CN102227847A - Electrolyte for photoelectric conversion element, photoelectric conversion element using electrolyte, and dye-sensitized solar cell - Google Patents
Electrolyte for photoelectric conversion element, photoelectric conversion element using electrolyte, and dye-sensitized solar cell Download PDFInfo
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- CN102227847A CN102227847A CN2009801475433A CN200980147543A CN102227847A CN 102227847 A CN102227847 A CN 102227847A CN 2009801475433 A CN2009801475433 A CN 2009801475433A CN 200980147543 A CN200980147543 A CN 200980147543A CN 102227847 A CN102227847 A CN 102227847A
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- conversion element
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005055 alkyl alkoxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- KVMPQUTWRWVTQP-UHFFFAOYSA-N cyanatoboronic acid Chemical compound OB(O)OC#N KVMPQUTWRWVTQP-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- PORCMJJTZXANLJ-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) Chemical class [Fe++].[Fe++].c1cc[cH-]c1.c1cc[cH-]c1.c1cc[cH-]c1.c1cc[cH-]c1 PORCMJJTZXANLJ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- NBVMCMSJGNOOCF-UHFFFAOYSA-N lithium;2,2,2-trifluoroacetic acid Chemical compound [Li].OC(=O)C(F)(F)F NBVMCMSJGNOOCF-UHFFFAOYSA-N 0.000 description 1
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
-
- 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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention provides an electrolyte for a photoelectric conversion element, which can achieve high energy conversion efficiency without substantially containing iodine; also a photoelectric conversion element using the electrolyte; and a dye-sensitized solar cell. The electrolyte for a photoelectric conversion element contains an ionic liquid (A) and a carbon material (B) having a specific surface area of 1,000 to 3,500 m2/g. The content of the carbon material (B) is 10 to 50 parts by mass relative to 100 parts by mass of the ionic liquid (A).
Description
Technical field
The present invention relates to photo-electric conversion element with electrolyte and used this electrolytical photo-electric conversion element and DSSC.
Background technology
In recent years, the environmental problems such as global warming that increase caused of carbon dioxide become seriously, and little and can reduce the solar cell of manufacturing cost as carrying capacity of environment, non-silicon is that solar cell receives publicity, and researchs and develops.
At non-silicon is in the solar cell, the DSSC of the people such as グ レ Star エ Le of Switzerland exploitation particularly, in the solar cell that has used organic material, have the photoelectric conversion efficiency height, be that solar cell is compared advantages such as cheap for manufacturing cost, receive publicity as novel solar battery with silicon.
Yet, because DSSC is an electrochemical cell, therefore used organic electrolyte, ionic liquid etc. as electrolyte, under the situation of using organic electrolyte, volatilization, exhaustion when existing owing to long-term the use make problems such as generating efficiency reduction, in addition, and under the situation of using ionic liquid, though there are the endurance issues such as structure deterioration that caused by leakage in the volatilization in the time of can preventing to use for a long time, exhaustion.
Therefore,, guarantee long-time stability, the durability of solar cell, carried out electrolyte from the aqueous research that becomes gel, solid, shaped for volatilization, the leakage that prevents electrolyte.
For example, in patent documentation 1, put down in writing " comprising ionic liquid and electroconductive particle gel-like electrolyte composition " ([claim 1] [claim 2]) as main component.
In addition, in patent documentation 2, put down in writing " a kind of dye sensitization type photo-electric conversion element; be have successively by through dye sensitization the dye sensitization type photo-electric conversion element of semiconductor particle the porousness optoelectronic pole layer, charge transport layer and the counter electrode layer that constitute; it is characterized in that charge transport layer is formed by the solid, shaped mixture that comprises p type electric conductive polymer 1～50 quality %, material with carbon element 5～50 quality % and ionic liquid 20～85 quality %." ([claim 1]).
Yet, under the situation of the electrolyte composition of in having used patent documentation 1, having put down in writing, from reaching the viewpoint of high energy conversion efficiency, under the situation of having used redox couple (redox couple), particularly iodine, there is following problems: owing to the corrosivity of iodine is corroded the metal wiring (collecting electrodes) that constitutes photo-electric conversion element, encapsulant etc., because the volatility of iodine and influential to electrolytical stability.
Patent documentation 1: international disclosing No. 2005/006482
Patent documentation 2: TOHKEMY 2007-227087 communique
Summary of the invention
In addition, the present inventor studies the dye sensitization type photo-electric conversion element of record in the patent documentation 2, and the result has shown that its energy conversion efficiency is insufficient.Think this be because, under the situation of mixture of using p type electric conductive polymer (for example polyaniline, polypyrrole etc.), material with carbon element (for example acetylene black etc.) and ionic liquid as charge transport layer, material with carbon element (particularly acetylene black) itself keeps the ability (hold facility) of ionic liquid low, and mixes with p type electric conductive polymer and its hold facility is further reduced.
Therefore, do not comprise photo-electric conversion element that iodine also can reach high energy conversion efficiency in fact with electrolyte and used this electrolytical photo-electric conversion element and DSSC even the purpose of this invention is to provide.
The present inventor furthers investigate, and found that, contains ionic liquid and specific area is 1000～3500m with special ratios
2The photo-electric conversion element electrolyte of the material with carbon element of/g can not reach high energy conversion efficiency even do not comprise iodine in fact yet, thereby finish the present invention.
That is, the invention provides following (a)～(o).
(a). a kind of photo-electric conversion element electrolyte, containing ionic liquid (A) and specific area is 1000～3500m
2The material with carbon element of/g (B),
The content of described material with carbon element (B) is 10～50 mass parts with respect to described ionic liquid (A) 100 mass parts.
(b). according to above-mentioned (a) described photo-electric conversion element electrolyte, 1 average grain diameter of described material with carbon element (B) is 0.5～120 μ m.
(c). according to above-mentioned (a) or (b) described photo-electric conversion element electrolyte, described ionic liquid (A) has the cation shown in following formula (1) or the formula (2),
In the formula (1), R
1Expression carbon number 1～20 can comprise heteroatomic alkyl, what it can have a carbon number 1～20 can comprise heteroatomic substituting group, R
2And R
3Represent the alkyl of hydrogen atom or carbon number 1～20 independently of one another, can comprise hetero-atom, but under the situation that has two keys on the nitrogen-atoms, R
3Do not exist,
In the formula (2), Q represents nitrogen-atoms, oxygen atom, phosphorus atoms or sulphur atom, R
4, R
5, R
6And R
7Representing the alkyl of hydrogen atom or carbon number 1～8 independently of one another, can comprise hetero-atom, is under the situation of oxygen atom or sulphur atom at Q still, R
7Do not exist.
(d). according to above-mentioned (c) described photo-electric conversion element electrolyte, described ionic liquid (A) has iodide ion as anion.
(e). according to each described photo-electric conversion element electrolyte of above-mentioned (a)～(d), other material with carbon element (C) as except described material with carbon element (B) also contains acetylene black.
(f). according to above-mentioned (e) described photo-electric conversion element electrolyte, described acetylene black is boron modification acetylene black.
(g). according to each described photo-electric conversion element electrolyte of above-mentioned (a)～(f), as other material with carbon element (C) except described material with carbon element (B), contain also that to measure the pH value that obtains by the pH assay method stipulated among the JIS Z8802 be 2～6 material with carbon element.
(h). according to above-mentioned (g) described photo-electric conversion element electrolyte, described pH value is that 1 average grain diameter of 2～6 material with carbon element is 0.010～0.050 μ m.
(i). according to each described photo-electric conversion element electrolyte of above-mentioned (a)～(h), as other material with carbon element (C) except described material with carbon element (B), also containing the nitrogen adsorption specific surface area is 90m
2The carbon black that/g is above.
(j). according to each described photo-electric conversion element electrolyte of above-mentioned (e)～(i), the total content of described material with carbon element (B) and described other material with carbon element (C) is 10～50 mass parts with respect to described ionic liquid (A) 100 mass parts.
(k). according to each described photo-electric conversion element electrolyte of above-mentioned (e)～(j), the ratio of the content of described material with carbon element (B) and described other material with carbon element (C), promptly material with carbon element (B)/other material with carbon element (C) is 99.9/0.1～60/40.
(l). according to each described photo-electric conversion element electrolyte of above-mentioned (e)～(k), be by described ionic liquid (A) and described other material with carbon element (C) mixing being obtained dispersion, mixing described material with carbon element (B) then and modulate.
(m). each the described photo-electric conversion element electrolyte according to above-mentioned (a)～(l), also contain silica and/or metal oxide.
(n). a kind of photo-electric conversion element comprises:
Have nesa coating and metal-oxide semiconductor (MOS) multiple aperture plasma membrane optoelectronic pole,
With described optoelectronic pole to the counter electrode of phase configuration and
The dielectric substrate that between described optoelectronic pole and described counter electrode, disposes,
Described dielectric substrate is each described photo-electric conversion element electrolyte of above-mentioned (a)～(m).
(o). a kind of DSSC supports photosensitive dye and gets on above-mentioned (n) described optoelectronic pole.
As following illustrated ground, according to the present invention, not comprising photo-electric conversion element that iodine also can reach high energy conversion efficiency in fact with electrolyte and used this electrolytical photo-electric conversion element and DSSC even can provide, is useful therefore.
In addition, even because photo-electric conversion element of the present invention does not use p type electric conductive polymer such as polyaniline can reach high energy conversion efficiency yet with electrolyte, so be very useful.
Description of drawings
Fig. 1 is the generalized section that shows the basic comprising of a routine photo-electric conversion element of the present invention.
Fig. 2 is the figure that shows the basic comprising of the solar cell of the present invention that uses among the embodiment etc.
Embodiment
Below, illustrate in greater detail the present invention.
Photo-electric conversion element of the present invention is to contain ionic liquid (A) and specific area is 1000～3500m with electrolyte (following also abbreviate as " electrolyte of the present invention ")
2The electrolyte that the photo-electric conversion element of the material with carbon element of/g (B) is used, the content of described material with carbon element (B) is 10～50 mass parts with respect to above-mentioned ionic liquid (A) 100 mass parts.
Next, electrolytical each composition of the present invention is described in detail.
(ionic liquid (A))
The ionic liquid (A) that uses in the electrolyte of the present invention is not limited especially, can use any ionic liquid that all the time uses as electrolyte.
For example can use, big wild great good fortune is compiled " the most preceding Line と of イ オ Application liquid-development future-(forefront of ionic liquid-exploitation and future-) " CMC and is published quaternary ammonium salt, the imidazoles of putting down in writing among (2003), " イ オ Application Ye Ti Machine Neng Chong System と ying with (the function initiative of ionic liquid and use) " エ ヌ テ イ one エ ス (2004) etc.
Salt, pyridine
Salt, pyrrolidines
Salt, piperidines
Salt etc.
Above-mentioned ionic liquid (A) has cation and as the anion of its gegenion.
Herein, as cation, the concrete preferred cation shown in following formula of illustration (1) or the formula (2).
In the formula (1), R
1Expression carbon number 1～20 can comprise heteroatomic alkyl, what it can have a carbon number 1～20 can comprise heteroatomic substituting group.R
2And R
3The alkyl of representing hydrogen atom or carbon number 1～20 independently of one another, R
2And R
3Can comprise hetero-atom.But under the situation that has two keys on the nitrogen-atoms, R
3Do not exist.
In the formula (2), Q represents nitrogen-atoms, oxygen atom, phosphorus atoms or sulphur atom, R
4, R
5, R
6And R
7Represent the alkyl of hydrogen atom or carbon number 1～8 independently of one another, they can comprise hetero-atom.But at Q is under the situation of oxygen atom or sulphur atom, R
7Do not exist.
Herein, as the R in the above-mentioned formula (1)
1Be carbon number 1～20 can comprise heteroatomic alkyl, preferably the nitrogen-atoms (ammonium ion) in above-mentioned formula (1) forms ring structure.
Next, as the R in the above-mentioned formula (1)
1The carbon number 1～20 that can have can comprise heteroatomic substituting group, be preferably the alkoxyalkyl (methoxy (CH for example of the alkyl (for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group etc.) of carbon number 1～12, the alkoxyl of carbon number 1～12 (for example methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentyloxy, just own oxygen base, 1,2-dimethyl butoxy etc.), carbon number 2～12
2OCH
3), methoxy ethyl (CH
2CH
2OCH
3), isopropoxy n-pro-pyl (CH
2CH
2CH
2OCH (CH
3)
2), tert-butoxy methyl (CH
2-O-C (CH
3)
3Deng).In addition, the R in the above-mentioned formula (1)
1Can have 2 above substituting groups.
In addition, as the R in the above-mentioned formula (1)
2And R
3Carbon number 1～20 can comprise heteroatomic alkyl, specifically can enumerate the alkyl alkoxy (methoxy (CH for example of the alkyl (for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group etc.) of carbon number 1～12, the alkoxyl of carbon number 1～12 (for example methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentyloxy, just own oxygen base, 1,2-dimethyl butoxy etc.), carbon number 2～12
2OCH
3), methoxy ethyl (CH
2CH
2OCH
3), isopropoxy n-pro-pyl (CH
2CH
2CH
2OCH (CH
3)
2), tert-butoxy methyl (CH
2-O-C (CH
3)
3Deng) etc.
In addition, in the above-mentioned formula (2), as R
4, R
5, R
6And R
7Carbon number 1～8 can comprise heteroatomic alkyl, specifically can enumerate the alkoxyalkyl (methoxy (CH for example of the alkyl (for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group etc.) of carbon number 1～8, the alkoxyl of carbon number 1～8 (for example methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentyloxy, just own oxygen base, 1,2-dimethyl butoxy etc.), carbon number 2～8
2OCH
3), methoxy ethyl (CH
2CH
2OCH
3), isopropoxy n-pro-pyl (CH
2CH
2CH
2OCH (CH
3)
2), tert-butoxy methyl (CH
2-O-C (CH
3)
3Deng) etc.
As the cation shown in the above-mentioned formula (1), for example can enumerate imidazoles
Ion, pyridine
Ion, pyrrolidines
Ion, piperidines
Ion etc.
The concrete preferred cation shown in arbitrary formula of the following formula of illustration (3)～(6).
Wherein, tend to better reason, the cation shown in preferred following formula (3) and (5) from the photoelectric conversion efficiency of having used electrolytical photo-electric conversion element of the present invention (below be also referred to as " photo-electric conversion element of the present invention ").
In formula (3)～(6), R
8～R
40The alkyl that can comprise nitrogen-atoms of representing carbon number 1～20 independently of one another.
More specifically can enumerate cation shown below.
As the cation shown in the above-mentioned formula (2), for example can enumerate, ammonium ion, sulfonium cation,
Organic cations such as ion.
Concrete preferred illustration cation shown below.
Wherein, tend to better reason, the preferred aliphat quaternary ammonium ion from the photoelectric conversion efficiency of photo-electric conversion element of the present invention.
On the other hand, the anion that is had as above-mentioned ionic liquid (A), specifically preferred illustration I
-, Br
-, AlCl
4 -, Al
2Cl
7 -, NO
3 -, BF
4 -, PF
6 -, CH
3COO
-, CF
3COO
-, CF
3SO
3 -, (CN)
4B
-, SCN
-, (CF
3SO
2)
2N
-, (CN)
2N
-, (CF
3SO
2)
3C
-, (CN)
3C
-, AsF
6 -, SbF
6 -, F (HF)
n -, CF
3CF
2CF
2CF
2SO
3 -, (CF
3CF
2SO
2)
2N
-, CF
3CF
2CF
2COO
-Deng.
Wherein, tend to better reason, preferred bromide ion (Br from the photoelectric conversion efficiency of photo-electric conversion element of the present invention
-), iodide ion (I
-), more preferably iodide ion (I
-).
As ionic liquid (A), for example can enumerate, by above-mentioned illustrated cation and the anionic ionic liquid that constitutes etc.
Wherein, preferably has imidazoles
Ion as cation, have iodide ion as anionic ionic liquid.
In the present invention, the synthetic method of ionic liquid (A) is not limited especially, can synthesize by above-mentioned illustrated cation and anion by known method in the past and make up the various ionic liquids that constitute.
As such ionic liquid (A), can use 1-methyl-3-methyl iodate imidazoles
1-ethyl-3-methyl iodate imidazoles
1-methyl-3-amyl group iodate imidazoles
1-hexyl-3-methyl iodate imidazoles
1-((2-methoxy ethoxy) ethyl)-3-((2-methoxy ethoxy) ethyl) iodate imidazoles
Etc. composite, can use commercially available product in addition, specifically for example can enumerate 1-methyl-3-propyl group iodate imidazoles
(Tokyo changes into society's system), 1-methyl-3-butyl iodate imidazoles
(Tokyo changes into society's system), 1-methyl isophthalic acid-methyl-iodate pyrrolidines
(ア Le De リ Star チ society system), 1-ethyl-3-methylimidazole
Four cyano borate (Merck society system), 1-ethyl-3-methylimidazole
Rhodanate (Merck society) etc.
In the present invention, the content of above-mentioned ionic liquid (A) is 50～95 quality % with respect to electrolytical gross mass of the present invention preferably, more preferably 65～95 quality %.If content is in this scope, then the photoelectric conversion efficiency of photo-electric conversion element of the present invention is better.
(material with carbon element (B))
The employed material with carbon element of electrolyte of the present invention (B) is that specific area is 1000～3500m
2The material with carbon element of/g.
Herein, specific area is meant the method for stipulating according among the JIS K1477, uses the BET method of utilizing nitrogen absorption to carry out to measure the measured value that obtains.
In the present invention, owing to the above-mentioned material with carbon element (B) that contains 10～50 mass parts with respect to above-mentioned ionic liquid (A) 100 mass parts, even therefore not comprising iodine in fact also can reach high energy conversion efficiency.
Think this be because, by using and carbon black (acetylene black), the graphite material with carbon element (B) that specific area is big mutually, can form the electrolyte that material with carbon element (B) has fully kept ionic liquid (A), and in metal-oxide semiconductor (MOS) multiple aperture plasma membrane described later, fill ionic liquid (A) fully by this electrolyte.Think that in addition reason is, because the big material with carbon element (B) of surface area has and can take out the function as sponge of putting into ionic liquid (A), therefore can be suppressed at each interface, promptly form the local layer (ionic liquid layer) that exists of ionic liquid (A) on the interface between interface, the interface between the carbon particle, electrolyte and the counter electrode between electrolyte and the metal-oxide semiconductor (MOS) multiple aperture plasma membrane described later.Known in addition, if there is not ionic liquid (A) in the electrolyte, then can not play a role as the electrolyte that photo-electric conversion element is used, for example, in the dye sensitization type photo-electric conversion element of in patent documentation 2, putting down in writing, ionic liquid may form the low ionic liquid layer of charge transport ability between above-mentioned interface, become the resistance components that photoelectric conversion efficiency is reduced.
In addition, from improving the functional point of view of ionic liquid (A) to the filling of metal-oxide semiconductor (MOS) multiple aperture plasma membrane and above-mentioned sponge, the content of above-mentioned material with carbon element (B) is 15～45 mass parts with respect to above-mentioned ionic liquid (A) 100 mass parts preferably, more preferably 25～40 mass parts.
In addition, in the present invention, the specific area of above-mentioned material with carbon element (B) is preferably 1100～3200m
2/ g, more preferably 1200～2800m
2/ g.If specific area in this scope, then can be carried out the filling of ionic liquid (A) to the metal-oxide semiconductor (MOS) multiple aperture plasma membrane effectively, and effectively bring into play the function of above-mentioned sponge, the photoelectric conversion efficiency of photo-electric conversion element of the present invention is better.
In addition, in the present invention, 1 average grain diameter of above-mentioned material with carbon element (B) is preferably 0.5～120 μ m, more preferably 0.8～80 μ m.If 1 average grain diameter is in this scope, then the photoelectric conversion efficiency of photo-electric conversion element of the present invention is better.
Herein, 1 average grain diameter is to measure the value that obtains by the assay method of 1 average grain diameter of common material with carbon element (for example active carbon etc.), in the present invention, be meant and use the aqueous solution that contains neutral detergent that material with carbon element (B) is disperseed, (for example use laser diffraction formula particle size distribution device, SALD2000J (registered trade mark, Shimadzu Seisakusho Ltd.'s system) etc.) measure the 50% volume cumulative path (D50) that obtains.
In addition, in the present invention, the resistivity of above-mentioned material with carbon element (B) is preferably 1 * 10
-4～5 * 10
2Ω cm, more preferably 1 * 10
-2～1 * 10
2Ω cm, more preferably 5 * 10
-2～50 Ω cm.If resistivity is in this scope, then surperficial graphitization is not carried out, and therefore is the high material with carbon element of hold facility good with the wetability of above-mentioned ionic liquid (A), ionic liquid (A).
Herein, resistivity is meant and uses the low-resistivity meter to measure the value that resistivity (volume intrinsic resistance value) obtains by 2 terminals measurement methods.
In addition, the resistivity of acetylene black described later is 3 * 10
-2Ω cm.
As such material with carbon element (B), specifically for example can enumerate active carbon (specific area: 1000～2800m
2/ g, 1 average grain diameter: 0.5～120 μ m, resistivity: 1.0 * 10
-1Ω cm), the porous matter material with carbon element (specific area: 1000～2000m of boracic
2/ g, 1 average grain diameter: 0.5～100 μ m, resistivity: 1 * 10
-1Ω cm), nitrogenous porous matter material with carbon element (specific area: 1000～2000m
2/ g, 1 average grain diameter: 0.5～100 μ m, resistivity: 1 * 10
-1Ω cm) etc., these material with carbon elements can use a kind separately, also can merge use more than 2 kinds.
Wherein, from the reason of obtaining easily, preferred active carbon.
Active carbon is not limited especially, can use the activated carbon particles of in known carbon electrode etc., using, as its concrete example, can enumerate the activated carbon particles of using steam, all ingredients, alkali etc. that cocoanut shell, wood powder, petroleum asphalt, phenol resin etc. are activated and getting, these active carbons can use a kind separately, also can merge use more than 2 kinds.
(other material with carbon element (C))
In electrolyte of the present invention, viewpoint from the photoelectric conversion efficiency of further raising photo-electric conversion element of the present invention, as other material with carbon element (C), can use that to be selected from acetylene black (C1), boron modification acetylene black (C2), to measure the pH value that obtains by the pH assay method of stipulating among the JIS Z8802 be that 2～6 material with carbon element (C3) and nitrogen adsorption specific surface area are 90m
2Material more than a kind in the carbon black (C4) more than/g.
These material with carbon elements (C) can merge use more than 2 kinds, the preferred merging used boron modification acetylene black described later (C2) and material with carbon element (C3).
＜acetylene black (C1) 〉
The acetylene black (C1) that can use in electrolyte of the present invention is not limited especially, is the high carbon black of crystallinity that the thermal decomposition by acetylene gas obtains, and can use the known in the past acetylene black of using as conductive agent.
As such acetylene black (C1), specifically for example can enumerate acetylene black (デ Application カ Block ラ Star Network, powdery, specific area: 68m
2/ g, 1 average grain diameter: 400nm, resistivity: 3 * 10
-2Ω cm, electrochemical industry society system) etc.
＜boron modification acetylene black (C2) 〉
The boron modification acetylene black (C2) that can use in electrolyte of the present invention is not limited especially,, can enumerate boron modification acetylene black (デ Application カ Block ラ Star Network BMAB, specific area: 50m as its concrete example
2/ g, 1 average grain diameter: 35nm, resistivity: 1 * 10
-2Ω cm, electrochemical industry society system) etc.
In addition, in the present invention, compare with using above-mentioned acetylene black (C1), better aspect the photoelectric conversion efficiency of photo-electric conversion element of the present invention when using boron modification acetylene black.
＜material with carbon element (C3) 〉
The material with carbon element (C3) that can use in electrolyte of the present invention is that to measure the pH value that obtains by the pH assay method stipulated among the JIS Z8802 be 2～6 material with carbon element.
The mensuration of above-mentioned pH value is specific as follows carries out.At first, measure material with carbon element sample 5g in beaker, to wherein adding entry 50mL, heating is seethed with excitement up to water.Then, the dispersion liquid cool to room temperature with heating staticly settles material with carbon element, removes supernatant then, residual mud shape thing.In this mud shape thing, put into the electrode of glass electrode pH meter, measure by the pH assay method of stipulating among the JIS Z8802-1984.
In addition, in the present invention, 1 average grain diameter of above-mentioned material with carbon element (C3) is preferably 0.010～0.050 μ m, more preferably 0.010～0.035 μ m.If 1 average grain diameter is in this scope, then the photoelectric conversion efficiency of photo-electric conversion element of the present invention is better.
Herein, 1 average grain diameter is to measure the value that obtains by the assay method of 1 average grain diameter of common material with carbon element (for example furnace black etc.), in the present invention, is meant the average diameter of obtaining with the electron microscope observation carbon black particle.
As such material with carbon element (C3), for example can enumerate, adhere to or combine the acidic black of acidic-groups such as phenol hydroxyl, carboxyl, quinonyl, lactone group; The pigment carbon black; Colour carbon black; Or the like, these material with carbon elements can use a kind separately, also can merge use more than 2 kinds.
Wherein, from mix, make the better reason of photoelectric conversion efficiency of photo-electric conversion element of the present invention, preferred acidic carbon black easily with above-mentioned ionic liquid (A).
, the carbon black of the hydroxyl grade used in the above-mentioned acidic black is not limited especially herein, can use oil furnace black, natural gas furnace black, thermal black, channel black normally used carbon blacks such as (channel blacks).
In addition,, for example can enumerate disclosed method etc. in the ozone treatment of carrying out, plasma treatment, liquid phase oxidation processing etc. usually, the TOHKEMY 2004-238311 communique as the method for hydroxyl grade.
In addition, as above-mentioned acidic black, can use carbon blacksurface to have a large amount of acidic-groups (above-mentioned illustrated phenol hydroxyl, carboxyl etc.) channel black (channel black) itself, also can use commercially available product, specifically for example can use, #2200B (the pH value: 3.5 of Mitsubishi Chemical society system, 1 average grain diameter: 0.018 μ m), #1000 (pH value: 3.5,1 average grain diameter: 0.018 μ m), #970 (pH value: 3.5,1 average grain diameter: 0.016 μ m), MA77 (pH value: 2.5,1 average grain diameter: 0.023 μ m), MA7 (pH value: 3,1 average grain diameter: 0.024 μ m), MA8 (pH value: 3,1 average grain diameter: 0.024 μ m), MA11 (pH value: 3.5,1 average grain diameter: 0.029 μ m), MA100 (pH value: 3.5,1 average grain diameter: 0.024 μ m), MA100R (pH value: 3.5,1 average grain diameter: 0.024 μ m), MA100S (pH value value: 3.5,1 average grain diameter: 0.024 μ m), MA230 (pH value: 3,1 average grain diameter: 0.030 μ m), MA200RB (pH value: 3,0.030 μ m) and MA14 (pH value: 3,1 average grain diameters: 0.040 μ m) 1 average grain diameter:;
Special Black6 (the pH value: 2.5 of デ グ サ エ ボ ニ Star Network society system, 1 average grain diameter: 17nm), Special Black5 (pH value: 3.0,1 average grain diameter: 20nm), Special Black4 (pH value: 3.0,1 average grain diameter: 25nm), Special Black4A (pH value: 3.0,1 average grain diameter: 25nm), Special Black550 (pH value: 2.8,1 average grain diameter: 25nm), Special Black100 (pH value: 3.3,1 average grain diameter: 50nm), Special Black250 (pH value: 3.1,1 average grain diameter: 56nm), Special Black350 (pH value: 3.5,1 average grain diameter: 31nm), Printex150T (pH value: 4.0,1 average grain diameter: 29nm), Color Black FW1 (pH value: 3.5,1 average grain diameter: 13nm), Color Black FW18 (pH value: 4.5,1 average grain diameter: 15nm), Color Black FW285 (pH value: 3.5,1 average grain diameter: 11nm), Color Black S170 (pH value: 4.5,1 average grain diameter: 17nm), Color Black S160 (pH value: 4.5,1 average grain diameter: 17nm), Color Black FW200 (pH value: 2.5,1 average grain diameter: 13nm), Color Black FW2 (pH value: 2.5,1 average grain diameter: 13nm) with Color Black FW2V (pH value: 2.5,1 average grain diameters: 13nm);
The ト one カ Block ラ Star Network #8300F of East sea カ one ボ Application society system (pH value: 5.0,1 average grain diameters: 16nm) with ト one カ Block ラ Star Network #8500F (pH value: 5.5,1 average grain diameters: 14nm); Or the like.
These acidic blacks can use a kind separately, also can merge use more than 2 kinds.
Wherein, from improving photo-electric conversion element of the present invention with electrolytical ageing stability, further improve the viewpoint of the photoelectric conversion efficiency of photo-electric conversion element of the present invention, preferred pH value is 3～5.5 acidic black.
＜carbon black (C4) 〉
The carbon black (C4) that can use in electrolyte of the present invention is as long as the nitrogen adsorption specific surface area is 90m
2/ g is above to get final product, and has no particular limits.
Herein, the nitrogen adsorption specific surface area is the characteristic that substitutes of the surface area that can utilize in the absorption of carbon black and rubber molecule, is to measure the value that the nitrogen adsorbance of carbon blacksurface obtains according to JIS K6217-7:2008 " the 7th one: rubber composition-multipoint method nitrogen specific area and statistical thickness specific area ask method ".
In addition, in the present invention, from the better reason of the photoelectric conversion efficiency that makes photo-electric conversion element of the present invention, preferably using the nitrogen adsorption specific surface area is 90～200m
2The carbon black of/g more preferably uses 100～180m
2The carbon black of/g.
In addition, in the present invention, it is 7～13 carbon black that above-mentioned carbon black (C4) is preferably measured the pH value that obtains according to the pH assay method stipulated among the JIS Z8802, is more preferably the pH value and is 7～11 carbon black.
Explanation in the mensuration of above-mentioned pH value and the above-mentioned material with carbon element (C3) is same, specific as follows carrying out.At first, measure carbon black sample 5g in beaker, to wherein adding entry 50mL, heating is seethed with excitement up to water.Then, the dispersion liquid cool to room temperature with heating staticly settles carbon black, removes supernatant then, residual mud shape thing.In this mud shape thing, put into the electrode of glass electrode pH meter, measure according to the pH assay method of stipulating among the JISZ8802-1984.
As such carbon black (C4), can use commercially available product.
Specifically for example can enumerate SAF (N134, nitrogen adsorption specific surface area: 151m
2/ g, pH value: 7.3, キ ヤ ボ Star ト ジ ヤ パ Application society system), ISAF (N234, nitrogen adsorption specific surface area: 117m
2/ g, pH value: 7.5, キ ヤ ボ Star ト ジ ヤ パ Application society system), ISAF (N220, nitrogen adsorption specific surface area: 119m
2/ g, pH value: 7.5, キ ヤ ボ Star ト ジ ヤ パ Application society system), ISAF (N219, nitrogen adsorption specific surface area: 106m
2/ g, 7.5 ， East sea カ one ボ Application society system), HAF (N339, nitrogen adsorption specific surface area: 93m pH value:
2/ g, pH value: 7.5 ， East sea カ one ボ Application society system) etc.
In the present invention, 1 average grain diameter of above-mentioned carbon black (C4) is preferably 5～30nm, more preferably 5～25nm.If 1 average grain diameter is in this scope, then the photoelectric conversion efficiency of photo-electric conversion element of the present invention is better.
Herein, the explanation in 1 average grain diameter and the above-mentioned material with carbon element (C3) is same, is meant the average diameter of obtaining with the electron microscope observation carbon black particle.
In the present invention, under the situation that contains above-mentioned other material with carbon element (C), even from not comprising the reason that iodine also can reach higher energy conversion efficiency in fact, preferably with respect to above-mentioned ionic liquid (A) 100 mass parts, above-mentioned material with carbon element (B) and above-mentioned other material with carbon element (C) add up to and contain 10～50 mass parts.
In addition, similarly, above-mentioned material with carbon element (B) is preferably 99.9/0.1～60/40 with the ratio [material with carbon element (B)/other material with carbon element (C)] of the content of above-mentioned other material with carbon element (C).
Herein, any in using acetylene black (C1), boron modification acetylene black (C2), material with carbon element (C3) and carbon black (C4) is more than 2 kinds under the situation as other material with carbon element (C), above-mentioned content is meant their total content, is closely using under any one the situation, is meant any one content.
Like this, also can to reach the concrete cause of high energy conversion efficiency not clear even do not comprise iodine in fact, but consider as follows.
Can think that in other material with carbon element (C), the ionic liquid (A) that the acetylene black that surface area is little (C1), boron modification acetylene black (C2) do not have to have kept with above-mentioned material with carbon element (B) helps lend some impetus to electric charge and moves.Think especially, because boron modification acetylene black (C2) is because of the importing possess hydrophilic property of boron, so the compatibility of itself and above-mentioned ionic liquid (A) uprises, and also transfiguration is easy for the dispersion in ionic liquid (A), (C1) compares with acetylene black, and the facilitation effect that electric charge moves is higher.
Think in addition, in other material with carbon element (C), about material with carbon element (C3), interact with the cation of above-mentioned ionic liquid (A) as acidic-group (above-mentioned illustrated phenol hydroxyl, the carboxyl etc.) anion (for example carboxylate radical, phenol root etc.) that derives that functional group exists by the surface of material with carbon element.Think in addition because the existence of the surface functional group of material with carbon element, therefore compare and become hydrophily, and think to also have the dispersion in above-mentioned ionic liquid (A) to be easier to as reason with general carbon black, graphite.
Think in addition, in other material with carbon element (C), the carbon black that the nitrogen specific area is big (C4), with above-mentioned material with carbon element (B) similarly, have and to take out the function that discharges above-mentioned ionic liquid (A) as sponge, therefore can be suppressed at each interface, it is the interface between between electrolyte and metal-oxide semiconductor (MOS) multiple aperture plasma membrane described later, interface between the carbon particle, form the local layer (ionic liquid layer) that exists of ionic liquid (A) on the interface between electrolyte and the counter electrode, in addition because the structure of carbon black (C4) is also flourishing, therefore electronic conductivity improves, based on these results, the open circuit voltage of photo-electric conversion element increases.
In addition, open circuit voltage is meant the voltage between the terminal when power supply terminal does not flow through electric current, be meant when electrode being applied reverse voltage (bias voltage) and when increasing bias voltage gradually the magnitude of voltage of (when current value is zero) when irradiates light and the electric current that produces flow against this bias voltage.
In addition, in the present invention, from improving ionic liquid (A) to viewpoints such as function, the electric charge of the filling of metal-oxide semiconductor (MOS) multiple aperture plasma membrane and above-mentioned sponge move, the total content of above-mentioned material with carbon element (B) and above-mentioned other material with carbon element (C) is 15～45 mass parts with respect to above-mentioned ionic liquid (A) 100 mass parts more preferably, more preferably 20～40 mass parts.
In addition, from same viewpoint, the ratio [material with carbon element (B)/other material with carbon element (C)] of the content of above-mentioned material with carbon element (B) and above-mentioned other material with carbon element (C) more preferably 99/1～65/35, more preferably 98/2～70/30.
Reason from the photoelectric conversion efficiency of further raising photo-electric conversion element of the present invention can contain silica and/or metal oxide in the electrolyte of the present invention.
Think this be because, cation (for example, the imidazoles that above-mentioned ionic liquid (A) is had
Ion) cause that orientation improves, movement of electrons is carried out smoothly.
The silica that can use in electrolyte of the present invention is not limited especially, can use known in the past silica.
As silica, specifically for example can enumerate, pyrogenic silica, burn till silicon dioxide, sedimentation silicon dioxide, pulverize silicon dioxide, fused silica, colloidal silica etc.
As such silica, can use commercially available product, specifically for example can use Z1165MP (Rodia society system), AEROSIL200 (Deguss society system), AEROSIL300 (Deguss society system) etc.
On the other hand, the metal oxide that can use in electrolyte of the present invention is not limited especially, can use known in the past metal oxide.
As above-mentioned metal oxide, specifically for example can enumerate, titanium oxide (titanium dioxide), tin oxide, zinc oxide, tungsten oxide, zirconia, hafnium oxide, strontium oxide strontia, vanadium oxide, niobium oxide etc., these metal oxides can use a kind separately, also can merge use more than 2 kinds.
Wherein, from viewpoints such as opto-electronic conversion ability height, be preferably titanium oxide, zinc oxide, niobium oxide, tungsten oxide, zirconia.
In the present invention, the total content of above-mentioned silica and/or metal oxide and above-mentioned material with carbon element (B) and above-mentioned other material with carbon element (C) of containing as required is 10～50 mass parts with respect to above-mentioned ionic liquid (A) 100 mass parts preferably, more preferably 15～45 mass parts, more preferably 20～40 mass parts.
If the total content of above-mentioned silica and/or metal oxide and above-mentioned material with carbon element (B) and above-mentioned other material with carbon element (C) of containing as required can not reach higher energy conversion efficiency even then do not comprise iodine in fact yet in this scope.
In addition, in the present invention, the ratio (silica etc./material with carbon element etc.) of the content of above-mentioned silica and/or metal oxide (following be called in this paragraph " silica etc. ") and above-mentioned material with carbon element (B) and above-mentioned other material with carbon element (C) (following be called in this paragraph " material with carbon element etc. ") of containing as required is preferably 1/99～50/50, and more preferably 2/98～40/60.
From the sight of the photoelectric conversion efficiency of further raising photo-electric conversion element of the present invention, can add redox couple (redox couple) in the electrolyte of the present invention.
As redox couple, in the scope of not destroying the object of the invention, can use general use or operable any redox couple in DSSC.
For example can enumerate metal complexs such as hydroferrocyanate-ferricyanide, ferrocene-ferrocene salt; The sulphur compound of disulphide and sulfhydryl compound; Quinhydrones; Benzoquinones; Or the like, these redox couples can use a kind separately, also can merge use more than 2 kinds.
In addition, from the viewpoint of the short circuit current that improves photo-electric conversion element of the present invention, can add inorganic salts and/or organic salt in the electrolyte of the present invention.
As inorganic salts, organic salt, for example can enumerate, alkali metal, alkali earth metal salt etc., specifically can enumerate lithium iodide, sodium iodide, KI, magnesium iodide, calcium iodide, trifluoroacetic acid lithium, sodium trifluoroacetate, lithium rhodanate, LiBF4, lithium hexafluoro phosphate, lithium perchlorate, trifluoromethanesulfonic acid lithium, two (fluoroform sulphonyl) imines lithium etc., these salt can use a kind separately, also can merge use more than 2 kinds.
Addition to inorganic salts, organic salt does not limit especially, only just can be with the same in the past otherwise destroy purpose of the present invention.
In addition, from the viewpoint of the open circuit voltage that improves photo-electric conversion element of the present invention, can add pyridines, benzimidazole in the electrolyte of the present invention.
Specifically can enumerate alkyl pyridine classes such as picoline, ethylpyridine, propyl group pyridine, butyl-pyridinium; Alkyl imidazoles such as methylimidazole, ethyl imidazol(e), propyl imidazole; Alkyl benzimidazole classes such as tolimidazole, ethyl benzo imidazole, propyl group benzimidazole; Or the like, they can use a kind separately, also can merge use more than 2 kinds.
Addition to pyridines, benzimidazole does not limit especially, only just can be with the same in the past otherwise destroy purpose of the present invention.
Organic solvent can be added in the electrolyte of the present invention,, carbonates such as ethylene carbonate, propylene carbonate can be enumerated as its concrete example; Ethers such as ethylene glycol bisthioglycolate alkyl ether, propylene glycol dialkyl ether; Alcohols such as ethylene glycol monoalkyl ether, propylene-glycol monoalky lether; Polyalcohols such as ethylene glycol, propylene glycol; Nitriles such as propionitrile, methoxypropionitrile, cyano group ether; Amide-types such as dimethyl formamide, N-methyl pyrrolidone; Aprotic polar solvent such as methyl-sulfoxide, sulfolane class; Or the like, these organic solvents can use a kind separately, also can merge use more than 2 kinds.
Content to organic solvent does not limit especially, only just can be with the same in the past otherwise destroy purpose of the present invention.
Electrolytical manufacture method of the present invention is not limited especially, can make by the following method: for example, with above-mentioned ionic liquid (A) and material with carbon element (B) and other material with carbon element (C) of containing as required, silica, metal oxides etc. mix, use ball mill, sand mill, the pigment dispersing machine, beat broken machine, ultrasonic dispersing machine, homogenizer, planetary-type mixer, Hobart's blender (Hobart mixer), roller, kneader etc. at room temperature or heating down (for example 40～150 ℃) it is mixed fully, make it disperse (mixing) equably, thereby make.
Herein, when the mixing of above-mentioned ionic liquid (A) and material with carbon element (B) and other material with carbon element (C) that contains as required, silica, metal oxide etc., can use as required and to merge with an organic solvent (for example toluene etc.), mix the method that organic solvent is removed in the final vacuum distillation.
In addition, when the mixing of above-mentioned ionic liquid (A) and material with carbon element (B) and other material with carbon element (C) that contains as required, silica, metal oxide etc., in order to make above-mentioned ionic liquid (A) fully flood above-mentioned material with carbon element (B), can use known pulverizers such as adopting ball mill, jet mill in advance to carry out fine above-mentioned material with carbon element (B).In addition, as same purpose, can be at room temperature or heating down (for example, 40～150 ℃) to the mixture enforcement reduced pressure treatment of above-mentioned ionic liquid (A) and material with carbon element (B) and other material with carbon element (C) that contains as required, silica, metal oxide etc.
In the present invention, about electrolytical manufacturing of the present invention, under the situation that contains above-mentioned other material with carbon element (C), preferably above-mentioned ionic liquid (A) and other material with carbon element (C) are mixed and (for example obtain dispersion, the dispersion of pasty state), mix above-mentioned material with carbon element (B) then and modulate.
Modulate by such method, can make the photoelectric conversion efficiency of photo-electric conversion element of the present invention better.Think this be because, above-mentioned other material with carbon element (C) is inhomogeneous to be present in the above-mentioned ionic liquid (A), the ionic liquid (A) that above-mentioned material with carbon element (B) does not have to have kept helps lend some impetus to electric charge and moves with acetylene black (C1), boron modification acetylene black (C2), or interactional cause takes place the cation of above-mentioned material with carbon element (C3) and above-mentioned ionic liquid (A).
Next, with reference to Fig. 1 photo-electric conversion element of the present invention and DSSC are described in detail.Fig. 1 is the generalized section that shows the basic comprising of a routine photo-electric conversion element of the present invention.
Photo-electric conversion element of the present invention has: have nesa coating and metal-oxide semiconductor (MOS) multiple aperture plasma membrane optoelectronic pole, and above-mentioned optoelectronic pole to the counter electrode of phase configuration, the dielectric substrate that between above-mentioned optoelectronic pole and above-mentioned counter electrode, disposes.
＜optoelectronic pole 〉
Above-mentioned optoelectronic pole for example, as shown in Figure 1, is made of transparency carrier 1, nesa coating 2 and oxide semiconductor multiple aperture plasma membrane 3.
Herein, the good material of transparency carrier 1 preferred light transmission, as its concrete example, can enumerate the resin substrate (film) of glass substrate and polystyrene, polyethylene, polypropylene, PETG, PEN, Merlon, polyphenylene sulfide, cyclic olefin polymer, polyether sulfone, polysulfones, Polyetherimide, polyarylate, triacetyl cellulose, polymethyl methacrylate etc.
In addition,, specifically for example can enumerate the zinc oxide of the tin oxide of mixed antimony and/or fluorine, mixed aluminium and/or gallium, the conductive metal oxides such as indium oxide of the tin that mixed as nesa coating 2.
In addition, the thickness of nesa coating 2 is preferably about 0.01～1.0 μ m.
In addition, to being used to be provided with the qualification especially of method of nesa coating 2, for example can enumerate rubbing method, sputtering method, vacuum vapour deposition, spray heating decomposition, chemical vapour deposition technique (CVD), sol-gal process etc.
Next, be coated on by dispersion liquid and obtain oxide semiconductor multiple aperture plasma membrane 3 on the nesa coating 2 the oxide semiconductor particulate.
As above-mentioned oxide semiconductor particulate, specifically for example can enumerate, titanium oxide, tin oxide, zinc oxide, tungsten oxide, zirconia, hafnium oxide, strontium oxide strontia, vanadium oxide, niobium oxide etc., these oxide semiconductor particulates can use a kind separately, also can merge use more than 2 kinds.
Obtain above-mentioned dispersion liquid by using dispersion machines such as sand mill, ball mill, ball mill, triple-roller mill, colloid mill, ultrasonic homogenizer, Henschel mixer, jet mill that above-mentioned oxide semiconductor particulate and decentralized medium are mixed.
In addition, preferably using dispersion machine to mix after obtaining above-mentioned dispersion liquid, be about to use (coating) before, use ultrasonic homogenizer etc. to above-mentioned dispersion liquid enforcement ultrasonic Treatment.By being about to implement ultrasonic Treatment before the use, the photoelectric conversion efficiency of photo-electric conversion element of the present invention is better.Think that this is the oxide semiconductor multiple aperture plasma membrane that forms owing to the dispersion liquid of having implemented ultrasonic Treatment for use before being about to use, the cause that above-mentioned ionic liquid (A) is filled easily.
In addition, in order to prevent the cohesion again of the above-mentioned oxide semiconductor particulate in the dispersion liquid, can in above-mentioned dispersion liquid, add acetylacetone,2,4-pentanedione, hydrochloric acid, nitric acid, surfactant, chelating agent etc., in order to make the dispersion liquid thickening, can add macromolecules such as polyoxyethylene, polyvinyl alcohol, cellulose-based thickener etc.
As above-mentioned dispersion liquid, also can use titanium oxide thickener SP100, SP200 (being clear and electrician society system), titanium oxide microparticle Ti-Nanoxide T (ソ one ラ ロ ニ Network ス society system), Ti-Nanoxide D (ソ one ラ ロ ニ Network ス society system), Ti-Nanoxide T/SP (ソ one ラ ロ ニ Network ス society system), Ti-Nanoxide D/SP (ソ one ラ ロ ニ Network ス society system), titanium dioxide-coated thickener PECC01 (ペ Network セ Le テ Network ノ ロ ジ one ズ society system), TiO 2 particles thickener PST-18NR (day waves catalyst and changes into), TiO 2 particles thickener PST400C commercially available products such as (day wave catalyst and changes into).
As the method that above-mentioned dispersion liquid is coated on the nesa coating, for example can use, known wet type becomes embrane method.
Become embrane method as wet type, specifically for example can enumerate, silk screen print method, ink jet printing method, rolling method, scrape the skill in using a kitchen knife in cookery, method of spin coating, spraying process etc.
In addition, be coated on above-mentioned dispersion liquid on the nesa coating after, for the tack that improves electrically contacting between the particulate, raising and nesa coating, improve film-strength, preferably carry out heat treated, chemical treatment, plasma, ozone treatment etc.
As the temperature of heat treated, be preferably 40 ℃～700 ℃, more preferably 40 ℃～650 ℃.In addition, as the time of heat treated, system is not limit especially, be generally 10 seconds～and about 24 hours.
As chemical treatment, specifically for example can enumerate, use the chemical plating of titanium tetrachloride aqueous solution to handle, used the chemisorbed of carboxylic acid derivates to handle, used the electrochemistry plating processing of titanium trichloride aqueous solution etc.
＜counter electrode 〉
Above-mentioned counter electrode, as shown in Figure 1, be and the electrode 5 of 4 pairs of phase configuration of optoelectronic pole, for example can use, metal substrate, surface have glass substrate, resin substrate of conducting film etc.
As metal substrate, can use metals such as platinum, gold, silver, copper, aluminium, indium, titanium.As resin substrate, in the transparency carrier 1 that constitutes optoelectronic pole 4, the illustrative substrate (film), can also use the general resin substrate of opaque or transparent difference.
In addition, as the conducting film that the surface is provided with, can enumerate metals such as platinum, gold, silver, copper, aluminium, indium, titanium; Carbon; Tin oxide; The tin oxide of antimony and/or fluorine has mixed; Zinc oxide; The zinc oxide of aluminium and/or gallium has mixed; The indium oxide of tin has mixed; Deng conductive metal oxide; Or the like.As thickness, the formation method of conducting film, can enumerate thickness, the formation method same with the nesa coating 2 that constitutes optoelectronic pole 4.
In the present invention, as counter electrode 5, can use the electrode, the electroconductive polymer membrane electrode that on substrate, have formed the electroconductive polymer film.
As electroconductive polymer, specifically for example can enumerate polythiophene, polypyrrole, polyaniline etc.
On substrate, form the method for electroconductive polymer film, can use as common wet type to become the known dip coated method of embrane method, method of spin coating etc. on substrate, to form conducting polymer film by high molecular dispersion liquid.
As the electroconductive polymer dispersion liquid, can use disclosed polyaniline dispersion liquid in the TOHKEMY 2006-169291 communique, as polythiofuran derivative aqueous dispersions (the バ イ ト ロ Application P of commercially available product, バ イ エ Le society system), レ イ ヨ Application society of Mitsubishi system (ア Network ア セ one Block, the polyaniline derivative aqueous solution) etc.
In addition, be under the situation of above-mentioned electrically-conductive backing plate at substrate, except said method, also can on substrate, form the electroconductive polymer film by the electrolysis polymerization method.The electroconductive polymer membrane electrode also can use the self-supporting film that the electroconductive polymer film that will form by the electrolysis polymerization method obtains from stripping electrode or use as wet type usually to become self-supporting film that the known The tape casting of embrane method, method of spin coating etc. form by the electroconductive polymer dispersion liquid etc. on electrode.So-called herein electroconductive polymer dispersion liquid, the state that for convenience state of electroconductive polymer microparticulate in solvent and electroconductive polymer is dissolved in the solvent mixes the dispersion liquid of existence as the electroconductive polymer dispersion liquid.
＜electrolyte 〉
Above-mentioned dielectric substrate as shown in Figure 1, is arranged on the dielectric substrate 6 between optoelectronic pole 4 and the counter electrode 5, in photo-electric conversion element of the present invention, uses above-mentioned electrolyte of the present invention.
Because photo-electric conversion element of the present invention uses above-mentioned electrolyte of the present invention, even therefore not comprising iodine in fact also can reach high energy conversion efficiency.
DSSC of the present invention is photo-electric conversion element a kind of who has supported photosensitive dye on the optoelectronic pole of above-mentioned formation photo-electric conversion element of the present invention.
Herein, as photosensitive dye, so long as in the visible region and/or the dyestuff of infrared light region with absorption get final product, do not limit especially, can use metal complex or organic dyestuff etc.
Specifically can use ruthenium complex dyestuff, porphyrin based dye, phthalocyanine based dye, cyanines based dye, merocyanine based dye, xanthene based dye of having carried out coordination with parts such as bipyridine structure, terpyridyl structures etc.To the method that supports system limit especially, above-mentioned dyestuff for example is dissolved in water, the alcohols, thereby oxide impregnation thing semiconductor porous plasma membrane 3 or dye solution is coated on the oxide semiconductor multiple aperture plasma membrane 3 support in dye solution.
Embodiment
Embodiment below is shown, specifically describes the present invention.Yet, the invention is not restricted to these embodiment.
(embodiment 1～34, comparative example 1～11)
＜electrolytical modulation 〉
In the 30mL mixer, use ball mill (ロ Star キ Application グ RM02, セ イ ワ skill is ground society's system) that the ionic liquid A1 shown in the following table 1 etc., toluene, zirconium oxide bead (diameter 3mm) were mixed 60 minutes according to the composition shown in the following table 1.
Toluene is removed in vacuum distillation from mixed dispersion liquid, thereby has obtained electrolyte.
The making of＜DSSC 〉
At transparent conductivity glass (FTO glass, sheet resistance 15 Ω/, NHTechno society system) goes up coating titanium oxide thickener Ti-Nanoxide D (Solaronix society system), make it at room temperature dry, under 450 ℃ temperature, toasted 30 minutes then, thereby produce at the transparent conductivity optoelectronic pole that is formed with the titanium oxide multiple aperture plasma membrane on glass.
Make the ethanolic solution (concentration 3 * 10 of the optoelectronic pole of making in ruthenium complex dyestuff (cis-(two thiocyano-s)-N, N '-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) closes ruthenium (II) complex compound) (Ruthenium 535-bisTBA, Solaronix society system)
-4The mole/L) in the dipping 4 hours.
Then,, in the dark under stream of nitrogen gas, carry out drying with acetonitrile washing, thus will on the titanium oxide electrode of optoelectronic pole, support sensitizing dyestuff and material as optoelectronic pole.
The above-mentioned electrolyte of coating modulation on the optoelectronic pole that has supported photosensitive dye, (conducting surface has the indium oxide of the tin that mixed at the transparent conductivity glass substrate with adopting sputtering method with it, sheet resistance: 8 Ω/mouths, NHTechno society system) the surface platinum counter electrode that formed the platinum film of the about 100nm of thickness sticks together, fix with anchor clamps then, thereby obtained DSSC.
The photoelectric conversion efficiency of the DSSC of gained is measured and is estimated by method shown below.It the results are shown in table 1.
＜photoelectric conversion efficiency 〉
As shown in Figure 2, use solar simulator as light source, with 100mW/cm
2Luminous intensity from the simulated solar irradiation of optoelectronic pole side irradiation AM1.5, use current/voltage determinator (the system デ ジ タ of ケ one ス レ one イ Application ス Star Le メ Application Star society Le ソ one ス メ one タ 1) to obtain conversion efficiency.
Table 1 (1)
Table 1 (4)
Table 1 (5)
Each composition in the table 1 is as follows.
Ionic liquid A1:1-methyl-3-propyl group iodate imidazoles
(Tokyo changes into society's system)
Material with carbon element B1: active carbon (NY1151, specific area: 1325m
2/ g, 1 average grain diameter: 5 μ m, resistivity: 1.5 * 10
-1Ω cm, Network ラ レ ケ ミ カ Le society system)
Material with carbon element B2: active carbon (NK261, specific area: 2300m
2/ g, 1 average grain diameter: 5 μ m, resistivity: 1.5 * 10
-1Ω cm, Network ラ レ ケ ミ カ Le society system)
Material with carbon element C1-1: acetylene black (デ Application カ Block ラ Star Network powdery, specific area: 68m
2/ g, 1 average grain diameter: 35nm, resistivity: 3 * 10
-2Ω cm, electrochemical industry society system)
Material with carbon element C2-1: boron modification acetylene black (デ Application カ Block ラ Star Network BMAB, specific area: 50m
2/ g, 1 average grain diameter: 35nm, resistivity: 1 * 10
-2Ω cm, electrochemical industry society system)
Material with carbon element C3-1: acidic black (Color Black FW1, pH value: 4.5,1 average grain diameter: 13nm, resistivity: 5 * 10
-1Ω cm, デ グ サ society system)
Material with carbon element C3-2:Special Black5 (pH value: 3.0,1 average grain diameter: 20nm, resistivity: 1.5 Ω cm, デ グ サ society system)
Material with carbon element C3-3: ト one カ Block ラ Star Network #8500F (pH value: 5.5,1 average grain diameter: 14nm, resistivity: 5 * 10
-1Ω cm ， East sea カ one ボ Application society system)
Material with carbon element C4-1:SAF (N134, nitrogen adsorption specific surface area: 151m
2/ g, the pH value: 7.3, average grain diameter: 19nm, キ ヤ ボ Star ト ジ ヤ パ Application society system)
Material with carbon element C4-2:ISAF (N234, nitrogen adsorption specific surface area: 117m
2/ g, the pH value: 7.5, average grain diameter: 23nm, キ ヤ ボ Star ト ジ ヤ パ Application society system)
Material with carbon element C4-3:HAF (N339, nitrogen adsorption specific surface area: 93m
2/ g, the pH value: 7.5, average grain diameter: 24nm ， East sea カ one ボ Application society system)
Silica: sedimentation silicon dioxide (Z1165MP, Rodia society system)
Titanium oxide: hot melt titanium oxide P25 (Degussa society system)
By the result shown in the above-mentioned table 1 as can be known, contain the electrolyte of the embodiment 1～5 that the mode of ionic liquid (A) and material with carbon element (B) modulates with special ratios, even do not comprise iodine in fact, photoelectric conversion efficiency also can fully improve, and reaches 4.3～4.9%.This demonstrates more excellent than the electrolyte that uses the comparative example of modulating as the acetylene black of conductive material 3～7, and the result makes us feeling surprised.
On the other hand as can be known, with respect to ionic liquid (A) 100 mass parts cooperate the comparative example 1 of material with carbon element (B) 5 mass parts modulation electrolyte, cooperate the electrolyte of the comparative example 2 of material with carbon element (B) 60 mass parts modulation with respect to ionic liquid (A) 100 mass parts, its photoelectric conversion efficiency is low.
In addition, even merging under the situation of using material with carbon element (C), with respect to ionic liquid (A) 100 mass parts, the electrolyte of the comparative example 8～11 of the content of material with carbon element (B) outside 10～50 mass parts, material with carbon element (B) and material with carbon element (C) though total content be 10～50 mass parts, photoelectric conversion efficiency also rests on about 4.0%.
Therewith relatively as can be known, contain ionic liquid (A) and material with carbon element (B), also contain material with carbon element (C) and the electrolyte of the embodiment 6～32 of modulation with special ratios, even do not comprise iodine in fact, photoelectric conversion efficiency also can fully improve, and reaches more than 5.0%.
Especially as can be known, use boron modification acetylene black as the embodiment 10 of material with carbon element (C) modulation and 15 electrolyte, even do not comprise iodine in fact, photoelectric conversion efficiency also can further improve, reach more than 6.0%, use the electrolyte of acidic black, even do not comprise iodine in fact as the embodiment 19～28 of material with carbon element (C) modulation, photoelectric conversion efficiency also can fully improve, and reaches more than 5.5%.
In addition we know, the electrolyte of embodiment 6～32 all is that the total content of material with carbon element (B) and material with carbon element (C) is 10～50 mass parts with respect to ionic liquid (A) 100 mass parts, but material with carbon element (B) is the embodiment 6～23,26～28 of 99.9/0.1～60/40 and 30～32 electrolyte with the ratio [material with carbon element (B)/material with carbon element (C)] of the content of material with carbon element (C), and its photoelectric conversion efficiency is tended to higher.
In addition, contain ionic liquid (A) and material with carbon element (B), also contain silica or titanium oxide and the embodiment 33 that modulates and 34 electrolyte with special ratios, even do not comprise iodine in fact, photoelectric conversion efficiency also can fully improve, and reaches more than 5.9%.
Description of reference numerals
1: transparency carrier
2: nesa coating
3: the oxide semiconductor multiple aperture plasma membrane
4: optoelectronic pole
5: counter electrode
6: dielectric substrate
11: transparency carrier
12: nesa coating (ITO, FTO)
13: metal oxide
14: electrolyte
15: platinum film
16: nesa coating (ITO, FTO)
17: substrate
18: counter electrode.
Claims (15)
1. photo-electric conversion element electrolyte, containing ionic liquid (A) and specific area is 1000～3500m
2The material with carbon element of/g (B),
The content of described material with carbon element (B) is 10～50 mass parts with respect to described ionic liquid (A) 100 mass parts.
2. photo-electric conversion element electrolyte according to claim 1,1 average grain diameter of described material with carbon element (B) is 0.5～120 μ m.
3. photo-electric conversion element electrolyte according to claim 1 and 2, described ionic liquid (A) have the cation shown in following formula (1) or the formula (2),
In the formula (1), R
1That represents carbon number 1～20 can comprise heteroatomic alkyl, R
1What can also have carbon number 1～20 can comprise heteroatomic substituting group, R
2And R
3The alkyl of representing hydrogen atom or carbon number 1～20 independently of one another, R
2And R
3Can comprise hetero-atom, but under the situation that has two keys on the nitrogen-atoms, R
3Do not exist,
In the formula (2), Q represents nitrogen-atoms, oxygen atom, phosphorus atoms or sulphur atom, R
4, R
5, R
6And R
7Represent the alkyl of hydrogen atom or carbon number 1～8 independently of one another, they can comprise hetero-atom, are under the situation of oxygen atom or sulphur atom at Q still, R
7Do not exist.
4. photo-electric conversion element electrolyte according to claim 3, described ionic liquid (A) has iodide ion as anion.
5. according to each described photo-electric conversion element electrolyte of claim 1～4, other material with carbon element (C) as except described material with carbon element (B) also contains acetylene black.
6. according to each described photo-electric conversion element electrolyte of claim 1～5, other material with carbon element (C) as except described material with carbon element (B) also contains boron modification acetylene black.
7. according to each described photo-electric conversion element electrolyte of claim 1～6, as other material with carbon element (C) except described material with carbon element (B), contain also that to measure the pH value that obtains by the pH assay method stipulated among the JIS Z8802 be 2～6 material with carbon element.
8. photo-electric conversion element electrolyte according to claim 7, described pH value are that 1 average grain diameter of 2～6 material with carbon element is 0.010～0.050 μ m.
9. according to each described photo-electric conversion element electrolyte of claim 1～8, as other material with carbon element (C) except described material with carbon element (B), also containing the nitrogen adsorption specific surface area is 90m
2The carbon black that/g is above.
10. according to each described photo-electric conversion element electrolyte of claim 5～9, the total content of described material with carbon element (B) and described other material with carbon element (C) is 10～50 mass parts with respect to described ionic liquid (A) 100 mass parts.
11. according to each described photo-electric conversion element electrolyte of claim 5～10, the ratio of the content of described material with carbon element (B) and described other material with carbon element (C), promptly material with carbon element (B)/other material with carbon element (C) is 99.9/0.1～60/40.
12., be by described ionic liquid (A) and described other material with carbon element (C) mixing being obtained dispersion, mixing described material with carbon element (B) then and modulate according to each described photo-electric conversion element electrolyte of claim 5～11.
13. each the described photo-electric conversion element electrolyte according to claim 1～12 also contains silica and/or metal oxide.
14. a photo-electric conversion element comprises:
Have nesa coating and metal-oxide semiconductor (MOS) multiple aperture plasma membrane optoelectronic pole,
With the counter electrode of described optoelectronic pole subtend configuration and
Be configured in the dielectric substrate between described optoelectronic pole and the described counter electrode,
The described photo-electric conversion element electrolyte of each that described dielectric substrate is a claim 1～13.
15. a DSSC supports photosensitive dye and gets on the described optoelectronic pole of claim 14.
Applications Claiming Priority (7)
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| JP2008302935 | 2008-11-27 | ||
| JP302935/2008 | 2008-11-27 | ||
| JP2008312336 | 2008-12-08 | ||
| JP312336/2008 | 2008-12-08 | ||
| JP2009172351 | 2009-07-23 | ||
| JP172351/2009 | 2009-07-23 | ||
| PCT/JP2009/069981 WO2010061901A1 (en) | 2008-11-27 | 2009-11-26 | Electrolyte for photoelectric conversion element, photoelectric conversion element using the electrolyte, and dye-sensitized solar cell |
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| CN (1) | CN102227847B (en) |
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| CN102265452A (en) * | 2008-12-26 | 2011-11-30 | 横滨橡胶株式会社 | Electrolyte for photoelectric conversion element, and photoelectric conversion element and dye-sensitized solar cell each utilizing the electrolyte |
| CN103137238A (en) * | 2011-11-23 | 2013-06-05 | 财团法人工业技术研究院 | Transparent conductive film and method for forming the same |
| CN107527999A (en) * | 2017-08-25 | 2017-12-29 | 京东方科技集团股份有限公司 | Semiconductor mixing material and preparation method thereof, thin film transistor (TFT) and electronic installation |
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| JP2010277854A (en) * | 2009-05-28 | 2010-12-09 | Tdk Corp | Dye-sensitized solar cell and organic solvent-free electrolyte for dye-sensitized solar cell |
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| CN101182384A (en) * | 2006-11-17 | 2008-05-21 | 三星Sdi株式会社 | Electrolyte composition for dye-sensitized solar cell, dye-sensitized solar cell including same, and method of preparing same |
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| JP4185490B2 (en) * | 2002-05-20 | 2008-11-26 | 松下電工株式会社 | Photoelectric conversion element |
| JP4041409B2 (en) | 2003-02-05 | 2008-01-30 | 独立行政法人科学技術振興機構 | Polycyclic aromatic carbon-based solid strong acid |
| WO2005006482A1 (en) | 2003-07-14 | 2005-01-20 | Fujikura Ltd. | Electrolyte composition, and photoelectric converter and dye-sensitized solar cell using same |
| JP2006169291A (en) | 2004-12-13 | 2006-06-29 | Yokohama Rubber Co Ltd:The | Modified conductive polymer and conductive member using the same |
| JP2007227087A (en) * | 2006-02-22 | 2007-09-06 | Toin Gakuen | Dye-sensitized photoelectric conversion element |
| JP2009238693A (en) * | 2008-03-28 | 2009-10-15 | Sumitomo Chemical Co Ltd | Photoelectric conversion element and its manufacturing method |
| JP2010009831A (en) * | 2008-06-25 | 2010-01-14 | Tdk Corp | Photoelectric conversion element |
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- 2009-11-26 CN CN200980147543.3A patent/CN102227847B/en not_active Expired - Fee Related
- 2009-11-26 JP JP2010513520A patent/JP4557097B2/en not_active Expired - Fee Related
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| CN101182384A (en) * | 2006-11-17 | 2008-05-21 | 三星Sdi株式会社 | Electrolyte composition for dye-sensitized solar cell, dye-sensitized solar cell including same, and method of preparing same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102265452A (en) * | 2008-12-26 | 2011-11-30 | 横滨橡胶株式会社 | Electrolyte for photoelectric conversion element, and photoelectric conversion element and dye-sensitized solar cell each utilizing the electrolyte |
| CN103137238A (en) * | 2011-11-23 | 2013-06-05 | 财团法人工业技术研究院 | Transparent conductive film and method for forming the same |
| CN107527999A (en) * | 2017-08-25 | 2017-12-29 | 京东方科技集团股份有限公司 | Semiconductor mixing material and preparation method thereof, thin film transistor (TFT) and electronic installation |
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| WO2010061901A1 (en) | 2010-06-03 |
| DE112009003578T5 (en) | 2012-04-26 |
| CN102227847B (en) | 2014-07-02 |
| DE112009003578B4 (en) | 2014-11-27 |
| JPWO2010061901A1 (en) | 2012-04-26 |
| JP4557097B2 (en) | 2010-10-06 |
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