CN105283936A - 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 - Google Patents
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 Download PDFInfo
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- CN105283936A CN105283936A CN201480030101.1A CN201480030101A CN105283936A CN 105283936 A CN105283936 A CN 105283936A CN 201480030101 A CN201480030101 A CN 201480030101A CN 105283936 A CN105283936 A CN 105283936A
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- electroconductive polymer
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- catalyst layer
- electrolyte
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- 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
- 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- KVMPQUTWRWVTQP-UHFFFAOYSA-N cyanatoboronic acid Chemical compound OB(O)OC#N KVMPQUTWRWVTQP-UHFFFAOYSA-N 0.000 description 1
- LSSYNNOILRNWCJ-UHFFFAOYSA-N diphenyl-(2,4,6-trimethylphenyl)sulfanium Chemical compound CC1=CC(C)=CC(C)=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 LSSYNNOILRNWCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000013007 heat curing Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance 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
- 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
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 229950004288 tosilate Drugs 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
The present invention addresses the problem of providing: a method for reactivating a counter electrode active material for a dye-sensitive solar cell capable of preventing a decrease in the power generation performance of a dye-sensitive solar cell, the method for reactivating a counter electrode active material allowing the temporarily decreased power generation performance of the dye-sensitive solar cell to be restored to the initial performance by regenerating an electroconductive polymer reduced by a redox pair in an electrolyte in the dye-sensitive solar cell; a method for regenerating a dye-sensitive solar cell in which said method is used; a catalyst layer for a dye-sensitive solar cell; a counter electrode; an electrolyte; and a dye-sensitive solar cell. The present invention is a method for reactivating a counter electrode active material for a dye-sensitive solar cell having a counter electrode configured from a catalyst layer that contains at least one electroconductive polymer as the counter electrode active material, wherein the method for reactivating a counter electrode active material for a dye-sensitive solar cell includes re-oxidizing the electroconductive polymer by chemical or electrochemical oxidation.
Description
Technical field
The renovation process of the process for reactivation to electrode active material that the present invention relates to a kind of DSSC and the DSSC applying the method, the catalyst layer of used by dye sensitization solar battery, to electrode, electrolyte and DSSC.
The application to advocate based on August 30th, 2013 in No. 2013-179849, the Japanese Patent Application of Japanese publication and on December 17th, 2013, in the priority of No. 2013-260073, the Japanese Patent Application of Japanese publication, to quote its content at this.
Background technology
In recent years, can utilize photovoltaic effect that luminous energy is directly converted to electric power and originate as the clean electric power generation of not discharging the polluters such as carbon dioxide, solar cell receives much concern.In solar cells, dye-sensitized solar cell has high conversion efficiency, can be manufactured, and raw material unit price is cheap by fairly simple method, therefore, is expected to as solar cell of new generation.
Usually known DSSC is the DSSC of so-called Graetzel type.(following in the DSSC of Graetzel type, referred to as DSSC) in, when light is irradiated to the sensitizing dyestuff on the surface being adsorbed in metal-oxide semiconductor (MOS) particle, electronics moves to optoelectronic pole, nesa coating, external circuit successively from sensitizing dyestuff, thus, it can be used as electric current and utilize (with reference to non-patent literature 1).On the other hand, the sensitizing dyestuff discharging electronics is reduced by accepting electronics from the redox couple in electrolyte.Consequently, the redox couple in electrolyte is oxidized, is then reduced by the catalyst layer of structure paired electrode.
As the catalyst layer to electrode forming existing DSSC, widely use platinum layer.This is because the catalyst ability of platinum to redox reaction is higher, and stability and conductivity higher.
As the formation method of the platinum layer of structure paired electrode, such as, have and on the base material such as glass substrate, metallic plate, be coated with platinum acid chloride solution and carry out the method for heat treated or carried out the method for film forming by vacuum evaporation, sputtering etc.
Platinum has advantage as above, on the other hand, because platinum is expensive noble metal, therefore has the problem of the manufacturing cost increasing DSSC.Therefore, the material of the raw catelyst layer replacing platinum is being studied.Such as in non-patent literature 2 and patent documentation 1,2, disclose a kind of DSSC, it is using electroconductive polymers such as polythiophene, polyaniline, polypyrroles as the material of catalyst layer.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-313317 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-317814 publication
Non-patent literature
Non-patent literature 1: " nature (Nature), " (Britain), 1991,353, p.737-740
Non-patent literature 2: " electrochemistry (Electrochemistry), " 2003,71,11, p.944-946
Summary of the invention
The problem that invention will solve
For employing the DSSC of above-mentioned electroconductive polymer, the deterioration of power generation performance (photoelectric conversion efficiency) can be there is significantly.This is because, redox couple (the such as I in electrolyte
-, Br
-deng) electroconductive polymer is reduced to neutral state (dedoping state) from the state of oxidation (dopant states), thus cause catalyst activity, conductivity to reduce.
The present invention is the invention completed in view of the foregoing, its problem is the process for reactivation to electrode active material providing a kind of DSSC, and apply the renovation process of DSSC of the method, the catalyst layer of used by dye sensitization solar battery, to electrode, electrolyte and DSSC, described DSSC the process for reactivation of electrode active material is comprised: by regenerating by the electroconductive polymer of the redox couple reduction in the electrolyte of DSSC, the power generation performance of temporarily-depressed DSSC can be returned to initial performance, or the reduction of the power generation performance of DSSC can be prevented.
For solving the technical scheme of problem
The present inventor etc. conduct in-depth research, found that: have by containing electroconductive polymer more than at least one as the catalyst layer of electrode active material is formed in the DSSC of electrode, by above-mentioned electroconductive polymer being carried out chemical oxidation or electrochemical oxidation and reoxidizing, above-mentioned problem can be solved.The present invention is completed based on above-mentioned opinion.
Below, in order to make easy understand of the present invention, enumerate basic feature of the present invention and preferred various mode.
The process for reactivation to electrode active material of a < 1 > DSSC, it is the method for electrode active material being carried out to reactivation to DSSC, described DSSC have by containing electroconductive polymer more than at least one as the catalyst layer of electrode active material is formed to electrode, the method comprises:
By chemical oxidation or electrochemical oxidation, described electroconductive polymer is reoxidized.
The process for reactivation to electrode active material of the DSSC of < 2 > as described in above-mentioned < 1 >, wherein, described chemical oxidation is implemented by described electroconductive polymer being impregnated in the solution being dissolved with oxidant.
The process for reactivation to electrode active material of the DSSC of < 3 > as described in above-mentioned < 1 >, wherein, described electrochemical oxidation by described electroconductive polymer be impregnated in solution containing supporting electrolyte as work electrode, and is implemented the voltage that described work electrode applies regulation.
The process for reactivation to electrode active material of the DSSC of < 4 > as described in above-mentioned < 1 >, wherein, described catalyst layer is also containing photoacid generator, producing acid by irradiating light to photoacid generator, carrying out described chemical oxidation thus.
The process for reactivation to electrode active material of the DSSC of < 5 > as described in above-mentioned < 1 >, wherein, described DSSC possesses the electrolyte of the oxidant that can be oxidized electroconductive polymer containing at least one, carries out described chemical oxidation by described oxidant.
The renovation process of a < 6 > DSSC, it is the renovation process that the above electroconductive polymer of at least one of the catalyst layer forming structure paired electrode is in the DSSC of reducing condition or neutral state, and the method comprises:
By chemical oxidation or electrochemical oxidation to the described operation reoxidized the described electroconductive polymer that electrode has.
< 7 > catalyst layer, it is the catalyst layer for DSSC, it is characterized in that, described catalyst layer contains more than one electroconductive polymer and photoacid generator.
The catalyst layer of < 8 > as described in above-mentioned < 7 >, wherein, described electroconductive polymer is the polymer of the thiophene compound that following general formula (1) represents.
[chemical formula 1]
[in formula, R
1and R
2separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro or sulfo group, at R
1and R
2when for described alkyl or aryl, described alkyl or aryl can be bonded to thiphene ring, at R via azo group or sulfonyl
1and R
2when for described alkyl or alkoxyl, the carbon atom of the end of described alkyl or alkoxyl can bond together and form ring.]
The catalyst layer of < 9 > as described in above-mentioned < 7 >, wherein, described electroconductive polymer is the polymer of the azole compounds that following general formula (2) represents.
[chemical formula 2]
[in formula, R
3and R
4separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro or sulfo group, at R
3and R
4when for described alkyl or aryl, described alkyl or aryl can be bonded to pyrrole ring, at R via azo group or sulfonyl
3and R
4when for described alkyl or alkoxyl, the carbon atom of the end of described alkyl or alkoxyl can bond together and form ring.]
The catalyst layer of < 10 > as described in above-mentioned < 7 >, wherein, described electroconductive polymer is the polymer of the aniline compound that following general formula (3) represents.
[chemical formula 3]
[in formula, R
5~ R
8separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro or sulfo group, at R
5~ R
8when for described alkyl or aryl, described alkyl or aryl can be bonded to phenyl ring, at R via azo group or sulfonyl
5and R
6, or R
7and R
8when for described alkyl or alkoxyl, the carbon atom of the end of described alkyl or alkoxyl can bond together and form ring.]
The catalyst layer of < 11 > according to any one of above-mentioned < 7 > ~ < 10 >, wherein, in described catalyst layer, the ratio of (gross mass of described photoacid generator)/(gross mass of described electroconductive polymer) is 0.01 ~ 10.
< 12 > mono-kind is to electrode, its be for DSSC to electrode, it is characterized in that, described have the base material defining the catalyst layer according to any one of above-mentioned < 7 > ~ < 11 > on surface to electrode.
< 13 > DSSC, it possesses: described in above-mentioned < 6 > to electrode, have sensitizing dyestuff optoelectronic pole and containing the electrolyte of redox couple.
The renovation process of a < 14 > DSSC, it is the method regenerated the DSSC described in above-mentioned < 13 > being in reducing condition or neutral state at least partially of the electroconductive polymer forming catalyst layer, and the method comprises:
Light is irradiated to photoacid generator contained in this catalyst layer described, thus described electroconductive polymer is reoxidized.
< 15 > electrolyte, is characterized in that, described electrolyte contains the oxidant that at least one can be oxidized electroconductive polymer.
The electrolyte of < 16 > as described in above-mentioned < 15 >, is characterized in that, described oxidant is be selected from the elementary gas group comprising oxygen, chlorine and bromine gas; Comprise the inorganic acid group of iron chloride (III) hexahydrate, anhydrous ferric chloride (III), ferric nitrate (III) nonahydrate, anhydrous nitric acid iron and ferric perchlorate (III); Comprise the organic acid group of DBSA, toluenesulfonic acid, trifluoroacetic acid and propionic acid; And at least one in the group to be made up of chlordene metaantimmonic acid three (4-bromophenyl) ammonium.
The electrolyte of < 17 > as described in above-mentioned < 16 >, is characterized in that, described oxidant is be selected from least one in described inorganic acid group.
The electrolyte of < 18 > according to any one of above-mentioned < 15 > ~ < 17 >, it is characterized in that, be when being selected from least one in described elementary gas group at described oxidant, when electrolyte entirety is set to 1L, the content of described oxidant is 1mg/L ~ 50mg/L.
The electrolyte of < 19 > according to any one of above-mentioned < 15 > ~ < 17 >, it is characterized in that, be when being selected from least one in described inorganic acid group and described organic acid group at described oxidant, when electrolyte entirety is set to 100 quality %, the content of described oxidant is 0.001 quality % ~ 10 quality %.
< 20 > DSSC, it possesses electrolyte according to any one of described < 15 > ~ < 19 >, have the work electrode of semiconductor and to electrode, it is characterized in that
Described work electrode contains the electrode layer be made up of semiconductor and the dyestuff being adsorbed in this electrode layer,
Described DSSC described work electrode and described to electrode between clamp electrolyte and formed.
The effect of invention
According to the process for reactivation to electrode active material of DSSC of the present invention, be reoxidized by chemical oxidation or electrochemical oxidation by the electroconductive polymer be reduced with electrolyte contacts, become the state of oxidation with positive charge.That is, be in electroconductive polymer the state that there is hole, electroconductive polymer is regenerated, the catalyst activity of the catalyst layer containing electroconductive polymer and conductivity can be made thus to recover or prevent it from reducing.
In addition, according to apply the renovation process of DSSC of the present invention of above-mentioned method, used by dye sensitization solar battery catalyst layer, to electrode, electrolyte and DSSC, can the catalyst activity of catalyst layer as above and the recovery of conductivity be realized by various method or prevent it from reducing.
Accompanying drawing explanation
Fig. 1 illustrates the profile had by the DSSC to electrode of the catalyst layer structure comprising electroconductive polymer.
Fig. 2 is the profile of the renovation process of DSSC for illustration of the 2nd aspect of the present invention.
Fig. 3 is the profile of the renovation process of DSSC for illustration of the 2nd aspect of the present invention.
Fig. 4 A is the figure for illustration of the formation method to electrode in embodiment 1, is the schematic diagram that the subtend base material defined conductive film is shown.
Fig. 4 B is the figure for illustration of the formation method to electrode in embodiment 1, is that the schematic diagram to electrode is shown.
Fig. 5 is the schematic diagram for illustration of the method for reducing to electrode in embodiment 1.
Fig. 6 A is the figure of the DSSC illustrated in embodiment 1, be illustrate have impregnated in gamma-butyrolacton solution before the schematic diagram of the DSSC to electrode of (0 hour).
Fig. 6 B is the figure of the DSSC illustrated in embodiment 1, is the schematic diagram with the dipping DSSC to electrode of 100 hours in gamma-butyrolacton solution is shown.
Fig. 6 C is the figure of the DSSC illustrated in embodiment 1, is the schematic diagram with the dipping DSSC to electrode of 300 hours in gamma-butyrolacton solution is shown.
Fig. 6 D is the figure of the DSSC illustrated in embodiment 1, is the schematic diagram with the dipping DSSC to electrode of 500 hours in gamma-butyrolacton solution is shown.
Fig. 7 is the schematic diagram for illustration of the reoxidation process to electrode in embodiment 1.
Fig. 8 be in embodiment 1 impregnated in gamma-butyrolacton solution before (0 hour) to electrode, flood in gamma-butyrolacton solution 500 hours to electrode and in acetonitrile solution, flood the photo to electrode of 5 minutes thereafter.
Fig. 9 is the schematic diagram for illustration of the reoxidation process to electrode in embodiment 2.
Figure 10 is the constructed profile possessing catalyst layer of the present invention and the DSSC to electrode.
Symbol description
10,10A, 10B, 10C, 10D, 10E, 10F, 10G: DSSC
12: to electrode
18: electroconductive polymer catalyst layer (catalyst layer)
Embodiment
Below, with reference to accompanying drawing, various execution mode of the present invention is described.It should be noted that, the accompanying drawing used in the following description is schematic, and the ratio etc. of length, width and thickness is not limited to identical with the ratio of reality, can suitably change.
" process for reactivation to electrode active material "
The DSSC of the 1st aspect of the present invention be the method for electrode active material being carried out to reactivation to having the DSSC to electrode be made up of the catalyst layer comprising the above electroconductive polymer of at least one to the process for reactivation of electrode active material.Illustrate DSSC to the process for reactivation of electrode active material before, the structure with the DSSC 10 to electrode be made up of the catalyst layer comprising electroconductive polymer is described with reference to Fig. 1.
It should be noted that, the structure of the DSSC 10 shown in Fig. 1 can apply the activation method to electrode active material of DSSC of the present invention and apply renovation process, the catalyst layer of used by dye sensitization solar battery, an example to the structure of electrode, electrolyte and DSSC of DSSC of the method.Namely, the DSSC applying various mode of the present invention as above is not limited to the structure of the DSSC 10 illustrated in Fig. 1, also can have and connect multiple and structure that is that formed using DSSC 10 as element cell at Width (the W direction namely shown in Fig. 1).
As shown in Figure 1, DSSC 10 at least possess that work electrode 11 and work electrode 11 subtend configure to electrode 12, form between work electrode 11 with to the electrolyte 20 between electrode 12.The side of electrolyte 20 is sealed by encapsulant 21.
Not shown external circuit is connected with at work electrode 11 with on electrode 12.
Below, each inscape is described successively.
Work electrode 11 is the electrode sequentially laminated with transparent base 13, nesa coating 14 and optoelectronic pole 15.
Transparent base 13 becomes the base station of nesa coating 14 and optoelectronic pole 15, is made up of the light transmissive material that irradiation can be made in optoelectronic pole 15.As this material, can enumerate such as: the resins such as the glass such as soda-lime glass, pyrex, quartz glass, pyrex, Vycor glass, alkali-free glass, blue color plane glass and white plate glass or PETG (PET), PEN (PEN), acrylic resin, Merlon, polyimides.
Nesa coating 14 is formed on a plate face of transparent base 13 by sputtering method, print process.Nesa coating 14 can use such as: tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), aluminium-doped zinc oxide (AZO), antimony-doped 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 DSSC, as the semiconducting compound forming optoelectronic pole, known metal oxide can be enumerated, there is the compound etc. of perovskite crystalline, can multiple compounds be selected to use from these compounds.As metal oxide, can titanium oxide, zinc oxide etc. be enumerated, as the compound with perovskite crystalline, can CH be enumerated
3nH
3pbX
3(X is halogen atom) etc.Not shown semiconducting compound can be particle shape.For semiconducting compound, sensitizing dyestuff can be made to support and to form in semiconducting compound.As metal-oxide semiconductor (MOS) particle, from the viewpoint of forming nano level porous layer and very large surface area compared with the surface area of lower floor can being obtained, preferential oxidation titanium (TiO
2) particle.
Sensitizing dyestuff discharges electronics by the light irradiated in optoelectronic pole 15.The electronics of release is received by metal-oxide semiconductor (MOS) particle and successfully moves to nesa coating 14, exports not shown external circuit to.As mentioned above, discharging the sensitizing dyestuff of electronics as the light by irradiating, can enumerate such as: the organic pigment that ruthenium complex, anthocyanin, chlorophyll are such.Wide and the light activated life-span is long, the electronic stability that received by the porous layer be made up of metal-oxide semiconductor (MOS) particle from the viewpoint of the wave-length coverage absorbed, as sensitizing dyestuff, preferred ruthenium complex.Ruthenium complex has such as: cis-two (thiocyano)-bis-(2,2'-bipyridyl-4,4'-dicarboxylic acids) ruthenium (II), these cis-two (thiocyano)-bis-(2,2'-bipyridyl-4,4'-dicarboxylic acids) two 4-butyl ammoniums (hereinafter referred to as N719) etc. of ruthenium (II).
Be lamination subtend base material 16, electrode that conductive film 17 and electroconductive polymer catalyst layer 18 (catalyst layer) formed successively to electrode 12.
Subtend base material 16 becomes the base station to conductive film 17 and electroconductive polymer catalyst layer 18, in a thickness direction configuration spaced apart with transparent base 13.As the material of subtend base material 16, the glass identical with transparent base 13, resin etc. can be enumerated, be not particularly limited.
Conductive film 17 is formed on a plate face of subtend base material 16 by sputtering method, print process.Can use such as on conductive film 17: tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), aluminium-doped zinc oxide (AZO), antimony-doped tin oxide (ATO), indium oxide/zinc oxide (IZO), Ga-doped zinc oxide (GZO) etc.It should be noted that, preferably formed conductive film 17 on electrode 12, but also can omit conductive film 17.
In addition, transmitance be need not be to conductive film 17, in addition to the foregoing materials, as the material formed conductive film 17, the metals such as titanium, aluminium, nickel, chromium, gold, silver, copper can also be used.
Electroconductive polymer catalyst layer 18 is formed on the face of the opposition side in the face connected with subtend base material 16 to conductive film 17, configures in the mode opposed with optoelectronic pole 15 across electrolyte 20.In addition, electroconductive polymer catalyst layer 18, containing electroconductive polymer more than at least one, reduces to redox couple contained in electrolyte 20.As electroconductive polymer contained in electroconductive polymer catalyst layer 18, can enumerate such as: polythiophene, polyaniline, polypyrrole, poly-(3,4-ethylene dioxythiophene) (PEDOT) etc.Electroconductive polymer can be any one in these materials, also can be mixed with two or more materials.Electroconductive polymer is made before DSSC 10 to be in the state of oxidation with positive charge in advance manufacturing.In addition, also can containing, for example the conductive material beyond the such electroconductive polymer of the material with carbon elements such as carbon nano-tube in electroconductive polymer catalyst layer 18.In addition, as the object lesson of electroconductive polymer, relevant to the catalyst layer of the 3rd aspect of the present invention, the polymer of the aniline compound that the polymer of the azole compounds that the polymer of the thiophene compound that the general formula (1) described after can enumerating represents, general formula (2) represent and general formula (3) represent.
As the amount of electroconductive polymer contained in electroconductive polymer catalyst layer 18, be preferably more than 10 quality %, be more preferably more than 20 quality %, be particularly preferably more than 30 quality %.
The thickness of catalyst layer 18 is not particularly limited, and when it was thin catalyst layer, there is the hidden danger that can not play sufficient catalytic performance, and is therefore such as preferably more than 0.001 μm.The upper limit of the thickness of catalyst layer 18 is not particularly limited, and is uneconomic, is therefore generally less than 10 μm when it is blocked up.
Catalyst layer 18 both can be fine and close layer, also can be porous layer.When it is porous layer, increase with the contact area of electrolyte 20, therefore, it is possible to improve the catalytic performance of catalyst layer 18.
As the method forming fine and close catalyst layer 18, can enumerate such as: the solution coat containing electroconductive polymer is made the method for its drying, under making conductive film 17 to be impregnated in the state in the solution of the monomer containing electroconductive polymer, executes alive electrolysis polymerization method etc. on the surface to conductive film 17.
As the method for catalyst layer 18 forming porous, can enumerate such as: induce phase separation method etc. by electrolysis polymerization the method high molecular method of coating conducting, poor solvent of adding poor solvent in containing the solution of electroconductive polymer on the surface of the porous body of electrically conductive microparticle.
Electrolyte 20 is injected into by work electrode 11, the space that surrounds electrode 12 and encapsulant 21, is the solution containing occurring for the redox couple of the redox reaction of energising in DSSC 10.As this redox couple, can enumerate such as: iodine and iodate dimethyl propyl imidazoles
, the iodide salt such as lithium iodide combination (iodide ion (I
-)/teriodide ion (I
3 -)), bromine and bromination dimethyl propyl imidazoles
, the bromide salt such as lithium bromide combination (bromide ion (Br
-)/tribromide ion (Br
3 -)).As the solvent of electrolyte 20, can enumerate such as: lactone nonaqueous solvents, the ethylmethylimidazolium such as the nitrile such as acetonitrile, propionitrile nonaqueous solvents, gamma-butyrolacton, gamma-valerolactone
four cyano borate or ethylmethylimidazolium
cdicynanmide plasma liquid.In addition, electrolyte 20 can by polyacrylonitrile isogel agent by gelation.
The concentration of above-mentioned halogen in electrolyte 20 is preferably 1 ~ 500mM, is more preferably 5 ~ 300mM, is particularly preferably 10 ~ 200mM.The concentration of above-mentioned halide salts in electrolyte 20 is preferably 0.1 ~ 10M, is more preferably 0.2 ~ 5M, is particularly preferably 0.5 ~ 3M.
In addition, above-mentioned halogen and the mol ratio of halide salts are preferably 1 ︰ 1 ~ 1 ︰ 1000, are more preferably 1 ︰ 5 ~ 1 ︰ 500, are particularly preferably 1 ︰ 10 ~ 1 ︰ 200.
As the material of encapsulant 21, the mixture etc. of such as light-cured resin and heat-curing resin can be enumerated.
In DSSC 10, when " generating light " is incident from the direction of the arrow shown in Fig. 1, the sensitizing dyestuff of optoelectronic pole 15 absorbs light, electronics is released into metal-oxide semiconductor (MOS) particle and is in the state of oxidation.D/d electronics moves and arrives nesa coating 14 in the porous layer be made up of metal-oxide semiconductor (MOS) particle.Then, the circuit of electronics by being connected with work electrode 11, move to via external circuit to electrode 12 to conductive film 17 or electroconductive polymer catalyst layer 18.On the other hand, the redox couple of oxidized sensitizing dyestuff contained by from electrolyte 20 accepts electronics and is reduced.In addition, redox couple is oxidized and move to conductivity polymer catalyst layer 18 side, is reduced by electroconductive polymer contained in electroconductive polymer catalyst layer 18.The redox reaction such by lasting repetition and electric current is flowed in DSSC 10.
Under the initial condition of DSSC 10, electroconductive polymer contained in electroconductive polymer catalyst layer 18 is made to be in the state of oxidation.On the other hand, after manufacture, in DSSC 10, by the contact with the redox couple in electrolyte 20, the electroconductive polymer that electroconductive polymer catalyst layer 18 possesses is reduced, and is in uncharged neutral state or electronegative reducing condition.The electroconductive polymer being in this neutral state or reducing condition can not play catalytic performance and conductivity, and therefore along with reduction is carried out, battery performance reduces.
Below, the process for reactivation of electrode active material is described to the DSSC of first method of the present invention.
The process for reactivation to electrode active material of DSSC of the present invention is that the electroconductive polymer contained in the electroconductive polymer catalyst layer 18 of DSSC 10 is (following, referred to as electroconductive polymer) due to DSSC 10 long use wait and be reduced time, method electroconductive polymer reoxidized by chemical oxidation or electrochemical oxidation.It should be noted that, said in the present invention " reactivation " refers to: after the manufacture of DSSC 10, after certain hour, make the carrying out of the reduction of the electroconductive polymer due to electroconductive polymer catalyst layer 18 and the described of DSSC 10 that power generation performance is reduced keeps the power generation performance of battery to electrode regeneration or by being reoxidized successively by the electroconductive polymer be reduced in electroconductive polymer catalyst layer 18 by reoxidizing of described electroconductive polymer.
Below, be described respectively to method electroconductive polymer reoxidized by chemical oxidation and by the method that electrochemical oxidation reoxidizes.
The method > that electroconductive polymer is reoxidized by chemical oxidation by <
Here, the example reoxidized by electroconductive polymer by flooding electroconductive polymer in the solution being dissolved with oxidant is described.The time of flooding electroconductive polymer in the solution being dissolved with oxidant such as can be set to 1 minute ~ about 10 minutes.
As long as oxidant does not damage the characteristic of electroconductive polymer and can make the material that electroconductive polymer is oxidized.As such material, can enumerate such as: organic acid and chlordene metaantimmonic acid three (4-bromophenyl) ammoniums such as the sulfonic acid such as inorganic compound, DBSA, toluenesulfonic acid, trifluoroacetic acid, propionic acid such as iron chloride (III), iron chloride (III) hydrate.From the viewpoint of to the dissolubility of general solvent is higher and oxidation is higher, as oxidant, preferably use iron chloride (III), iron chloride (III) hydrate.
As the solvent of oxidant, can enumerate can dissolved oxidant and do not make the solvent of electroconductive polymer catalyst layer 18 stripping be made up of electroconductive polymer, such as, can use the miscellaneous organic solvents such as acetonitrile, ethanol, acetone, toluene.
In the method, can directly be coated with the solution being dissolved with oxidant on electroconductive polymer, solution also can be made to evaporate and make it contact with steam.
In addition, also can by using containing the catalyst layer of photoacid generator, and illumination is carried out to above-mentioned photoacid generator penetrate and produce acid, carry out above-mentioned chemical oxidation thus.About the concrete structure of above-mentioned catalyst layer and material and light-struck method, the catalyst layer in conjunction with the 3rd aspect of the present invention describes later.
In addition, the electrolyte containing at least one oxidant that can be oxidized electroconductive polymer can also be used, utilize above-mentioned oxidant to carry out above-mentioned chemical oxidation.About composition and the operable oxidant of above-mentioned electrolyte, the electrolyte in conjunction with the 7th aspect of the present invention describes later.
The method > that electroconductive polymer is reoxidized by electrochemical oxidation by <
Here, to by electroconductive polymer be impregnated in solution containing supporting electrolyte as work electrode, and given voltage is applied to this work electrode, thus the example that electroconductive polymer reoxidizes is described.
The time that electroconductive polymer be impregnated in the solution containing supporting electrolyte can be such as 1 minute ~ about 10 minutes.For the given voltage putting on work electrode, preferably consider the material of reference electrode and set.When the material of reference electrode is silver, the voltage putting on work electrode can be set to such as-1.0V ~ 1.0V.
Supporting electrolyte for be easily dissolved in general solvent, and gives the material of enough ionic conductivities to solvent.As such material, can enumerate such as: the trifluoro-methanyl sulfonates such as the tetrafluoroborates such as the perchlorate such as tetraethyl ammonium perchlorate, tetrabutylammonium perchlorate, tetraethyl ammonium tetrafluoroborate and two (trifluoromethane sulfonyl group) imide li.
As the solvent of supporting electrolyte, can use and can dissolve supporting electrolyte, and do not make the solvent of electroconductive polymer catalyst layer 18 stripping be made up of electroconductive polymer, such as can use acetonitrile, propene carbonate, gamma-butyrolacton, carrene, methyl alcohol etc.
By implementing " method reoxidized by electroconductive polymer by chemical oxidation " or " method reoxidized by electroconductive polymer by electrochemical oxidation " of above-mentioned explanation, the electroconductive polymer that can be reduced long-time use due to DSSC 10 etc. regenerates.
" renovation process of DSSC "
Then, be described with reference to the renovation process of Fig. 2 and Fig. 3 to the DSSC of second method of the present invention.
The renovation process of DSSC of the present invention is the renovation process that the above electroconductive polymer of at least one of the electroconductive polymer catalyst layer 18 of the structure paired electrode 12 formed as shown in Figure 1 is in the DSSC 10 of reducing condition or neutral state.That is, the renovation process of DSSC of the present invention possesses and carries out by chemical oxidation or electrochemical oxidation to the electroconductive polymer of major general's electroconductive polymer catalyst layer 18 operation that reoxidizes.Here, to except possessing the operation that reoxidized by electroconductive polymer, also possess and take out the operation of electrode 12 from DSSC 10 and use the renovation process to electrode 12 assembles the DSSC of the operation of DSSC 10 to be again described.
Below, each operation is described.
< takes out the operation > to electrode from DSSC
As shown in Figure 2, encapsulant 21 is cut into two encapsulants 21A, 21B on thickness direction, takes out electrode 12 from DSSC 10.
The operation > that the electroconductive polymer possessed electrode is reoxidized by chemical oxidation or electrochemical oxidation by <
In this operation, to the electroconductive polymer of the electroconductive polymer catalyst layer 18 to electrode 12 forming DSSC 10 implement the DSSC of the invention described above first method to " method electroconductive polymer reoxidized by chemical oxidation " or " method electroconductive polymer reoxidized by electrochemical oxidation " in the process for reactivation of electrode active material.Omit the explanation of each method.By this operation, by possess electrode 12 and the electroconductive polymer being in reducing condition or neutral state is reoxidised into the state of oxidation, make the catalytic activity of electroconductive polymer and conductivity return to initial performance.
< uses operation > electrode being assembled again to DSSC
Next, as shown in Figure 3, make to possess the electroconductive polymer be reoxidized to the electroconductive polymer catalyst layer 18 of electrode 12 and the optoelectronic pole 15 of work electrode 11 opposed, separate given interval configuration to electrode 12 relative to work electrode 11, by heat treatment etc., encapsulant 21A, 21B are engaged.Then, the hand-hole 22 for injecting electrolyte 20 is formed in a part for encapsulant 21.
It should be noted that, hand-hole 22 can be formed in the part to electrode 12 as the illustrated by dashed lines of Fig. 3.Then, electrolyte 20 is injected from hand-hole 22 to by work electrode 11, the space S of surrounding and being formed electrode 12 and encapsulant 21.By this operation, use and DSSC 10 can be assembled again electrode 12.
By above operation, the electroconductive polymer that can obtain more than at least one of the electroconductive polymer catalyst layer 18 by forming structure paired electrode 12 carries out the DSSC 10 reoxidized.
As described above, first method of the present invention DSSC in the process for reactivation of electrode active material, by chemical oxidation or electrochemical oxidation, the electroconductive polymer of DSSC 10 is reoxidized, described DSSC 10 have by the electroconductive polymer catalyst layer 18 of the electroconductive polymer comprising more than at least one form to electrode 12.
Thus, can be made because DSSC 10 long-time uses etc. by chemical oxidation or electrochemical oxidation that the electroconductive polymer that is reduced is in the state of oxidation, namely there is the state in hole with positive charge, thus can regenerate.Consequently, the catalytic activity of the catalyst layer containing electroconductive polymer and conductivity can be returned to electroconductive polymer be reduced before initial performance.
First method of the present invention DSSC in the process for reactivation of electrode active material, when by electroconductive polymer being impregnated in the solution that is dissolved with oxidant and implementing chemical oxidation, from electroconductive polymer, electronics is captured by the oxidant in solution, and oxidant is reduced, electroconductive polymer is oxidized.Therefore, can by room temperature process simply by electroconductive polymer regenerate, the catalytic activity of electroconductive polymer catalyst layer and conductivity are returned to electroconductive polymer be reduced before initial condition.
First method of the present invention DSSC in the process for reactivation of electrode active material, by electroconductive polymer be impregnated in solution containing supporting electrolyte as work electrode, and when given voltage being applied to implement electrochemical oxidation to work electrode after flooding reference electrode, auxiliary electrode, the oxidation reaction that electronics is caused by capturing is there is at work electrode place, accept electronics at auxiliary electrode place and the reduction reaction caused, the electroconductive polymer as work electrode is oxidized.Therefore, electroconductive polymer can be regenerated, the catalytic activity of electroconductive polymer catalyst layer and conductivity can be returned to electroconductive polymer be reduced before initial performance.
In addition, the renovation process of DSSC of the present invention comprises the operation reoxidized by the electroconductive polymer of the electroconductive polymer catalyst layer 18 forming structure paired electrode 12 by chemical oxidation or electrochemical oxidation.
Thus, can will to be used because of DSSC 10 long-time etc. by the chemical oxidation of above-mentioned explanation or electrochemical oxidation and the electroconductive polymer of the electroconductive polymer catalyst layer 18 to electrode 12 that is reduced reoxidizes, catalyst activity and the conductivity of electroconductive polymer catalyst layer 18 can be improved.
Therefore, by making the electroconductive polymer of electroconductive polymer catalyst layer 18 reduce, the power generation performance of the DSSC 10 that power generation performance can be reduced reliably returns to initial performance, DSSC 10 can be regenerated.Consequently, long life between the operating period that can make DSSC 10.
It should be noted that, when using the above-mentioned catalyst layer containing photoacid generator, light-struck easy method (6th aspect of the present invention) can be carried out by not decomposing DSSC 10 to the catalyst layer of structure paired electrode and power generation performance is recovered.
In addition, when using the above-mentioned electrolyte containing oxidant, when using DSSC 10, progressively the electroconductive polymer be reduced is reoxidized by utilizing oxidant contained in electrolyte, the reduction of the power generation performance of battery can be prevented, therefore, usually do not need to implement renovation process as above.
" catalyst layer "
The catalyst layer of Third Way of the present invention is the catalyst layer of used by dye sensitization solar battery, is containing more than one electroconductive polymer and the catalyst layer of photoacid generator.
As the mode of catalyst layer, the mode such as on the surface being formed at conductive board can be enumerated.This catalyst layer both can be fine and close layer, also can be porous layer.In addition, the thickness of catalyst layer is not particularly limited, such as, can be set as 0.001 μm ~ 10 μm.
(electroconductive polymer)
As the electroconductive polymer forming described catalyst layer, as long as redox couple supply electronics that can be contained in electrolyte is just not particularly limited, such as, known electroconductive polymer as above can be applied in conjunction with the process for reactivation to electrode active material of first method of the present invention.
Electroconductive polymer is preferably selected from least one in the polymer of the polymer of thiophene compound, the polymer of azole compounds and aniline compound.
As the polymer of thiophene compound, the compound that thiophene compound that such as following general formula (1) represents is polymerized can be enumerated.
[chemical formula 4]
[in formula, R
1and R
2separately represent that ((R' represents the alkyl of carbon number 1 ~ 8 to R'OOC-for the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group.)), aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro or sulfo group.R
1and R
2during for abovementioned alkyl or aryl, abovementioned alkyl or aryl can be bonded to thiphene ring via azo group or sulfonyl.At R
1and R
2during for abovementioned alkyl or alkoxyl, the carbon atom of the end of abovementioned alkyl or alkoxyl can bond together and form ring.]
Abovementioned alkyl is preferably straight-chain or branched-chain alkyl, is more preferably straight-chain alkyl.
The carbon number of abovementioned alkyl is preferably 1 ~ 8, is more preferably 1 ~ 5, and more preferably 1 ~ 3.
As above-mentioned alkoxyl, be preferably methoxyl group, ethyoxyl, propoxyl group, butoxy, be more preferably methoxy or ethoxy.
As above-mentioned aryl, can enumerate: phenyl, benzyl, tolyl, naphthyl etc.
As above-mentioned halogen atom, can enumerate: fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.
As the object lesson of the thiophene compound that above-mentioned general formula (1) represents, the compound that following formula (1-1) ~ (1-4) represents can be enumerated.
[chemical formula 5]
In addition, as the polymer of azole compounds, the compound that azole compounds that such as following general formula (2) represents is polymerized can be enumerated.
[chemical formula 6]
[in formula, R
3and R
4separately represent that ((R' represents the alkyl of carbon number 1 ~ 8 to R'OOC-for the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group.)), aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro or sulfo group.At R
3and R
4during for abovementioned alkyl or aryl, abovementioned alkyl or aryl can be bonded to pyrrole ring via azo group or sulfonyl.At R
3and R
4during for abovementioned alkyl or alkoxyl, the carbon atom of the end of abovementioned alkyl or alkoxyl can bond together and form ring.]
Abovementioned alkyl is preferably straight-chain or branched-chain alkyl, is more preferably straight-chain alkyl.
The carbon number of abovementioned alkyl is preferably 1 ~ 8, is more preferably 1 ~ 5, and more preferably 1 ~ 3.
As above-mentioned alkoxyl, be preferably methoxyl group, ethyoxyl, propoxyl group, butoxy, be more preferably methoxy or ethoxy.
As above-mentioned aryl, can enumerate: phenyl, benzyl, tolyl, naphthyl etc.
As above-mentioned halogen atom, can enumerate: fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.
As the object lesson of the azole compounds that above-mentioned general formula (2) represents, the compound that following formula (2-1) ~ (2-4) represents can be enumerated.
[chemical formula 7]
In addition, as the polymer of aniline compound, the compound that aniline compound that such as following general formula (3) represents is polymerized can be enumerated.
[chemical formula 8]
[in formula, R
5~ R
8separately represent that ((R' represents the alkyl of carbon number 1 ~ 8 to R'OOC-for the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group.)), aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro or sulfo group.At R
5~ R
8during for abovementioned alkyl or aryl, abovementioned alkyl or aryl can be bonded to phenyl ring via azo group or sulfonyl.At R
5and R
6, or R
7and R
8during for abovementioned alkyl or alkoxyl, the carbon atom of the end of abovementioned alkyl or alkoxyl can bond together and form ring.]
Abovementioned alkyl is preferably straight-chain or branched-chain alkyl, is more preferably straight-chain alkyl.
The carbon number of abovementioned alkyl is preferably 1 ~ 8, is more preferably 1 ~ 5, and more preferably 1 ~ 3.
As above-mentioned alkoxyl, be preferably methoxyl group, ethyoxyl, propoxyl group, butoxy, be more preferably methoxy or ethoxy.
As above-mentioned aryl, can enumerate: phenyl, benzyl, tolyl, naphthyl etc.
As above-mentioned halogen atom, can enumerate: fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.
As the object lesson of the aniline compound that above-mentioned general formula (3) represents, the compound that following formula (3-1) ~ (3-4) represents can be enumerated.
[chemical formula 9]
The known doping treatment for improving its conductivity can be implemented to the electroconductive polymer forming above-mentioned catalyst layer.Such as, can by halogen, the perchloric acid (ClO such as sulfonic acid, iodine, bromine, chlorine such as polystyrolsulfon acid (PSS), p-methyl benzenesulfonic acid (PTS)
4 -), two trifluoromethanesulfonimide (TFSI), four cyano quinone bismethane (TCNQ) etc. make an addition to electroconductive polymer as dopant.
More than one electroconductive polymer contained in above-mentioned catalyst layer is the electroconductive polymer being carried out by redox couple contained in electrolyte reducing.As the object lesson of this electroconductive polymer, such as polythiophene, polyaniline, polypyrrole, poly-(3,4-ethylene dioxythiophene) (PEDOT) etc. can be enumerated.Electroconductive polymer contained in catalyst layer can be a kind of, also can be two or more.Electroconductive polymer in catalyst layer is preferably in the state of oxidation with positive charge before the manufacture of DSSC.
More than one electroconductive polymer contained in above-mentioned catalyst layer both can separately containing a kind of, also can combinationally use two kinds and contain, and can also combinationally use more than three kinds and contain.The upper limit of the kind of the electroconductive polymer combinationally used is not particularly limited, and is generally less than 10 kinds.
When combinationally using more than two or three, such as, can combinationally use the electroconductive polymer being selected from above-mentioned thiophene compound and being polymerized, the electroconductive polymer of any more than two or three in electroconductive polymer that above-mentioned azole compounds is polymerized and the electroconductive polymer that above-mentioned aniline compound is polymerized.For the mixing ratio of the electroconductive polymer for more than two or three, consider conductivity and suitably set.
(photoacid generator)
As long as the photoacid generator forming above-mentioned catalyst layer can be penetrated by illumination such as ultraviolets and produce acid and just be not particularly limited, known photoacid generator can be applied.As object lesson, can enumerate: the photoacid generator of the sulfone classes such as biconjugate tosyl diazomethane, dual-tert-butyl sulfonyidiazomethanes; Photoacid generator, two-4-tert-butyl-phenyl iodine of the sulfonium classes such as diphenyl-4-aminomethyl phenyl sulfonium fluoroform sulphonate, diphenyl-2,4,6-trimethylphenyl sulfonium tosilate, 4-methoxyphenyl diphenyl sulfonium fluoroform sulphonate
the iodine such as two perfluorinated butane sulfimides
the photoacid generator etc. of class.The photoacid generator forming above-mentioned catalyst layer can be used alone one, also can combinationally use two or more.
Photoacid generator contained in above-mentioned catalyst layer preferably absorbs the light of the wave-length coverage of more than 300nm.Its reason is, by the light of above-mentioned wave-length coverage is irradiated as the reproduced light described below, can reduce reproduced light and be configured the possibility that the base material (such as FTO glass, ITO-PET film, ITO-PEN film etc.) to electrode absorbs, light photoacid generator (catalyst layer) being irradiated to q.s becomes easy.
In above-mentioned catalyst layer, the ratio of (gross mass of above-mentioned photoacid generator)/(gross mass of above-mentioned electroconductive polymer) is preferably 0.01 ~ 10, is more preferably 0.05 ~ 5, and more preferably 0.1 ~ 1.
When above-mentioned mass ratio is more than 0.01, can be penetrated by illumination and produce the acid of q.s.When above-mentioned mass ratio is less than 10, can avoid excessive photoacid generator that the conductivity of catalyst layer is reduced.
Relative to the gross mass of above-mentioned catalyst layer, the gross mass of above-mentioned electroconductive polymer is preferably more than 10 quality %, is more preferably more than 20 quality %, more preferably more than 50 quality %.
When it is more than 10 quality %, catalytic performance and the conductivity of catalyst layer can be improved fully.The upper limit of the gross mass of above-mentioned electroconductive polymer is not particularly limited, such as, can be set to below 90 quality %.
Relative to the gross mass of above-mentioned catalyst layer, the gross mass of above-mentioned photoacid generator is preferably 1 ~ 90 quality %, is more preferably more than 5 ~ 70 quality %, more preferably more than 10 ~ 50 quality %.
When it is more than 1 quality %, the acid of q.s can be produced by Ultraviolet radiation.When it is below 90 quality %, can avoid excessive photoacid generator that the conductivity of catalyst layer is reduced.
(auxiliary agent)
Can containing the conductive material beyond electroconductive polymer in above-mentioned catalyst layer.As such conductive material, the such as material with carbon element such as carbon nano-tube, acetylene black can be enumerated.By form the electroconductive polymer of catalyst layer be set to 100 mass parts time, about the content of above-mentioned conductive material is preferably 10 ~ 500 mass parts.
" to electrode "
The 4th aspect of the present invention to electrode be used by dye sensitization solar battery to electrode, there is the base material that surface defines the catalyst layer of Third Way.
The mode of above-mentioned base material is not particularly limited, and can enumerate the modes such as the substrate of such as tabular, film.Above-mentioned base material can be transmitance, also can be non-transmitance, but carry out light-struck viewpoint consideration from the easy catalyst layer to forming DSSC, and above-mentioned base material is preferably transmitance.
The surface of above-mentioned base material can be conductivity, also can be dielectric.Because the catalyst layer that formed on its surface is from as conductivity, even if therefore the surface of base material is dielectric, also can play a role fully as to electrode.It should be noted that, from the viewpoint of improving conductivity to electrode, the above-mentioned surface that is preferably formed electroconductive polymer is conductivity.
Be the transmitance substrate of conductivity as at least surface, the transparent conductive substrate being such as formed with nesa coating on the surface of glass substrate or transparent resin substrate can be enumerated.In addition, as the substrate of above-mentioned non-transmitance, metal substrate or unglazed radioparent resin substrate can be exemplified.It should be noted that, the transmitance of resin substrate can change according to the thickness of substrate.
As above-mentioned resin, can enumerate such as: the resins such as PETG (PET), PEN (PEN), acrylic resin, Merlon, polyimides.
The thickness of the catalyst layer that the surface of above-mentioned base material is formed is not particularly limited, and when it was thin catalyst layer, there is the hidden danger that can not play sufficient catalytic performance, therefore, such as, is preferably the thickness of more than 0.001 μm.The upper limit of the thickness of catalyst layer is not particularly limited, uneconomical when it is blocked up, is therefore generally less than 10 μm.
The catalyst layer that the surface of above-mentioned base material is formed can be fine and close layer, also can be porous layer.When it is porous layer, increase with the contact area of electrolyte, therefore, it is possible to improve the catalytic performance of catalyst layer.
When measuring the specific area of porous layer with gas adsorption method, be preferably 0.1m
2/ more than g, is more preferably 1m
2/ more than g, more preferably 3m
2/ more than g.
As the method forming fine and close catalyst layer, can enumerate such as, the solution coat containing electroconductive polymer and photoacid generator is carried out the method for drying on the surface of above-mentioned base material.
As the method for the catalyst layer of formation porous, can enumerate such as, on the surface of above-mentioned base material, be pre-formed the porous layer be made up of metal-oxide semiconductor (MOS)s such as titanium oxide microparticles by utilizing known roasting method or particle spraying method and the solution containing electroconductive polymer and photoacid generator be impregnated in this porous layer and carry out dry method.
As other formation method, can by containing form electroconductive polymer monomer molecule solution in dipping be formed with the base material of above-mentioned porous layer and under the state making described monomer molecule be spread in this porous layer, compositing conducting macromolecule in this porous layer come to the electrolysis polymerization method that this porous layer is energized.According to this electrolysis polymerization method, also electroconductive polymer can be configured in the deep in porous layer.Then, the solution containing photoacid generator is impregnated in this porous layer and carries out drying except desolventizing, thus can at the surface of this porous layer and the inner catalyst layer forming electroconductive polymer and photoacid generator and coexist.As above-mentioned monomer molecule, routine above-mentioned thiophene compound, azole compounds, aniline compound etc. can be enumerated.
" DSSC "
The DSSC of the present invention the 5th mode possesses: above-mentioned fourth way to electrode, have sensitizing dyestuff optoelectronic pole and containing the electrolyte of redox couple.
Figure 10 illustrates the profile of the DSSC 10 of an example as the 5th mode.The structure of the DSSC 10 shown in Figure 10, material and function are substantially as described in the DSSC 10 shown in about Fig. 1, but catalyst layer 18 is the catalyst layer of above-mentioned Third Way.
" renovation process of DSSC "
The renovation process of the DSSC of the present invention the 6th mode be electroconductive polymer by forming catalyst layer be in reducing condition or neutral state at least partially, the method for the DSSC regeneration of above-mentioned 5th mode, the method penetrates by carrying out illumination to photoacid generator contained in above-mentioned catalyst layer the method reoxidized by above-mentioned electroconductive polymer.
Such as, when the DSSC 10 shown in Figure 10 is regenerated, irradiate the light (such as ultraviolet) that can make the acidic wave-length coverage of photoacid generator by the direction from the arrow " reproduced light " shown in Figure 10, make the subtend base material 16 through the transmitance of structure paired electrode 12 and the reproduced light to conductive film 17 arrive catalyst layer 18.The photoacid generator absorbing reproduced light produces acid, makes electroconductive polymer contained in identical catalyst layer 18 turn back to the state of oxidation.Consequently, catalytic performance and the conductivity of catalyst layer 18 are recovered, and battery performance preferably returns to initial condition.
As the light source of above-mentioned reproduced light (ultraviolet etc.), as long as the light than sun light intensity can be irradiated, can enumerate such as: high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, metal halide lamp, xenon lamp, sterilamp and laser etc.Irradiation time is different according to the reducing condition of electroconductive polymer contained in catalyst layer 18, the light source of use, the kind of photoacid generator and consumption etc., therefore broadly can not specify, preferably 10 ~ 600 seconds, is more preferably for 30 ~ 300 seconds.
In the common occupation mode (generating) of DSSC 10, the light (generating light) of the generating such as sunlight is incident from the direction of the arrow " generating light " shown in Figure 10, therefore, the generating optical attenuation of catalyst layer 18 is arrived through work electrode 11 and electrolyte 20.Therefore, under common occupation mode (do not intend regenerate occupation mode), there is not depleted hidden danger in photoacid generator contained in catalyst layer 18.It should be noted that, even if generating light arrives catalyst layer 18 and discharges acid from photoacid generator, this acid also contributes to the state of oxidation keeping electroconductive polymer, and therefore, a small amount of generating light arrives catalyst layer 18 and is not a problem.
" electrolyte "
The electrolyte of the 7th aspect of the present invention to be oxidized electroconductive polymer, electrolyte containing at least one oxidant.More specifically, the electrolyte of present embodiment is the solution be made up of following substances: the oxidant that catalyst layer that can make formation dye-sensitized solar cell, that be made up of electroconductive polymer reoxidizes; The redox couple of the redox reaction for making current flowing is there is in dye-sensitized solar cell; And solvent.
(oxidant)
As long as oxidant can be oxidized the material of electroconductive polymer, be just not particularly limited.As oxidant, can enumerate such as: be selected from the elementary gas group comprising oxygen, chlorine, bromine gas, ozone etc.; Comprise the inorganic acid group of iron chloride (III) hexahydrate, anhydrous ferric chloride (III), ferric nitrate (III) nonahydrate, anhydrous nitric acid iron and ferric perchlorate (III) etc.; Comprise the organic acid group of DBSA, toluenesulfonic acid, trifluoroacetic acid and propionic acid; And at least one in the group to be made up of chlordene metaantimmonic acid three (4-bromophenyl) ammonium.Wherein, from the viewpoint of higher to the dissolubility of general solvent and stronger to the oxidation of electroconductive polymer, preferred use is selected from least one in elementary gas group and inorganic acid group, more preferably uses oxygen, bromine gas, iron chloride (III).
Be when being selected from least one in elementary gas group at oxidant, when electrolyte being totally set to 1L, the content of oxidant is preferably 1mg/L ~ 50mg/L, is more preferably 5mg/L ~ 50mg/L, more preferably 10mg/L ~ 50mg/L.
When the oxidant content overall relative to electrolyte is lower than 1mg/L%, be difficult to the electroconductive polymer of oxidized reduction to reduction is reoxidized.On the other hand, when the oxidant content overall relative to electrolyte is more than 50mg/L, exists and hinder the redox reaction of redox couple and the hidden danger that makes electric current obstructed.
It should be noted that, be, when being selected from least one in elementary gas group, monomer gas being contained by monomer gas is passed into electrolyte or is dissolved in electrolyte at oxidant.
In addition, when oxidant is at least one be selected from monomer gas, these monomer gas exist as molecule in the electrolytic solution.
In addition, when monomer gas is oxygen, the dissolved oxygen content in electrolyte can utilize such as dissolved oxygen meter to measure.
Be when being selected from least a kind in inorganic acid group and organic acid group at oxidant, when electrolyte being totally set to 100 quality %, the content of oxidant is preferably 0.001 quality % ~ 10 quality %, be more preferably 0.005 quality % ~ 5 quality %, more preferably 0.01 quality % ~ 1 quality %.
When the oxidant content overall relative to electrolyte is lower than 0.001 quality %, be difficult to the electroconductive polymer of oxidized reduction to reduction is reoxidized.On the other hand, when the oxidant content overall relative to electrolyte is more than 10 quality %, exists and hinder the redox reaction of redox couple and the hidden danger that makes electric current obstructed.
It should be noted that, be that when being selected from least one in inorganic acid group and organic acid group, these acid carry out dissociation in the electrolytic solution, exist as ion at oxidant.
(redox couple and solvent)
As redox couple and solvent, redox couple same as described above and solvent can be used in conjunction with the process for reactivation to electrode active material of first method of the present invention.
Electrolyte according to the present embodiment, due to containing at least one oxidant, therefore when being applied to dye-sensitized solar cell etc., by oxidant contained in electrolyte can make by redox couple contained in electrolyte reduction, the electroconductive polymer that forms catalyst layer is oxidized again.That is, by making oxidized dose of electroconductive polymer again be oxidized, the deterioration of the power generation performance (photoelectric conversion efficiency) of dye-sensitized solar cell can be prevented.
But, oxidant is contained by making electrolyte, form the electroconductive polymer of catalyst layer by electrolyte in contained redox couple be neutral state from oxidation state reduction time, can by oxidant contained in electrolyte immediately (automatically) this electroconductive polymer is oxidized again.
" dye-sensitized solar cell "
The dye-sensitized solar cell of the 8th aspect of the present invention possesses: the electrolyte of the 7th mode, have semiconductor work electrode and to electrode, work electrode and to electrode between be clamped with electrolyte.About all parts, the basic structure of the dye-sensitized solar cell of eighth mode, it can be made with above-mentioned all parts with reference to Fig. 1, basic structure is identical.
DSSC 10 according to the present embodiment, as electrolyte 20, due to the electrolyte containing the 7th mode, therefore, even if use electroconductive polymer in catalyst layer 18, also can prevent the deterioration of power generation performance when using for a long time.In addition, because the electroconductive polymer forming catalyst layer 18 is reduced by redox couple contained in electrolyte 20, power generation performance can not be deteriorated, therefore, DSSC 10 is not needed to decompose and the operation of regeneration catalyzing oxidant layer 18, thus, maintenance cost, the administration fee of DSSC 10 can be cut down.
Above, preferred embodiment describe in detail of the present invention, but the present invention is not limited to above-mentioned specific execution mode, in the scope of main points of the present invention that can be described in claim, carries out various distortion, change.In addition, only otherwise damage object of the present invention, also can appropriately combined above-mentioned of the present invention various mode.
In the present invention, as confirming that electroconductive polymer is in the method for the reducing condition of which kind of degree, the method such as employing spectrophotometric spectra can be enumerated.Because the shape of the spectrophotometric spectra of electroconductive polymer under the state of oxidation, neutral state, reducing condition is different, therefore, by measuring the spectrophotometric spectra of electroconductive polymer catalyst layer, reducing condition can be judged quantitatively.Therefore, can in the hope of being reduced process in the various embodiments of the present invention to which kind of degree.
Embodiment
Next, by following embodiment, the present invention is described in more detail, but the present invention is not limited to these embodiments.
(embodiment 1)
The formation > of < work electrode
As transparent base 13, prepare the glass substrate being formed with FTO film on plate face.By the TiO by average grain diameter 14nm on FTO film
2particle: 19 quality %, ethyl cellulose: 9 quality %, terpineol: the slurry that 72 quality % are formed utilizes silk screen print method to carry out film forming with size 4mm × 4mm, in 500 DEG C of roastings 30 minutes under air atmosphere, thus form by TiO
2the porous layer that particle is formed.Then, dissolve the N719 as sensitizing dyestuff using the concentration of 0.3mM in the mixed liquid made mixing acetonitrile and the tert-butyl alcohol with mass ratio 1 ︰ 1, flood in the sensitizing dyestuff solution obtained and possess by TiO
2the glass substrate of the porous layer that particle is formed and FTO film 20 hours, then with acetonitrile cleaning, thus makes sensitizing dyestuff be adsorbed in the surface of porous layer.Thus, the work electrode 11 having nesa coating 14 and optoelectronic pole 15 at transparent base 13 superimposed layer has been made.
< is to the formation > of electrode
Then, prepare the material identical with work electrode 11 and be formed with the glass substrate of FTO film, define run through FTO film and glass substrate hand-hole as the hand-hole 22 for injecting electrolyte 20.Thus, as shown in Figure 4 A, define and comprise the subtend base material 16 that lamination has the glass to conductive film 17 be made up of FTO.It should be noted that, in Fig. 4 A, Fig. 4 B and Fig. 5, omit the diagram of the hand-hole that electrolyte injects.Then, on FTO film using by containing the polyaniline of sulfonate as dopant: 10 quality %, toluene: the polyaniline solutions that 90 quality % are formed carries out film forming by spin coating (rotating speed: 3000rpm, 20 seconds).Then, electric hot plate carries out the heat treated of 10 minutes in 100 DEG C, thus form containing the electroconductive polymer catalyst layer 18 as the polyaniline of electroconductive polymer.Thus, as shown in Figure 4 B, made subtend base material 16 superimposed layer have to conductive film 17 and electroconductive polymer catalyst layer 18 to electrode 12.
Next, as shown in Figure 5, impregnated in containing iodine by what make of said method to electrode 12: 0.05M and 1,3-dimethyl-2-propyl group iodate imidazoles
: in the gamma-butyrolacton solution of 1.0M, in order to promote that the reducing of electroconductive polymer is heated to 85 DEG C, thus the electroconductive polymer of the electroconductive polymer catalyst layer 18 to electrode 12 is reduced.At this moment, be 0 hour (before dipping) using dip time, each of 100 hours, 300 hours, 500 hours take out as to electrode 12A ~ 12D electrode 12, respectively with acetonitrile cleaning, and carry out drying.
The assembling > of < DSSC
Below, as shown in Fig. 6 A ~ Fig. 6 D, make the electroconductive polymer catalyst layer 18 having carried out reduction treatment as mentioned above opposed with the optoelectronic pole 15 of work electrode 11, will to electrode 12A, 12B, 12C, 12D separate given interval relative to work electrode 11 respectively and configure, configure not shown encapsulant at work electrode 11 and to the side in the space between electrode 12, and make sealing material cured by heat treatment etc.Then, never illustrated hand-hole injects electrolyte 20 to by work electrode 11, the space that surrounds electrode 12 and encapsulant, has made DSSC 10A ~ 10D.Electrolyte 20 is used in the acetonitrile as solvent and is dissolved with iodine: 0.03M, 1,3-dimethyl-2-propyl group iodate imidazoles
: the solution of 0.6M, lithium iodide: 0.10M, tert .-butylpyridine: 0.5M.
The evaluation > of the power generation performance of < DSSC
Then, use solar simulator (model: XES-301S, K.K. Minaga Denki Seisakusho's system) to measure projects of the photoelectric conversion efficiency of DSSC 10A ~ 10D, short-circuit current density, open voltage, fill factor, curve factor (fillfactor), evaluate the power generation performance of DSSC 10A ~ 10D thus.
< takes out electrode > from DSSC
Then, operating in the same manner as " taking out the operation to electrode from DSSC " in the renovation process of above-mentioned DSSC, taking out electrode 12D in the DSSC 10D of the electroconductive polymer be reduced from having dipping 500 hours gamma-butyrolacton solution.
The electroconductive polymer that < is caused by chemical oxidation reoxidize >
Then, as shown in Figure 7, by what take out, acetonitrile solution containing iron chloride (hexahydrate): 0.01M be impregnated in 5 minutes to electrode 12D, by chemical oxidation, the electroconductive polymer of the electroconductive polymer catalyst layer 18 to electrode 12D is reoxidized.Thus, made possess the electroconductive polymer that is reoxidized from reducing condition to electrode 12E.Fig. 8 is for impregnated in containing iodine: 0.05M and 1,3-dimethyl-2-propyl group iodate imidazoles
: before the gamma-butyrolacton solution of 1.0M to electrode 12D, impregnated in containing iodine: 0.05M and 1,3-dimethyl-2-propyl group iodate imidazoles
: the gamma-butyrolacton solution 500 hours of 1.0M to electrode 12D, the acetonitrile solution photo to electrode 12E of 5 minutes containing iron chloride (hexahydrate): 0.01M will be impregnated in electrode 12D.
The evaluation > of the assembling again of < DSSC, power generation performance
Then, use electrode 12E, operate in the same manner as above-mentioned " assembling of DSSC ", assemble DSSC 10E.In addition, be used in the solar simulator used when carrying out above-mentioned " evaluation of the power generation performance of DSSC ", measure projects of the photoelectric conversion efficiency of DSSC 10E, short-circuit current density, open voltage, fill factor, curve factor, evaluate the power generation performance of DSSC 10E thus.
(embodiment 2)
Reoxidizing the electroconductive polymer possessed electrode 12 to change to and implement to replace chemical oxidation by electrochemical oxidation, in addition, implements the operation identical with embodiment 1.Below, " reoxidizing of the electroconductive polymer that electrochemical oxidation causes " and " evaluation of the assembling again of DSSC, power generation performance " carried out thereafter is described, omits the explanation about the operation identical with embodiment 1 beyond these.
The electroconductive polymer that < is caused by electrochemical oxidation reoxidize >
As shown in Figure 9, using the electroconductive polymer catalyst layer 18 to electrode 12D of the DSSC 10D shown in Fig. 6 A ~ Fig. 6 D as work electrode, impregnated in and contain as LiTFSI (two trifluoromethanesulfonimide lithium): 10 of supporting electrolyte
-1the acetonitrile solution of M.Then, using platinum line and silver-colored line as auxiliary electrode and normal electrode, utilize potentiostat (IVIUM Inc.) to apply voltage 120 second of 1.0V to the electroconductive polymer catalyst layer 18 as work electrode, reoxidized by the electroconductive polymer of electrochemical oxidation by the electroconductive polymer catalyst layer 18 to electrode 12D.Thus, made possess the electroconductive polymer that is reoxidized from reducing condition to electrode 12F.
The evaluation > of the assembling again of < DSSC, power generation performance
Then, use electrode 12F, operate in the same manner as above-mentioned " assembling of DSSC ", assemble DSSC 10F.In addition, be used in the solar simulator used when carrying out above-mentioned " evaluation of the power generation performance of DSSC ", determine projects of the photoelectric conversion efficiency of DSSC 10F, short-circuit current density, open voltage, fill factor, curve factor, evaluate the power generation performance of DSSC 10F thus.
(comparative example 1)
Except not carrying out " reoxidizing of the electroconductive polymer that chemical oxidation causes ", implement the operation identical with embodiment 1.That is, electrode 12D acetonitrile being cleaned and carrying out drying and paired electrode 12G processed (diagram slightly) of also reducing for 500 hours will be flooded in gamma-butyrolacton solution, and then use and DSSC 10G is assembled to electrode 12G.Then, be used in the solar simulator used when carrying out above-mentioned " evaluation of the power generation performance of DSSC ", determine projects of the photoelectric conversion efficiency of DSSC 10G, short-circuit current density, open voltage, fill factor, curve factor, evaluate the power generation performance of DSSC 10G thus.
The evaluation result of the power generation performance of the DSSC 10A ~ 10G in embodiment 1,2 and comparative example 1 is shown in table 1 by (evaluation result about the power generation performance of the DSSC in embodiment 1,2 and comparative example 1).It should be noted that, the recovery rate reoxidizing the photoelectric conversion efficiency caused of table 1 utilizes the photoelectric conversion efficiency of DSSC 10E ~ 10G to calculate relative to the ratio of the photoelectric conversion efficiency of DSSC 10A.
As shown in table 1, for the DSSC 10E of embodiment 1, be 0.97 to the recovery rate of the photoelectric conversion efficiency reoxidized of electrode 12D, obtain the value close to 1.About short-circuit current density, open voltage, the fill factor, curve factor of DSSC 10E, the result with projects same degree in DSSC 10A also can be obtained.Its reason is, being flooded 5 minutes by the electroconductive polymer be reduced, being undertaken reoxidizing thus and regenerate by chemical oxidation by flooding 500 hours in gamma-butyrolacton solution in acetonitrile solution.In addition, its reason is, is regenerated by electroconductive polymer, substantially returns to electroconductive polymer be reduced former initial performance to the catalytic activity of the electroconductive polymer catalyst layer 18 of electrode 12E and conductivity.
In addition, for the DSSC 10F of embodiment 2, be also 0.98 to the recovery rate of the photoelectric conversion efficiency reoxidized of electrode 12D, obtain the value close to 1.About short-circuit current density, open voltage, the fill factor, curve factor of DSSC 10F, the result with projects same degree in DSSC 10A also can be obtained.Its reason is, impregnated in the electroconductive polymer be reduced by flooding 500 hours in gamma-butyrolacton solution containing LiTFSI:10
-1the acetonitrile solution of M, simultaneously using platinum line and silver-colored line as auxiliary electrode and normal electrode, is applied voltage to the electroconductive polymer catalyst layer 18 as work electrode, is undertaken thus reoxidizing and regenerating by electrochemical oxidation.In addition, its reason is, is regenerated by electroconductive polymer, substantially returns to electroconductive polymer be reduced former initial performance to the catalytic activity of the electroconductive polymer catalyst layer 18 of electrode 12F and conductivity.
Relative to these embodiments, for the DSSC 10G of comparative example 1, photoelectric conversion efficiency is not almost recovered.About short-circuit current density, open voltage, the fill factor, curve factor of DSSC 10G, be also lower value compared with the value of the projects in DSSC 10A.Its reason is, within 500 hours, be reduced by dipping in gamma-butyrolacton solution and the electroconductive polymer possessed electrode 12G of DSSC 10G all do not carry out any by chemical oxidation cause reoxidize, reoxidizing of being caused by electrochemical oxidation, still be in reducing condition, be not reproduced.
By embodiment 1 described above, the evaluation result of the power generation performance of the DSSC in 2 can confirm: according to the present invention, the electroconductive polymer be reduced by making the long-time use due to DSSC wait reoxidizes, can by be made up of the catalyst layer comprising this electroconductive polymer to electrode regeneration, the catalytic activity of catalyst layer and conductivity recovery can be returned to electroconductive polymer and be reduced former initial performance, simultaneously, the power generation performance of DSSC reliably can be returned to initial performance, DSSC is regenerated.
(embodiment 3)
The making > of < optoelectronic pole
The slurry be made up of Titanium particles (particle diameter Φ 14nm) 19 quality %, ethyl cellulose 9 quality %, terpineol 72 quality % is used to carry out being formed of perforated membrane.As transparent conductive substrate, use the glass substrate being configured with the sheet resistance 10 ohm (Ω) of FTO film, above-mentioned slurry silk screen print method is coated on FTO film with the area of 4mm × 4mm, then under air atmosphere in 500 DEG C of roastings 30 minutes, nesa coating defines porous layer (thickness 10 μm).
Be dissolved with in the pigment solution of sensitizing dyestuff N719 with the concentration of 0.3mM in the mixed liquid of 1 ︰ 1 of acetonitrile and the tert-butyl alcohol, after the substrate possessing above-mentioned porous layer is flooded 20 hours, with acetonitrile cleaning, make to possess and make sensitizing dyestuff be adsorbed in porous layer and the optoelectronic pole of electric layer that formed.
< is to the making > of electrode
The glass substrate being formed with FTO film is formed the hand-hole for injecting electrolyte in rear operation.This glass substrate is contained by spin coating (rotating speed 3000rpm20 second) coating the solution of electroconductive polymer and photoacid generator, electric hot plate carries out in 60 DEG C the heat treated of 5 minutes, thus, FTO film is formed the catalyst layer be made up of electroconductive polymer and photoacid generator.
In above-mentioned solution, relative to the gross mass of solution, electroconductive polymer is (containing sulfonate as poly-3 of dopant, 4-ethylenedioxy thiophene (PEDOT)) content be 85 quality %, the content of photoacid generator (IrgacurePAG103 (IR103, BASF AG's system)) is 15 quality %.In addition, use methyl alcohol as solvent.
The preparation > of < electrolyte
Be 0.05M to make iodine, 1,3-dimethyl-2-propyl group iodate imidazoles
for the mode of the concentration of 1.0M is dissolved in the gamma-butyrolacton as solvent, prepare electrolyte thus.
The assembling > of < DSSC (DSC)
By possessing configuring face-to-face with the form clipping encapsulant electrode and the optoelectronic pole possessing electric layer of catalyst layer, by heat treated, encapsulant being solidified, being assembled into DSC battery thus.Then, from being formed at, to by optoelectronic pole, the space that surrounds electrode and encapsulant, electrolyte is injected to the above-mentioned hand-hole of electrode, and hand-hole is sealed.
The evaluation > of the power generation performance of < DSSC
Use solar simulator (model: XES-301S, K.K. Minaga Denki Seisakusho's system), luminous intensity 100mW/cm is determined to the DSC battery made
2simulated solar irradiation irradiate under photoelectric conversion efficiency (generating efficiency).The results are shown in the hurdle of " generating efficiency (before 85 DEG C) " of table 2.
Heat resistant test (accelerated test) > of < DSSC
Then, the DSC battery determining generating efficiency is placed 300 hours in the electric furnace of 85 DEG C, then measures its power generation performance as described above.The results are shown in the hurdle of " generating efficiency (after 85 DEG C) " of table 2.
The regeneration test > of < DSSC
Then, use UVSPOTCURE (USHIO Inc.) to the DSC battery irradiating ultraviolet light determining generating efficiency after heat resistant test.At this moment, in order to improve the illumination efficiency of electroconductive polymer to forming catalyst layer, to electrode side irradiating ultraviolet light.Then, again power generation performance is evaluated.The results are shown in the hurdle of " generating efficiency (the having ultraviolet light) " of table 2.
In addition, the result of the embodiment 4 ~ 7 described and comparative example 2 is recorded in table 2 together below.
Table 2
(embodiment 4)
" containing the poly-3,4-ethylene dioxythiophene of sulfonate as dopant " that use in embodiment 3 is changed to " containing the polyaniline of sulfonate as dopant ".Implement similarly to Example 3 in addition.
(embodiment 5)
" containing the poly-3,4-ethylene dioxythiophene of sulfonate as dopant " that use in embodiment 3 is changed to " containing the polypyrrole of four cyano tetrazanaphthalene as dopant ".Implement similarly to Example 3 in addition.
(embodiment 6)
" IrgacurePAG103 " that use in embodiment 3 is changed to " IrgacurePAG121 (BASF AG's system) ".Implement similarly to Example 3 in addition.
(embodiment 7)
" IrgacurePAG103 " that use in embodiment 3 is changed to " IrgacurePAG290 (BASF AG's system) ".Implement similarly to Example 3 in addition.
(comparative example 2)
Except not containing except IrgacurePAG103, implement similarly to Example 3.
Investigate above result.First, due to the accelerated test of keeping long-time at 85 DEG C, initial power generation performance is deteriorated.Can this is presumably because, the electroconductive polymer forming catalyst layer is chemically reduced or neutralization by the redox couple in electrolyte.Then, by catalyst layer irradiating ultraviolet light, its power generation performance is significantly recovered.Can this is presumably because, in the DSC battery of embodiment 3 ~ 7, by the effect of the acid of photoacid generator contained from catalyst layer release, make electroconductive polymer turn back to the state of oxidation.On the other hand, owing to not containing photoacid generator in the catalyst layer of the DSC battery of comparative example 2, therefore, even if irradiation ultraviolet radiation, power generation performance does not recover yet.
As known from the above: possess catalyst layer even if of the present invention and to the DSSC of electrode due to the contact through long-time electrolyte and catalyst layer, the electroconductive polymer forming catalyst layer is made power generation performance reduce by neutralization or reduction, also its power generation performance can be recovered by irradiating the light (reproduced light) that photoacid generator can be made to discharge acid to catalyst layer.
(embodiment 8)
The formation > of < electric layer (work electrode)
As transparent conductive substrate, prepared to be formed on plate face FTO film, the glass substrate of sheet resistance 10 ohm (Ω).
By the TiO by average grain diameter 14nm on FTO film
2particle: 19 quality %, ethyl cellulose: 9 quality %, terpineol: the slurry that 72 quality % are formed utilizes silk screen print method to carry out film forming with size 4mm × 4mm, in 500 DEG C of roastings 30 minutes under air atmosphere, thus form by TiO
2the porous layer that particle is formed.
Then, dissolve the N719 as sensitizing dyestuff using the concentration of 0.3mM in the mixed liquid made mixing acetonitrile and the tert-butyl alcohol with mass ratio 1 ︰ 1, flood in the sensitizing dyestuff solution obtained and possess by TiO
2the glass substrate of the porous layer that particle is formed and FTO film 20 hours, then with acetonitrile cleaning, thus makes sensitizing dyestuff be adsorbed in the surface of porous layer.Thus, the work electrode having nesa coating and optoelectronic pole at transparent conductive substrate superimposed layer has been made.
The formation > of < catalyst layer (to electrode)
Then, prepared the glass substrate being defined FTO film by the material identical with work electrode, and define run through FTO film and glass substrate hand-hole as the hand-hole for injecting electrolyte.Thus, define and comprise the subtend base material that lamination has the glass to conductive film be made up of FTO film.
Then, using by containing the poly-3,4-ethylene dioxythiophene (PEDOT) of sulfonate as dopant on FTO film: 1 ~ 2 quality % and methyl alcohol: the PEDOT solution that 98 ~ 99 quality % are formed carries out film forming by spin coating (rotating speed: 3000rpm, 20 seconds).Then, electric hot plate carries out the heat treated of 5 minutes in 80 DEG C, thus form containing the catalyst layer as the PEDOT of electroconductive polymer.Thus, made subtend base material superimposed layer have by the catalyst layer formed conductive film and electroconductive polymer to electrode.
< contains the formation > of the electrolyte of oxidant
Dissolve the iodine 0.05M as redox couple and 1,3-dimethyl-2-propyl group iodate imidazoles in as the gamma-butyrolacton of solvent
1.0M, prepares electrolyte.
Then, by passing into oxygen 10 minutes in this electrolyte, electrolyte is made to contain aerobic (oxidant).At this moment, the dissolved oxygen content in dissolved oxygen meter measurement electrolyte is utilized.Consequently, the dissolved oxygen content in electrolyte is 10g/L (water saturation rate conversion).
The assembling > of < DSSC
Making the electric layer of making as mentioned above opposed with catalyst layer, configuring separating given interval to electrode relative to work electrode, at work electrode and the side configuration encapsulant to the space between electrode, make sealing material cured by heat treatment etc.Then, from being formed at, to by work electrode, the space that surrounds electrode and encapsulant, the electrolyte made as mentioned above is injected to the hand-hole of electrode, then by encapsulant hot curing is blocked hand-hole, DSSC has been made.
The evaluation > of the power generation performance of < DSSC
Use solar simulator, be determined at luminous intensity 100mW/cm
2simulated solar irradiation irradiate under photoelectric conversion efficiency, evaluate the power generation performance of DSSC thus.Show the result in table 3.
85 DEG C of heat resistant tests (the heat-resisting accelerated test of the catalyst layer) > of < DSSC
By DSSC in electric furnace in 85 DEG C of keepings 500 hours.
Then, the photoelectric conversion efficiency of DSSC is determined as mentioned above.Show the result in table 3.
In addition, calculate the photoelectric conversion efficiency after 85 DEG C of heat resistant tests relative to the photoelectric conversion efficiency ((photoelectric conversion efficiencys after 85 DEG C of heat resistant tests)/(photoelectric conversion efficiencys before 85 DEG C of heat resistant tests) × 100 (%)) before 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, be set to the conservation rate of photoelectric conversion efficiency.Show the result in table 3.
(embodiment 9)
In the formation > of < catalyst layer (to electrode), polyaniline solutions is used to replace poly-3,4-ethylenedioxy thiophene (PEDOT) solution, in addition, operate similarly to Example 8, made the DSSC of embodiment 9.
To the DSSC obtained, operate similarly to Example 8, carry out the evaluation of the power generation performance of DSSC and 85 DEG C of heat resistant tests of DSSC.Show the result in table 3.
(embodiment 10)
Contain in the formation > of the electrolyte of oxidant at <, make electrolyte contain iron chloride (III) 1mmol/L to replace pass into oxygen in electrolyte, in addition, operate similarly to Example 1, made the DSSC of embodiment 3.
To the DSSC obtained, operate similarly to Example 8, carry out the evaluation of the power generation performance of DSSC and 85 DEG C of heat resistant tests of DSSC.Show the result in table 3.
(comparative example 3)
Containing at < in the formation > of the electrolyte of oxidant, except not passing into except oxygen in electrolyte, operating similarly to Example 8, made the DSSC of comparative example 3.
To the DSSC obtained, operate similarly to Example 8, carry out the evaluation of the power generation performance of DSSC and 85 DEG C of heat resistant tests of DSSC.Show the result in table 3.
(comparative example 4)
Containing at < in the formation > of the electrolyte of oxidant, except not passing into except oxygen in electrolyte, operating similarly to Example 9, made the DSSC of comparative example 3.
To the DSSC obtained, operate similarly to Example 8, carry out the evaluation of the power generation performance of DSSC and 85 DEG C of heat resistant tests of DSSC.Show the result in table 3.
Table 3
As can be known from the results of Table 3: in embodiment 8 ~ 10, due in the electrolytic solution containing as the oxygen of oxidant or iron chloride (III), therefore, the conservation rate of photoelectric conversion efficiency is higher.
On the other hand, known: in comparative example 3 and 4, owing to not containing oxidant in the electrolytic solution, therefore, the conservation rate of photoelectric conversion efficiency is lower.
Claims (20)
1. the process for reactivation to electrode active material of a DSSC, it is the method for electrode active material being carried out to reactivation to DSSC, described DSSC have by containing electroconductive polymer more than at least one as the catalyst layer of electrode active material is formed to electrode, the method comprises:
By chemical oxidation or electrochemical oxidation, described electroconductive polymer is reoxidized.
2. the process for reactivation to electrode active material of DSSC as claimed in claim 1, wherein, described chemical oxidation is implemented by described electroconductive polymer being impregnated in the solution being dissolved with oxidant.
3. the process for reactivation to electrode active material of DSSC as claimed in claim 1, wherein, described electrochemical oxidation by described electroconductive polymer be impregnated in solution containing supporting electrolyte as work electrode, and applies given voltage to implement to described work electrode.
4. the process for reactivation to electrode active material of DSSC as claimed in claim 1, wherein, described catalyst layer, also containing photoacid generator, producing acid by irradiating light to photoacid generator, carrying out described chemical oxidation thus.
5. the process for reactivation to electrode active material of DSSC as claimed in claim 1, wherein, described DSSC possesses the electrolyte of the oxidant that can be oxidized electroconductive polymer containing at least one, carries out described chemical oxidation by described oxidant.
6. a renovation process for DSSC, it is the renovation process that the above electroconductive polymer of at least one of the catalyst layer forming structure paired electrode is in the DSSC of reducing condition or neutral state, and the method comprises:
By chemical oxidation or electrochemical oxidation to the described operation reoxidized the described electroconductive polymer that electrode has.
7. a catalyst layer, it is the catalyst layer for DSSC, and described catalyst layer contains more than one electroconductive polymer and photoacid generator.
8. catalyst layer as claimed in claim 7, wherein, described electroconductive polymer is the polymer of the thiophene compound that following general formula (1) represents,
In formula, R
1and R
2separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro or sulfo group, at R
1and R
2when for described alkyl or aryl, described alkyl or aryl can be bonded to thiphene ring, at R via azo group or sulfonyl
1and R
2when for described alkyl or alkoxyl, the carbon atom of the end of described alkyl or alkoxyl can bond together and form ring.
9. catalyst layer as claimed in claim 7, wherein, described electroconductive polymer is the polymer of the azole compounds that following general formula (2) represents,
In formula, R
3and R
4separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro or sulfo group, at R
3and R
4when for described alkyl or aryl, described alkyl or aryl can be bonded to pyrrole ring, at R via azo group or sulfonyl
3and R
4when for described alkyl or alkoxyl, the carbon atom of the end of described alkyl or alkoxyl can bond together and form ring.
10. catalyst layer as claimed in claim 7, wherein, described electroconductive polymer is the polymer of the aniline compound that following general formula (3) represents,
In formula, R
5~ R
8separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro or sulfo group, at R
5~ R
8when for described alkyl or aryl, described alkyl or aryl can be bonded to phenyl ring, at R via azo group or sulfonyl
5and R
6, or R
7and R
8when for described alkyl or alkoxyl, the carbon atom of the end of described alkyl or alkoxyl can bond together and form ring.
11. catalyst layers according to any one of claim 7 ~ 10, wherein, in described catalyst layer, the ratio of (gross mass of described photoacid generator)/(gross mass of described electroconductive polymer) is 0.01 ~ 10.
12. 1 kinds to electrode, its be for DSSC to electrode, described base material electrode to the catalyst layer defined from the teeth outwards according to any one of claim 7 ~ 11.
13. 1 kinds of DSSC, it possesses: according to claim 6 to electrode, have sensitizing dyestuff optoelectronic pole and containing the electrolyte of redox couple.
The renovation process of 14. 1 kinds of DSSC, it is the method regenerated the DSSC according to claim 13 being in reducing condition or neutral state at least partially of the electroconductive polymer forming catalyst layer, and the method comprises:
Light is irradiated to photoacid generator contained in this catalyst layer described, thus described electroconductive polymer is reoxidized.
15. 1 kinds of electrolyte, it contains the oxidant that at least one can be oxidized electroconductive polymer.
16. electrolyte as claimed in claim 15, wherein, described oxidant is be selected from the elementary gas group comprising oxygen, chlorine and bromine gas; Comprise the inorganic acid group of iron chloride (III) hexahydrate, anhydrous ferric chloride (III), ferric nitrate (III) nonahydrate, anhydrous nitric acid iron and ferric perchlorate (III); Comprise the organic acid group of DBSA, toluenesulfonic acid, trifluoroacetic acid and propionic acid; And at least one in the group to be made up of chlordene metaantimmonic acid three (4-bromophenyl) ammonium.
17. electrolyte as claimed in claim 16, wherein, described oxidant is be selected from least one in described inorganic acid group.
18. electrolyte according to any one of claim 15 ~ 17, wherein, be when being selected from least one in described elementary gas group at described oxidant, when electrolyte entirety is set to 1L, the content of described oxidant is 1mg/L ~ 50mg/L.
19. electrolyte according to any one of claim 15 ~ 17, wherein, be when being selected from least one in described inorganic acid group and described organic acid group at described oxidant, when electrolyte entirety is set to 100 quality %, the content of described oxidant is 0.001 quality % ~ 10 quality %.
20. 1 kinds of DSSC, it possesses electrolyte according to any one of claim 15 ~ 19, have the work electrode of semiconductor and to electrode,
Described work electrode contains the electrode layer be made up of semiconductor and the dyestuff being adsorbed in this electrode layer,
Described DSSC described work electrode and described to electrode between clamp electrolyte and formed.
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| JP2013179849 | 2013-08-30 | ||
| JP2013-179849 | 2013-08-30 | ||
| JP2013-260073 | 2013-12-17 | ||
| JP2013260073 | 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 |
Publications (2)
| Publication Number | Publication Date |
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| CN105283936A true CN105283936A (en) | 2016-01-27 |
| CN105283936B CN105283936B (en) | 2018-09-11 |
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| CN201480030101.1A Expired - Fee Related CN105283936B (en) | 2013-08-30 | 2014-08-29 | Active material process for reactivation, battery recycling method, catalyst layer, to electrode |
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| Country | Link |
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| JP (1) | JP5960921B2 (en) |
| KR (1) | KR102286239B1 (en) |
| CN (1) | CN105283936B (en) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108231421A (en) * | 2016-12-22 | 2018-06-29 | 台湾染敏光电股份有限公司 | Dye-sensitized photovoltaic type battery, module and its manufacturing method |
| CN109979755A (en) * | 2017-12-27 | 2019-07-05 | 太阳诱电株式会社 | Dye-sensitized solar cells |
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| TWI566451B (en) * | 2015-10-08 | 2017-01-11 | 台灣染敏光電股份有限公司 | Dye-sensitized photovoltaic cell, module and method for packaging the same |
| 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 |
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Also Published As
| Publication number | Publication date |
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| TW201517354A (en) | 2015-05-01 |
| KR20160052462A (en) | 2016-05-12 |
| WO2015030193A1 (en) | 2015-03-05 |
| JPWO2015030193A1 (en) | 2017-03-02 |
| KR102286239B1 (en) | 2021-08-06 |
| CN105283936B (en) | 2018-09-11 |
| JP5960921B2 (en) | 2016-08-02 |
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