japan). 200mJ / c
It was cured by irradiating with ultraviolet rays of m ² . To this cured product,
(0.3M lithium iodide-0.03M iodine) / 10g of propylene carbonate solution was added and kneaded with a kneading roll to form a gel electrolyte, which was applied to a porous titanium oxide porous substrate B carrying a dye, Was attached to a counter electrode substrate A on which was vapor-deposited, and lead wires were attached to both electrodes to obtain a photoelectric conversion element. The photoelectric conversion element was irradiated with AM1.5 solar simulator (1000 W / m ² ) light, and current and voltage characteristics were measured. As a result, the open-circuit voltage was 0.50 V, the short-circuit current was 5.55 mA, the fill factor (fill factor) was 0.50, and the conversion efficiency was 1.37% per 1 cm ² .

From the above description of Examples and Comparative Examples, the photoelectric conversion elements of Examples 1 to 17 were compared with those of Comparative Example.
It can be seen that the open-circuit voltage, the short-circuit current, the fill factor, and the conversion efficiency are almost the same or higher.

Next, as a stability test of the polymer electrolyte prepared according to the present invention, a liquid leakage test by pin sticking was performed. A device was prepared in the same manner as in each example except that the substrate A in each of the examples and comparative examples was replaced with a pet film, and a hole was formed in the device with a thumbtack from the film side, and leakage of the solution or resin from the hole was observed. Table 1 shows the results.

Table 1 Liquid leakage resistance Liquid leakage resistance Example 1 ○ Example 12 ○ Example 2 ○ Example 13 ○ Example 3 ○ Example 14 ○ Example 4 ○ Example 15 ○ Example 5 ○ Example Example 16 ○ Example 6 ○ Example 17 ○ Example 7 ○ Comparative Example 1 × Example 8 ○ Comparative Example 2 × Example 9 ○ Comparative Example 3 △ Example 10 ○ Example 11 ○

The evaluation criteria for observation are as follows. ：: No liquid leakage was observed. Δ: No liquid leakage occurred immediately after piercing the pin, but when pressure was applied, liquid leakage occurred from the location where the pin was pierced. ×: Liquid leakage occurred at the same time as piercing with a pin.

As is clear from Table 1, Examples 1 to 17
In contrast, the device of the present invention corresponding to (1) did not leak any liquid, whereas the devices corresponding to Comparative Examples 1 and 2 suffered liquid leakage at the same time as being stabbed with a pin. In Comparative Example 3 using the monofunctional acrylate, no liquid leakage occurred immediately after piercing the pin, but when pressure was applied, liquid leakage occurred from the location where the pin was pierced.

[0061]

According to the method of the present invention, a polymer matrix can be easily produced in a short light irradiation time, and a polymer electrolyte for a photoelectric conversion element can be prepared by a simple method of immersion in a redox electrolyte solution. As a result, time and energy can be saved. Further, the polymer electrolyte obtained according to the present invention is excellent in mechanical strength, stability and processability. In addition, compared to the electrolyte solution system, it shows almost the same or higher open-circuit voltage, short-circuit current, fill factor, conversion efficiency, and there is no fear of liquid leakage, so long-term stability and high safety photoelectric conversion It is considered that it can be used for devices, battery devices, and the like.

[0062]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08K 5/00 C08L 101/00 C08L 101/00 H01G 9/035 H01G 9/02 311 9 / 028 331Z // H01L 31/04 H01L 31/04 Z

Claims (16)

[Claims] 1. A method for producing a polymer electrolyte, comprising impregnating a polymer matrix with a redox electrolyte. 2. The method for producing a polymer electrolyte according to claim 1, which is for a photoelectric conversion element. 3. The method for producing a polymer electrolyte according to claim 1, wherein the redox electrolyte comprises a halogen compound having a halogen ion as a counter ion and a halogen molecule. 4. The method for producing a polymer electrolyte according to claim 3, wherein the halogen compound is an iodine compound and the halogen molecule is iodine. 5. The method for producing a polymer electrolyte according to claim 1, wherein the impregnation of the redox electrolyte is performed by immersing the polymer matrix in a redox electrolyte solution. 6. The method for producing a polymer electrolyte according to claim 5, wherein the solvent of the redox electrolyte solution is a polar organic solvent. 7. The method for producing a polymer electrolyte according to claim 1, wherein the polymer matrix is a solvent-containing polymer matrix. 8. The method for producing a polymer electrolyte according to claim 7, wherein the solvent-containing polymer matrix is a cured product of a polymerizable monomer solution. 9. The method for producing a polymer electrolyte according to claim 8, wherein the polymerizable monomer is a monomer having an acryloyl group or a methacryloyl group. 10. The method for producing a polymer electrolyte according to claim 8, wherein the polymerizable monomer is a monomer having a vinyl ether group. 11. A polymerizable monomer having an ethylene oxide chain or a propylene oxide chain.
3. The method for producing a polymer electrolyte according to item 1. 12. The polymer electrolyte and the production method according to claim 8, wherein the polymerizable monomer is a monomer having a fluorinated alkyl group. 13. The polymer electrolyte and the method according to claim 8, wherein the polymerizable monomer has a quaternary nitrogen base. 14. The method for producing a polymer electrolyte according to claim 9, wherein the polymerizable monomer is a mixture of a polyfunctional monomer and a monofunctional monomer. 15. A photoelectric conversion device comprising the polymer electrolyte according to claim 1. 16. A solvent-containing polymer matrix for a photoelectric conversion element which does not substantially contain an electrolyte.