WO2004112184A1 - 電解質組成物およびこれを用いた光電変換素子 - Google Patents
電解質組成物およびこれを用いた光電変換素子 Download PDFInfo
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- WO2004112184A1 WO2004112184A1 PCT/JP2004/007644 JP2004007644W WO2004112184A1 WO 2004112184 A1 WO2004112184 A1 WO 2004112184A1 JP 2004007644 W JP2004007644 W JP 2004007644W WO 2004112184 A1 WO2004112184 A1 WO 2004112184A1
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- WIPO (PCT)
- Prior art keywords
- electrolyte
- electrolyte composition
- polyhalide
- composition according
- photoelectric conversion
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 300
- 239000000203 mixture Substances 0.000 title claims abstract description 132
- 229920000642 polymer Polymers 0.000 claims abstract description 128
- -1 halide ion Chemical class 0.000 claims abstract description 95
- 150000001875 compounds Chemical class 0.000 claims abstract description 94
- 239000007787 solid Substances 0.000 claims abstract description 49
- 150000001768 cations Chemical group 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims abstract description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 107
- 239000004065 semiconductor Substances 0.000 claims description 76
- 239000000758 substrate Substances 0.000 claims description 67
- 229910052736 halogen Inorganic materials 0.000 claims description 34
- 150000001450 anions Chemical class 0.000 claims description 32
- 150000002367 halogens Chemical class 0.000 claims description 30
- 150000002500 ions Chemical class 0.000 claims description 19
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 13
- 239000011630 iodine Substances 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 6
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- 239000001307 helium Substances 0.000 claims 1
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 5
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
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- 125000005843 halogen group Chemical group 0.000 description 4
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
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- ZQFYJHMUAWCEBH-UHFFFAOYSA-N furan-3-carbonitrile Chemical compound N#CC=1C=COC=1 ZQFYJHMUAWCEBH-UHFFFAOYSA-N 0.000 description 1
- MZUZVRHTPRROKN-UHFFFAOYSA-N furo[3,4-d][1,3]dioxole Chemical compound O1C=C2OCOC2=C1 MZUZVRHTPRROKN-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- KLYHSJRCIZOUHE-UHFFFAOYSA-N hept-3-yne Chemical compound CCCC#CCC KLYHSJRCIZOUHE-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 150000004693 imidazolium salts Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 229940070891 pyridium Drugs 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- AVBCFBRGFCGJKX-UHFFFAOYSA-N thieno[3,4-d][1,3]dioxole Chemical compound S1C=C2OCOC2=C1 AVBCFBRGFCGJKX-UHFFFAOYSA-N 0.000 description 1
- GSXCEVHRIVLFJV-UHFFFAOYSA-N thiophene-3-carbonitrile Chemical compound N#CC=1C=CSC=1 GSXCEVHRIVLFJV-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920003194 trans-1,4-polybutadiene polymer Polymers 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
-
- 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
- H01G9/2009—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
Definitions
- the present invention relates to an electrolyte composition used for a photoelectric conversion device such as a dye-sensitized solar cell, and a photoelectric conversion device using the same.
- Patent No. 2664194 Japanese Patent Application Laid-Open No. 2001-160427, and M. Graetzel et al., Nature, (UK), 1991, No. 73 No. 7, p. 353, etc.
- the dye-sensitized solar cell was developed by Gretzul et al. Of Switzerland, and has advantages such as high photoelectric conversion efficiency and low manufacturing cost. It is attracting attention as a new type of solar cell.
- the schematic configuration of a dye-sensitized solar cell consists of a porous film composed of oxide semiconductor fine particles (nanoparticles) such as titanium dioxide on a transparent conductive electrode substrate and carrying a photosensitizing dye.
- the oxide semiconductor fine particles are sensitized by a photosensitizing dye that has absorbed incident light such as sunlight, and an electromotive force is generated between the working electrode and the counter electrode.
- the dye-sensitized solar cell functions as a photoelectric conversion element that converts light energy into electric power.
- electrolyte it is common to use an electrolyte in which a redox couple such as I-I / I- 31 is dissolved in an organic solvent such as acetonitrile.
- a non-volatile ionic liquid or a liquid electrolyte (electrolyte) is gelled with an appropriate gelling agent as an electrolyte to form a pseudo solid.
- a dye-sensitized solar cell using a solidified electrolyte, a solid semiconductor such as a p-type semiconductor, or the like is known.
- a solid electrolyte such as a solid electrolyte such as a solid electrolyte such as a solid electrolyte such as a gelled liquid electrolyte (electrolyte solution) or a P-type semiconductor
- the handleability is improved.
- the photoelectric conversion characteristics and output stability are low, and improvements are desired. Disclosure of the invention
- An object of the present invention is to provide a photoelectric conversion element which can avoid volatilization and leakage of an electrolyte and have improved photoelectric conversion characteristics and output stability, and an electrolytic solution composition suitable for the photoelectric conversion element.
- the electrolyte composition according to the first aspect of the present invention has, in a main chain or a side chain of a polymer, any one of a cation structure selected from the group consisting of ammonium, phospho-am, and sulfonium. However, it contains a polymer compound having a halide ion and / or a polyhalogenated compound as an anion, and is in a solid state.
- the properties are solid, the volatility and fluidity are poor, and there is no alteration or loss of the electrolyte due to evaporation of the solvent.
- an electrolyte composition as an electrolyte of a photoelectric conversion element, it is possible to stably achieve high output and photoelectric conversion characteristics.
- leakage of electrolyte from a gap in the container and scattering when the element is damaged are suppressed, and the handleability is excellent.
- the polymer compound may contain both a halide ion and a polyhalide as a pair of anions, and the metal halide ion and the polyhalide may form a redox pair.
- the characteristics when using as an electrolyte of a photoelectric conversion element It is more preferable in terms of properties.
- the halide ion or the polyhalide may be an anion containing iodine.
- the photoelectric conversion element according to the first aspect of the present invention uses the electrolyte composition according to the first aspect of the present invention as an electrolyte.
- a photoelectric conversion element includes: a working electrode having an oxide semiconductor porous film supporting a dye on an electrode substrate; and a counter electrode disposed to face the working electrode.
- a dye-sensitized solar cell may be provided with an electrolyte layer made of the electrolyte composition according to the first aspect of the present invention between the working electrode and the counter electrode.
- the electrolyte composition according to the second aspect of the present invention has a cation structure formed by partially oxidizing a ⁇ -conjugated polymer as a main chain of the polymer, and a halide ion and ⁇ or poly as anion. It contains a high molecular compound having a halide and is in a solid state.
- the properties are solid, the volatility and fluidity are poor, and there is no alteration or loss of the electrolyte due to evaporation of the solvent.
- an electrolyte composition as an electrolyte of a photoelectric conversion element, a high output, high photoelectric conversion characteristics, and a function that can function stably for a long time can be obtained.
- leakage of electrolyte from gaps in the container, scattering when the element is damaged, and the like are suppressed, and the handleability is excellent.
- the polymer compound may contain both a halide ion and a polyhalide as a pair of anions, and the halide ion and the polyhalide may form a redox pair. This case is more preferable in terms of characteristics when used as an electrolyte of a photoelectric conversion element.
- the halide ion or polyhalide may be an anion containing iodine.
- I one Z 1 3 may be one.
- the photoelectric conversion element according to the second aspect of the present invention uses the electrolyte composition according to the second aspect of the present invention as an electrolyte.
- a photoelectric conversion element includes: a working electrode having a dye-supported oxide semiconductor porous film on an electrode substrate; and a counter electrode disposed to face the working electrode.
- a dye-sensitized solar cell may be provided with an electrolyte layer made of the electrolyte composition according to the second aspect of the present invention between the working electrode and the counter electrode.
- the electrolyte composition according to the third aspect of the present invention has a cation structure formed by a halogen molecule acting on a polymer having a partially ⁇ -conjugated structure in a main chain or a side chain of the polymer,
- a polymer compound having a halide ion and / or a polyhalide is contained as a counter anion of the cationic structure, and is in a solid state.
- the properties are solid, the volatility and fluidity are poor, and there is no alteration or loss of the electrolyte due to evaporation of the solvent.
- an electrolyte composition as an electrolyte of a photoelectric conversion element, a high output and photoelectric conversion characteristics can be obtained in the photoelectric conversion element, and the photoelectric conversion element can function stably for a long time.
- leakage of the electrolyte from a gap in the container and scattering when the element is damaged are suppressed, and the handleability is excellent.
- the polymer compound may contain both a halide ion and a polyhalide as a pair of anions, and the halide ion and the polyhalide may form a redox pair. This case is more preferable in terms of characteristics when used as an electrolyte of a photoelectric conversion element.
- the halide ion or the polyhalide may be an anion containing iodine.
- Redox couple formed from said trick gap Gen product Ion and polyhalide, I one / I 3 - may be.
- the photoelectric conversion element according to the third aspect of the present invention uses the electrolyte composition according to the third aspect of the present invention as an electrolyte.
- a photoelectric conversion element includes: a working electrode having an oxide semiconductor porous film supporting a dye on an electrode substrate; and a counter electrode disposed to face the working electrode.
- a dye-sensitized solar cell provided with an electrolyte layer made of the electrolyte composition according to the third aspect of the present invention between the working electrode and the counter electrode.
- FIG. 1 is a schematic sectional view showing a dye-sensitized solar cell according to one embodiment of the photoelectric conversion element of the present invention.
- FIG. 2A is a top view showing a glass plate for testing the properties of the electrolyte composition.
- FIG. 2B is a side view showing a state in which the glass plate on which the electrolyte membrane is formed is upright.
- FIG. 3 is a graph showing a measurement result of a current-voltage curve of the photoelectric conversion element (test cell) of the example.
- FIG. 1 is a schematic sectional view showing a dye-sensitized solar cell according to an embodiment of the photoelectric conversion element of the present invention.
- FIG. 1 is a schematic sectional view showing a dye-sensitized solar cell according to an embodiment of the photoelectric conversion element of the present invention.
- the dye-sensitized solar cell 1 has a working electrode 6 having an oxide semiconductor porous film 5 made of fine particles of an oxide semiconductor such as titanium oxide and carrying a photosensitizing dye on a transparent electrode substrate 2; And a counter electrode 8 provided opposite to the working electrode 6. An electrolyte layer 7 is formed between the working electrode 6 and the counter electrode 8.
- the electrolyte composition and the photoelectric conversion element according to the first embodiment of the present invention will be described based on the dye-sensitized solar cell of one embodiment shown in FIG.
- the electrolyte composition forming the electrolyte layer 7 has, as an essential component, any one of cation structures selected from the group consisting of ammonium, phosphonium, and sulfonium on the main chain or side chain of the polymer, As a high molecular compound having a halide ion and a poly- or poly-halide.
- the polymer compound may be a single type of polymer compound or a mixture obtained by appropriately mixing a plurality of types of polymer compounds.
- the range of the molecular weight of the polymer compound is several hundreds to several millions, preferably several thousand to several hundred thousand, and more preferably tens of thousands.
- the polymer compound has one or more kinds of at least one of the cation structures described below.
- ammonium structure and the phosphonium structure are structures represented by any of the following formulas (111) and (112).
- the cation center E represents an atom of nitrogen (N) or phosphorus (P).
- R a , R b , R c , and R d are any adjacent atoms forming a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylamino group, an alkenyl group, or the like. is there.
- Two or more of R a , R b , R °, and R d may be an atomic group that forms a heterocyclic ring including the cation center E.
- R e is an alkylidene group, an alkylimino group
- Aruke - is any adjacent atoms forming a like benzylidene group
- R f and Rs are any adjacent atoms forming a hydrogen atom, an alkyl group, an alkoxy group, an alkylamino group, an alkenyl group, or the like.
- Two or more of R e , R f , and R g are in the cation It may be an atomic group that forms a heterocyclic ring including the center E '.
- the sulfonium structure is a structure represented by the following formula (1-3) or (1-4).
- the cation center E represents a sulfur (S) atom.
- R h and RR j are any adjacent atoms forming a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylamino group, an alkenyl group and the like. Two or more of R h and RR j may be an atomic group including a cation center E to form a heterocyclic ring.
- R k is any adjacent atom forming an alkylidene group, an alkylimino group, an alkenylidene group or the like.
- R 1 is any adjacent atom forming a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylamino group, an alkyl group or the like.
- R k and R 1 form a heterocycle including the cation center E It may be an atomic group that performs Chemical formula (1-3)
- ammonium structure examples include those in which a cationic nitrogen atom is not contained in a cyclic structure (such as tetraalkylammonium) and those in which a cationic nitrogen atom is contained in a cyclic structure.
- cyclic structure heterocycle
- examples of the cyclic structure include an imidazolium structure (an imidazole derivative), a pyridinium structure (a pyridine derivative), a diazolium structure (a diazole derivative), a triazolium structure (a triazole derivative), a quinolinium structure (a quinoline derivative), and a triazine structure.
- Triazine derivatives Triazine derivatives), aziridinium structures (aziridine derivatives), virazolyme structures (pyrazole derivatives), pyrazinium structures (virazine derivatives), ataridium structures (atalizine derivatives), indolium structures (indole derivatives), bipyridinium structures (bipyridine derivatives) Body), etc.
- Tapirijiniumu structures include various structures.
- the above-mentioned polymer compound has a non-cationized nitrogen atom (such as amine), a phosphorus atom (such as phosphine), and a sulfur atom (such as sulfide). You may have.
- the ratio of cationized N, P, S atoms to the total number of N, P, S atoms is preferably at least 1% (including 100%).
- polymer compound examples include a polymer chain having a conjugated unsaturated bond such as a poly (methylene) chain; a poly (ethylene oxide) chain; a fluorocarbon chain; and polyene, polyarylene, and polyyne.
- a polymer compound having at least one of an ammonium structure, a phosphonium structure, and a sulfonium structure can be used.
- a polymer compound having a cationic structure in the side chain for example, a polymer compound represented by the following formulas (1-5) and (1-6) can be used.
- a polymer compound represented by the following formulas (1-5) and (1-6) can be used.
- the notation in which a wavy line is followed by parentheses and a suffix n is an abbreviation of the main chain of the polymer compound.
- the substituent R is a hydrogen atom; such as methyl, ethyl, propynole, n -petit / le, n-pentynole, n-hexynole, and n-octynole Linear alkyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, and neopentyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert — Straight-chain or branched alkoxy groups such as butoxy; alkenyl groups such as bier, propenyl, aryl, butyr, butyryl and oleyl; anolekinyl groups such as ethel, provyl and butynyl; methoxymethyl, 2-methoxyl,
- the groups R 1 , R 2 , R 3 , and R 4 can be independently selected from each other, and the options are a hydrogen atom; methyl, ethyl, propyl, butyl (n-butyl), and pentyl.
- linear alkyl groups such as (n-pentyl), hexyl, octyl, dodecyl, hexadecyl, octadecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl and neopentyl; Linear or branched alkoxy groups such as xy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec.
- Alkyl group C 2 H 5 O (CH 2 CH 2 0) m CH 2 CH 2 group (m is an integer of 1 or more), CH 30 (CH 2 CH 20 ) ra CH 2 CH 2 group (m is 1
- a polyether group such as the above integer; a fluoromethyl group; a halogen-substituted derivative of the above substituent such as fluorine;
- divalent groups R 5 and R 6 a direct bond between the polymer main chain and the heterocyclic ring; a linear or branched alkylene group such as methylene, ethylene, propylene, trimethylene, and tetramethylene; vinylene, methylvinyl Alkenylene groups such as diene and propenylene; alkynylene groups such as ethinylene; divalent groups having an ether bond such as alkyleneoxyalkylene; polyether groups.
- the polyhalide ion is an anion composed of a plurality of halogen atoms, and can be obtained by reacting a halide ion such as CI—, Br—, I-, and the like with a halogen molecule.
- the halogen molecule, C l 2, B r 2 , 1 2 single halogen content terminal and / or C 1 I, such as, B r I, interhalogen compounds such as B r C 1 be used (interhalogen compound) it can.
- the ratio of halogen molecules to halide ions is not particularly limited, but is more preferably 0% to 100% in terms of molar ratio.
- the addition of halogen molecules is not particularly essential, but it is preferable to add halogen molecules. When a halogen molecule is added and a polyhalide ion is interposed, the halide ion and the polyhalide ion form a redox pair, and characteristics such as photoelectric conversion characteristics can be improved.
- the polymer compounds represented by the above formulas (1-5) and (1-6) can be produced by a known synthesis technique.
- a tertiary amine precursor represented by the following formula (1-7) or (1-8) is reacted with an alkyl halide such as alkynole iodide (RI) to quaternize the nitrogen atom.
- R alkynole iodide
- the ratio (quaternization rate) of the quaternary ammonium structure to the total number of nitrogen atoms (sum of the number of tertiary amine structures and quaternary ammonium structures) in the polymer compound should be 1% or more. Preferably, it can be 100%.
- Polymer compounds having a tertiary ammonium structure poly (ethyleneimine) hydrochloride, poly (141-vinylpyridinium chloride), poly (121-vinylpyridinium chloride) and the like.
- Polymer compounds having an aliphatic quaternary ammonium structure poly (vinyltrialkylammonium chloride) such as poly (vinyltrimethylammonium chloride), and poly (aryltrimethylammonium chloride) Such as poly (aryltrialkylammonium chloride) and poly (oxoshetyl-1-methylenetrimethylammonium chloride).
- a polymer compound having a quaternary ammonium structure contained in a heterocyclic structure poly (mono-N-alkyl-2-bulpyri) such as poly (mono-N-methyl-2-vinylpyridin-chloride) Poly (N-methyl-4-vinylpyridinium chloride) and poly (N-alkyl-4-vinylpyridinium chloride), poly (N-vinyl-1-vinyl-1,2,3-dimethylimidazo) Poly (monochlorinated N-vinyl-2)
- Acrylic polymer compound having an ammonium structure Poly (1-2-hydroxy-3-methacryloyloxypropyl chloride) such as poly (12-hydroxy-13-methacryloyloxypropyltrimethylammonium) Poly (chlorinated-3-acrylamide propyltrialkylammonium) such as trialkylammonium) and poly (chlorinated-3-nacrylamidopropyltrimethylammonium).
- Polymer compounds having a sulfonium structure poly (chlorinated-2-acrylyloxyethyldialkylsulfonium) such as poly (chlorinated-2-ataryllooxyshethyldimethylsulfonium); Poly (glycidyldialkylsulfonium chloride), etc.
- Polymer compounds having a phosphonium structure poly (glycidyl trialkylphosphonium chloride) such as poly (glycidyl triplylphosphonium chloride). Further, in the above specific examples, they are listed as chlorides. However, polymer compounds usable in the present invention are not particularly limited to chlorides, and include bromide, iodide, tribromide (salt of Br 3 —), and trichloride. Other halides and salts of polyhalides, such as iodide (salt of I), may be used.
- a polymer compound having at least one of an ammonium structure, a phosphonium structure, and a sulfonium structure in a main chain can be used.
- Structural units that can be included in the main chain and that have an ammonium structure include pyridinium, biperidinium, pillar gem, and aliphatic ammonium.
- examples of the structural unit that can be contained in the main chain include methylene, ethylene, vinylene, phenylene, and an ether bond.
- this kind of cationic polymer include poly (mono-N, N-dimethyl-3,5-methylenepiperidinium chloride).
- the polymer plays a role of a curing agent for curing the liquid electrolyte.
- the polymer compound itself has conductivity, and plays a main role of charge transfer in the electrolyte composition containing a redox couple. And is solid.
- the electrolyte composition may contain, as necessary, an ionic liquid; organic nitrogen compounds such as 4-tert-butylpyridine, 2-butylpyridine, N-vinyl-12-pyrrolidone; lithium salts, sodium salts, and magnesium salts Various additives such as iodide salts, iodide salts, thiocyanates, and water can be added as long as the properties and characteristics of the electrolyte composition are not impaired.
- organic nitrogen compounds such as 4-tert-butylpyridine, 2-butylpyridine, N-vinyl-12-pyrrolidone
- lithium salts sodium salts
- magnesium salts lithium salts, sodium salts, and magnesium salts
- additives such as iodide salts, iodide salts, thiocyanates, and water can be added as long as the properties and characteristics of the electrolyte composition are not impaired.
- the ionic liquid examples include cations such as quaternized imidazolidum, quaternized pyridinium, and quaternized ammonium, and tertiary ion, bistrifluoromethylsulfonylimidoimidione, hexafluorophosphate ion (PFF).
- cations such as quaternized imidazolidum, quaternized pyridinium, and quaternized ammonium, and tertiary ion, bistrifluoromethylsulfonylimidoimidione, hexafluorophosphate ion (PFF).
- PFF hexafluorophosphate ion
- Six examples are salts composed of anions such as tetrafluoroborate ion (BF 4 —), which are liquid at room temperature.
- the ratio of the plasticizer is preferably 50% or less, more preferably 10% or less, based on the amount of the composition material.
- the transparent electrode substrate 2 is obtained by forming a conductive layer 3 made of a conductive material on a transparent substrate 4 such as a glass plate or a plastic sheet.
- a material having high light transmittance is preferable for use, and glass
- a transparent plastic sheet such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyether sulfone (PES), and a polished plate of ceramics such as titanium oxide and alumina must be used. Can be.
- the conductive layer 3 is made of a transparent oxide semiconductor such as tin-doped indium oxide (ITO), tin oxide (SnO 2 ), and fluorine-doped tin oxide (FTO) from the viewpoint of the light transmittance of the transparent electrode substrate 2. It is preferable to use singly or in combination of two or more. However, the material is not particularly limited to these, and an appropriate material suitable for the intended use may be selected and used from the viewpoint of light transmittance and conductivity. Further, in order to improve the current collection efficiency from the oxide semiconductor porous film 5 and the electrolyte layer 7, the area ratio of the gold, silver, platinum, aluminum, and aluminum is set so as not to significantly impair the light transmittance of the transparent electrode substrate 2.
- a transparent oxide semiconductor such as tin-doped indium oxide (ITO), tin oxide (SnO 2 ), and fluorine-doped tin oxide (FTO) from the viewpoint of the light transmittance of the transparent electrode substrate 2.
- ITO
- a metal wiring layer made of nickel, titanium, or the like may be used in combination.
- the transparent electrode substrate 2 is arranged in a pattern such as a lattice, a stripe, or a comb so as to transmit light as uniformly as possible.
- the conductive layer 3 As a method for forming the conductive layer 3, a known appropriate method according to the material of the conductive layer 3 may be used.
- the conductive layer 3 is formed from an oxide semiconductor such as ITO, a sputtering method, Thin-film formation methods such as CVD, SPD (spray pyrolysis deposition), and vapor deposition are listed. Then, in consideration of light transmittance and conductivity, the film is usually formed to a thickness of about 0.05 ⁇ to 2.0 ⁇ .
- the oxide semiconductor porous film 5 titanium oxide (T I_ ⁇ 2), tin oxide (Sn_ ⁇ 2), oxidation of tungsten (W0 3), zinc oxide (ZnO), niobium oxide (Nb 2 0 5), such as It is a porous thin film mainly composed of oxide semiconductor fine particles with an average particle diameter of 1 to 1000 nm and a thickness of about 0.5 to 50 m.
- the oxide semiconductor porous film 5 As a method for forming the oxide semiconductor porous film 5, for example, a commercially available dispersion liquid in which fine particles of an oxide semiconductor are dispersed in a desired dispersion medium or a colloid solution that can be adjusted by a sol-gel method is required. After the desired additives are added, a known coating method such as a screen printing method, an ink jet printing method, a roll coating method, a doctor blade method, a spin coating method, or a spray coating method can be applied. Also, the electrode substrate 2 is immersed in the colloid solution, and the oxide semiconductor is electrophoresed.
- Electrophoretic electrodeposition method for attaching microparticles to the electrode substrate 2 a method of mixing and applying a foaming agent to the above-mentioned colloid solution or dispersion, and then sintering the mixture to make it porous; the above-mentioned colloid solution or dispersion After mixing and applying the polymer microbeads to the liquid, the polymer microbeads may be removed by heat treatment or chemical treatment to form voids to make the solution porous.
- the sensitizing dye supported on the oxide semiconductor porous film 5 is not particularly limited, and may be, for example, a ruthenium complex having a ligand containing a biviridine structure or a terpyridine structure, an iron complex, or a porphyrin-based compound. And phthalocyanine-based metal complexes, and organic dyes such as cyanine, rhodamine, merocyanine, and tamarin. One or more of the above compounds can be appropriately selected and used depending on the application and the material of the porous oxide semiconductor film.
- the counter electrode 8 is, for example, a thin film made of a conductive oxide semiconductor such as ITO or FTO formed on a substrate made of a non-conductive material such as glass, or gold, platinum, or carbon on a substrate.
- a material in which an electrode is formed by providing a conductive material such as a system material by vapor deposition, coating, or the like can be used.
- a thin film of a conductive oxide semiconductor such as a single-electrode or the like in which a layer of platinum, carbon, or the like is formed is also applicable.
- a method for producing such a counter electrode 8 for example, a method of forming a platinum layer by performing a heat treatment after applying chloroplatinic acid can be mentioned.
- a method in which an electrode is formed on a substrate by an evaporation method or a sputtering method may be used.
- the polymer compound is mixed with an appropriate organic solvent, and if necessary, a haeogen molecule and various additives are added, and the mixture is stirred.
- an electrolyte composition solution is prepared by dissolving the components uniformly, and the obtained electrolyte composition solution is dropped on the working electrode 6 little by little and dried.
- organic solvent for dissolving the polymer compound examples include acetonitrile, methoxyacetonitrile, propionitrile, propylene carbonate, and getylka. Carbonate, methanol, ⁇ -butyrolactone, and ⁇ -methylpyrrolidone.
- the polymer compound desirably has a sufficient solubility in at least one of these organic solvents.
- the electrolyte composition of the present invention has a solid property, it has poor volatility and fluidity, and when used in a photoelectric conversion element such as a dye-sensitized solar cell, alteration of the electrolyte due to volatilization of a solvent or the like. It is possible to stably achieve high output and photoelectric conversion characteristics without any defects or defects. In addition, leakage of electrolyte from gaps in the container, scattering when the element is damaged, etc. are suppressed, and handling is excellent.
- the solid state in the present invention can be easily detected by the following test.
- a solution of the electrolyte and the composition is dropped into the central portion 12 surrounded by the adhesive tape 13.
- the adhesive tape 13 is peeled off to obtain a glass plate 11 on which the electrolyte membrane 14 is formed.
- the thickness of the electrolyte membrane 14 is about 30 / im.
- the glass plate 11 is set upright on the floor surface 15 and left at room temperature for 10 hours.
- the electrolyte composition has low fluidity and is determined to be solid. Conversely, when the electrolyte membrane 14 comes into contact with the floor surface 15, it is determined that the electrolyte thread has high fluidity and is liquid.
- a pyridinium-based polymer represented by the following formula (1-9) and an imidazolium-based polymer represented by the following formula (1-10) were used. These polymer compounds use poly (4-vinylpyridine), poly (N-vinylimidazole), and poly (2-methyl-N-vinylimidazole) as precursors having a tertiary amine structure. It was quaternized by the action of alkyl iodide on the body, and was repeatedly purified to remove unreacted raw materials and the like, thereby preparing an iodide salt. Chemical formula (1-9)
- the electrolyte composition solution was prepared by dissolving the above-mentioned polymer compound (iodide salt) in an appropriate solvent with an organic solvent, adding an iodine solution thereto, and stirring the mixture until it became uniform.
- the organic solvent was appropriately selected from methanol, acetonitrile and methoxyacetonitrile in accordance with the solubility of the polymer compound, and a solvent having good solubility was selected and used.
- the solvent for the iodine solution the same organic solvent used for dissolving the polymer compound was used.
- a glass substrate with an FTO film was used as the transparent electrode substrate, and the surface of the transparent electrode substrate 2 on the FTO film (conductive layer) side was coated with a slurry of titanium oxide having an average particle size of 20 nm.
- a spray solution was applied, dried, and heated at 450 ° C. for 1 hour to form a 7-m-thick porous oxide semiconductor film.
- a working electrode was fabricated by immersing 1 ⁇ in an ethanol solution of a ruthenium biviridine complex (N3 dye) to carry the dye.
- N3 dye ruthenium biviridine complex
- As a counter electrode an FTO glass electrode substrate provided with an electrode layer made of platinum by a sputtering method was prepared.
- an electrolytic solution serving as an electrolyte an acetonitrile solution containing quaternized imidazolymodiiodide, lithium iodide, iodine, and 4-tert-butylpyridine was prepared.
- the working electrode and the counter electrode faced each other, and the electrolyte was injected between the working electrode and the counter electrode to form an electrolyte layer.
- a dye-sensitized solar cell serving as the test cell of Comparative Example 11 was produced.
- the working electrode was the same as that described above except that a slurry containing titanium oxide nanoparticles and titanium tetraisopropoxide was used instead of the titanium oxide slurry used in the procedures of Examples (la) and (lb) above. It was produced in the same manner as in the example.
- the same platinum-coated FTO electrode substrate as in the above Examples (la) and (lb) was used.
- Copper iodide (Cu I) was used as the electrolyte for the electrolyte layer.
- the counter electrode was overlapped while pressing the counter electrode against the electrolyte layer to join the counter electrode and the electrolyte layer. Further, the solvent of the electrolyte composition solution was sufficiently dried and removed.
- Table 1 shows the initial photoelectric conversion efficiency (initial conversion efficiency) for each test cell.
- Table 1 also shows the properties of the electrolyte layer inspected by the test method shown in Fig. 2.
- FIG. 3 shows a measurement example of the current-voltage curve of the test cell of the example.
- ⁇ indicates the measurement result in the test cell corresponding to (la) -2 in Table 1
- ⁇ indicates the measurement result in the test cell corresponding to (lb) -4 in Table 1.
- the electrolyte layer had an appearance similar to that of plastic, and was determined to be solid by the property test.
- test cells of Examples (la) and (lb) had high photoelectric conversion characteristics and were durable for long-term continuous use.
- the solvent of the electrolyte gradually evaporates from the start of the measurement of the photoelectric conversion characteristics, and the photoelectric conversion efficiency reaches the initial value of 10 by 3 hours. %, And hardly functioned as a photoelectric conversion element.
- the working electrode and the counter electrode are opposed to each other with a 50-im thick thermoplastic polyolefin-based resin sheet interposed therebetween, and between the working electrode and the counter electrode by thermal melting of the resin sheet. And secured. At this time, a small hole was made in a part of the counter electrode side to serve as the electrolyte injection port.
- the electrolyte was injected from the liquid inlet to form an electrolyte layer, and the liquid inlet was closed using both an epoxy-based sealing resin and a polyolefin-based resin to prepare a dye-sensitized solar cell. . This is the test cell of Comparative Examples 1 to 3.
- Example (1c) One of the test cells of Example (1c) and one of the test cells of Comparative Examples 13 to 13 were left in a thermostat at 80 ° C. for 7 days. Then, the test cell was taken out of the thermostat and the appearance of the test cell was visually observed.In the test cells of Comparative Examples 13 and 13, the sealing of the polyolefin deteriorated and part of the electrolyte was volatilized. Bubbles were generated. For this reason, it hardly functions as a photoelectric conversion element.
- Example (1c) When one of the test cells of Example (1c) and one of the test cells of Comparative Examples 13 and 13 were broken with a hammer from the glass substrate side, and the broken portions were held downward, In the test cells of Comparative Examples 13 and 13, the electrolyte leaked. On the other hand, in the test cell of Example (lc), the electrolyte layer did not leak because the charge layer was solid.
- the electrolyte composition solution was prepared in the same manner as in Examples (la) and (lb) except that one of the following formulas (1-11) to (1-20) was used as the polymer compound.
- the electrolyte composition solution was used to prepare a dye-sensitive solar cell to be a test cell.
- the photoelectric conversion characteristics of the test cells were measured.
- Table 2 shows the initial value of the photoelectric conversion efficiency (initial conversion efficiency) for each test cell.
- Table 2 also shows the properties of the electrolyte layer inspected by the test method shown in Fig. 2.
- Chemical formula (111) Chemical formula (1-12)
- Example (Id) has high photoelectric conversion characteristics and does not volatilize like the conventional volatile electrolyte (Comparative Examples 11-1), and is used continuously for a long time. Turned out to be possible.
- test cell (l a)-1 (lb)-1 was capable of generating power, and the short-circuit current value after 14 days was less than 80% of the initial value.
- the short-circuit current value after 14 days was 85% or more of the initial value.
- the electrolyte layer expands and contracts due to a change in heat or the like. Therefore, when the dye-sensitized solar cell is used continuously, the expansion and contraction of the electrolyte layer may cause separation between the electrolyte layer and the working electrode or between the electrolyte layer and the counter electrode, resulting in a decrease in the short-circuit current value.
- the polymer compounds represented by the formulas (1-1-1) to (1-14) and (1-16) to (1-20) have a polyethylene oxide structure (CH 3 —O— CH 2 — group), which is more flexible than the polymer compounds used in Examples (1a) and (1).
- a polymer compound having such a cation structure and an anion and having excellent flexibility is used as an essential component of the electrolyte composition, the adhesion between the electrolyte layer and the working electrode and between the electrolyte layer and the counter electrode can be improved. Can be maintained stably.
- the electrolyte composition according to the first embodiment of the present invention preferably has high flexibility.
- an electrolyte thread is used as an electrolyte layer of a dye-sensitized solar cell having an electrolyte layer provided between a working electrode and a counter electrode
- the electrolyte composition and the working electrode And the adhesion at each interface between the electrolyte composition and the counter electrode can be stably maintained.
- a dye-sensitized solar cell having more excellent durability and excellent battery characteristics even after a long time has elapsed can be obtained.
- Example (1e) A dye-sensitized solar cell was manufactured in the same procedure as the test cell of Id). This was designated as Example (1e).
- Example (1e) The test cell of Example (1e) was left in a thermostat at a temperature of 80 ° C. for 7 days. Thereafter, the test cell was taken out of the thermostat and the appearance of the test cell was visually observed.
- Example (1e) The test cell of Example (1e) was broken with a hammer from the glass substrate side, and the broken part was held downward. In the test cell of Example (le), the electrolyte layer did not leak because the charge layer was solid.
- the electrolyte composition and the photoelectric conversion element according to the second embodiment of the present invention will be described based on the dye-sensitized solar cell of one embodiment shown in FIG.
- the difference of the photoelectric conversion device according to the second aspect of the present invention from the first aspect is the electrolyte composition.
- the dye-sensitized solar cell 1 shown in FIG. 1 has, on a transparent electrode substrate 2, oxide semiconductor fine particles such as titanium oxide, and an oxide semiconductor porous material S5 carrying a photosensitizing dye. It has a working electrode 6 and a counter electrode 8 provided opposite to the working electrode 6. An electrolyte layer 7 is formed between the working electrode 6 and the counter electrode 8.
- the electrolyte composition forming the electrolyte layer 7 has a cation structure formed by partially oxidizing a ⁇ -conjugated polymer as a main chain of a polymer, and a halide ion as an anion. And a high molecular compound having z or polyhalide as an essential component.
- the polymer compound may be a single type of polymer compound or a mixture obtained by appropriately mixing a plurality of types of polymer compounds.
- the range of the molecular weight of the polymer compound is several hundreds to several millions, preferably several thousand to several hundred thousand, and more preferably tens of thousands.
- polymer compound examples include a polythiophene-based polymer represented by the following formula (2-1), a polyfuran-based polymer represented by the following formula (2-2), and a polypyrrole-based polymer represented by the following formula (2_3).
- Halogen such as iodine or other oxidizing agents is added to an undoped polymer having a main chain such as a molecule or polyaniline and a derivative thereof, and polyphenylenevinylene and a derivative thereof represented by the following formula (2-4). It is possible to use a polymer obtained by doping and thereby partially oxidizing the polymer to form a cation structure.
- the groups R 1 , R 2 , R 3 , and R 4 can be independently selected from each other. And hydrogen atoms; fluorine, chlorine, bromine, iodine, etc .; halogen atoms; cyano group; methyl, ethylenole, propyl, petit / n (n-butynole), pentynole (n-pentynole), and Straight-chain alkyl groups such as xyl, octyl, dodecyl, hexadecyl, and octadecyl; branched alkyl groups such as isopopenolole, isobutinole, sec-butyl, tert-butyl, isopentinole, and neopentyl; methoxy, ethoxy, propoxy Linear or branched alkoxy groups such as isopropoxy,
- the substituent RR 2 may be cyclic structure formed in the molecule, the substituents RR 2, to at least one or more from 3 together with the carbon atoms 7-membered ring (three-membered (Cyclic, 4-membered, 5-membered, 6-membered, or 7-membered) saturated or unsaturated hydrocarbons.
- the cyclic bond chain may optionally contain a bond such as carbonyl, ether, ester, amide, sulfide, snorfeienole, snorehoninole, imino and the like.
- Examples of such a cyclic bonding chain include linear or branched anolexylene groups such as methylene, ethylene, propylene, trimethylene, and tetramethylene; and anorene alkylene groups such as vinylene, methinolevylene, and propenylene.
- the substituent R may be a straight-chain alkyl group such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, and the like; isopropynole, isoptinole, branched alkyl groups such as sec-butynole, tert-butyl, isopentynole, and neopentyl; linear or branched alkyl groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy Certain alkoxy groups; alkenyl groups such as vinyl, propenyl, aryl, butenyl, and oleyl; alkynyl groups such as ethynyl, propynyl, and butyr; alkoxy groups such as methoxymethyl, 2-methoxyl, 2-
- the undoped polymer can be obtained by a known polymerization method using, for example, thiophene, furan, pyrrole, aniline or a derivative thereof as a raw material.
- thiophene furan
- pyrrole aniline
- aniline aniline
- generally commercially available polymers may be prepared and used, but of course, the present invention is not limited to these.
- thiophene derivatives include 3-methylthiophene, 3-ethylthiophene, 3-propynolethiophene, 3-butynolethiophene, 3-pentynolethiophene, 3-1-hexynolethiophene, and 3-heptyne / Rethiophene, 3-octynolethiophene, 3-nonylthiophene, 3 _decylthiophene, 3-dodecylthiophene, 3 — Xadecylthiophene, 3-octadecylthiophene, 3-fluorothiophene, 3-chlorothiophene, 3-promothiophene, 3-cyanothiophene, 3,4 dimeti / rethiophene, 3,4-getinole Thiophene, 3,4-butylenethiophene, 3,4-methylenedioxythiophene, 3,4-ethylened
- polythiophene polymer examples include polythiophene in which R 1 and R 2 in the formula (2-1) are both hydrogen, polyhexylthiophene in which R 1 is a hexyl group and R 2 is hydrogen, 1 and R 2 are bonded to the ring, the whole of the combined R 1 and R 2 include polyethylenedioxythiophene O carboxymethyl Chio phen (PEDOT) can be mentioned, et al is an ethylene Jiokishi group.
- PEDOT polyethylenedioxythiophene O carboxymethyl Chio phen
- At least one of R 1 and R 2 has a relatively long chain structure. In this case, since the solubility in the organic solvent is high, the operation of forming the electrolyte layer on the electrode substrate by the procedure described below is facilitated.
- Examples of the pyrrole derivatives include 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrupoyl, 3-butylpyrole, 3-pentylpyrole, 3-hexylpyrrole, 3-heptylpyrrole, and 3-heptylpyrrole.
- furan derivatives 3-methylfuran, 3-ethylfuran, 3-propylfuran, 3-petit / refran, 3-pentch / refran, 3-hexynolefuran, 3-heptylfuran, 3-octylfuran, 3-noninolefuran, 3 1 decyl franc, 3 de decyl franc, 3 hexadecyl franc, 3 octadecyl franc, 3 fu Fluorofuran, 3-chlorofuran, 3-bromofuran, 3-cyanofuran, 3,4-dimethylfuran, 3,4-getylfuran, 3,4-butylenefuran, 3,4-methylenedioxyfuran, 3,4-ethylenediene And derivatives such as oxyfuran.
- Furan or a polyfuran-based polymer obtained by polymerization of the above-mentioned furan derivative can be suitably used for the electrolyte composition of the present invention.
- aniline derivative examples include derivatives such as N-alkylaniline, 1-aminovillene, o-phenylenediamine, and arylamine.
- Aniline or polyaniline or a derivative thereof obtained by polymerization of the aniline derivative can be suitably used in the electrolyte composition of the present invention.
- Polyphenylenevinylene and derivatives thereof can be synthesized by a known method using heat treatment or the like via a precursor polymer.
- Such an undoped polymer is partially oxidized by, for example, the addition of a dopant such as halogen, and is a polymer compound having a cationic structure (cationic polymer) as shown in formulas (2-5) to (2-7). It becomes.
- Formula (2-5) represents a cationic polymer generated by partial oxidation of the polythiophene-based polymer shown in Formula (2-1).
- Equation (2-6) represents a cationic polymer generated by partial oxidation of the polypyrrole polymer shown in equation (2_2).
- Equation (2-7) represents a force-thione polymer generated by partial oxidation of the polyfuran-based polymer shown in equation (2-3).
- ⁇ + represents a positive charge of the cationic polymer.
- Chemical formula (2-5) represents a cationic polymer generated by partial oxidation of the polythiophene-based polymer shown in Formula (2-1).
- Equation (2-6) represents a cationic polymer generated by partial oxidation of the
- the pair Anion of the cationic polymer, ® ⁇ halide ions, bromide ion, halide ions such as chloride ions; B r 3 -, I 3 -, 1 5 I 7 -, C 1 2 I-, C 1 1 2 B r 2 1 ⁇ B r 1 2 - include polyhalide ions, such as.
- a halogen salt such as lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, or potassium bromide is added to the electrolyte composition. It may be mashed.
- the counter cation of the halogen salt include an alkali metal ion such as lithium.
- a polyhalide ion is an anion composed of a plurality of halogen atoms.
- a halogen ion such as C11, Br-, or 1 is reacted with a halogen molecule.
- the halogen molecule may be used C l 2, B r 2, 1 2 single molecular halogen and / or CII such, B r I, halogen sown compounds such as B r C 1 (the interhalogen compound) .
- halogen molecules is not particularly essential, but it is preferable to add halogen molecules.
- a halogen molecule is added and a polyhalide ion is interposed, the halide ion and the polyhalide ion form an oxidation-reduction pair, thereby improving properties such as photoelectric conversion characteristics.
- the polymer plays a role of a curing agent for curing the liquid electrolyte.
- the polymer compound itself has conductivity, and plays a main role of charge transfer in the electrolyte composition containing a redox couple. And solid.
- the electrolyte composition may contain, as necessary, an ionic liquid; an organic nitrogen compound such as 4-tert-butylpyridine, 2-vinylpyridine, N-vinyl-2-pyrrolidone; a lithium salt, a sodium salt, a magnesium salt, and iodine.
- organic nitrogen compound such as 4-tert-butylpyridine, 2-vinylpyridine, N-vinyl-2-pyrrolidone
- a lithium salt such as sodium salt, a magnesium salt, and iodine.
- Various additives such as halide salts, thiocyanates, and water can be added as long as the properties and characteristics of the electrolyte composition are not impaired.
- Examples of the above ionic liquid include cations such as quaternized imidazolidum, quaternized pyridium, and quaternized ammonium, iodide ion, bistrifluoromethylsulfonylimidoimidione, hexafluorophosphate ion (PF 6 (1) Salts composed of anions such as tetrafluoroborate ion (BF 4 —) and liquid at room temperature are exemplified.
- the ratio of the plasticizer is preferably 50% or less, more preferably 10% or less, based on the weight of the electrolyte composition.
- the transparent electrode substrate 2 is obtained by forming a conductive layer 3 made of a conductive material on a transparent substrate 4 such as a glass plate or a plastic sheet.
- the material of the transparent substrate 4 is preferably a material having high light transmittance in terms of application.
- a material having high light transmittance in terms of application.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PC polycarbonate
- PES polyether sulfone
- Transparent A polished plate of a ceramic sheet such as a plastic sheet, titanium oxide, or alumina can be used.
- the conductive layer 3 is made of transparent oxide such as tin-doped tin oxide (ITO), tin oxide (SnO 2 ), and fluorine-doped tin oxide (FTO) from the viewpoint of the light transmittance of the transparent electrode substrate 2. It is preferable to use the compound semiconductor alone or in combination of plural kinds. However, the material is not particularly limited to these, and an appropriate material suitable for the intended use may be selected and used from the viewpoints of light transmittance and conductivity. Further, in order to improve the current collection efficiency from the oxide semiconductor porous film 5 and the electrolyte layer 7, the area ratio of the gold, silver, platinum, aluminum, and aluminum is set so as not to significantly impair the light transmittance of the transparent electrode substrate 2.
- ITO tin-doped tin oxide
- SnO 2 tin oxide
- FTO fluorine-doped tin oxide
- a metal wiring layer made of nickel, titanium, or the like may be used in combination.
- the transparent electrode substrate 2 is arranged in a pattern such as a lattice, a stripe, or a comb so as to transmit light as uniformly as possible.
- the conductive layer 3 As a method for forming the conductive layer 3, a known appropriate method according to the material of the conductive layer 3 may be used.
- the conductive layer 3 is formed from an oxide semiconductor such as ITO, Method, SPD method (spray pyrolysis deposition method), and vapor deposition method.
- ITO oxide semiconductor
- Method spray pyrolysis deposition method
- vapor deposition method In consideration of light transmittance and conductivity, 0.05 ⁇ ! It is formed to a thickness of about 2.0 // m.
- the oxide semiconductor porous film 5 titanium oxide (T I_ ⁇ 2), tin oxide (S n 0 2), oxidation of tungsten (W0 3), zinc oxide (Z n O), niobium oxide (N b 2 0 5 )
- a porous thin film mainly composed of oxide semiconductor particles with an average particle diameter of 1 to 100 nm and a thickness of about 0.5 to 50 m It is.
- a method for forming the oxide semiconductor porous film 5 for example, a commercially available dispersion liquid in which fine particles of an oxide semiconductor are dispersed in a desired dispersion medium or a colloid solution which can be adjusted by a sol-gel method is used. After adding a desired additive as required, a known coating method such as a screen printing method, an ink jet printing method, a roll coating method, a doctor blade method, a spin coating method, or a spray coating method can be applied.
- an electrophoretic electrodeposition method in which the electrode substrate 2 is immersed in the colloid solution and the oxide semiconductor fine particles are adhered to the electrode substrate 2 by electrophoresis, and a foaming agent is mixed with the above-mentioned colloid solution or dispersion and applied. After sintering to make it porous, After mixing and applying the polymer micro-beads to the solution or dispersion, the polymer micro-beads may be removed by heat treatment or chemical treatment to form voids and make porous.
- the sensitizing dye supported on the oxide semiconductor porous film 5 is not particularly limited, and may be, for example, a ruthenium complex having a ligand containing a biviridine structure or a terpyridine structure, an iron complex, or a porphyrin-based compound. And phthalocyanine-based metal complexes, and organic dyes such as eosin, rhodamine, merocyanine, and tamarin.
- a ruthenium complex having a ligand containing a biviridine structure or a terpyridine structure an iron complex, or a porphyrin-based compound.
- phthalocyanine-based metal complexes, and organic dyes such as eosin, rhodamine, merocyanine, and tamarin.
- One or more of the above compounds can be appropriately selected and used depending on the application and the material of the porous oxide semiconductor film.
- the counter electrode 8 may be, for example, a thin film made of a conductive oxide semiconductor such as ITO or FTO formed on a substrate made of a nonconductive conductive material such as glass, or gold, platinum, or the like on a substrate.
- a conductive material such as a carbon-based material is provided by vapor deposition, coating, or the like to form an electrode can be used.
- a thin film of a conductive oxide semiconductor such as ITO or FTO formed with a layer of platinum, carbon, or the like formed thereon is also applicable.
- a method for producing such a counter electrode 8 for example, a method of forming a platinum layer by performing a heat treatment after applying chloroplatinic acid can be mentioned.
- a method in which an electrode is formed on a substrate by an evaporation method or a sputtering method may be used.
- the polymer compound is mixed with an appropriate organic solvent, and if necessary, a haeogen molecule and various additives are added, and the mixture is stirred.
- an electrolyte composition solution is prepared by dissolving the components uniformly, and the obtained electrolyte composition solution is dropped on the working electrode 6 little by little and dried.
- organic solvent for dissolving the polymer compound examples include tetrahydrofuran, methylethylketone, dimethylformamide, acetonitrile, methoxysetonitrile, propionitrile, propylene carbonate, getylcarbonate, methanol, and butyrolataton. N-methylpyrrolidone You.
- the polymer compound desirably has a sufficient solubility in at least one of these organic solvents.
- a method may be used in which a monomer constituting the polymer compound is filled in advance in a semiconductor porous electrode and polymerized by a chemical and / or electrochemical technique to form an electrolyte layer.
- the electrolyte composition of the present invention has a solid property, it has poor volatility and fluidity, and when used in a photoelectric conversion element such as a dye-sensitized solar cell, alteration of the electrolyte due to volatilization of a solvent or the like. It has no output, high output and photoelectric conversion characteristics, and can function stably for a long time. In addition, leakage of electrolyte from gaps in the container and scattering when the element is damaged are suppressed, and the handleability is excellent.
- the solid state in the present invention can be easily inspected by the following test.
- an adhesive tape 13 is attached to one surface of a square glass plate 11 of about 5 cm square, leaving a central part 12 of about 20 mm square.
- a solution of the electrolyte composition is dropped into a central portion 12 surrounded by an adhesive tape 13.
- the adhesive tape 13 is peeled off to obtain a glass plate 11 on which the electrolyte membrane 14 is formed.
- the thickness of the electrolyte membrane 14 is about 30 ⁇ .
- the glass plate 11 is set upright on the floor surface 15 and left at room temperature for 10 hours.
- the electrolyte composition After 10 hours, when the electrolyte membrane 14 has not contacted the floor 15, the electrolyte composition has low fluidity and is determined to be solid. Conversely, when the electrolyte membrane 14 comes into contact with the floor surface 15, the electrolyte composition has high fluidity and is determined to be liquid.
- a glass substrate with an FTO film as the transparent electrode substrate Apply a slurry-like aqueous dispersion of titanium oxide with an average particle size of 20 nm to the surface of this transparent electrode substrate 2 on the side of the FTO film (conductive layer), and dry. After that, heat treatment was performed at 450 ° C. for 1 hour to form an oxide semiconductor porous film having a thickness of 7 m. Further, the working electrode was prepared by immersing 1 ⁇ in an ethanol solution of ruthenium biviridine complex (N 3 dye) to carry the dye. Also, as a counter electrode, an FTO gas with a platinum electrode layer provided by sputtering A lath electrode substrate was prepared.
- an electrolyte layer was formed on the working electrode by the following method.
- soluble polythiophene was synthesized by a known chemical oxidative polymerization method. This soluble polythiophene was dissolved in tetrahydrofuran to prepare an electrolyte precursor solution. The operation of dropping the electrolyte precursor solution little by little on the oxide semiconductor porous film of the working electrode and drying was repeated. Through this operation, a polythiophene film was formed on the porous oxide semiconductor film. Then, the Porichiofen film was oxidized by electrochemical technique in a state dipped in L i I and 1 2 and the carbon-flop ⁇ pyrene solution containing. As a result, an oxidation-reduction pair consisting of iodide ions and a polyiodide was doped into the polythiophene film to form an electrolyte layer.
- Example (2b) is different from Example (2a) in that the electrolyte layer is composed of a polypyrrole film.
- the other configuration is the same as that of the embodiment (2a), and the description is omitted. A method for forming the electrolyte layer will be described.
- soluble polypyrrole was synthesized by a known chemical oxidative polymerization method. This soluble polypyrrole was dissolved in N-methyl-2-pyrrolidone to prepare an electrolyte precursor solution.
- Example (2b) -1 As shown in Table 3.
- Example (2c) differs from Example (2a) in that the electrolyte layer is made of a polyaniline film.
- the other configuration is the same as that of the embodiment (2a), and the description is omitted. A method for forming the electrolyte layer will be described.
- soluble polyaniline was synthesized by a known chemical oxidative polymerization method. This soluble polyaniline was dissolved in N-methyl-2-pyrrolidone to prepare an electrolyte precursor solution.
- Example (2c) -1 as shown in Table 3.
- the working electrode and the counter electrode faced each other, and the electrolyte was injected between the working electrode and the counter electrode to form an electrolyte layer.
- a dye-sensitized solar cell serving as a test cell of Comparative Example 2-1 was produced.
- a slurry containing titanium oxide nanoparticles and titanium tetraisopropoxide was used instead of the titanium oxide slurry used in the procedures of Examples (2a), (2b), and (2c) above. Except for that, it was manufactured in the same manner as the procedure of the above example.
- Ma As the counter electrode, a platinum-coated FTO electrode substrate similar to those in Examples (2a), (2b) and (2c) above was used.
- Copper iodide (Cu I) was used as the electrolyte for the electrolyte layer.
- the counter electrode was overlapped while pressing the counter electrode against the electrolyte layer to join the counter electrode and the electrolyte layer. Further, the solvent of the electrolyte composition solution was sufficiently dried and removed.
- Table 3 shows the initial value of the photoelectric conversion efficiency (initial conversion efficiency) for each test cell.
- the 1- / 1 2 ratio of propylene carbonate solution was used to dope the redox couple in the polymer film to be the electrolyte layer consisting of iodide ions and port Ryou compound I- / 1 2 (molar ratio, charge ratio).
- the electrolyte layer had an appearance similar to that of plastic, and was determined to be solid by the property test.
- test cells of Examples (2a), (2b), and (2c) have high photoelectric conversion characteristics and can withstand long-term intermittent use. was understood.
- the electrolyte solvent gradually volatilized after the measurement of the photoelectric conversion characteristics was started, and the photoelectric conversion efficiency was 10% of the initial value by 3 hours. It has been reduced to below, and has hardly functioned as a photoelectric conversion element.
- Dye-sensitized solar cells were fabricated by the same procedure as in the test cells 2a), (2b), and (2c). This is Example (2d).
- the working electrode and the counter electrode were opposed to each other with a thermoplastic polyolefin resin sheet having a thickness of 50 m interposed, and a gap was secured between the working electrode and the counter electrode by thermal melting of the resin sheet. .
- a small hole was made in a part of the counter electrode side to serve as the electrolyte injection port.
- the electrolyte solution is injected from the liquid injection port to form an electrolyte layer, and the liquid injection port is sealed with a combination of an epoxy-based sealing resin and a polyolefin-based lubricating liquid to obtain a dye-sensitized solar cell. Produced. This is the test cell of Comparative Example 2-3.
- test cells in Example (2d) and one of the test cells in Comparative Example 2-3 were Each was left for 7 days in a thermostat at a temperature of 80 ° C. After that, the test cell was taken out of the thermostat and the appearance of the test cell was visually observed. In the test cell of Comparative Example 2-3, the polyolefin sealing deteriorated and a part of the electrolyte was volatilized. Bubbles were generated. For this reason, it hardly functions as a photoelectric conversion element.
- the electrolyte composition and the photoelectric conversion element according to the third embodiment of the present invention will be described based on the dye-sensitized solar cell of one embodiment shown in FIG.
- the point that the photoelectric conversion element according to the third aspect of the present invention is different from the first aspect is an electrolyte composition.
- the dye-sensitized solar cell 1 shown in FIG. 1 has an oxide semiconductor porous film 5 made of fine particles of an oxide semiconductor such as titanium oxide and carrying a photosensitizing dye on a transparent electrode substrate 2.
- An electrode 6 and a counter electrode 8 provided opposite to the working electrode 6 are provided.
- An electrolyte layer 7 is formed between the working electrode 6 and the counter electrode 8.
- the electrolyte composition forming the electrolyte layer 7 has a cation structure formed by a halogen molecule acting on a polymer having a partially ⁇ -conjugated structure in a main chain or a side chain of the polymer.
- a polymer compound having a halide ion and / or a polyhalide as a structure anion is contained as an essential component.
- the polymer compound may be a single type of polymer compound or a mixture obtained by appropriately mixing a plurality of types of polymer compounds.
- the range of the molecular weight of the polymer compound is several hundreds to several millions, preferably several thousand to several hundred thousand, and more preferably tens of thousands.
- “Partially forming a ⁇ -conjugated structure” means that one unsaturated bond is isolated or continuous (conjugated) via a single bond within the range of 2 to 10 Means that
- Such a polymer (undoped polymer) generates a cationic structure by doping with a halogen molecule.
- the undoped polymer examples include a cis_1,4-polygen polymer represented by the following formula (3-1), and a trans-1,4_polygen polymer represented by the following formula (3-2).
- Polymers include 1,2-polygen-based polymers represented by the following formula (3-3). Chemical formula (3-1)
- each of the groups R 1 and R 2 can be independently selected from each other; a hydrogen atom; fluorine, chlorine, bromine, iodine, etc.
- a straight-chain alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group;
- R 1 and R 2 when both R 1 and R 2 are hydrogen atoms, it is a 1,2-polybutadiene; when R 1 is a methyl group, and when R 2 is a hydrogen atom, it is a 1,2-polyisobutane.
- the undoped polymer can be obtained, for example, by polymerizing a known monomer such as butadiene and isoprene by an appropriate method.
- a known monomer such as butadiene and isoprene
- generally commercially available polymers may be prepared and used, but, of course, the present invention is not limited to these.
- a copolymer may be formed with styrene, acrylonitrile, isobutene, or the like.
- the undoped polymer is partially oxidized, for example, by adding a dopant such as a halogen molecule, to become a polymer compound having a cationic structure (cationic polymer).
- a dopant such as a halogen molecule
- a polymer compound having a cationic structure cationic polymer
- halide ions such as iodide ions, bromide ions, and chloride ions; Br 3 _, I 3 —, I 5 —, and I 7 —, Cl 2 I—, C 1 I 2 Br 2 I—, Br 12 — and the like.
- the polyhalide ion is an aion composed of a plurality of halogen atoms, and can be obtained by reacting a halide ion such as C 1 ⁇ Br-, I-, or the like with a halogen molecule.
- a halide ion such as C 1 ⁇ Br-, I-, or the like
- the halogen molecules using C l 2, B r 2, 1 single molecular halogen and / or C 1 I, such as 2, B r I, halogen sown compounds such as B r C 1 (the interhalogen compound) Can be.
- halogen molecules is not particularly essential, but it is preferable to add halogen molecules.
- a halogen molecule is added and a polyhalide ion is interposed, the halogen ion and the polyhalide ion form a redox pair, and characteristics such as photoelectric conversion characteristics can be improved.
- the ratio of the halogen molecule to the halide ion is not particularly limited, it is more preferably 0% to 100% by molar ratio.
- the polymer plays a role of a curing agent for curing the liquid electrolyte.
- the polymer compound itself has conductivity, and plays a main role of charge transfer in the electrolyte composition containing a redox couple. And solid.
- the electrolyte yarn may contain, if necessary, an ionic liquid; an organic nitrogen compound such as 4-tert-butylpyridine, 2-vinylpyridine, N-vinyl-2-pyrrolidone; lithium salt, sodium salt, magnesium Various additives such as salt, iodide salt, thiocyanate, and water can be added as long as the properties and characteristics of the electrolyte composition are not impaired.
- an organic nitrogen compound such as 4-tert-butylpyridine, 2-vinylpyridine, N-vinyl-2-pyrrolidone
- lithium salt sodium salt
- additives such as salt, iodide salt, thiocyanate, and water can be added as long as the properties and characteristics of the electrolyte composition are not impaired.
- Ion liquid As the Ion liquid, quaternized Imidazoriumu, quaternized pyridine Yuumu ,, and cations such as quaternized Anmoniumu, iodide, Bisutorifuru O b methylsulfonyl Imi door two on, the Kisafuruororin acid ion (PF 6 one ), Tetrafluoroborate ions (BF 4 ), and other salts that are liquid at room temperature.
- quaternized Imidazoriumu As the Ion liquid, quaternized Imidazoriumu, quaternized pyridine Yuumu , and cations such as quaternized Anmoniumu, iodide, Bisutorifuru O b methylsulfonyl Imi door two on, the Kisafuruororin acid ion (PF 6 one ), Tetrafluoroborate ions (BF 4 ), and other salts that are liquid at room temperature.
- PF 6 one the Kisafur
- the ratio of the plasticizer is preferably 50% or less, more preferably 10% or less, based on the weight of the electrolyte composition.
- the transparent electrode substrate 2 is obtained by forming a conductive layer 3 made of a conductive material on a transparent substrate 4 such as a glass plate or a plastic sheet.
- the material of the transparent substrate 4 is preferably a material having high light transmittance in terms of application.
- a material having high light transmittance in terms of application.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PC polycarbonate
- PES polyether sulfone
- a transparent plastic sheet, a polished plate of ceramics such as titanium oxide and alumina can be used.
- the conductive layer 3 is made of transparent oxide such as tin-doped tin oxide (ITO), tin oxide (SnO 2 ), and fluorine-doped tin oxide (FTO) from the viewpoint of the light transmittance of the transparent electrode substrate 2. It is preferable to use the compound semiconductor alone or in combination of plural kinds. However, the material is not particularly limited to these, and an appropriate material suitable for the intended use may be selected and used from the viewpoints of light transmittance and conductivity. Further, in order to improve the current collection efficiency from the oxide semiconductor porous film 5 and the electrolyte layer 7, the area ratio of the gold, silver, platinum, aluminum, and aluminum is set so as not to significantly impair the light transmittance of the transparent electrode substrate 2.
- ITO tin-doped tin oxide
- SnO 2 tin oxide
- FTO fluorine-doped tin oxide
- a metal wiring layer made of nickel, titanium, or the like may be used in combination.
- the transparent electrode substrate 2 may be provided in a pattern such as a lattice, stripe, or comb so as to transmit light as uniformly as possible.
- a known appropriate method according to the material of the conductive layer 3 may be used.
- the conductive layer 3 is formed from an oxide semiconductor such as ITO, a sputtering method is used. , CVD, SPD (spray pyrolysis deposition), and vapor deposition.
- CVD chemical vapor deposition
- SPD spray pyrolysis deposition
- vapor deposition In consideration of light transmittance and conductivity, 0.05 ⁇ ! It is formed to a thickness of about 2.0 ⁇ .
- the oxide semiconductor porous film 5 titanium oxide (T I_ ⁇ 2), tin oxide (S N_ ⁇ 2), oxidation of tungsten (W0 3), zinc oxide (Z N_ ⁇ ), niobium oxide (N b 2 0 5 )
- the main component is an oxide semiconductor fine particle having an average particle diameter of 1 nm to 100 nm, which is a combination of one or more of these compounds, and a thickness of 0.5! It is a porous thin film of about 50 ⁇ .
- a commercially available dispersion liquid in which fine particles of an oxide semiconductor are dispersed in a desired dispersion medium or a colloid solution that can be adjusted by a sol-gel method is required.
- a known coating method such as a screen printing method, an ink jet printing method, a roll coating method, a doctor blade method, a spin coating method, or a spray coating method can be applied.
- an electrophoretic electrodeposition method in which the electrode substrate 2 is immersed in the colloid solution and the oxide semiconductor fine particles are adhered to the electrode substrate 2 by electrophoresis, and a foaming agent is mixed with the above-mentioned colloid solution or dispersion and applied.
- the sensitizing dye supported on the oxide semiconductor porous film 5 is not particularly limited, and may be, for example, a ruthenium complex / iron complex having a ligand having a biviridine structure, a terpyridine structure, or the like, a porphyrin-based And phthalocyanine-based metal complexes, and organic dyes such as eosin, rhodamine, merocyanine, and coumarin.
- a ruthenium complex / iron complex having a ligand having a biviridine structure, a terpyridine structure, or the like a porphyrin-based And phthalocyanine-based metal complexes, and organic dyes such as eosin, rhodamine, merocyanine, and coumarin.
- organic dyes such as eosin, rhodamine, merocyanine, and coumarin.
- the counter electrode 8 may be, for example, a substrate made of a non-conductive material such as glass.
- a thin film of a conductive oxide semiconductor such as ITO or FTO on which a layer of platinum, carbon, or the like is formed is also applicable.
- a method for producing such a counter electrode 8 for example, a method of forming a platinum layer by performing a heat treatment after applying chloroplatinic acid can be mentioned.
- a method in which an electrode is formed on a substrate by an evaporation method or a sputtering method may be used.
- the polymer compound is mixed with an appropriate organic solvent, and if necessary, a haeogen molecule and various additives are added, and the mixture is stirred.
- an electrolyte composition solution is prepared by uniformly dissolving the components, and the obtained electrolyte composition solution is dropped on the working electrode 6 little by little and dried. Thereby, when the electrolyte composition is cast on the working electrode 6, the electrolyte composition solution can be well penetrated into the voids of the porous oxide semiconductor film 5 and filled.
- organic solvent for dissolving the polymer compound examples include acetonitrile, methoxyacetonitrile, propionitrile, propylene carbonate, ethyl carbonate, methanol, ⁇ -butyrolactone, and ⁇ ⁇ ⁇ -methylpyrrolidone.
- the polymer compound desirably has a sufficient solubility in at least one of these organic solvents.
- the electrolyte composition of the present invention has a solid property, it has poor volatility and fluidity, and when used in a photoelectric conversion element such as a dye-sensitized solar cell, alteration of the electrolyte due to volatilization of a solvent or the like. It has no output, high output and photoelectric conversion characteristics, and can function stably for a long time. In addition, leakage of electrolyte from gaps in the container and scattering when the element is damaged are suppressed, and the handleability is excellent.
- the solid state in the present invention can be easily inspected by the following test.
- an adhesive tape 13 is attached to one surface of a square glass plate 11 of about 5 cm square, leaving a central part 12 of about 20 mm square.
- a solution of the electrolyte composition is dropped into a central portion 12 surrounded by the adhesive tape 13. After drying, sticky
- the tape 13 is peeled off to obtain the glass plate 11 on which the electrolyte membrane 14 is formed.
- the thickness of the electrolyte membrane 14 is about 30 / m.
- the glass plate 11 is set upright on the floor surface 15 and left at room temperature for 10 hours.
- the electrolyte composition After 10 hours, when the electrolyte membrane 14 has not contacted the floor surface 15, the electrolyte composition has low fluidity and is determined to be solid. Conversely, when the electrolyte membrane 14 comes into contact with the floor surface 15, the electrolyte composition is judged to be highly fluid and liquid.
- a glass substrate with an FTO film was used as the transparent electrode substrate.
- a slurry-like aqueous dispersion of titanium oxide with an average particle diameter of 20 nm was applied to the surface of this transparent electrode substrate 2 on the side of the FTO film (conductive layer). By heating at 450 ° C. for 1 hour, a 7-m-thick porous oxide semiconductor film was formed.
- ruthenium biviridine complex
- an electrolyte layer was formed on the working electrode by the following method.
- Example (3b) is different from Example (3a) in that polyisoprene is used as the polygen-based polymer. Other configurations are the same as in the embodiment (3a). Description is omitted.
- Example (3a) A dye-sensitized solar cell serving as a test cell was manufactured in the same manner as in Example (3a). This is from Example (3b) -1 to (3b) -2 as shown in Table 4.
- an electrolytic solution serving as an electrolyte an acetonitrile solution containing a quaternized imidazolymide, lithium iodide, iodine, and 4-tert-butylpyridine was prepared.
- the working electrode was replaced by a slurry containing titanium oxide nanoparticles and titanium tetraisopropoxide, instead of the titanium oxide slurry used in the procedures of the above Examples (3a) and (3b). Then, it was produced in the same manner as the procedure of the above example.
- a platinum-coated FTO electrode substrate similar to that in the above Examples (3a) and (3b) was used.
- Table 4 shows the initial value of the photoelectric conversion efficiency (initial conversion efficiency) for each test cell.
- the electrolyte layer had an appearance similar to that of plastic, and was determined to be solid by the property test.
- test cells of Examples (3a) and (3b) had sufficiently high photoelectric conversion characteristics and were durable for long-term continuous use. .
- the electrolyte solvent gradually volatilized after the measurement of the photoelectric conversion characteristics was started, and the photoelectric conversion efficiency was 10% of the initial value by 3 hours. It has been reduced to below, and has hardly functioned as a photoelectric conversion element.
- the working electrode and the counter electrode are opposed to each other with a 50 / zm-thick thermoplastic polyolefin resin sheet interposed therebetween, and the resin sheet is thermally fused to secure a gap between both the working electrode and the counter electrode. Fixed. At this time, a small hole was made in a part of the counter electrode side to serve as the electrolyte injection port. The electrolyte was injected from the liquid inlet to form an electrolyte layer, and the liquid inlet was closed using both an epoxy-based sealing resin and a polyolefin-based resin, thereby producing a dye-sensitized solar cell. . This is the test cell of Comparative Example 3-3.
- Example (3c) One of the test cells of Example (3c) and one of the test cells of Comparative Example 3-3 were left in a thermostat at a temperature of 80 ° C. for 7 days. Then, the test cell was taken out of the thermostat and the appearance of the test cell was visually observed. In the test cell of Comparative Example 3-3, the sealing of the polyolefin deteriorated and part of the electrolyte was volatilized. Bubbles were generated. For this reason, it hardly functions as a photoelectric conversion element.
- Example (3c) One of the test cells of Example (3c) and one of the test cells of Comparative Example 3-3 were ruptured with a hammer from the glass substrate side, and the broken portions were held downward. However, in the test cell of Comparative Example 3-3, the electrolyte leaked. On the other hand, in the test cell of Example (3c), the electrolyte layer did not leak because the charge layer was solid. Industrial potential
- the electrolyte composition of the present invention can be used as an electrolyte layer of a photoelectric conversion element such as a dye-sensitized solar cell.
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Abstract
Description
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EP04745532A EP1655799B1 (en) | 2003-05-30 | 2004-05-27 | Electrolyte composition and photoelectric converter using same |
DE602004031853T DE602004031853D1 (de) | 2003-05-30 | 2004-05-27 | Elektrolyt-zusammensetzung und fotoelektrischer umsetzer damit |
CA002526185A CA2526185A1 (en) | 2003-05-30 | 2004-05-27 | Electrolyte composition and photoelectric conversion element using same |
AU2004248778A AU2004248778B2 (en) | 2003-05-30 | 2004-05-27 | Electrolyte composition and photoelectric converter using same |
JP2005505038A JP4286833B2 (ja) | 2003-05-30 | 2004-05-27 | 色素増感太陽電池用電解質組成物およびこれを用いた色素増感太陽電池 |
AT04745532T ATE502415T1 (de) | 2003-05-30 | 2004-05-27 | Elektrolyt-zusammensetzung und fotoelektrischer umsetzer damit |
CN2004800146205A CN1795580B (zh) | 2003-05-30 | 2004-05-27 | 电解质组合物及使用该电解质组合物的光电转换元件 |
US11/287,424 US20060076051A1 (en) | 2003-05-30 | 2005-11-28 | Electrolyte composition and photoelectric conversion element using same |
US12/873,832 US20100319762A1 (en) | 2003-05-30 | 2010-09-01 | Electrolyte composition and photoelectric conversion element using same |
US12/873,933 US20100326500A1 (en) | 2003-05-30 | 2010-09-01 | Electrolyte composition and photoelectric conversion element using same |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10208543A (ja) * | 1997-01-21 | 1998-08-07 | Tdk Corp | 固体電解質および二酸化炭素センサ |
JPH11126515A (ja) * | 1997-10-24 | 1999-05-11 | Naoya Ogata | 高分子固体電解質 |
JP2000243466A (ja) * | 1999-02-23 | 2000-09-08 | Aisin Seiki Co Ltd | 光電変換素子 |
JP2000285974A (ja) * | 1999-03-30 | 2000-10-13 | Toshiba Corp | 光増感型太陽光発電素子 |
JP2001067931A (ja) * | 1999-08-25 | 2001-03-16 | Fuji Photo Film Co Ltd | 電解質組成物、光電変換素子および光電気化学電池 |
JP2001167630A (ja) * | 1999-09-29 | 2001-06-22 | Fuji Photo Film Co Ltd | 電解質組成物、光電変換素子及び光電気化学電池 |
JP2001199961A (ja) * | 2000-01-21 | 2001-07-24 | Fuji Photo Film Co Ltd | 重合性溶融塩モノマー、電解質組成物および電気化学電池 |
JP2002343133A (ja) * | 2001-05-18 | 2002-11-29 | Hitachi Maxell Ltd | イオン伝導性高分子電解質、その製造方法およびそれを用いた非水二次電池 |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3401152A (en) * | 1966-11-03 | 1968-09-10 | Dow Chemical Co | Polyelectrolytes from bis sulfonium salts |
US4282118A (en) * | 1978-11-15 | 1981-08-04 | Calgon Corporation | Electroconductive polymer composition |
US4488943A (en) * | 1980-11-18 | 1984-12-18 | The United States Of America As Represented By The United States Department Of Energy | Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends |
JPS61281237A (ja) * | 1985-06-07 | 1986-12-11 | Fuji Photo Film Co Ltd | 銀塩拡散転写法写真要素 |
US5196484A (en) * | 1986-10-27 | 1993-03-23 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Polymeric ion conductors |
JPH0678492B2 (ja) * | 1986-11-27 | 1994-10-05 | 昭和電工株式会社 | 高電導性重合体組成物及びその製造方法 |
JPS6474712A (en) * | 1987-09-17 | 1989-03-20 | Japan Carlit Co Ltd | Manufacture of solid electrolytic capacitor |
CH674596A5 (ja) | 1988-02-12 | 1990-06-15 | Sulzer Ag | |
DE3814730A1 (de) * | 1988-04-30 | 1989-11-09 | Bayer Ag | Feststoff-elektrolyte und diese enthaltende elektrolyt-kondensatoren |
US5679757A (en) * | 1990-12-12 | 1997-10-21 | The Regents Of The University Of California | Highly organic solvent soluble, water insoluble electroluminescent polyphenylene vinylenes having pendant steroid groups and products and uses thereof |
GB9206732D0 (en) * | 1992-03-27 | 1992-05-13 | Sandoz Ltd | Photovoltaic cells |
CA2203384C (en) * | 1994-10-22 | 2001-01-09 | Teruo Umemoto | Conjugated n-fluoropyridinium salt-containing polymer and use of the same |
JP4318324B2 (ja) * | 1996-07-17 | 2009-08-19 | 四国化成工業株式会社 | 溶融塩型高分子電解質用溶融塩ポリマーの調製方法及び溶融塩型高分子電解質 |
JP3579200B2 (ja) * | 1996-11-07 | 2004-10-20 | 東洋紡績株式会社 | 耐熱性高分子電解質ゲルおよびその製造方法 |
JP2000100483A (ja) * | 1998-09-22 | 2000-04-07 | Sharp Corp | 光電変換素子及びその製造方法及びこれを用いた太陽電池 |
JP3946947B2 (ja) | 1999-09-24 | 2007-07-18 | 株式会社東芝 | 光増感型太陽電池用電解質組成物、光増感型太陽電池及び光増感型太陽電池の製造方法 |
ATE385609T1 (de) * | 1999-09-29 | 2008-02-15 | Fujifilm Corp | Elektrolyt-zusammensetzung, photoelektrische umwandlungsvorrichtung und photoelektrochemische zelle |
JP2001148491A (ja) * | 1999-11-19 | 2001-05-29 | Fuji Xerox Co Ltd | 光電変換素子 |
JP4636644B2 (ja) * | 2000-01-17 | 2011-02-23 | 富士フイルム株式会社 | 電解質組成物、電気化学電池およびイオン性液晶モノマー |
US6900382B2 (en) * | 2002-01-25 | 2005-05-31 | Konarka Technologies, Inc. | Gel electrolytes for dye sensitized solar cells |
JP4799776B2 (ja) * | 2000-08-22 | 2011-10-26 | 富士フイルム株式会社 | 電解質組成物及びそれを用いた電気化学電池 |
JP4926325B2 (ja) * | 2001-02-15 | 2012-05-09 | 富士フイルム株式会社 | 電解質組成物、電気化学電池、光電気化学電池及び非水二次電池 |
JP2002289271A (ja) * | 2001-03-26 | 2002-10-04 | Sharp Corp | 色素増感型太陽電池 |
JP2003156019A (ja) | 2001-09-05 | 2003-05-30 | Horizumi Mokkosho:Kk | 家具用部材連結・調整装置および回転工具 |
US7431903B2 (en) * | 2001-10-30 | 2008-10-07 | Catalysts & Chemicals Industries Co., Ltd. | Tubular titanium oxide particles and process for preparing same |
JP2003156020A (ja) | 2001-11-16 | 2003-05-30 | Sekisui House Ltd | 釘、及び該釘を用いた表面基材と金属枠の締結方法 |
JP3980872B2 (ja) | 2001-11-22 | 2007-09-26 | アイホン株式会社 | 付属部品の脱着構造 |
-
2004
- 2004-05-27 JP JP2005505038A patent/JP4286833B2/ja not_active Expired - Fee Related
- 2004-05-27 AT AT10001438T patent/ATE526701T1/de not_active IP Right Cessation
- 2004-05-27 CA CA002683031A patent/CA2683031A1/en not_active Abandoned
- 2004-05-27 CN CN2007101284439A patent/CN101093862B/zh not_active Expired - Fee Related
- 2004-05-27 KR KR1020077013449A patent/KR100869816B1/ko not_active IP Right Cessation
- 2004-05-27 DE DE602004031853T patent/DE602004031853D1/de not_active Expired - Lifetime
- 2004-05-27 WO PCT/JP2004/007644 patent/WO2004112184A1/ja active Application Filing
- 2004-05-27 CN CN2004800146205A patent/CN1795580B/zh not_active Expired - Fee Related
- 2004-05-27 KR KR1020077028745A patent/KR100837367B1/ko not_active IP Right Cessation
- 2004-05-27 TW TW093115095A patent/TWI345840B/zh not_active IP Right Cessation
- 2004-05-27 KR KR1020057022243A patent/KR100869817B1/ko not_active IP Right Cessation
- 2004-05-27 EP EP10001438A patent/EP2204875B8/en not_active Expired - Lifetime
- 2004-05-27 CA CA002526185A patent/CA2526185A1/en not_active Abandoned
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-
2005
- 2005-11-28 US US11/287,424 patent/US20060076051A1/en not_active Abandoned
-
2008
- 2008-07-22 JP JP2008189200A patent/JP4959643B2/ja not_active Expired - Lifetime
-
2010
- 2010-09-01 US US12/873,933 patent/US20100326500A1/en not_active Abandoned
- 2010-09-01 US US12/873,832 patent/US20100319762A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10208543A (ja) * | 1997-01-21 | 1998-08-07 | Tdk Corp | 固体電解質および二酸化炭素センサ |
JPH11126515A (ja) * | 1997-10-24 | 1999-05-11 | Naoya Ogata | 高分子固体電解質 |
JP2000243466A (ja) * | 1999-02-23 | 2000-09-08 | Aisin Seiki Co Ltd | 光電変換素子 |
JP2000285974A (ja) * | 1999-03-30 | 2000-10-13 | Toshiba Corp | 光増感型太陽光発電素子 |
JP2001067931A (ja) * | 1999-08-25 | 2001-03-16 | Fuji Photo Film Co Ltd | 電解質組成物、光電変換素子および光電気化学電池 |
JP2001167630A (ja) * | 1999-09-29 | 2001-06-22 | Fuji Photo Film Co Ltd | 電解質組成物、光電変換素子及び光電気化学電池 |
JP2001199961A (ja) * | 2000-01-21 | 2001-07-24 | Fuji Photo Film Co Ltd | 重合性溶融塩モノマー、電解質組成物および電気化学電池 |
JP2002343133A (ja) * | 2001-05-18 | 2002-11-29 | Hitachi Maxell Ltd | イオン伝導性高分子電解質、その製造方法およびそれを用いた非水二次電池 |
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JP2007087611A (ja) * | 2005-09-20 | 2007-04-05 | Yokohama National Univ | 光電変換素子 |
WO2009013942A1 (ja) * | 2007-07-25 | 2009-01-29 | Soken Chemical & Engineering Co., Ltd. | 色素増感太陽電池 |
JP5224604B2 (ja) * | 2007-07-25 | 2013-07-03 | 綜研化学株式会社 | 色素増感太陽電池 |
WO2012133786A1 (ja) | 2011-03-31 | 2012-10-04 | 日本ゼオン株式会社 | ポリエーテル化合物、架橋性組成物および電解質 |
WO2012133769A1 (ja) | 2011-03-31 | 2012-10-04 | 日本ゼオン株式会社 | ポリエーテル化合物および電解質組成物 |
US9278348B2 (en) | 2011-03-31 | 2016-03-08 | Zeon Corporation | Polyether compound, cross-linkable composition, and electrolyte |
US9469612B2 (en) | 2011-03-31 | 2016-10-18 | Zeon Corporation | Polyether compound and electrolyte composition |
JP2014056805A (ja) * | 2012-08-10 | 2014-03-27 | Pgs Home Co Ltd | 色素増感太陽電池 |
WO2014050944A1 (ja) | 2012-09-28 | 2014-04-03 | 日本ゼオン株式会社 | ポリエーテル共重合体、架橋性ポリエーテル共重合体組成物及び電解質 |
US10199683B2 (en) | 2012-09-28 | 2019-02-05 | Zeon Corporation | Polyether copolymer, crosslinkable polyether copolymer composition and electrolyte |
WO2014148598A1 (ja) | 2013-03-21 | 2014-09-25 | 日本ゼオン株式会社 | 色素増感太陽電池素子 |
JP2018152516A (ja) * | 2017-03-14 | 2018-09-27 | 株式会社豊田中央研究所 | 太陽電池、太陽電池モジュール及び太陽電池の製造方法 |
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