CN105283936B - Active material process for reactivation, battery recycling method, catalyst layer, to electrode - Google Patents
Active material process for reactivation, battery recycling method, catalyst layer, to electrode Download PDFInfo
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- CN105283936B CN105283936B CN201480030101.1A CN201480030101A CN105283936B CN 105283936 B CN105283936 B CN 105283936B CN 201480030101 A CN201480030101 A CN 201480030101A CN 105283936 B CN105283936 B CN 105283936B
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- Prior art keywords
- dye
- solar cells
- sensitized solar
- electrode
- electroconductive polymer
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- 238000000034 method Methods 0.000 title claims abstract description 124
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- 239000011149 active material Substances 0.000 title description 2
- 238000004064 recycling Methods 0.000 title description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004410 anthocyanin Substances 0.000 description 1
- 229930002877 anthocyanin Natural products 0.000 description 1
- 235000010208 anthocyanin Nutrition 0.000 description 1
- 150000004636 anthocyanins Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N cis-p-Menthan-1,8-diol Natural products CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KVMPQUTWRWVTQP-UHFFFAOYSA-N cyanatoboronic acid Chemical compound OB(O)OC#N KVMPQUTWRWVTQP-UHFFFAOYSA-N 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GVINIKRAUKVLRA-UHFFFAOYSA-N ethane-1,2-diol;naphthalene-1,2-dicarboxylic acid Chemical compound OCCO.C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 GVINIKRAUKVLRA-UHFFFAOYSA-N 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FZAXZVHFYFGNBX-UHFFFAOYSA-M lithium iodate Chemical compound [Li+].[O-]I(=O)=O FZAXZVHFYFGNBX-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229930006948 p-menthane-3,8-diol Natural products 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- RBNWAMSGVWEHFP-WAAGHKOSSA-N terpin Chemical compound CC(C)(O)[C@H]1CC[C@@](C)(O)CC1 RBNWAMSGVWEHFP-WAAGHKOSSA-N 0.000 description 1
- 229950010257 terpin Drugs 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 description 1
- 229950004288 tosilate Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
Problem of the present invention is that, a kind of process for reactivation to electrode active material of dye-sensitized solar cells is provided, and apply the regeneration method of the dye-sensitized solar cells of this method, the catalyst layer of dye-sensitized solar cells, to electrode, electrolyte and dye-sensitized solar cells, the regeneration method of the wherein described dye-sensitized solar cells includes by regenerating the electroconductive polymer of the redox couple reduction in the electrolyte by dye-sensitized solar cells, the power generation performance of temporarily-depressed dye-sensitized solar cells can be made to restore to initial performance, it can prevent the reduction of the power generation performance of dye-sensitized solar cells.The present invention is a kind of process for reactivation to electrode active material of dye-sensitized solar cells, it is the method being re-activated to electrode active material to dye-sensitized solar cells, the dye-sensitized solar cells have by contain at least one above electroconductive polymer as the catalyst layer to electrode active material constitute to electrode, this method includes：The electroconductive polymer is reoxidized by chemical oxidation or electrochemical oxidation.
Description
Technical field
The present invention relates to a kind of dye-sensitized solar cells to the process for reactivation of electrode active material and application
The regeneration method of the dye-sensitized solar cells of this method, used by dye sensitization solar battery catalyst layer, to electrode,
Electrolyte and dye-sensitized solar cells.
This application claims based on August in 2013 30 days Japanese publication Japanese Patent Application No. 2013-179849 and 2013
December 17 in the priority of the Japanese Patent Application 2013-260073 of Japanese publication, was hereby incorporated its content.
Background technology
In recent years, using photovoltaic effect luminous energy can be converted directly into electric power and as the dirts such as carbon dioxide are not discharged
The clean electric power generation source of substance is contaminated, solar cell is concerned.In solar cells, dye-sensitized solar cell has
There is high transfer efficiency, can be manufactured by comparing simple method, and raw material unit price is cheap, therefore, as a new generation
Solar cell and be expected to.
Commonly known dye-sensitized solar cells is the dye-sensitized solar cells of so-called Graetzel types.
In the dye-sensitized solar cells (hreinafter referred to as dye-sensitized solar cells) of Graetzel types, to being adsorbed in metal
When the sensitizing dyestuff irradiation light on the surface of oxide semiconductor particle, electronics is moved to optoelectronic pole, transparent from sensitizing dyestuff successively
Conductive film, external circuit utilize as a result, as electric current (with reference to non-patent literature 1).On the other hand, electronics is discharged
Sensitizing dyestuff is reduced by receiving electronics from the redox couple in electrolyte.As a result, the oxidation in electrolyte is also
Then original is reduced to being aoxidized by the catalyst layer of structure paired electrode.
As the catalyst layer to electrode for constituting existing dye-sensitized solar cells, it is widely used for platinum layer.This is
Since platinum is higher to the catalyst ability of redox reaction, and stability and electric conductivity are higher.
The forming method of platinum layer as structure paired electrode, such as have and be coated with chlorine on the base materials such as glass substrate, metallic plate
Platinic acid solution and the method heated or the method to be formed a film by vacuum evaporation, sputtering etc..
Platinum has the advantages that as described above, another aspect, since platinum is expensive noble metal, has increase dyestuff quick
The problem of changing the manufacturing cost of solar cell.Therefore, the material of the raw catelyst layer instead of platinum is being studied.Such as non-special
A kind of dye-sensitized solar cells is disclosed in sharp document 2 and patent document 1,2, with polythiophene, polyaniline, polypyrrole etc.
Material of the electroconductive polymer as catalyst layer.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-313317 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2003-317814 bulletins
Non-patent literature
Non-patent literature 1：" natural (Nature), " (Britain), 1991,353, p.737-740
Non-patent literature 2：" electrochemistry (Electrochemistry), " 2003,71,11, p.944-946
Invention content
The subject that the invention solves
For having used the dye-sensitized solar cells of above-mentioned electroconductive polymer, power generation property can significantly occur
The deterioration of energy (photoelectric conversion efficiency).This is because, redox couple (such as the I in electrolyte-、Br-Deng) by electric conductivity high score
Son is reduced to neutral state (dedoping state) from the state of oxidation (dopant states), is dropped so as to cause catalyst activity, electric conductivity
It is low.
Invention that the present invention has been made in view of the above-described circumstances, project are to provide a kind of dye-sensitized solar cells
To the regeneration method of the process for reactivation of electrode active material and the dye-sensitized solar cells for applying this method,
The catalyst layer of used by dye sensitization solar battery, to electrode, electrolyte and dye-sensitized solar cells, the dye sensitization
The process for reactivation to electrode active material of solar cell includes：By will be by the electrolyte of dye-sensitized solar cells
In redox couple reduction electroconductive polymer regenerated, can be by temporarily-depressed dye-sensitized solar cells
Power generation performance restores to initial performance, or can prevent the reduction of the power generation performance of dye-sensitized solar cells.
A technical solution to solve project
The inventors of the present invention have made intensive studies, as a result, it has been found that：With by high containing at least one above electric conductivity
Molecule is as in the dye-sensitized solar cells to electrode to the catalyst layer of electrode active material composition, by will be above-mentioned
Electroconductive polymer carries out chemical oxidation or electrochemical oxidation and reoxidizes, and can solve the above subject.It is complete based on above-mentioned opinion
At the present invention.
Hereinafter, in order to make the present invention be readily appreciated that, the basic feature of the present invention and preferred various modes are enumerated.
A kind of process for reactivation to electrode active material of dye-sensitized solar cells of 1 ＞ of ＜, is quick to dyestuff
Change the method for solar cell being re-activated to electrode active material, the dye-sensitized solar cells has by containing
At least one above electroconductive polymer is as the catalyst layer composition to electrode active material to electrode, this method packet
It includes：
The electroconductive polymer is reoxidized by chemical oxidation or electrochemical oxidation.
The process for reactivation to electrode active material of dye-sensitized solar cells of 2 ＞ of ＜ as described in 1 ＞ of above-mentioned ＜,
Wherein, the chemical oxidation is implemented by the way that the electroconductive polymer is impregnated in the solution dissolved with oxidant.
The process for reactivation to electrode active material of dye-sensitized solar cells of 3 ＞ of ＜ as described in 1 ＞ of above-mentioned ＜,
Wherein, the electrochemical oxidation is impregnated in by regarding the electroconductive polymer as working electrode containing the molten of supporting electrolyte
Liquid, and defined voltage is applied to the working electrode to implement.
The process for reactivation to electrode active material of dye-sensitized solar cells of 4 ＞ of ＜ as described in 1 ＞ of above-mentioned ＜,
Wherein, the catalyst layer also contains photoacid generator, by generating acid to photoacid generator irradiation light, thus carries out the chemistry
Oxidation.
The process for reactivation to electrode active material of dye-sensitized solar cells of 5 ＞ of ＜ as described in 1 ＞ of above-mentioned ＜,
Wherein, the dye-sensitized solar cells has the electrolysis containing at least one oxidant that can aoxidize electroconductive polymer
Liquid carries out the chemical oxidation by the oxidant.
A kind of regeneration methods of dye-sensitized solar cells of 6 ＞ of ＜, are the catalyst layers to form structure paired electrode
At least one above electroconductive polymer is in the regeneration method of the dye-sensitized solar cells of reducing condition or neutral state,
This method includes：
Oxygen again is carried out to the electroconductive polymer having on electrode to described by chemical oxidation or electrochemical oxidation
The process of change.
A kind of catalyst layers of 7 ＞ of ＜ are the catalyst layers for dye-sensitized solar cells, which is characterized in that institute
State the electroconductive polymer and photoacid generator that catalyst layer contains more than one.
Catalyst layers of 8 ＞ of ＜ as described in 7 ＞ of above-mentioned ＜, wherein the electroconductive polymer indicates for the following general formula (1)
Thiophene compound polymer.
[chemical formula 1]
[in formula, R1And R2Separately indicate the alcoxyl of hydrogen atom, the alkyl of carbon atom number 1~8, carbon atom number 1~4
Base, the aryl of carbon atom number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano, amino, nitro or sulfo group, in R1
And R2In the case of for the alkyl or aryl, the alkyl or aryl can be bonded to thiophene via azo group or sulfonyl
Ring, in R1And R2In the case of for the alkyl or alkoxy, the carbon atom of the end of the alkyl or alkoxy can key each other
It closes and forms ring.]
Catalyst layers of 9 ＞ of ＜ as described in 7 ＞ of above-mentioned ＜, wherein the electroconductive polymer indicates for the following general formula (2)
Azole compounds polymer.
[chemical formula 2]
[in formula, R3And R4Separately indicate the alcoxyl of hydrogen atom, the alkyl of carbon atom number 1~8, carbon atom number 1~4
Base, the aryl of carbon atom number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano, amino, nitro or sulfo group, in R3
And R4In the case of for the alkyl or aryl, the alkyl or aryl can be bonded to pyrroles via azo group or sulfonyl
Ring, in R3And R4In the case of for the alkyl or alkoxy, the carbon atom of the end of the alkyl or alkoxy can key each other
It closes and forms ring.]
Catalyst layers of 10 ＞ of ＜ as described in 7 ＞ of above-mentioned ＜, wherein the electroconductive polymer is the following general formula (3) table
The polymer of the aniline compound shown.
[chemical formula 3]
[in formula, R5~R8Separately indicate the alcoxyl of hydrogen atom, the alkyl of carbon atom number 1~8, carbon atom number 1~4
Base, the aryl of carbon atom number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano, amino, nitro or sulfo group, in R5
~R8In the case of for the alkyl or aryl, the alkyl or aryl can be bonded to phenyl ring via azo group or sulfonyl,
In R5And R6Or R7And R8In the case of for the alkyl or alkoxy, the carbon atom of the end of the alkyl or alkoxy can be with
It bonds together and forms ring.]
Catalyst layers of 11 ＞ of ＜ as described in any one of above-mentioned 7 ＞ of ＜~＜, 10 ＞, wherein in the catalyst layer
In, the ratio between (gross mass of the photoacid generator)/(gross mass of the electroconductive polymer) is 0.01~10.
12 ＞ of ＜ are a kind of to electrode, are for dye-sensitized solar cells to electrode, which is characterized in that described right
Electrode has forms the base material of the catalyst layer described in any one of above-mentioned 7 ＞ of ＜~＜, 11 ＞ on surface.
A kind of dye-sensitized solar cells of 13 ＞ of ＜, has：Being contaminated to electrode, with sensitization described in 6 ＞ of above-mentioned ＜
The optoelectronic pole of material and electrolyte containing redox couple.
A kind of regeneration methods of dye-sensitized solar cells of 14 ＞ of ＜ are the electric conductivity high scores to constituting catalyst layer
At least part of son is in the progress of the dye-sensitized solar cells described in reducing condition or 13 ＞ of above-mentioned ＜ of neutral state
Regeneration method, this method include：
To photoacid generator irradiation light contained in the described catalyst layer, to carry out oxygen again to the electroconductive polymer
Change.
A kind of electrolyte of 15 ＞ of ＜, which is characterized in that the electrolyte, which contains at least one, can aoxidize electric conductivity high score
The oxidant of son.
Electrolyte of 16 ＞ of ＜ as described in 15 ＞ of above-mentioned ＜, which is characterized in that the oxidant is selected from including oxygen, chlorine
The elementary gas group of gas and bromine gas；Including iron chloride (III) hexahydrate, anhydrous ferric chloride (III), nine water of ferric nitrate (III)
Close object, anhydrous nitric acid iron and the inorganic acid group of ferric perchlorate (III)；Including dodecyl benzene sulfonic acid, toluenesulfonic acid, trifluoroacetic acid
And the organic acid group of propionic acid；And at least one of the group being made of chlordene metaantimmonic acid three (4- bromophenyls) ammonium.
Electrolyte of 17 ＞ of ＜ as described in 16 ＞ of above-mentioned ＜, which is characterized in that the oxidant is selected from the inorganic acid
At least one of group.
Electrolyte of 18 ＞ of ＜ as described in any one of above-mentioned 15 ＞ of ＜~＜, 17 ＞, which is characterized in that in the oxidation
Agent be in the case of at least one of described elementary gas group, when electrolyte whole is set as 1L, the oxidant
Content be 1mg/L~50mg/L.
Electrolyte of 19 ＞ of ＜ as described in any one of above-mentioned 15 ＞ of ＜~＜, 17 ＞, which is characterized in that in the oxidation
Agent is that electrolyte whole is being set as 100 in the case of at least one of the inorganic acid group and the organic acid group
When quality %, the content of the oxidant is 0.001 mass of mass %~10 %.
A kind of dye-sensitized solar cells of 20 ＞ of ＜ has the electricity described in any one of described 15 ＞ of ＜~＜, 19 ＞
Solve liquid, the working electrode with semiconductor and to electrode, which is characterized in that
The dyestuff that the working electrode contains the electrode layer being made of semiconductor and is adsorbed in the electrode layer,
The dye-sensitized solar cells is described electrolyte and shape to be clamped in the working electrode and between electrode
At.
The effect of invention
The process for reactivation to electrode active material of dye-sensitized solar cells according to the present invention, by with electrolysis
The electroconductive polymer that liquid is contacted and is reduced is reoxidized by chemical oxidation or electrochemical oxidation, is become with positive charge
The state of oxidation.That is, in, there are the state in hole, electroconductive polymer being made to regenerate in electroconductive polymer, thus, it is possible to
The catalyst activity and electric conductivity for making the catalyst layer containing electroconductive polymer restore or prevent its reduction.
In addition, according to the regeneration method of the dye-sensitized solar cells for the present invention for applying above-mentioned method, dyestuff
The catalyst layer of sensitization solar battery, to electrode, electrolyte and dye-sensitized solar cells, can be by various methods
It realizes the catalyst activity of catalyst layer as described above and the recovery of electric conductivity or prevents its reduction.
Description of the drawings
Fig. 1 is to show the dye sensitization of solar to electrode with by the catalyst layer structure comprising electroconductive polymer
The sectional view of battery.
Fig. 2 is the sectional view of the regeneration method of the dye-sensitized solar cells for illustrating the 2nd aspect of the present invention.
Fig. 3 is the sectional view of the regeneration method of the dye-sensitized solar cells for illustrating the 2nd aspect of the present invention.
Fig. 4 A are the figures for illustrating the forming method to electrode in embodiment 1, are to show to form to conductive film
Opposite base material schematic diagram.
Fig. 4 B are the figures for illustrating the forming method to electrode in embodiment 1, are the schematic diagrames shown to electrode.
Fig. 5 is the schematic diagram for illustrating the restoring method to electrode in embodiment 1.
Fig. 6 A are the figures for showing the dye-sensitized solar cells in embodiment 1, are to show to have to be impregnated in gamma-butyrolacton
The schematic diagram of the dye-sensitized solar cells to electrode of (0 hour) before solution.
Fig. 6 B are the figures for showing the dye-sensitized solar cells in embodiment 1, are to show to have in gamma-butyrolacton solution
The schematic diagram of middle 100 hours dye-sensitized solar cells to electrode of dipping.
Fig. 6 C are the figures for showing the dye-sensitized solar cells in embodiment 1, are to show to have in gamma-butyrolacton solution
The schematic diagram of middle 300 hours dye-sensitized solar cells to electrode of dipping.
Fig. 6 D are the figures for showing the dye-sensitized solar cells in embodiment 1, are to show to have in gamma-butyrolacton solution
The schematic diagram of middle 500 hours dye-sensitized solar cells to electrode of dipping.
Fig. 7 is the schematic diagram for illustrating the reoxidation process to electrode in embodiment 1.
Fig. 8 be in embodiment 1 be impregnated in gamma-butyrolacton solution before (0 hour) to electrode, it is molten in gamma-butyrolacton
500 hours photos to electrode for impregnating 5 minutes in acetonitrile solution to electrode and thereafter are impregnated in liquid.
Fig. 9 is the schematic diagram for illustrating the reoxidation process to electrode in embodiment 2.
Figure 10 is the catalyst layer for having the present invention and the constructed profile of the dye-sensitized solar cells to electrode.
Symbol description
10、10A、10B、10C、10D、10E、10F、10G：Dye-sensitized solar cells
12：To electrode
18：Electroconductive polymer catalyst layer (catalyst layer)
Specific implementation mode
Hereinafter, being illustrated to the various embodiments of the present invention with reference to attached drawing.It should be noted that in the following description
The attached drawing used be it is schematical, the ratio etc. of length, width and thickness be not limited to it is identical as actual ratio, can suitably more
Change.
《To the process for reactivation of electrode active material》
The process for reactivation to electrode active material of the dye-sensitized solar cells of the 1st aspect of the present invention is pair
With the dye-sensitized solar cells to electrode being made of the catalyst layer comprising at least one above electroconductive polymer
The method that electrode active material is re-activated.Illustrate dye-sensitized solar cells to electrode active material again
Before activation method, referring to Fig.1 to the dye sensitization to electrode being made of the catalyst layer comprising electroconductive polymer
The structure of solar cell 10 illustrates.
It should be noted that the structure of dye-sensitized solar cells 10 shown in FIG. 1 is can to apply the dye of the present invention
Material sensitization solar battery to the activation method of electrode active material and apply the dye sensitization of solar electricity of this method
The regeneration method in pond, the catalyst layer of used by dye sensitization solar battery, to electrode, electrolyte and dye-sensitized solar cells
Structure an example.That is, the dye-sensitized solar cells of application various modes present invention as described above and unlimited
The structure of the dye-sensitized solar cells 10 illustrated by Fig. 1, it is possible to have made with dye-sensitized solar cells 10
For element cell multiple structures formed are connected in width direction (directions W i.e. shown in FIG. 1).
As shown in Figure 1, dye-sensitized solar cells 10 at least has working electrode 11, oppositely disposed with working electrode 11
The electrolyte 20 to electrode 12, between working electrode 11 and between electrode 12 and constitute.The side of electrolyte 20 is by sealing
Material 21 seals.
In working electrode 11 and to being connected with external circuit (not shown) on electrode 12.
Hereinafter, being illustrated successively to each integral part.
Working electrode 11 be sequentially laminated with transparent base 13, transparent conductive film 14 and optoelectronic pole 15 electrode.
Transparent base 13 becomes the base station of transparent conductive film 14 and optoelectronic pole 15, by the light that can make to be irradiated in optoelectronic pole 15
The material of transmission is constituted.As this material, can enumerate for example：Soda-lime glass, pyrex, quartz glass, borosilicic acid
Glass or the polyethylene terephthalates such as glass, Vycor glass, alkali-free glass, blue color plane glass and white plate glass
The resins such as ester (PET), polyethylene naphthalate (PEN), acrylic resin, makrolon, polyimides.
Transparent conductive film 14 is formed in by sputtering method, print process in a plate face of transparent base 13.In electrically conducting transparent
It can be used for example on film 14：Tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), aluminium-doped zinc oxide (AZO), antimony are mixed
Miscellaneous tin oxide (ATO), indium oxide/zinc oxide (IZO), Ga-doped zinc oxide (GZO) etc..
Optoelectronic pole 15 plays a role as the electric layer of dye-sensitized solar cells, as the semiconductor for constituting optoelectronic pole
Compound can enumerate well known metal oxide, the compound etc. with perovskite crystalline, can be selected from these compounds
Select multiple compounds use.As metal oxide, titanium oxide, zinc oxide etc. can be enumerated, as with perovskite crystalline
Compound can enumerate CH3NH3PbX3(X is halogen atom) etc..Semiconducting compound (not shown) can be particle shape.For half
For conductor compound, sensitizing dyestuff can be made to support and constituted in semiconducting compound.As metal-oxide semiconductor (MOS) grain
Son from the nano level porous layer of formation and can obtain compared with the surface area of lower layer from the viewpoint of very big surface area,
It is preferred that titanium oxide (TiO2) particle.
Sensitizing dyestuff discharges electronics by being irradiated in the light of optoelectronic pole 15.The electronics of release is by metal-oxide semiconductor (MOS)
Particle receives and is successfully moved to transparent conductive film 14, output to external circuit (not shown).As described above, as photograph is passed through
The light penetrated and the sensitizing dyestuff for discharging electronics, can enumerate for example：Ruthenium complex, anthocyanin, organic pigment as chlorophyll.
Wide from the wave-length coverage of absorption and light activated long lifespan is connect by the porous layer being made of metal-oxide semiconductor (MOS) particle
From the viewpoint of the electronic stability of receipts, as sensitizing dyestuff, preferably ruthenium complex.Ruthenium complex has for example：Cis--two (cyanogen sulphur
Base)-bis- (2,2'- bipyridyl -4,4'- dicarboxylic acids) rutheniums (II), cis--two (thiocyanos)-it is bis- (bipyridyl -4 2,2'-,
4'- dicarboxylic acids) ruthenium (II) double 4-butyl ammoniums (hereinafter referred to as N719) etc..
To electrode 12 for the opposite base material 16 of lamination successively, to conductive film 17 and electroconductive polymer catalyst layer 18
(catalyst layer) and formed electrode.
Opposite base material 16 becomes the base station to conductive film 17 and electroconductive polymer catalyst layer 18, in a thickness direction
It is configured with 13 interval of transparent base.As the material of opposite base material 16, can enumerate glass identical with transparent base 13,
Resin etc., is not particularly limited.
Conductive film 17 is formed in by sputtering method, print process in a plate face of opposite base material 16.To conductive film
It can be used for example on 17：Tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), aluminium-doped zinc oxide (AZO), Sb doped
Tin oxide (ATO), indium oxide/zinc oxide (IZO), Ga-doped zinc oxide (GZO) etc..It should be noted that it is preferred that electrode
It is formed to conductive film 17, but can also be omitted to conductive film 17 on 12.
In addition, transmitance need not be to conductive film 17, it is in addition to the foregoing materials, opposite as being formed
The material of conductive film 17 can also use the metals such as titanium, aluminium, nickel, chromium, gold, silver, copper.
Opposite side of the electroconductive polymer catalyst layer 18 in the face to connect with opposite base material 16 to conductive film 17
Formed on face, by across electrolyte 20 it is opposed with optoelectronic pole 15 in a manner of configure.In addition, electroconductive polymer catalyst layer 18 contains
There is at least one above electroconductive polymer, redox couple contained in electrolyte 20 is restored.As electric conductivity
Electroconductive polymer contained in polymer catalyst layer 18 can be enumerated for example：Polythiophene, polyaniline, polypyrrole, it is poly- (3,
4- ethylenedioxy thiophenes) (PEDOT) etc..Electroconductive polymer can be any one of these substances, can also be to be mixed with
Two or more substances.Electroconductive polymer is set to be in positive charge in advance before manufacturing dye-sensitized solar cells 10
The state of oxidation.It is led as the carbon materials such as carbon nanotube in addition, can also contain in electroconductive polymer catalyst layer 18
Conductive material other than electrical macromolecule.In addition, the specific example as electroconductive polymer, with the 3rd aspect of the present invention
Catalyst layer it is related, polymer, general formula (2) expression of the thiophene compound that the general formula (1) described below indicates can be enumerated
Azole compounds polymer and general formula (3) indicate aniline compound polymer.
As the amount of electroconductive polymer contained in electroconductive polymer catalyst layer 18, preferably 10 mass % with
On, more preferably 20 mass % or more, particularly preferably 30 mass % or more.
The thickness of catalyst layer 18 is not particularly limited, and when it is excessively thin catalyst layer, existing cannot play fully
Catalytic performance hidden danger, therefore for example be preferably 0.001 μm or more.The upper limit of the thickness of catalyst layer 18 does not limit especially
System, is uneconomic when its is blocked up, therefore usually 10 μm or less.
Catalyst layer 18 can also be porous layer either fine and close layer.When it is porous layer, with electrolyte 20
Contact area increases, therefore can improve the catalytic performance of catalyst layer 18.
As the method for forming fine and close catalyst layer 18, can enumerate for example：By the solution containing electroconductive polymer
It is coated on the method on the surface to conductive film 17 and made it dry, makes to be impregnated in containing conductive height conductive film 17
Alive electrolysis polymerization method etc. is applied in the state of in the solution of the monomer of molecule.
As the method for the catalyst layer 18 for forming porous, can enumerate for example：By electrolysis polymerization method in electric conductivity
The high molecular method of coating conducting on the surface of the porous body of particle, added in the solution containing electroconductive polymer it is bad
Poor solvent induction phase separation method of solvent etc..
Electrolyte 20 is injected by working electrode 11, the space surrounded to electrode 12 and sealing material 21, being containing hair
The solution of the redox couple of the raw redox reaction for being powered in dye-sensitized solar cells 10.As this oxygen
Change reduction pair, can enumerate for example：Iodine and iodate dimethyl propyl imidazoles, the iodide salts such as lithium iodide combination (iodide
Ion (I-)/teriodide ion (I3 -)), bromine and bromination dimethyl propyl imidazoles, the bromide salts such as lithium bromide combination (bromine
Compound ion (Br-)/tribromide ion (Br3 -)).As the solvent of electrolyte 20, can enumerate for example：Acetonitrile, propionitrile etc.
The lactones such as nitrile nonaqueous solvents, gamma-butyrolacton, gamma-valerolactone nonaqueous solvents, ethylmethylimidazoliumFour cyano borate
Or ethylmethylimidazoliumCdicynanmide plasma liquid.In addition, electrolyte 20 can by polyacrylonitrile isogel agent by
Gelation.
Concentration of the above-mentioned halogen in electrolyte 20 is preferably 1~500mM, more preferably 5~300mM, particularly preferably
For 10~200mM.Concentration of the above-mentioned halide salts in electrolyte 20 is preferably 0.1~10M, more preferably 0.2~5M, special
It You Xuanwei not 0.5~3M.
In addition, the molar ratio of above-mentioned halogen and halide salts is preferably 1 ︰, 1~1 ︰ 1000,5~1 ︰ of more preferably 1 ︰
10~1 ︰ 200 of 500, particularly preferably 1 ︰.
As the material of sealing material 21, the mixture of such as light-cured resin and heat-curing resin can be enumerated
Deng.
In dye-sensitized solar cells 10, " power generation light " from when the direction incidence of arrow shown in FIG. 1, optoelectronic pole 15
Sensitizing dyestuff absorb light, by electronics discharge to metal-oxide semiconductor (MOS) particle and be in the state of oxidation.The electronics being released
It is moved in the porous layer being made of metal-oxide semiconductor (MOS) particle and reaches transparent conductive film 14.Then, electronics by with
The circuit that working electrode 11 connects, is moved to electrode 12 via external circuit to conductive film 17 or electroconductive polymer
Catalyst layer 18.On the other hand, the sensitizing dyestuff aoxidized redox couple contained in the electrolyte 20 receive electronics and by
Reduction.In addition, redox couple is moved by oxidation and to 18 side of electric conductivity polymer catalyst layer, it is catalyzed by electroconductive polymer
Electroconductive polymer contained in oxidant layer 18 restores.By continuing to keep electric current quick in dyestuff by repeating such redox reaction
Change and is flowed in solar cell 10.
Under the original state of dye-sensitized solar cells 10, make to lead contained in electroconductive polymer catalyst layer 18
Electrical macromolecule is in the state of oxidation.On the other hand, after manufacture, in dye-sensitized solar cells 10, by with electrolyte
The contact of redox couple in 20, the electroconductive polymer that electroconductive polymer catalyst layer 18 has are reduced, are in
Uncharged neutral state or negatively charged reducing condition.Electroconductive polymer in the neutral state or reducing condition
Catalytic performance and electric conductivity cannot be played, therefore as reduction carries out, battery performance reduces.
In the following, the process for reactivation to electrode active material of the dye-sensitized solar cells to first method of the present invention
It illustrates.
The present invention dye-sensitized solar cells the process for reactivation to electrode active material be dye sensitization too
Electroconductive polymer (the hreinafter referred to as electric conductivity high score contained in the electroconductive polymer catalyst layer 18 of positive energy battery 10
Son) when being reduced due to prolonged use of dye-sensitized solar cells 10 etc., pass through chemical oxidation or electrochemistry oxygen
Change the method for reoxidizing electroconductive polymer.It should be noted that " reactivation " described in the present invention refers to：It is quick in dyestuff
After the manufacture for changing solar cell 10, after certain time, made due to leading by reoxidizing for the electroconductive polymer
The progress of the reduction of the electroconductive polymer of electrical polymer catalyst layer 18 and make the dye sensitization that power generation performance reduces too
It is positive can battery 10 it is described to electrode regeneration or the electric conductivity by will be reduced in electroconductive polymer catalyst layer 18
Macromolecule reoxidizes and keeps the power generation performance of battery successively.
Hereinafter, method to being reoxidized electroconductive polymer by chemical oxidation and being carried out by electrochemical oxidation
The method reoxidized illustrates respectively.
The method ＞ that ＜ is reoxidized electroconductive polymer by chemical oxidation
Here, to by impregnating electroconductive polymer in the solution dissolved with oxidant by electroconductive polymer oxygen again
The example of change illustrates.The time of electroconductive polymer is impregnated in the solution dissolved with oxidant can for example be set as 1 point
Clock~10 minute or so.
As long as oxidant does not damage the characteristic of electroconductive polymer and can make the substance of electroconductive polymer oxidation i.e.
It can.As such substance, can enumerate for example：Inorganic compounds, 12 such as iron chloride (III), iron chloride (III) hydrate
The organic acids such as the sulfonic acid such as alkyl benzene sulphonate, toluenesulfonic acid, trifluoroacetic acid, propionic acid and chlordene metaantimmonic acid three (4- bromophenyls) ammonium.From right
The dissolubility of general solvent is higher and the higher viewpoint of oxidation considers, as oxidant, it is preferable to use iron chloride (III),
Iron chloride (III) hydrate.
As the solvent of oxidant, energy dissolved oxidant can be enumerated and do not make the conduction being made of electroconductive polymer
Property 18 dissolution of polymer catalyst layer solvent, the miscellaneous organic solvents such as acetonitrile, ethyl alcohol, acetone, toluene can be used for example.
In the method, it can directly be coated with the solution dissolved with oxidant on electroconductive polymer, can also make molten
Liquid evaporates and it is made to be contacted with steam.
Alternatively, it is also possible to carry out light irradiation by using the catalyst layer containing photoacid generator, and to above-mentioned photoacid generator
Acid is generated, thus carries out above-mentioned chemical oxidation.What specific structure and material and light about above-mentioned catalyst layer were irradiated
Method is described below in conjunction with the catalyst layer of the 3rd aspect of the present invention.
Furthermore it is also possible to using the electrolyte containing at least one oxidant that can aoxidize electroconductive polymer, utilize
Above-mentioned oxidant carries out above-mentioned chemical oxidation.Composition about above-mentioned electrolyte and the oxidant that can use, in conjunction with the present invention
The electrolyte of the 7th mode be described below.
The method ＞ that ＜ is reoxidized electroconductive polymer by electrochemical oxidation
Here, to being impregnated in the solution containing supporting electrolyte by regarding electroconductive polymer as working electrode, and it is right
The working electrode applies given voltage, thus illustrates the example that electroconductive polymer reoxidizes.
The time that electroconductive polymer is impregnated in the solution containing supporting electrolyte for example can be 1 minute~10 minutes
Left and right.For the given voltage for being applied to working electrode, it is considered preferred to the material of reference electrode and set.In reference electricity
In the case that the material of pole is silver, the voltage for being applied to working electrode can be set as such as -1.0V~1.0V.
Supporting electrolyte is to be easy to be dissolved in general solvent, and assign the substance of enough ionic conductivities i.e. to solvent
It can.As such substance, can enumerate for example：The perchlorate such as tetraethyl ammonium perchlorate, tetrabutylammonium perchlorate, tetraethyl
The trifluoro-methanyl sulfonates such as the tetrafluoroborates such as ammonium tetrafluoroborate and bis- (trifluoromethane sulfonyl group) imide lis.
As the solvent of supporting electrolyte, can use can dissolve supporting electrolyte, and do not make by electroconductive polymer structure
At electroconductive polymer catalyst layer 18 dissolve out solvent, acetonitrile, propene carbonate, gamma-butyrolacton, two can be used for example
Chloromethanes, methanol etc..
By implementing " by the method that chemical oxidation reoxidizes electroconductive polymer " or " pass through electricity that above description is crossed
The method that chemical oxidation reoxidizes electroconductive polymer ", can be to being made due to the long-time of dye-sensitized solar cells 10
The electroconductive polymer being reduced with equal is regenerated.
《The regeneration method of dye-sensitized solar cells》
Then, the regeneration method of the dye-sensitized solar cells of second method of the present invention is said with reference to Fig. 2 and Fig. 3
It is bright.
The regeneration method of the dye-sensitized solar cells of the present invention is to form leading for structure paired electrode 12 as shown in Figure 1
At least one above electroconductive polymer of electrical polymer catalyst layer 18 is in reducing condition or the dyestuff of neutral state is quick
Change the regeneration method of solar cell 10.That is, the regeneration method of the dye-sensitized solar cells of the present invention, which has, passes through chemistry
The process that oxidation or electrochemical oxidation at least reoxidize the electroconductive polymer of electroconductive polymer catalyst layer 18.This
In, to other than having the process for reoxidizing electroconductive polymer, being also equipped with from dye-sensitized solar cells 10
Take out the process to electrode 12 and the dye sensitization using the process for assembling dye-sensitized solar cells 10 again to electrode 12 too
The regeneration method of positive energy battery illustrates.
Hereinafter, being illustrated to each process.
＜ takes out the process ＞ to electrode from dye-sensitized solar cells
As shown in Fig. 2, sealing material 21 is cut into two sealing materials 21A, 21B on thickness direction, from dye sensitization
It is taken out to electrode 12 in solar cell 10.
The work that ＜ will reoxidize the electroconductive polymer that electrode has by chemical oxidation or electrochemical oxidation
Sequence ＞
In this process, to forming the electroconductive polymer catalyst layer to electrode 12 of dye-sensitized solar cells 10
18 electroconductive polymer implement the dye-sensitized solar cells of aforementioned present invention first method to electrode active material
It " method for being reoxidized electroconductive polymer by chemical oxidation " in process for reactivation or " will be conductive by electrochemical oxidation
The method that property macromolecule reoxidizes ".Omit the explanation of each method.It, will be having to electrode 12 and be in by this process
Reducing condition or the electroconductive polymer of neutral state are reoxidised into the state of oxidation, make the catalytic activity of electroconductive polymer and lead
Electrically restore to initial performance.
＜ uses the process ＞ for assembling dye-sensitized solar cells again to electrode
Next, as shown in figure 3, making the electroconductive polymer to electrode 12 for having the electroconductive polymer being reoxidized
Catalyst layer 18 is opposed with the optoelectronic pole 15 of working electrode 11, and separating given interval relative to working electrode 11 configures to electrode
12, sealing material 21A, 21B are engaged by heat treatment etc..Then, it is formed in a part for sealing material 21 for injecting electricity
Solve the injection hole 22 of liquid 20.
It should be noted that injection hole 22 can be formed in one to electrode 12 such as the illustrated by dashed lines of Fig. 3
On point.Then, it is noted from injection hole 22 by working electrode 11, the space S surrounded and formed to electrode 12 and sealing material 21
Enter electrolyte 20.By this process, dye-sensitized solar cells 10 can be assembled again using to electrode 12.
By above process, it can obtain being formed the electroconductive polymer catalyst layer 18 of structure paired electrode 12 extremely
Dye-sensitized solar cells 10 made of more than one few electroconductive polymer is reoxidized.
As described above, in the living again to electrode active material of the dye-sensitized solar cells of first method of the present invention
In change method, the electroconductive polymer of dye-sensitized solar cells 10 is reoxidized by chemical oxidation or electrochemical oxidation,
The dye-sensitized solar cells 10 has is urged by the electroconductive polymer comprising at least one above electroconductive polymer
Agent layer 18 constitute to electrode 12.
Thus, it is possible to make the long-time due to dye-sensitized solar cells 10 make by chemical oxidation or electrochemical oxidation
The electroconductive polymer being reduced with equal is in the state of oxidation, that is, carries positive charge and the state there are hole, so as to
Regeneration.As a result, the catalytic activity of the catalyst layer containing electroconductive polymer and electric conductivity can be restored to electric conductivity
Macromolecule be reduced before initial performance.
In the process for reactivation to electrode active material of the dye-sensitized solar cells of first method of the present invention,
When implementing chemical oxidation by being impregnated in electroconductive polymer dissolved with the solution of oxidant, pass through the oxidant in solution
Capture electronics from electroconductive polymer, and oxidant is made to be reduced, electroconductive polymer is aoxidized.Therefore, room can be passed through
Temperature electroconductive polymer is regenerated simple for processly, by the catalytic activity of electroconductive polymer catalyst layer and electric conductivity restore to
Electroconductive polymer be reduced before original state.
In the process for reactivation to electrode active material of the dye-sensitized solar cells of first method of the present invention, lead to
It crosses using electroconductive polymer as working electrode and is impregnated in the solution containing supporting electrolyte, and in dipping reference electrode, auxiliary
It helps after electrode and given voltage is applied come when implementing electrochemical oxidation, generation electronics is captured at working electrode to working electrode
Caused by oxidation reaction, receive reduction reaction caused by electronics at auxiliary electrode, the conduction as working electrode
Property macromolecule is aoxidized.Therefore, electroconductive polymer can be regenerated, the catalysis of electroconductive polymer catalyst layer can be lived
Property and electric conductivity restore to electroconductive polymer the initial performance before being reduced.
In addition, the regeneration method of the dye-sensitized solar cells of the present invention includes passing through chemical oxidation or electrochemical oxidation
The process that the electroconductive polymer for the electroconductive polymer catalyst layer 18 for forming structure paired electrode 12 is reoxidized.
Thus, it is possible to which the chemical oxidation or electrochemical oxidation crossed by above description will be because of dye-sensitized solar cells 10
The long-time electroconductive polymer of the electroconductive polymer catalyst layer 18 to electrode 12 that uses etc. and be reduced reoxidize,
The catalyst activity and electric conductivity of electroconductive polymer catalyst layer 18 can be improved.
Therefore, by making the electroconductive polymer of electroconductive polymer catalyst layer 18 restore, power generation performance can be dropped
The power generation performance of low dye-sensitized solar cells 10 reliably restores to initial performance, can be by dye sensitization of solar
Battery 10 regenerates.As a result, it is possible to make the long life during use of dye-sensitized solar cells 10.
It should be noted that when stating the catalyst layer containing photoacid generator in use, it can be by not decomposing dye sensitization
Solar cell 10 and the easy method (6th aspect of the present invention) that light irradiation is carried out to the catalyst layer of structure paired electrode
Power generation performance is set to restore.
In addition, in the case of stating the electrolyte containing oxidant in use, when using dye-sensitized solar cells 10,
Gradually the electroconductive polymer being reduced is reoxidized by using oxidant contained in electrolyte, battery can be prevented
The reduction of power generation performance therefore be not usually required to implement regeneration method as described above.
《Catalyst layer》
The catalyst layer of Third Way of the present invention be used by dye sensitization solar battery catalyst layer, be containing one kind with
On electroconductive polymer and photoacid generator catalyst layer.
As the mode of catalyst layer, the mode for example on being formed in the surface of conductive board can be enumerated.This is urged
Agent layer can also be porous layer either fine and close layer.In addition, the thickness of catalyst layer is not particularly limited, such as can
To be set as 0.001 μm~10 μm.
(electroconductive polymer)
As the electroconductive polymer for constituting the catalyst layer, as long as can be to redox couple contained in electrolyte
It is just not particularly limited for electron, for example, can be in conjunction with the reactivation side to electrode active material of first method of the present invention
Method and apply electroconductive polymer as described above well known.
Electroconductive polymer is preferably selected from the polymer of thiophene compound, the polymer of azole compounds and aniline chemical combination
At least one of polymer of object.
As the polymer of thiophene compound, can enumerate the thiophene compound polymerization that such as the following general formula (1) indicates and
At compound.
[chemical formula 4]
[in formula, R1And R2Separately indicate the alcoxyl of hydrogen atom, the alkyl of carbon atom number 1~8, carbon atom number 1~4
((R' indicates the alkyl of carbon atom number 1~8 to R'OOC- for base, the aryl of carbon atom number 6 or 8, carboxyl, ester group.)), aldehyde radical, hydroxyl,
Halogen atom, cyano, amino, nitro or sulfo group.R1And R2For abovementioned alkyl or aryl when, abovementioned alkyl or aryl can be via
Azo group or sulfonyl are bonded to thiphene ring.In R1And R2For abovementioned alkyl or alkoxy when, the end of abovementioned alkyl or alkoxy
Carbon atom can bond together and form ring.]
Abovementioned alkyl is preferably straight-chain or branched-chain alkyl, more preferably straight-chain alkyl.
The carbon atom number of abovementioned alkyl is preferably 1~8, more preferably 1~5, further preferably 1~3.
As above-mentioned alkoxy, preferably methoxyl group, ethyoxyl, propoxyl group, butoxy, more preferably methoxyl group or ethoxy
Base.
As above-mentioned aryl, can enumerate：Phenyl, benzyl, tolyl, naphthalene etc..
As above-mentioned halogen atom, can enumerate：Fluorine atom, chlorine atom, bromine atom, iodine atom etc..
As the specific example for the thiophene compound that above-mentioned general formula (1) indicates, following formula (1-1)~(1-4) can be enumerated
The compound of expression.
[chemical formula 5]
In addition, the polymer as azole compounds, it is poly- can to enumerate the azole compounds that for example the following general formula (2) indicates
Compound made of conjunction.
[chemical formula 6]
[in formula, R3And R4Separately indicate the alcoxyl of hydrogen atom, the alkyl of carbon atom number 1~8, carbon atom number 1~4
((R' indicates the alkyl of carbon atom number 1~8 to R'OOC- for base, the aryl of carbon atom number 6 or 8, carboxyl, ester group.)), aldehyde radical, hydroxyl,
Halogen atom, cyano, amino, nitro or sulfo group.In R3And R4For abovementioned alkyl or aryl when, abovementioned alkyl or aryl can be through
Pyrrole ring is bonded to by azo group or sulfonyl.In R3And R4For abovementioned alkyl or alkoxy when, the end of abovementioned alkyl or alkoxy
The carbon atom at end can bond together and form ring.]
Abovementioned alkyl is preferably straight-chain or branched-chain alkyl, more preferably straight-chain alkyl.
The carbon atom number of abovementioned alkyl is preferably 1~8, more preferably 1~5, further preferably 1~3.
As above-mentioned alkoxy, preferably methoxyl group, ethyoxyl, propoxyl group, butoxy, more preferably methoxyl group or ethoxy
Base.
As above-mentioned aryl, can enumerate：Phenyl, benzyl, tolyl, naphthalene etc..
As above-mentioned halogen atom, can enumerate：Fluorine atom, chlorine atom, bromine atom, iodine atom etc..
As the specific example for the azole compounds that above-mentioned general formula (2) indicates, following formula (2-1)~(2-4) can be enumerated
The compound of expression.
[chemical formula 7]
In addition, the polymer as aniline compound, it is poly- can to enumerate the aniline compound that for example the following general formula (3) indicates
Compound made of conjunction.
[chemical formula 8]
[in formula, R5~R8Separately indicate the alcoxyl of hydrogen atom, the alkyl of carbon atom number 1~8, carbon atom number 1~4
((R' indicates the alkyl of carbon atom number 1~8 to R'OOC- for base, the aryl of carbon atom number 6 or 8, carboxyl, ester group.)), aldehyde radical, hydroxyl,
Halogen atom, cyano, amino, nitro or sulfo group.In R5~R8For abovementioned alkyl or aryl when, abovementioned alkyl or aryl can be through
Phenyl ring is bonded to by azo group or sulfonyl.In R5And R6Or R7And R8For abovementioned alkyl or alkoxy when, abovementioned alkyl or alkane
The carbon atom of the end of oxygroup can bond together and form ring.]
Abovementioned alkyl is preferably straight-chain or branched-chain alkyl, more preferably straight-chain alkyl.
The carbon atom number of abovementioned alkyl is preferably 1~8, more preferably 1~5, further preferably 1~3.
As above-mentioned alkoxy, preferably methoxyl group, ethyoxyl, propoxyl group, butoxy, more preferably methoxyl group or ethoxy
Base.
As above-mentioned aryl, can enumerate：Phenyl, benzyl, tolyl, naphthalene etc..
As above-mentioned halogen atom, can enumerate：Fluorine atom, chlorine atom, bromine atom, iodine atom etc..
As the specific example for the aniline compound that above-mentioned general formula (3) indicates, following formula (3-1)~(3-4) can be enumerated
The compound of expression.
[chemical formula 9]
It can implement the well known doping for improving its electric conductivity to the electroconductive polymer for constituting above-mentioned catalyst layer
Processing.For example, can be by halogens, perchloric acid such as sulfonic acid, iodine, bromine, the chlorine such as polystyrolsulfon acid (PSS), p-methyl benzenesulfonic acid (PTS)
(ClO4 -), double trifluoromethanesulfonimides (TFSI), four cyano quinone bismethane (TCNQ) etc. make an addition to electric conductivity as dopant
Macromolecule.
More than one electroconductive polymer contained in above-mentioned catalyst layer is by redox contained in electrolyte
To the electroconductive polymer restored.As the specific example of this electroconductive polymer, such as polythiophene can be enumerated, gathered
Aniline, polypyrrole, poly- (3,4- ethylenedioxy thiophenes) (PEDOT) etc..Electroconductive polymer contained in catalyst layer can be
It is a kind of, or two or more.Electroconductive polymer in catalyst layer is preferably in the manufacture of dye-sensitized solar cells
It is preceding to be in the state of oxidation with positive charge.
More than one electroconductive polymer contained in above-mentioned catalyst layer both can individually contain one kind, can also group
Conjunction is contained using two kinds, can also be applied in combination three kinds or more and be contained.The type for the electroconductive polymer being applied in combination
The upper limit is not particularly limited, usually 10 kinds or less.
When being applied in combination two or three or more, such as it can be applied in combination and be polymerized selected from above-mentioned thiophene compound
Electroconductive polymer, the electroconductive polymer that is polymerized of above-mentioned azole compounds and above-mentioned aniline compound be polymerized
Electroconductive polymer in arbitrary two or three or more of electroconductive polymer.For two or three or more of electric conductivity
For high molecular mixing ratio, considers electric conductivity and suitably set.
(photoacid generator)
The photoacid generator for constituting above-mentioned catalyst layer is no special as long as it can generate acid by the light such as ultraviolet light irradiate
It does not limit, well known photoacid generator can be applied.As specific example, can enumerate：It is double p-toluenesulfonyl diazomethanes, double
The photoacid generator of the sulfones class such as tert. butylsulfonyl diazomethane；Diphenyl -4- aminomethyl phenyl sulfoniums fluoroform sulphonate, diphenyl -
The light production acid of the sulfoniums classes such as 2,4,6- trimethylphenyl sulfoniums tosilate, 4- methoxyphenyl diphenyl sulfonium fluoroform sulphonates
Agent, double -4- tert-butyl-phenyls iodineThe iodine such as double perfluorinated butane sulfimidesThe photoacid generator etc. of class.Constitute above-mentioned catalyst
The photoacid generator of layer can be used alone, and can also be applied in combination two or more.
Photoacid generator contained in above-mentioned catalyst layer preferably absorbs the light of the wave-length coverage of 300nm or more.Its reason
It is to be irradiated by regarding the light of above-mentioned wave-length coverage as the reproduced light described below, reproduced light can be reduced and be configured pair
The possibility that the base material (such as FTO glass, ITO-PET films, ITO-PEN films etc.) of electrode absorbs, to photoacid generator (catalyst
Layer) irradiation sufficient amount light become easy.
In above-mentioned catalyst layer, (gross mass of above-mentioned photoacid generator)/(gross mass of above-mentioned electroconductive polymer) it
Than being preferably 0.01~10, more preferably 0.05~5, further preferably 0.1~1.
When above-mentioned mass ratio is 0.01 or more, the acid of sufficient amount can be generated by the way that light irradiates.Above-mentioned mass ratio is 10
When following, the electric conductivity of catalyst layer can be made to reduce to avoid excessive photoacid generator.
Relative to the gross mass of above-mentioned catalyst layer, the gross mass of above-mentioned electroconductive polymer be preferably 10 mass % with
On, more preferably 20 mass % or more, further preferably 50 mass % or more.
When it is 10 mass % or more, the catalytic performance and electric conductivity of catalyst layer can be fully improved.It is above-mentioned to lead
The upper limit of electrical high molecular gross mass is not particularly limited, such as can be set as 90 mass % or less.
Relative to the gross mass of above-mentioned catalyst layer, the gross mass of above-mentioned photoacid generator is preferably 1~90 mass %, more excellent
It is selected as 5~70 mass % or more, further preferably 10~50 mass % or more.
When it is 1 mass % or more, the acid of sufficient amount can be generated by the way that ultraviolet light irradiates.When it is 90 mass %
When following, the electric conductivity of catalyst layer can be made to reduce to avoid excessive photoacid generator.
(auxiliary agent)
The conductive material other than electroconductive polymer can be contained in above-mentioned catalyst layer.As such electric conductivity
Material can enumerate the carbon material such as carbon nanotube, acetylene black.The electroconductive polymer for constituting catalyst layer is set as 100
When mass parts, the content of above-mentioned conductive material is preferably 10~500 mass parts or so.
《To electrode》
The 4th aspect of the present invention to electrode be used by dye sensitization solar battery to electrode, formd with surface
The base material of the catalyst layer of Third Way.
The mode of above-mentioned base material is not particularly limited, and can enumerate the mode such as the substrate of plate, film.Above-mentioned base material can
Think transmitance, or non-transmitance, but from be easy to constitute dye-sensitized solar cells catalysis
From the viewpoint of oxidant layer carries out light irradiation, above-mentioned base material is preferably transmitance.
The surface of above-mentioned base material can be electric conductivity, or dielectric.Due to being formed by its surface
Catalyst layer itself is electric conductivity, therefore even if the surface of base material is dielectric, be can also be used as abundant to electrode
Ground plays a role.It should be noted that from the viewpoint of improving the electric conductivity to electrode, it is preferably formed as electroconductive polymer
Above-mentioned surface is electric conductivity.
As the transmitance substrate that at least surface is electric conductivity, can enumerate for example in glass substrate or transparent resin matrix
The surface of plate is formed with the transparent conductive substrate of transparent conductive film.In addition, the substrate as above-mentioned non-transmitance, it can example
Metal substrate or unglazed radioparent resin substrate are shown.It should be noted that the transmitance of resin substrate can be according to base
The thickness of plate and change.
As above-mentioned resin, can enumerate for example：Polyethylene terephthalate (PET), poly- naphthalenedicarboxylic acid ethylene glycol
The resins such as ester (PEN), acrylic resin, makrolon, polyimides.
The thickness of the catalyst layer formed on the surface of above-mentioned base material is not particularly limited, when it is excessively thin catalyst
When layer, there is the hidden danger that cannot play sufficient catalytic performance, thus, for example preferably 0.001 μm or more of thickness.Catalyst
The upper limit of the thickness of layer is not particularly limited, uneconomical when its is blocked up, therefore usually 10 μm or less.
The catalyst layer formed on the surface of above-mentioned base material can be the layer of densification, can also be porous layer.When it is
When porous layer, increase with the contact area of electrolyte, therefore the catalytic performance of catalyst layer can be improved.
When measuring the specific surface area of porous layer with gas adsorption method, preferably 0.1m2/ g or more, more preferably 1m2/ g with
On, further preferably 3m2/ g or more.
As the method for forming fine and close catalyst layer, can enumerate for example, electroconductive polymer and light production acid will be contained
The solution coating of agent is on the surface of above-mentioned base material and the method that is dried.
As the method for the catalyst layer for forming porous, can enumerate for example, by using well known roasting method or grain
Sub- gunite be pre-formed on the surface of above-mentioned base material the porous layer being made of metal-oxide semiconductor (MOS)s such as titanium oxide microparticles,
And the solution containing electroconductive polymer and photoacid generator is made to be impregnated in the method in the porous layer and being dried.
It, can be by being impregnated in the solution containing the monomer molecule for constituting electroconductive polymer as other forming methods
It is formed with the base material of above-mentioned porous layer and the porous layer is led in the state of so that the monomer molecule is spread in the porous layer
The electrolysis polymerization method of electricity in the porous layer synthesizes electroconductive polymer.It, can be in porous layer according to the electrolysis polymerization method
Deep also configure electroconductive polymer.Then, so that the solution containing photoacid generator is impregnated in the porous layer and remove solvent
And be dried, thus, it is possible in the surface of the porous layer and the internal catalysis for forming electroconductive polymer and being coexisted with photoacid generator
Oxidant layer.As above-mentioned monomer molecule, the above-mentioned thiophene compound of example, azole compounds, aniline compound etc. can be enumerated.《Dyestuff
Sensitization solar battery》
The dye-sensitized solar cells of 5th mode of the invention has：Above-mentioned fourth way to electrode, have it is quick
Change the optoelectronic pole of dyestuff and the electrolyte containing redox couple.
Figure 10 is shown as the sectional view of the dye-sensitized solar cells 10 of an example of the 5th mode.Shown in Figure 10
Dye-sensitized solar cells 10 structure, material and function substantially such as about dye sensitization of solar shown in FIG. 1 electricity
Described in pond 10, but the catalyst layer that catalyst layer 18 is above-mentioned Third Way.
《The regeneration method of dye-sensitized solar cells》
The regeneration method of the dye-sensitized solar cells of 6th mode of the invention is will to constitute the electric conductivity of catalyst layer
High molecular at least part is in reducing condition or neutral state, the 5th above-mentioned mode dye-sensitized solar cells
Regeneration method, this method are by carrying out light irradiation by above-mentioned electric conductivity to photoacid generator contained in above-mentioned catalyst layer
The method that macromolecule reoxidizes.
For example, when dye-sensitized solar cells 10 shown in Fig. 10 is regenerated, by from arrow shown in Fig. 10 " again
The direction irradiation of the third contact of a total solar or lunar eclipse " can make photoacid generator generate the light (such as ultraviolet light) of sour wave-length coverage, make to have penetrated composition pair
The opposite base material 16 of the transmitance of electrode 12 and catalyst layer 18 is reached to the reproduced light of conductive film 17.Absorb reproduced light
Photoacid generator generate acid, make electroconductive polymer contained in identical catalyst layer 18 return to the state of oxidation.Its result
It is that the catalytic performance and electric conductivity of catalyst layer 18 are restored, battery performance is preferred to be restored to original state.
As the light source of above-mentioned reproduced light (ultraviolet light etc.), as long as the light than sun light intensity, Ke Yilie can be irradiated
Citing is such as：High-pressure mercury-vapor lamp, Cooper-Hewitt lamp, metal halide lamp, xenon lamp, sterilamp and laser etc..Irradiation time is according to urging
The reducing condition of electroconductive polymer, the light source used, the type of photoacid generator and dosage etc. contained in agent layer 18 without
Together, it therefore cannot broadly provide, preferably 10~600 seconds, more preferably 30~300 seconds.
In the common occupation mode (power generation) of dye-sensitized solar cells 10, the light (hair of the power generations such as sunlight
Electric light) it is incident from the direction of arrow shown in Fig. 10 " power generation light ", therefore, reaches and urge through working electrode 11 and electrolyte 20
The power generation optical attenuation of agent layer 18.Therefore, under common occupation mode (being not intended to regenerated occupation mode), catalyst layer 18
Contained in photoacid generator the hidden danger that is depleted is not present.It should be noted that even if power generation light reach catalyst layer 18 and from
Photoacid generator release acid, the acid also contribute to keep the state of oxidation of electroconductive polymer, and therefore, the arrival of a small amount of power generation light is urged
Agent layer 18 is not a problem.
《Electrolyte》
The electrolyte of the 7th aspect of the present invention is can to aoxidize electroconductive polymer, containing at least one oxidant
Electrolyte.More specifically, the electrolyte of present embodiment is the solution being made of following substances：It can make composition dye sensitization
Type solar cell, the oxidant that is reoxidized by the catalyst layer that electroconductive polymer is constituted；In dye-sensitized solar
The redox couple of the redox reaction for making electric current flowing occurs in battery；And solvent.
(oxidant)
As long as oxidant can aoxidize the substance of electroconductive polymer, just it is not particularly limited.It, can be with as oxidant
It enumerates for example：Selected from the elementary gas group for including oxygen, chlorine, bromine gas, ozone etc.；Including iron chloride (III) hexahydrate, nothing
The inorganic acid group of water iron chloride (III), ferric nitrate (III) nonahydrate, anhydrous nitric acid iron and ferric perchlorate (III) etc.；Including
The organic acid group of dodecyl benzene sulfonic acid, toluenesulfonic acid, trifluoroacetic acid and propionic acid；And by chlordene metaantimmonic acid three (4- bromophenyls) ammonium
At least one of group of composition.Wherein, higher from the dissolubility to general solvent and to the oxidation of electroconductive polymer make
With stronger viewpoint consider, it is preferable to use be selected from least one of elementary gas group and inorganic acid group, more preferably use oxygen,
Bromine gas, iron chloride (III).
In the case where oxidant is selected from least one of elementary gas group, when electrolyte is totally set as 1L,
The content of oxidant is preferably 1mg/L~50mg/L, more preferably 5mg/L~50mg/L, and further preferably 10mg/L~
50mg/L。
When oxidant is less than 1mg/L% relative to the content of electrolyte totality, it is difficult to make to be restored by redox couple
Electroconductive polymer reoxidizes.On the other hand, when oxidant is more than 50mg/L relative to the content of electrolyte totality, there is resistance
The hidden danger for hindering the redox reaction of redox couple and keeping electric current obstructed.
It should be noted that when oxidant is selected from least one of elementary gas group, by the way that monomer gas is led to
Enter electrolyte and monomer gas is made to contain or be dissolved in electrolyte.
In addition, when oxidant is selected from least one of monomer gas, the conduct in the electrolytic solution of these monomer gas
Molecule exists.
In addition, when monomer gas is oxygen, the dissolved oxygen content in electrolyte can be surveyed using such as dissolved oxygen meter
Amount.
In the case where oxidant is at least one kind of in inorganic acid group and organic acid group, electrolyte is totally being set
For 100 mass % when, the content of oxidant is preferably the 0.001 mass % of mass %~10, more preferably 0.005 mass %~5
Quality %, further preferably 0.01 mass of mass %~1 %.
When oxidant is less than 0.001 mass % relative to the content of electrolyte totality, it is difficult to make by redox couple also
Former electroconductive polymer reoxidizes.On the other hand, when oxidant is more than 10 mass % relative to the content of electrolyte totality,
The hidden danger for keeping electric current obstructed in the presence of the redox reaction for hindering redox couple.
It should be noted that when oxidant is selected from least one of inorganic acid group and organic acid group, these acid exist
It is dissociated in electrolyte, is existed as ion.
(redox couple and solvent)
It, can be in conjunction with the reactivation side to electrode active material of first method of the present invention as redox couple and solvent
Method and use redox couple and solvent same as described above.
Electrolyte according to the present embodiment, due to containing at least one oxidant, applied to dye sensitization type
In the case of solar cell etc., the redox couple contained in electrolyte can be made by oxidant contained in electrolyte
Reduction, composition catalyst layer electroconductive polymer re-oxidation.That is, by making electroconductive polymer by oxidant oxygen again
Change, the deterioration of the power generation performance (photoelectric conversion efficiency) of dye-sensitized solar cell can be prevented.
But by making electrolyte contain oxidant, the institute in the electroconductive polymer for constituting catalyst layer is by electrolyte
The redox couple contained from oxidation state reduction be neutral state when, the oxidant contained in electrolyte is (automatic immediately
Ground) by the electroconductive polymer re-oxidation.
《Dye-sensitized solar cell》
The dye-sensitized solar cell of the 8th aspect of the present invention has：The electrolyte of 7th mode has and partly leads
The working electrode of body and to electrode is clamped in working electrode and between electrode electrolyte.Dyestuff about eighth mode is quick
The all parts of change type solar cell, basic structure, being referred to Fig. 1 keeps it identical as above-mentioned all parts, basic structure.
Dye-sensitized solar cells 10 according to the present embodiment, as electrolyte 20, due to containing the 7th mode
Electrolyte, therefore, even if using electroconductive polymer in catalyst layer 18, power generation when being also possible to prevent to use for a long time
The deterioration of energy.In addition, due to constituting electroconductive polymer redox couple contained in electrolyte 20 of catalyst layer 18 also
Original, power generation performance will not deteriorate, and therefore, there is no need to decompose dye-sensitized solar cells 10 and the behaviour of regeneration catalyzing oxidant layer 18
Make, thus, it is possible to cut down the maintenance cost of dye-sensitized solar cells 10, administration fee.
More than, detailed narration is carried out to the preferred embodiments of the present invention, but the present invention is not limited to above-mentioned
Specific embodiment, the main points of the present invention that can be recorded in claim in the range ofs, carry out various modifications, change.
As long as in addition, do not damage the purpose of the present invention, can also the appropriately combined above-mentioned present invention various modes.
In the present invention, it as the method for confirming that electroconductive polymer is in the reducing condition of which kind of degree, can enumerate
Such as the method for having used spectrophotometric spectra.Due to light splitting of the electroconductive polymer under the state of oxidation, neutral state, reducing condition
The shape of spectrum is different, therefore, by measuring the spectrophotometric spectra of electroconductive polymer catalyst layer, can quantitatively judge to restore
State.Which kind of therefore, can be handled to degree in the hope of being reduced in the various embodiments of the present invention.
Embodiment
Next, be illustrated in more details to the present invention by embodiment below, but the present invention and not only limit
In these embodiments.
(embodiment 1)
The formation ＞ of ＜ working electrodes
As transparent base 13, the glass substrate that FTO films are formed in plate face is prepared.It will be by average on FTO films
The TiO of grain size 14nm2Particle：19 mass %, ethyl cellulose：9 mass %, terpineol：The slurry that 72 mass % are constituted is with ruler
Very little 4mm × 4mm is formed a film using silk screen print method, under air atmosphere in 500 DEG C roast 30 minutes, thus form by
TiO2The porous layer that particle is constituted.Then, with mass ratio 1 ︰ 1 mixing acetonitrile and the tert-butyl alcohol and in manufactured mixed liquor with
The concentration of 0.3mM dissolves the N719 as sensitizing dyestuff, impregnates and has by TiO in obtained sensitizing dyestuff solution2Particle structure
At porous layer and FTO films glass substrate 20 hours, then cleaned with acetonitrile, to make sensitizing dyestuff be adsorbed in porous layer
Surface.The working electrode 11 for having transparent conductive film 14 and optoelectronic pole 15 in 13 superimposed layer of transparent base has been made as a result,.
Formation ＞s of the ＜ to electrode
Then, prepare material identical with working electrode 11 and be formed with the glass substrate of FTO films, form through FTO
The injection hole of film and glass substrate is as the injection hole 22 for injecting electrolyte 20.As a result, as shown in Figure 4 A, it forms and includes
Lamination has by the opposite base material 16 of the FTO glass to conductive film 17 constituted.It should be noted that in Fig. 4 A, Fig. 4 B and Fig. 5
In, omit the diagram of the injection hole of electrolyte injection.It then, will be by containing sulfonate as the poly- of dopant on FTO films
Aniline：10 mass %, toluene：The polyaniline solutions that 90 mass % are constituted pass through spin coating (rotating speed：3000rpm, 20 seconds) carry out
Film forming.Then, the heat treatment for carrying out 10 minutes in 100 DEG C on electric hot plate, thus forms containing as electric conductivity high score
The electroconductive polymer catalyst layer 18 of the polyaniline of son.As a result, as shown in Figure 4 B, having made has in 16 superimposed layer of opposite base material
To conductive film 17 and electroconductive polymer catalyst layer 18 to electrode 12.
Next, being impregnated in electrode 12 containing iodine as shown in figure 5, will make in aforementioned manners：0.05M and 1,3- bis-
Methyl-2-propyl iodate imidazoles：In the gamma-butyrolacton solution of 1.0M, add to promote the reducing of electroconductive polymer
Thus heat will restore the electroconductive polymer of the electroconductive polymer catalyst layer 18 of electrode 12 to 85 DEG C.At this moment, will
Dip time be 0 hour (before dipping), 100 hours, 300 hours, 500 hours it is each to electrode 12 as to electrode 12A~
12D takes out, and is cleaned respectively with acetonitrile, and be dried.
The assembling ＞ of ＜ dye-sensitized solar cells
In the following, as shown in Fig. 6 A~Fig. 6 D, make the electroconductive polymer catalyst layer for having carried out reduction treatment as described above
18 is opposed with the optoelectronic pole 15 of working electrode 11, will be respectively relative to working electrode 11 to electrode 12A, 12B, 12C, 12D and separate
Given interval and configure, configure sealing material (not shown) in the side in working electrode 11 and the space between electrode 12,
And the sealing material is set to cure by heat treatment etc..Then, from injection hole (not shown) to by working electrode 11, to 12 and of electrode
Electrolyte 20 is injected in space made of sealing material surrounds, and has made dye-sensitized solar cells 10A~10D.Electrolyte
20 use in the acetonitrile as solvent dissolved with iodine：0.03M, 1,3- dimethyl -2- propyl iodate imidazoles：0.6M, iodate
Lithium：0.10M, tert .-butylpyridine：The solution of 0.5M.
The evaluation ＞ of the power generation performance of ＜ dye-sensitized solar cells
Then, using solar simulator (model：XES-301S, K.K. Minaga Denki Seisakusho's system) measure dyestuff it is quick
Change the photoelectric conversion efficiency of solar cell 10A~10D, short-circuit current density, open voltage, fill factor (fill
Factor projects) thus evaluate the power generation performance of dye-sensitized solar cells 10A~10D.
＜ takes out from dye-sensitized solar cells to electrode ＞
Then, in the regeneration method of above-mentioned dye-sensitized solar cells " from dye-sensitized solar cells take out
To the process of electrode " similarly operate, from having the electric conductivity for impregnating 500 hours and being reduced in gamma-butyrolacton solution
It is taken out to electrode 12D in high molecular dye-sensitized solar cells 10D.
＜ electroconductive polymers caused by chemical oxidation reoxidize ＞
Then, as shown in fig. 7, being impregnated in taking-up electrode 12D containing iron chloride (hexahydrate)：The second of 0.01M
Nitrile solution 5 minutes is made by chemical oxidation to the electroconductive polymer of the electroconductive polymer catalyst layer 18 of electrode 12D oxygen again
Change.Made as a result, have the electroconductive polymer being reoxidized from reducing condition to electrode 12E.Fig. 8 be impregnated in containing
Iodine：0.05M and 1,3- dimethyl -2- propyl iodate imidazoles：The gamma-butyrolacton solution of 1.0M is pervious to electrode 12D, dipping
In containing iodine：0.05M and 1,3- dimethyl -2- propyl iodate imidazoles：The gamma-butyrolacton solution 500 hours of 1.0M to electricity
Pole 12D, electrode 12D will be impregnated in containing iron chloride (hexahydrate)：The acetonitrile solution 5 minutes of 0.01M to electrode 12E's
Photo.
The assembling again of ＜ dye-sensitized solar cells, the evaluation ＞ of power generation performance
Then, it using to electrode 12E, operates, assembles in the same manner as above-mentioned " assembling of dye-sensitized solar cells "
Dye-sensitized solar cells 10E.In addition, using carry out it is above-mentioned " power generation performance of dye-sensitized solar cells
Used solar simulator when evaluation ", photoelectric conversion efficiency, the short circuit current for measuring dye-sensitized solar cells 10E are close
Projects of degree, open voltage, fill factor, thus evaluate the power generation performance of dye-sensitized solar cells 10E.
(embodiment 2)
Reoxidizing for the electroconductive polymer having to electrode 12 is changed to replace by electrochemical oxidation implementation
In addition to this chemical oxidation implements process same as Example 1.Hereinafter, to " electric conductivity caused by electrochemical oxidation is high
Molecule reoxidizes " and " dye-sensitized solar cells assemble again, the evaluation of power generation performance " followed by illustrate,
Omit the explanation about the process same as Example 1 other than these.
＜ electroconductive polymers caused by electrochemical oxidation reoxidize ＞
As shown in figure 9, by the electric conductivity to electrode 12D of dye-sensitized solar cells 10D shown in Fig. 6 A~Fig. 6 D
Polymer catalyst layer 18 is used as working electrode, is impregnated in containing LiTFSI (double fluoroform sulphonyl as supporting electrolyte
Imine lithium)：10-1The acetonitrile solution of M.Then, using platinum line and silver wire as auxiliary electrode and normal electrode, constant potential is utilized
Instrument (IVIUM corporations) leads to applying the voltage 120 seconds of 1.0V as the electroconductive polymer catalyst layer 18 of working electrode
The electroconductive polymer of the electroconductive polymer catalyst layer 18 of electrode 12D will be reoxidized by crossing electrochemical oxidation.It makes as a result,
Have the electroconductive polymer being reoxidized from reducing condition to electrode 12F.
The assembling again of ＜ dye-sensitized solar cells, the evaluation ＞ of power generation performance
Then, it using to electrode 12F, operates, assembles in the same manner as above-mentioned " assembling of dye-sensitized solar cells "
Dye-sensitized solar cells 10F.In addition, using carrying out, above-mentioned " power generation performance of dye-sensitized solar cells is commented
Used solar simulator when valence ", photoelectric conversion efficiency, the short circuit current for determining dye-sensitized solar cells 10F are close
Projects of degree, open voltage, fill factor, thus evaluate the power generation performance of dye-sensitized solar cells 10F.
(comparative example 1)
Other than not carrying out " reoxidizing for electroconductive polymer caused by chemical oxidation ", implement and 1 phase of embodiment
Same process.That is, will be impregnated 500 hours in gamma-butyrolacton solution and what is restored is cleaned and done with acetonitrile to electrode 12D
Then paired electrode 12G (diagram is omited) dry and processed uses to electrode 12G assembling dye-sensitized solar cells 10G.Then, make
Used in used solar simulator when carrying out above-mentioned " evaluation of the power generation performance of dye-sensitized solar cells ", dye is determined
Expect the photoelectric conversion efficiency of sensitization solar battery 10G, projects of short-circuit current density, open voltage, fill factor, thus
Evaluate the power generation performance of dye-sensitized solar cells 10G.
(evaluation result of the power generation performance about the dye-sensitized solar cells in embodiment 1,2 and comparative example 1) will
The power generation performance of dye-sensitized solar cells 10A~10G in embodiment 1,2 and comparative example 1 evaluation result is shown in table 1.
It should be noted that the recovery rate for reoxidizing caused photoelectric conversion efficiency of table 1 is to utilize dye-sensitized solar cells 10E
The photoelectric conversion efficiency of~10G is calculated relative to the ratio of the photoelectric conversion efficiency of dye-sensitized solar cells 10A.
As shown in table 1, for the dye-sensitized solar cells 10E of embodiment 1, to reoxidizing for electrode 12D
The recovery rate of photoelectric conversion efficiency is 0.97, has obtained the value close to 1.Short circuit about dye-sensitized solar cells 10E
Current density, open voltage, fill factor, can also obtain journey identical as projects in dye-sensitized solar cells 10A
The result of degree.The reason is that the electroconductive polymer that will be reduced by being impregnated 500 hours in gamma-butyrolacton solution
It is impregnated 5 minutes in acetonitrile solution, is reoxidized and regenerated from there through chemical oxidation.In addition, which is because, by leading
Electrical macromolecule regeneration, catalytic activity and electric conductivity to the electroconductive polymer catalyst layer 18 of electrode 12E restore substantially to
Electroconductive polymer is reduced pervious initial performance.
In addition, for the dye-sensitized solar cells 10F of embodiment 2, the photoelectricity of electrode 12D reoxidized is turned
The recovery rate for changing efficiency is also 0.98, has obtained the value close to 1.Short circuit current about dye-sensitized solar cells 10F
Density, open voltage, fill factor, also can be obtained the knot with projects same degree in dye-sensitized solar cells 10A
Fruit.The reason is that the electroconductive polymer being reduced by being impregnated 500 hours in gamma-butyrolacton solution is impregnated in
Contain LiTFSI：10-1The acetonitrile solution of M, while using platinum line and silver wire as auxiliary electrode and normal electrode, to as work
The electroconductive polymer catalyst layer 18 for making electrode applies voltage, is reoxidized and is regenerated from there through electrochemical oxidation.
In addition, which is because, being regenerated by electroconductive polymer, the catalysis to the electroconductive polymer catalyst layer 18 of electrode 12F
Activity and electric conductivity are restored to be reduced pervious initial performance to electroconductive polymer substantially.
Relative to these embodiments, for the dye-sensitized solar cells 10G of comparative example 1, photoelectric conversion efficiency
Almost without recovery.About the short-circuit current density, open voltage, fill factor of dye-sensitized solar cells 10G, with dyestuff
It is lower value that the value of projects in sensitization solar battery 10A, which is compared also,.The reason is that by gamma-butyrolacton
It impregnates 500 hours and is reduced and the electric conductivity of dye-sensitized solar cells 10G having to electrode 12G in solution
Macromolecule do not carry out it is any reoxidize caused by chemical oxidation, reoxidized caused by electrochemical oxidation, be still within also
Original state is not reproduced.
It can be true by the evaluation result of the power generation performance of the dye-sensitized solar cells in embodiments illustrated above 1,2
Recognize：According to the present invention, the electric conductivity high score that is reduced bys use etc. by making the long-time due to dye-sensitized solar cells
Son reoxidizes, can by by the catalyst layer comprising the electroconductive polymer constitute to electrode regeneration, can be by catalyst layer
Catalytic activity and electric conductivity restore and restore to be reduced pervious initial performance to electroconductive polymer, meanwhile, can be by dyestuff
The power generation performance of sensitization solar battery reliably restores to initial performance, and dye-sensitized solar cells is regenerated.
(embodiment 3)
The making ＞ of ＜ optoelectronic poles
Using by Titanium particles (grain size Φ 14nm) 19 mass %, 9 mass % of ethyl cellulose, 72 mass % of terpineol
The slurry of composition carries out the formation of perforated membrane.As transparent conductive substrate, 10 ohm of the sheet resistance configured with FTO films is used
Above-mentioned slurry is coated on the area of 4mm × 4mm on FTO films, then in air by the glass substrate of (Ω) with silk screen print method
It is roasted 30 minutes in 500 DEG C under atmosphere, forms porous layer (10 μm of film thickness) on nesa coating.
It is molten with pigment of the concentration of 0.3mM dissolved with sensitizing dyestuff N719 in the mixed liquor of acetonitrile and 1 ︰ 1 of the tert-butyl alcohol
In liquid, will be provided with above-mentioned porous layer substrate impregnate 20 hours after, cleaned with acetonitrile, making has that so that sensitizing dyestuff is adsorbed in more
Aperture layer and the optoelectronic pole of electric layer formed.
Making ＞s of the ＜ to electrode
The injection hole for injecting electrolyte in rear process is formed on the glass substrate for being formed with FTO films.In the glass
The solution containing electroconductive polymer and photoacid generator is coated with by spin coating (rotating speed 3000rpm 20 seconds) on glass substrate, in electricity
In the heat treatment of 60 DEG C of progress 5 minutes on hot plate, formed as a result, by electroconductive polymer and photoacid generator structure on FTO films
At catalyst layer.
In above-mentioned solution, relative to the gross mass of solution, electroconductive polymer (contains sulfonate as the poly- of dopant
3,4-ethylene dioxythiophene (PEDOT)) content be 85 mass %, photoacid generator (Irgacure PAG103 (IR 103, BASF
Corporation)) content be 15 mass %.In addition, using methanol as solvent.
The preparation ＞ of ＜ electrolyte
So that iodine is 0.05M, 1,3- dimethyl -2- propyl iodate imidazolesMode for the concentration of 1.0M is dissolved in conduct
In the gamma-butyrolacton of solvent, electrolyte is thus prepared.
The assembling ＞ of ＜ dye-sensitized solar cells (DSC)
It will be provided with the face-to-face in the form of clipping sealing material to electrode and the optoelectronic pole that has electric layer of catalyst layer
Configuration makes sealing material cure, is thus assembled into DSC batteries by heat treatment.Then, from the above-mentioned note being formed in electrode
Enter hole to by optoelectronic pole, electrode and sealing material are surrounded made of inject electrolyte in space, and injection hole is sealed.
The evaluation ＞ of the power generation performance of ＜ dye-sensitized solar cells
Use solar simulator (model：XES-301S, K.K. Minaga Denki Seisakusho's system), to the DSC electricity of making
Pond is measured in luminous intensity 100mW/cm2Simulated solar irradiation irradiation under photoelectric conversion efficiency (generating efficiency).The result is shown
In the column of " generating efficiency (before 85 DEG C) " of table 2.
Heat resistant test (accelerated test) ＞ of ＜ dye-sensitized solar cells
Then, the DSC batteries for determining generating efficiency are placed 300 hours in 85 DEG C of electric furnace, then with it is above-mentioned same
Measure to sample its power generation performance.The results are shown in the columns of " generating efficiency (after 85 DEG C) " of table 2.
The regeneration test ＞ of ＜ dye-sensitized solar cells
Then, electric to the DSC for determining generating efficiency after heat resistant test using UV SPOTCURE (USHIO corporations)
Pond irradiating ultraviolet light.At this moment, it in order to improve the illumination efficiency of the electroconductive polymer to constituting catalyst layer, is shone to electrode side
Penetrate ultraviolet light.Then, power generation performance is evaluated again.The results are shown in the columns of " generating efficiency (the having ultraviolet light) " of table 2.
In addition, the result of the embodiment 4~7 described below and comparative example 2 is recorded in table 2 together.
Table 2
(embodiment 4)
" the poly- 3,4- ethylenedioxy thiophenes for containing sulfonate as dopant " that is used in embodiment 3 is changed to " contain
There is polyaniline of the sulfonate as dopant ".Implement similarly to Example 3 in addition to this.
(embodiment 5)
" the poly- 3,4- ethylenedioxy thiophenes for containing sulfonate as dopant " that is used in embodiment 3 is changed to " contain
There is polypyrrole of the four cyano tetrazanaphthalene as dopant ".Implement similarly to Example 3 in addition to this.
(embodiment 6)
" the Irgacure PAG103 " that is used in embodiment 3 is changed to " Irgacure PAG121 (BASF AG
System) ".Implement similarly to Example 3 in addition to this.
(embodiment 7)
" the Irgacure PAG103 " that is used in embodiment 3 is changed to " Irgacure PAG290 (BASF AG
System) ".Implement similarly to Example 3 in addition to this.
(comparative example 2)
Other than not containing Irgacure PAG103, implement similarly to Example 3.
Result more than investigation.Firstly, since the accelerated test taken care of for a long time at 85 DEG C, initial power generation performance becomes
Difference.It is considered that this is because, constitute catalyst layer electroconductive polymer by the redox couple in electrolyte chemically
Reduction or neutralisation.Then, by catalyst layer irradiating ultraviolet light, its power generation performance being made substantially to restore.It is considered that this is
Due in the DSC batteries of embodiment 3~7, by the effect for the acid that the photoacid generator contained in the catalyst layer discharges, making
Electroconductive polymer returns to the state of oxidation.On the other hand, due to not contained in the catalyst layer of the DSC batteries of comparative example 2
Photoacid generator, therefore, even if not restoring if irradiation ultraviolet light power generation performance.
As known from the above：Even if the present invention's has catalyst layer and to the dye-sensitized solar cells of electrode due to warp
Contact of the long-time electrolyte with catalyst layer is crossed, constitute the electroconductive polymer of catalyst layer makes hair by neutralisation or reduction
Electrical property reduces, and can also make its power generation by that can make the light (reproduced light) of photoacid generator release acid to catalyst layer irradiation
Performance recovery.
(embodiment 8)
The formation ＞ of ＜ electric layers (working electrode)
As transparent conductive substrate, the glass of FTO films are formed in plate face sheet resistance 10 ohm (Ω) is prepared
Substrate.
It will be by the TiO of average grain diameter 14nm on FTO films2Particle：19 mass %, ethyl cellulose：9 mass %, terpin
Alcohol：The slurry that 72 mass % are constituted is formed a film with size 4mm × 4mm using silk screen print method, in 500 DEG C under air atmosphere
Roasting 30 minutes, thus forms by TiO2The porous layer that particle is constituted.
Then, it is dissolved and is made with the concentration of 0.3mM in manufactured mixed liquor with 1 ︰ 1 of mass ratio mixing acetonitriles and the tert-butyl alcohol
For the N719 of sensitizing dyestuff, impregnates and have by TiO in obtained sensitizing dyestuff solution2The porous layer and FTO films that particle is constituted
Glass substrate 20 hours, then cleaned with acetonitrile, to make sensitizing dyestuff be adsorbed in the surface of porous layer.It makes as a result,
There is the working electrode of transparent conductive film and optoelectronic pole in transparent conductive substrate superimposed layer.
The formation ＞ of ＜ catalyst layers (to electrode)
Then, prepared to form the glass substrate of FTO films by material identical with working electrode, and formd and run through
The injection hole of FTO films and glass substrate is as the injection hole for injecting electrolyte.Foring as a result, has comprising lamination by FTO
The opposite base material for the glass to conductive film that film is constituted.
It then, will be by containing poly- 3,4-ethylene dioxythiophene (PEDOT) of the sulfonate as dopant on FTO films：1~
2 mass % and methanol：The PEDOT solution that 98~99 mass % are constituted passes through spin coating (rotating speed：3000rpm, 20 seconds) carry out at
Film.Then, the heat treatment for carrying out 5 minutes in 80 DEG C on electric hot plate, thus forms containing as electroconductive polymer
The catalyst layer of PEDOT.Having made as a result, has in opposite base material superimposed layer by being constituted to conductive film and electroconductive polymer
Catalyst layer to electrode.
＜ contains the formation ＞ of the electrolyte of oxidant
Iodine 0.05M and 1,3- dimethyl -2- propyl of the dissolving as redox couple in the gamma-butyrolacton as solvent
Iodate imidazoles1.0M prepares electrolyte.
Then, by being passed through oxygen in the electrolyte 10 minutes, electrolyte is made to contain aerobic (oxidant).At this moment, it utilizes
Dissolved oxygen meter measures the dissolved oxygen content in electrolyte.As a result, the dissolved oxygen content in electrolyte is that 10g/L (change by water saturation rate
It calculates).
The assembling ＞ of ＜ dye-sensitized solar cells
Keep the electric layer made as described above opposed with catalyst layer, it is given by being separated relative to working electrode to electrode
It is spaced and configures, configure sealing material in the side in working electrode and the space between electrode, keep this close by heat treatment etc.
Closure material cures.Then, from be formed in the injection hole of electrode to by working electrode, electrode and sealing material are surrounded made of
The electrolyte made as described above is injected in space has made dye then by the way that sealing material heat cure is blocked injection hole
Expect sensitization solar battery.
The evaluation ＞ of the power generation performance of ＜ dye-sensitized solar cells
Using solar simulator, measure in luminous intensity 100mW/cm2Simulated solar irradiation irradiation under photoelectric conversion efficiency,
Thus the power generation performance of dye-sensitized solar cells is evaluated.Show the result in table 3.
85 DEG C of heat resistant tests (the heat-resisting accelerated test of catalyst layer) ＞ of ＜ dye-sensitized solar cells
By dye-sensitized solar cells in 85 DEG C of keepings 500 hours in electric furnace.
Then, the photoelectric conversion efficiency of dye-sensitized solar cells is determined as described above.Show the result in table 3.
In addition, calculating the light after 85 DEG C of heat resistant tests by the measurement result of the photoelectric conversion efficiency before and after 85 DEG C of heat resistant tests
Photoelectric transformation efficiency relative to before 85 DEG C of heat resistant tests photoelectric conversion efficiency ((photoelectric conversion efficiency after 85 DEG C of heat resistant tests)/
(photoelectric conversion efficiency before 85 DEG C of heat resistant tests) × 100 (%)), it is set as the conservation rate of photoelectric conversion efficiency.It shows the result in
Table 3.
(embodiment 9)
In the formation ＞ of ＜ catalyst layers (to electrode), replace poly- 3,4-ethylene dioxythiophene using polyaniline solutions
(PEDOT) in addition to this solution operates similarly to Example 8, made the dye-sensitized solar cells of embodiment 9.
It to obtained dye-sensitized solar cells, operates similarly to Example 8, carries out dye-sensitized solar cells
Power generation performance evaluation and dye-sensitized solar cells 85 DEG C of heat resistant tests.Show the result in table 3.
(embodiment 10)
In the formation ＞ for containing the electrolyte of oxidant in ＜, electrolyte is made to contain iron chloride (III) 1mmol/L to replace
It is passed through oxygen into electrolyte, in addition to this, operates similarly with example 1, has made the dye sensitization of solar of embodiment 3
Battery.
It to obtained dye-sensitized solar cells, operates similarly to Example 8, carries out dye-sensitized solar cells
Power generation performance evaluation and dye-sensitized solar cells 85 DEG C of heat resistant tests.Show the result in table 3.
(comparative example 3)
In the formation ＞ for containing the electrolyte of oxidant in ＜, other than not being passed through oxygen into electrolyte, with implementation
Example 8 similarly operates, and has made the dye-sensitized solar cells of comparative example 3.
It to obtained dye-sensitized solar cells, operates similarly to Example 8, carries out dye-sensitized solar cells
Power generation performance evaluation and dye-sensitized solar cells 85 DEG C of heat resistant tests.Show the result in table 3.
(comparative example 4)
In the formation ＞ for containing the electrolyte of oxidant in ＜, other than not being passed through oxygen into electrolyte, with implementation
Example 9 similarly operates, and has made the dye-sensitized solar cells of comparative example 3.
It to obtained dye-sensitized solar cells, operates similarly to Example 8, carries out dye-sensitized solar cells
Power generation performance evaluation and dye-sensitized solar cells 85 DEG C of heat resistant tests.Show the result in table 3.
Table 3
As can be known from the results of Table 3：In embodiment 8~10, due to containing oxygen or chlorine as oxidant in the electrolytic solution
Change iron (III), therefore, the conservation rate of photoelectric conversion efficiency is higher.
On the other hand, it is known that：In comparative example 3 and 4, due to not containing oxidant in the electrolytic solution, opto-electronic conversion
The conservation rate of efficiency is relatively low.
Claims (19)
1. a kind of process for reactivation to electrode active material of dye-sensitized solar cells, is to dye sensitization of solar
The method of battery being re-activated to electrode active material, the dye-sensitized solar cells have by containing at least one
As the catalyst layer composition to electrode active material to electrode, this method includes above electroconductive polymer：
The electroconductive polymer is reoxidized by chemical oxidation or electrochemical oxidation.
2. the process for reactivation to electrode active material of dye-sensitized solar cells as described in claim 1, wherein institute
Chemical oxidation is stated by the way that the electroconductive polymer is impregnated in the solution dissolved with oxidant to implement.
3. the process for reactivation to electrode active material of dye-sensitized solar cells as described in claim 1, wherein institute
It states electrochemical oxidation and is impregnated in the solution containing supporting electrolyte by regarding the electroconductive polymer as working electrode, and is right
The working electrode applies given voltage to implement.
4. the process for reactivation to electrode active material of dye-sensitized solar cells as described in claim 1, wherein institute
It states catalyst layer and also contains photoacid generator, by generating acid to photoacid generator irradiation light, thus carry out the chemical oxidation.
5. the process for reactivation to electrode active material of dye-sensitized solar cells as described in claim 1, wherein institute
It states dye-sensitized solar cells and has the electrolyte containing at least one oxidant that can aoxidize electroconductive polymer, pass through
The oxidant carries out the chemical oxidation.
6. a kind of regeneration method of dye-sensitized solar cells is at least one for the catalyst layer to form structure paired electrode
The above electroconductive polymer is in the regeneration method of the dye-sensitized solar cells of reducing condition or neutral state, this method packet
It includes：
The electroconductive polymer having on electrode is reoxidized to described by chemical oxidation or electrochemical oxidation
Process.
7. a kind of catalyst layer, is the catalyst layer for dye-sensitized solar cells, the catalyst layer contains one kind
Above electroconductive polymer and photoacid generator.
8. catalyst layer as claimed in claim 7, wherein the electroconductive polymer is the thiophene that the following general formula (1) indicates
The polymer of compound,
In formula, R1And R2Separately indicate hydrogen atom, the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~4, carbon
Aryl, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano, amino, nitro or the sulfo group of atomicity 6 or 8, in R1And R2For
In the case of the alkyl or aryl, the alkyl or aryl is optionally bonded to thiphene ring via azo group or sulfonyl, in R1
And R2In the case of for the alkyl or alkoxy, the carbon atom of the end of the alkyl or alkoxy optionally bonds together and shape
Cyclization.
9. catalyst layer as claimed in claim 7, wherein the electroconductive polymer is the pyrroles that the following general formula (2) indicates
The polymer of compound,
In formula, R3And R4Separately indicate hydrogen atom, the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~4, carbon
Aryl, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano, amino, nitro or the sulfo group of atomicity 6 or 8, in R3And R4For
In the case of the alkyl or aryl, the alkyl or aryl is optionally bonded to pyrrole ring via azo group or sulfonyl, in R3
And R4In the case of for the alkyl or alkoxy, the carbon atom of the end of the alkyl or alkoxy optionally bonds together and shape
Cyclization.
10. catalyst layer as claimed in claim 7, wherein the electroconductive polymer is the aniline that the following general formula (3) indicates
The polymer of compound,
In formula, R5~R8Separately indicate hydrogen atom, the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~4, carbon
Aryl, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano, amino, nitro or the sulfo group of atomicity 6 or 8, in R5~R8For
In the case of the alkyl or aryl, the alkyl or aryl is optionally bonded to phenyl ring via azo group or sulfonyl, in R5With
R6Or R7And R8In the case of for the alkyl or alkoxy, the carbon atom of the end of the alkyl or alkoxy optionally key each other
It closes and forms ring.
11. the catalyst layer as described in any one of claim 7~10, wherein in the catalyst layer, (the light production
The gross mass of sour agent)/the ratio between (gross mass of the electroconductive polymer) be 0.01~10.
12. it is for dye-sensitized solar cells to electrode a kind of to electrode, it is described that there is shape on the surface to electrode
At the base material of the catalyst layer described in any one of claim 7~11.
13. a kind of dye-sensitized solar cells, has：The light to electrode, with sensitizing dyestuff described in claim 12
Electrode and electrolyte containing redox couple.
14. a kind of regeneration method of dye-sensitized solar cells is to constituting the electroconductive polymer of catalyst layer extremely
Dye-sensitized solar cells described in few claim 13 of the part in reducing condition or neutral state carries out regenerated
Method, this method include：
To photoacid generator irradiation light contained in the catalyst layer, to be reoxidized to the electroconductive polymer.
15. a kind of electrolyte, is used for dye-sensitized solar cells, contain：
Can making composition dye-sensitized solar cells, catalyst layer re-oxidation comprising electroconductive polymer at least one
Kind oxidant,
Occur in dye-sensitized solar cells redox reaction for making electric current flowing redox couple and
Solvent,
The oxidant is selected from the elementary gas group comprising oxygen, chlorine and bromine gas；Including iron chloride (III) hexahydrate,
Anhydrous ferric chloride (III), ferric nitrate (III) nonahydrate, anhydrous nitric acid iron and the inorganic acid group of ferric perchlorate (III)；Including
The organic acid group of dodecyl benzene sulfonic acid, toluenesulfonic acid, trifluoroacetic acid and propionic acid；And by chlordene metaantimmonic acid three (4- bromophenyls) ammonium
At least one of group of composition.
16. electrolyte as claimed in claim 15, wherein the oxidant is at least one in the inorganic acid group
Kind.
17. the electrolyte as described in claim 15 or 16, wherein in the oxidant in the elementary gas group
In the case of at least one, when electrolyte whole is set as 1L, the content of the oxidant is 1mg/L~50mg/L.
18. the electrolyte as described in claim 15 or 16, wherein in the oxidant be selected from the inorganic acid group and described
In the case of at least one of organic acid group, when electrolyte whole is set as 100 mass %, the content of the oxidant is
0.001 mass of mass %~10 %.
19. a kind of dye-sensitized solar cells has the electrolyte described in any one of claim 15~18, has half
The working electrode of conductor and to electrode,
The dyestuff that the working electrode contains the electrode layer being made of semiconductor and is adsorbed in the electrode layer,
The dye-sensitized solar cells is formed in the working electrode and the clamping electrolyte between electrode.
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| JP2013-260073 | 2013-12-17 | ||
| PCT/JP2014/072785 WO2015030193A1 (en) | 2013-08-30 | 2014-08-29 | Method for reactivating counter electrode active material for dye-sensitive solar cell, method for regenerating dye-sensitive solar cell in which said method is used, catalyst layer for dye-sensitive solar cell, counter electrode, electrolyte, and dye-sensitive solar cell |
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| TWI639261B (en) | 2016-12-22 | 2018-10-21 | 台灣染敏光電股份有限公司 | Dye-sensitized photovoltaic cell, module, and manufacturing method thereof |
| CN108231421B (en) * | 2016-12-22 | 2019-12-24 | 台湾染敏光电股份有限公司 | Dye-sensitized photovoltaic cell, dye-sensitized photovoltaic module, and method for manufacturing the same |
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| JP2582893B2 (en) * | 1989-03-31 | 1997-02-19 | 日立マクセル株式会社 | Organic electrolyte battery |
| JP3259751B2 (en) * | 1994-12-28 | 2002-02-25 | 日本電信電話株式会社 | Temperature difference battery |
| JP3560181B2 (en) * | 1995-04-13 | 2004-09-02 | 東洋紡績株式会社 | Electrode material for liquid flow type electrolytic cell |
| JP3428428B2 (en) * | 1998-04-03 | 2003-07-22 | 松下電器産業株式会社 | Negative electrode for non-aqueous electrolyte battery and method for producing the same |
| JP2002367860A (en) * | 2001-06-13 | 2002-12-20 | Matsushita Electric Ind Co Ltd | Electrolyte used for electrochemical rechargeable device, and electrochemical rechargeable device using the electrolyte |
| JP2003317814A (en) | 2002-04-24 | 2003-11-07 | Shozo Yanagida | Photovoltaic cell |
| JP2003313317A (en) | 2002-04-24 | 2003-11-06 | Shozo Yanagida | pi-CONJUGATED POLYMER SELF-SUPPORTING FILM, METHOD OF MANUFACTURING THE FILM, AND SOLAR CELL AND LAMINATE USING THE FILM |
| JP4938288B2 (en) * | 2005-11-04 | 2012-05-23 | エレクセル株式会社 | Dye-sensitized solar cell |
| JP5741599B2 (en) * | 2005-12-22 | 2015-07-01 | 三菱化学株式会社 | Lithium secondary battery and assembled battery connecting the same |
| WO2007125852A1 (en) * | 2006-04-25 | 2007-11-08 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Method for producing conductive polymer electrode and dye-sensitized solar cell comprising the conductive polymer electrode |
| JP5088863B2 (en) * | 2007-03-05 | 2012-12-05 | 日本カーリット株式会社 | Counter electrode for dye-sensitized solar cell and dye-sensitized solar cell including the same |
| JP5181173B2 (en) * | 2007-03-27 | 2013-04-10 | 国立大学法人 鹿児島大学 | Photoelectric storage battery and method for manufacturing optical storage electrode |
| JP2008266744A (en) * | 2007-04-23 | 2008-11-06 | Japan Carlit Co Ltd:The | Corrosion resistant conductive coating material, and its use |
| KR101518871B1 (en) * | 2008-03-20 | 2015-05-21 | 주식회사 동진쎄미켐 | Method of preparing the dye-sensitized solar cell |
| WO2010095650A1 (en) * | 2009-02-17 | 2010-08-26 | 綜研化学株式会社 | Complex conductive polymer composition, manufacturing method thereof, solution containing said composition, and applications for said composition |
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