CN101847512A - Photo-electric conversion element is with constituent and use the photo-electric conversion element of this photo-electric conversion element with constituent - Google Patents
Photo-electric conversion element is with constituent and use the photo-electric conversion element of this photo-electric conversion element with constituent Download PDFInfo
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- CN101847512A CN101847512A CN201010141421A CN201010141421A CN101847512A CN 101847512 A CN101847512 A CN 101847512A CN 201010141421 A CN201010141421 A CN 201010141421A CN 201010141421 A CN201010141421 A CN 201010141421A CN 101847512 A CN101847512 A CN 101847512A
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- Prior art keywords
- photo
- conversion element
- electric conversion
- phosphonium
- constituent
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 67
- 239000000470 constituent Substances 0.000 title claims abstract description 65
- 239000003792 electrolyte Substances 0.000 claims abstract description 60
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 24
- 150000001450 anions Chemical class 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 halide ion Chemical class 0.000 claims description 78
- 230000000052 comparative effect Effects 0.000 claims description 25
- 239000004065 semiconductor Substances 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 11
- 210000001745 uvea Anatomy 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 6
- 229940006461 iodide ion Drugs 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 19
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000031709 bromination Effects 0.000 description 10
- 238000005893 bromination reaction Methods 0.000 description 10
- 238000005660 chlorination reaction Methods 0.000 description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- GAMJGSYWIZSNEK-UHFFFAOYSA-N iodo(methyl)phosphane Chemical compound CPI GAMJGSYWIZSNEK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001350 alkyl halides Chemical class 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- DRDWGCXXOYQOCH-UHFFFAOYSA-N CN1C(N(C=C1)CCC)C.I(=O)(=O)O Chemical compound CN1C(N(C=C1)CCC)C.I(=O)(=O)O DRDWGCXXOYQOCH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
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- 238000004040 coloring Methods 0.000 description 3
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
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- 125000001424 substituent group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ALSIFQIAIHCPAA-UHFFFAOYSA-N 1,2-dimethyl-3-propyl-2h-imidazole Chemical compound CCCN1C=CN(C)C1C ALSIFQIAIHCPAA-UHFFFAOYSA-N 0.000 description 2
- TYOCDPIZUIQUSO-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1C TYOCDPIZUIQUSO-UHFFFAOYSA-N 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 description 2
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- MZSUDHKFNNYUGD-UHFFFAOYSA-N C(C)S(=O)(=O)O.[F] Chemical compound C(C)S(=O)(=O)O.[F] MZSUDHKFNNYUGD-UHFFFAOYSA-N 0.000 description 2
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- HWIUYZBEKKGMCW-UHFFFAOYSA-N CN1CN(C=C1)CCCC.I(=O)(=O)O Chemical compound CN1CN(C=C1)CCCC.I(=O)(=O)O HWIUYZBEKKGMCW-UHFFFAOYSA-N 0.000 description 2
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
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- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 2
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- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical group CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910000065 phosphene Inorganic materials 0.000 description 1
- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical group C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 description 1
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical group C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 1
- FBOJNMRAZJRCNS-UHFFFAOYSA-M tetraethylphosphanium;chloride Chemical compound [Cl-].CC[P+](CC)(CC)CC FBOJNMRAZJRCNS-UHFFFAOYSA-M 0.000 description 1
- WKSYTZHMRBAPAO-UHFFFAOYSA-M tetraethylphosphanium;iodide Chemical compound [I-].CC[P+](CC)(CC)CC WKSYTZHMRBAPAO-UHFFFAOYSA-M 0.000 description 1
- ZTXFOCMYRCGSMU-UHFFFAOYSA-M tetramethylphosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C ZTXFOCMYRCGSMU-UHFFFAOYSA-M 0.000 description 1
- NJFUXFRJVIXVSG-UHFFFAOYSA-M tetramethylphosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)C NJFUXFRJVIXVSG-UHFFFAOYSA-M 0.000 description 1
- TVVPMLFGPYQGTG-UHFFFAOYSA-M tetramethylphosphanium;iodide Chemical compound [I-].C[P+](C)(C)C TVVPMLFGPYQGTG-UHFFFAOYSA-M 0.000 description 1
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
Abstract
The invention provides a kind of photo-electric conversion element electrolyte constituent that higher photoelectric conversion efficiency is provided.Photo-electric conversion element of the present invention is characterised in that with the electrolyte constituent, contain represented Si Ji phosphonium salt of following general formula (1) and the represented imidazole salts of following formula (2), with respect to both total amounts, described Si Ji phosphonium salt contains 20mol%～80mol%, and described imidazole salts contains 20mol%～80mol%.In general formula (1), R
1, R
2And R
3All be identical alkyl, R
4Carbon number be less than R
1, R
2And R
3Each carbon number.
In the formula, R
1, R
2, R
3, R
4The alkyl of expression carbon number 1～6 can be the same or different R
1With R
2Can form ring.X
1-expression univalent anion.
In the formula, R
5～R
9The alkyl of expression hydrogen or carbon number 1～8 can be the same or different.X
2-expression univalent anion.
Description
Technical field
The present invention relates to a kind of photo-electric conversion element constituent.In addition, the present invention relates to a kind of photo-electric conversion element that uses this photo-electric conversion element with constituent.
Background technology
Use the silicon class solar cell of monocrystalline silicon, polysilicon and amorphous silicon (amorphous silicon) to have to reach the photoelectric conversion efficiency of 20% excellence, be practical as main force's technology of photovoltaic power generation system.Yet the cost of energy that this silicon class solar cell spends in the raw material manufacturing is higher, is restricted with regard to viewpoints such as price and material supply.On the other hand, the dye-sensitized solar cell that is proposed by Gratzel etc. receives publicity in recent years.It has, and Jie, can reduce cost with regard to the aspect of material and method for making etc. significantly every the structure of electrolyte between titanium oxide porous electrode that carries sensitizing coloring matter and comparative electrode.
In this dye-sensitized solar cell, usually use the halogen of dissolving formation halogen redox couple (halogen redox couple) in organic solvent such as nitrile or carbonates or ionic liquid (normal temperature fuse salt) and the electrolyte that electrolyte forms.Being used as electrolytical mainly is the level Four halide salts that imidazolium halides, pyridinium halide, level Four ammonium halide, pyrrolidines halide, piperidines halide etc. have the nitrogen cationoid.Yet the nitrogen cationoid of these level Four halide salts has active site in its molecular structure, and therefore when being used as the electrolyte of dye-sensitized solar cell, the liquid that might produce electrolysis decomposes.
On the other hand, the also known Si Ji Phosphonium halide that has based on Phosphorus Si Ji phosphonium cation.Known four grades of halid chemical of Phosphonium and hot stable, and known its has anti-flammability (self-extinguishment (self-extinguishing)) owing to containing phosphorus.In the application aspect the electrolyte of dye-sensitized solar cell, for example open that 2000-299139 communique, Japan Patent spy are opened the 2001-35253 communique, the Japan Patent spy opens in the 2003-092153 communique and records about Si Ji Phosphonium halide the Japan Patent spy: contain comprise the alkyl or alkenyl of bond on nitrogen-atoms or phosphorus atoms quarternary ammonium salt Ji the electrolyte constituent that phosphonium salt forms.Yet, use put down in writing in these documents contain the halid electrolytical dye-sensitized solar cell of Si Ji Phosphonium, aspect photoelectric conversion efficiency and electrolyte stable, need further improvement.
Summary of the invention
The invention provides a kind of photo-electric conversion element of eliminating the various shortcomings that described prior art has with the electrolyte constituent and use the photo-electric conversion element of this photo-electric conversion element with the electrolyte constituent.
The invention provides a kind of photo-electric conversion element electrolyte constituent, it is characterized in that, contain represented Si Ji phosphonium salt of following general formula (1) and the represented imidazole salts of following formula (2), and with respect to both total amounts, described Si Ji phosphonium salt contains 20mol%～80mol%, and described imidazole salts contains 20mol%～80mol%.
[changing 1]
In the formula, R
1, R
2, R
3, R
4The alkyl of expression carbon number 1～6 can be the same or different R
1With R
2Can form ring; X
1-expression univalent anion.
In the formula, R
5～R
9The alkyl of expression hydrogen or carbon number 1～8 can be the same or different; X
2-expression univalent anion.
[effect of invention]
Photo-electric conversion element of the present invention can provide higher photoelectric conversion efficiency with the electrolyte constituent.In addition, this constituent has fine solubility, and is rich in thermal endurance and anti-flammability.
Description of drawings
Fig. 1 is the schematic diagram of structure of an execution mode of the expression photo-electric conversion element that uses electrolyte constituent of the present invention.
[symbol description]
10 photo-electric conversion elements
11 semiconductor layers
12 uveas
13 transparent electrode layers
14 comparative electrodes
15 dielectric substrates
Embodiment
Below, based on preferred embodiment the present invention being illustrated.Photo-electric conversion element of the present invention electrolyte constituent (below, also be called for short and make " electrolyte constituent ") be characterised in that, contain described four grades of phosphonium salts and imidazole salts.In electrolyte constituent of the present invention, by with the ratio of regulation and with this Si Ji phosphonium salt and imidazole salts, and can reach higher photoelectric conversion efficiency.Below, these compounds are described respectively.
In the represented Si Ji phosphonium salt of general formula (1), 4 alkyl are 1～6 as condition with carbon number, can identical or also can be different.According to circumstances, in 4 alkyl, R
1With R
2Bond can form ring.People such as present inventor are through research, the result is clear and definite: be used as photo-electric conversion element electrolyte constituent by four grades of phosphonium salts that will be as mentioned above directly be binding on the structure that phosphorus atoms forms than the alkyl of short chain relatively with the represented imidazole salts of general formula (2), can make photoelectric conversion efficiency more before become very high.Also clear and definite in addition: by using the represented Si Ji phosphonium salt of general formula (1), the chemical stability and the thermal endurance that contain the electrolyte constituent of this Si Ji phosphonium salt are improved.People such as present inventor think that reason is, the represented De phosphonium cation of general formula (1) does not have as the reactive hydrogen position as the glyoxaline cation.And four grades of represented phosphonium salts of general formula (1) compare with corresponding nitrogen cationoid salt, and are higher to the dissolubility of solvent, improve anionic concentration easily, also comparatively favourable with regard to this viewpoint.
Particularly with regard to the aspect of further raising photoelectric conversion efficiency, preferably in 4 alkyl, R
1～R
33 alkyl be identical alkyl, R
4For with R
1～R
3Different alkyl.This moment can be clear and definite: R
4Carbon number be less than R
1～R
3The situation and the R of carbon number
4Carbon number more than R
1～R
3The situation of carbon number compare, can further improve photoelectric conversion efficiency.Under the former situation, R
4Carbon number and R
1～R
3The difference of carbon number be preferably 1～5, be preferably 2～4 especially.R
4Carbon number be less than R
1～R
3The situation of carbon number can improve photoelectric conversion efficiency, its reason is not understood fully at present as yet fully.People such as present inventor think that its reason may be, owing to existing the represented Si Ji phosphonium salt of general formula (1) to improve the redox efficient of redox couple, thereby improve the charge migration efficient in the electrolyte constituent.
In general formula (1), R
1～R
4Concrete alkyl can enumerate: methyl, ethyl, n-pro-pyl, normal-butyl, n-hexyl, isopropyl, isobutyl group, n-pentyl, isohesyl, cyclopenta, cyclohexyl etc.At R
1With R
2Form under the situation of ring, ring for example can be enumerated as mentioned above: tetrahydrochysene phosphene (tetrahydrophosphole) ring, pentahydro-phosphorus element (pentahydrophosphorin) ring, 9-H-9-phospha bicyclic nonane ring etc.These alkyl can be replaced by the monovalence substituting group.Aforesaid substituent example can be enumerated: thiazolinyl; alkynyl; alkoxyl; carboxyl; alkyl carbonyl oxy; alkoxy carbonyl; sulfonyl (sulfoxy); alkyl sulphonyl; hydroxyl; the hydroxyl sulfonyl; aryl; aryloxy group; acyloxy; amine formyl; sulfonic group; sulfamic; cycloalkyl; cyano group; nitro; amino; alkyl amino; heterocyclic radical; amino-sulfonyl; halogen atom; the 2-butoxyethyl group; 6-bromine hexyl; the 2-carboxy ethyl; 3-sulfonyl propyl group; 4-sulfonyl butyl; the 2-hydroxyethyl; phenyl methyl; 4-butyl phenyl ether ylmethyl etc.
At R
1～R
3Be identical alkyl, and R
4Carbon number be less than R
1～R
3The situation of carbon number under, R
1～R
3For example can enumerate: ethyl, n-pro-pyl, normal-butyl, n-hexyl, isopropyl, isobutyl group, n-pentyl, isohesyl, cyclopenta, cyclohexyl etc.These alkyl can be replaced by the monovalence substituting group.Aforesaid substituent example can be enumerated the substituting group identical with described substituting group.On the other hand, R
4Be less than R with carbon number
1～R
3As condition, can enumerate: methyl, ethyl, n-pro-pyl, normal-butyl, isopropyl, isobutyl group, n-pentyl, cyclopenta etc.R
4Also can by with R
1～R
3Identical substituting group replaces.
R
1～R
4Particularly preferred combination can enumerate following combination: R
1～R
3Be ethyl, and R
4Be methyl; R
1～R
3Be n-pro-pyl, and R
4Be methyl; R
1～R
3Be isopropyl, and R
4Be methyl; R
1～R
3Be normal-butyl, and R
4Be methyl; R
1～R
3Be isobutyl group, and R
4Be methyl; R
1～R
3Be n-pentyl, and R
4Be methyl; R
1～R
3Be cyclopenta, and R
4Be methyl; R
1～R
3Be n-hexyl, and R
4Be methyl; R
1～R
3Be cyclohexyl, and R
4Be methyl.The particularly preferred R that is combined as
1～R
3Be normal-butyl, and R
4Combination for methyl.
In general formula (1), X
1-represented univalent anion for example can be enumerated: halide ion, tetrafluoroborate (BF
4), hexafluoro-phosphate radical (PF
6), two (trifluoromethyl sulfonyl) acid imide root (N (SO
2CF
3)
2), two (fluorosulfonyl) acid imide root (N (SO
2F)
2), four cyano borate (B (CN)
4), trifluoromethanesulfonic acid root (SO
3CF
3), five fluorine ethyl sulfonic acid root (SO
3CF
2CF
3), tetrafluoro ethyl sulfonic acid root (SO
3CHFCF
3), methanesulfonate (SO
3CH
3), ethyl sulfonic acid root (SO
3C
2H
5), three (pentafluoroethyl group) trifluoro phosphate radical ((C
2F
5)
3PF
3), trifluoroacetic acid root (CF
3COO), amino acid group, two oxalic acid ylboronic acid root (B (C
2O
4)
2), p-methyl benzenesulfonic acid root (SO
3C
6H
4CH
3), thiocyanate radical (SCN), cdicynanmide root (N (CN)
2), dialkyl group phosphate radical ((RO)
2POO), dialkyl dithiophosphoric acid root ((RO)
2PSS), aliphatic carboxylic acid root (RCOO) etc.In these anion, with regard to the aspect of further raising photoelectric conversion efficiency, preferably use halide ion.Particularly if use iodide ion, and the imidazole salts that itself and general formula (2) is represented is in addition and usefulness, then can reach excellent photoelectric conversion efficiency, thereby preferably.
The preferred concrete example of the Si Ji phosphonium salt that general formula (1) is represented can be enumerated: the tetramethyl phosphonium chloride, the tetramethyl phosphonium bromide, the tetramethyl phosphonium iodide, the tetraethyl phosphonium chloride, the tetraethyl phosphonium bromide, the tetraethyl phosphonium iodide, triethyl group Jia Ji phosphonium chloride, triethyl group methyl phosphonium bromide, triethyl group methyl phosphonium iodide, four-n-pro-pyl chlorination Phosphonium, four-n-pro-pyl bromination Phosphonium, four-n-pro-pyl iodate Phosphonium, three-n-pro-pyl Jia Ji phosphonium chloride, three-n-pro-pyl methyl phosphonium bromide, three-n-pro-pyl methyl phosphonium iodide, three-n-pro-pyl ethyl phosphonium iodide, four-normal-butyl chlorination Phosphonium, four-normal-butyl bromination Phosphonium, four-normal-butyl iodate Phosphonium, three-normal-butyl Jia Ji phosphonium chloride, three-normal-butyl methyl phosphonium bromide, three-normal-butyl methyl phosphonium iodide, three-normal-butyl ethyl phosphonium iodide, three-isobutyl ylmethyl phosphonium chloride, three-isobutyl group methyl phosphonium bromide, three-isobutyl group methyl phosphonium iodide, four-n-pentyl chlorination Phosphonium, four-n-pentyl bromination Phosphonium, four-n-pentyl iodate Phosphonium, three-n-pentyl Jia Ji phosphonium chloride, three-n-pentyl methyl phosphonium bromide, three-n-pentyl methyl phosphonium iodide, three-n-pentyl ethyl phosphonium iodide, three-n-pentyl-n-pro-pyl iodate Phosphonium, three cyclopentyl-methyl phosphonium iodides, four-n-hexyl phosphonium chloride, four-n-hexyl phosphonium bromide, four-n-hexyl phosphonium iodide, three-n-hexyl Jia Ji phosphonium chloride, three-n-hexyl methyl phosphonium bromide, three-n-hexyl methyl phosphonium iodide, three-n-hexyl ethyl phosphonium iodide, three-n-hexyl-n-pro-pyl iodate Phosphonium, three-n-hexyl-normal-butyl iodate Phosphonium, three-n-hexyl-isobutyl group iodate Phosphonium, thricyclohexyl methyl phosphonium iodide etc.In these compounds, with regard to showing extra high chemical stability and stable on heating viewpoint, preferred triethyl group methyl phosphonium iodide, three-n-pro-pyl methyl phosphonium iodide, three-isopropyl methyl phosphonium iodide, three-normal-butyl methyl phosphonium iodide, three-isobutyl group methyl phosphonium iodide, three-n-pentyl methyl phosphonium iodide, three cyclopentyl-methyl phosphonium iodides, three-n-hexyl methyl phosphonium iodide, thricyclohexyl methyl phosphonium iodide etc.And in these compounds, three-normal-butyl methyl phosphonium iodide is preferred owing to show excellent especially photoelectric conversion efficiency.
The represented Si Ji phosphonium salt of general formula (1) can use commercially available product.Aforesaid commercially available product can be enumerated Hishicolin PX-4MI that the applicant makes sale etc.In addition, the represented Si Ji phosphonium salt of general formula (1) also can utilize following method to synthesize.That is, under the halid situation for example, can utilize the necleophilic reaction (nucleophilic reaction) of trialkyl phosphine and corresponding alkyl halide and synthesize at this salt.For example, with respect to trialkyl phosphine, the preferred alkyl halide that adds 0.5 times of mole～2 times mole, be more preferably the alkyl halide that adds 0.9 times of mole～1.2 times mole,,, be more preferably for example in the toluene at not chloride atent solvent with 30 ℃～100 ℃ preferably with 20 ℃～150 ℃, preferred reaction was more preferably reaction 5 hours～12 hours more than or equal to 3 hours.Because trialkyl phosphine is oxidized easily, so reaction environment is preferably the environment that does not have oxygen.For example preferred nitrogen environment or ar gas environment.If exist under the environment of oxygen, make the reaction of trialkyl phosphine and alkyl halide, then there is following situation: generate the trialkyl phosphine that the oxygen bond forms on trialkyl phosphine, and productive rate is reduced.Though trialkyl phosphine can be removed by utilizing suitable organic solvent to be cleaned,, then exist four grades of Phosphonium halide also to be dissolved in tendency in the organic solvent, thereby be difficult to its removal if the halid total carbon numbers of four grades of Phosphonium become big.Therefore, in order not generate trialkyl phosphine, and preferably under inert gas environment, react.
The Si Ji Phosphonium halide of gained can utilize crystallization again and purifying.Crystallization is preferably suitably carried out repeatedly till impurity content reduces again.The impurity that should utilize crystallization again and remove can be enumerated unreacting material and trialkyl phosphine.The organic solvent that can be used for crystallization more for example preferably is used alone or as a mixture water, methyl alcohol, acetone, toluene, hexane etc.
In order to remove moisture or organic solvent, preferably the Si Ji Phosphonium halide of purifying carries out drying to utilizing crystallization again.About seasoning, sneak into owing to can prevent impurity, and once remove moisture and organic solvent, therefore preferred boulton process.In boulton process, preferred 70 ℃～120 ℃ of baking temperature is more preferably 80 ℃～100 ℃, and the preferred 0.1kPa～1.0kPa of vacuum degree is more preferably 0.1kPa～0.5kPa.Preferred about 2 hours～8 hours of drying time, be more preferably 5 hours～about 12 hours.
Then, to the represented Si Ji phosphonium salt of general formula (1) and the compound of usefulness, promptly the represented imidazole salts of general formula (2) describes.R in this imidazole salts
5～R
9The alkyl of expression hydrogen or carbon number 1～8 can be the same or different.
At R
5～R
9Under the situation for alkyl, its concrete example can be enumerated: methyl, ethyl, n-pro-pyl, normal-butyl, n-hexyl, isopropyl, isobutyl group, n-pentyl, isohesyl, n-heptyl, different heptyl, n-octyl, iso-octyl, cyclopenta, cyclohexyl etc.These alkyl can be replaced by the monovalence substituting group.Aforesaid substituent example can be enumerated: thiazolinyl; alkynyl; alkoxyl; carboxyl; alkyl carbonyl oxy; alkoxy carbonyl; sulfonyl; alkyl sulphonyl; hydroxyl; the hydroxyl sulfonyl; aryl; aryloxy group; acyloxy; amine formyl; sulfonic group; sulfamic; cycloalkyl; cyano group; nitro; amino; alkyl amino; heterocyclic radical; amino-sulfonyl; halogen atom; the 2-butoxyethyl group; 6-bromine hexyl; the 2-carboxy ethyl; 3-sulfonyl propyl group; 4-sulfonyl butyl; the 2-hydroxyethyl; phenyl methyl; 4-butyl phenyl ether ylmethyl etc.
With regard to the aspect of reaching high-photoelectric transformation efficiency, in general formula (2), R preferably
5～R
9In R
8And R
9Be hydrogen.In the case, R preferably
5～R
7Alkyl for hydrogen or carbon number 1～8.R
5～R
7Particularly preferably be: (i) 2 in these are alkyl, and all the other 1 is hydrogen; Perhaps (ii) 3 all be alkyl.Under the situation of (i), R preferably
5And R
7Be alkyl, R
6Be hydrogen.R
5And R
7Can be the same or different, preferably one is methyl, and another is the alkyl of carbon number 1～8.Under situation (ii), R preferably
5And R
6Be identical alkyl, R
7For being different from R
5And R
6Alkyl.In the case, R
7Preferably carbon number is than R
5And R
6Bigger alkyl.Particularly preferably be R
5And R
5Be methyl, R
7Alkyl for carbon number 2～4.
Univalent anion X in the general formula (2)
2 -For example can enumerate: halide ion, tetrafluoroborate (BF
4), hexafluoro-phosphate radical (PF
6), two (trifluoromethyl sulfonyl) acid imide root (N (SO
2CF
3)
2), two (fluorosulfonyl) acid imide root (N (SO
2F)
2), four cyano borate (B (CN)
4), trifluoromethanesulfonic acid root (SO
3CF
3), five fluorine ethyl sulfonic acid root (SO
3CF
2CF
3), tetrafluoro ethyl sulfonic acid root (SO
3CHFCF
3), methanesulfonate (SO
3CH
3), ethyl sulfonic acid root (SO
3C
2H
5), three (pentafluoroethyl group) trifluoro phosphate radical ((C
2F
5)
3PF
3), trifluoroacetic acid root (CF
3COO), amino acid group, two oxalic acid ylboronic acid root (B (C
2O
4)
2), p-methyl benzenesulfonic acid root (SO
3C
6H
4CH
3), thiocyanate radical (SCN), cdicynanmide root (N (CN)
2), dialkyl group phosphate radical ((RO)
2POO), dialkyl dithiophosphoric acid root ((RO)
2PSS), aliphatic carboxylic acid root (RCOO) etc.In these anion, with regard to the aspect of further raising photoelectric conversion efficiency, preferably use halide ion, particularly if use iodide ion, and with itself and the represented De phosphonium salt of general formula (1) in addition and usefulness, then can reach excellent photoelectric conversion efficiency, and preferred.In addition, X
2 -Also preferably with general formula (1) in X
1 -Be identical type.X most preferably
1 -With X
2 -Be the situation of iodide ion.
With regard to the viewpoint that shows higher open circuit voltage (open-circuit voltage) and form factor, the preferred concrete example of imidazole salts can be enumerated: iodate 1, the 3-methylimidazole, iodate 1,3-diethyl imidazoles, chlorination 1-ethyl-3-methylimidazole, chlorination 1-propyl group-3-methylimidazole, chlorination 1-butyl-3-methylimidazole, chlorination 1-hexyl-3-methylimidazole, chlorination 1-octyl group-3-methylimidazole, bromination 1-ethyl-3-methylimidazole, bromination 1-propyl group-3-methylimidazole, bromination 1-butyl-3-methylimidazole, bromination 1-hexyl-3-methylimidazole, bromination 1-octyl group-3-methylimidazole, iodate 1-ethyl-3-methylimidazole, iodate 1-propyl group-3-methylimidazole, iodate 1-butyl-3-methylimidazole, iodate 1-hexyl-3-methylimidazole, iodate 1-octyl group-3-methylimidazole, iodate 1,2-dimethyl-3-ethyl imidazol(e), chlorination 1,2-dimethyl-3-propyl imidazole, bromination 1,2-dimethyl-3-propyl imidazole, iodate 1,2-dimethyl-3-propyl imidazole, chlorination 1,2-dimethyl-3-butyl imidazole, bromination 1,2-dimethyl-3-butyl imidazole, iodate 1,2-dimethyl-3-butyl imidazole etc.In these compounds, preferred iodate 1-ethyl-3-methylimidazole, iodate 1-propyl group-3-methylimidazole, iodate 1-butyl-3-methylimidazole, iodate 1-hexyl-3-methylimidazole, iodate 1-octyl group-3-methylimidazole, iodate 1,2-dimethyl-3-ethyl imidazol(e), iodate 1,2-dimethyl-3-propyl imidazole, iodate 1,2-dimethyl-3-butyl imidazole etc.In addition, among these, iodate 1, the 2-dimethyl-excellent especially photoelectric conversion efficiency of 3-propyl imidazole performance, and preferred.
The represented imidazole salts of general formula (2) is known material in the technical field for this reason, can obtain from commercial channels.
One of feature of the present invention is, uses represented Si Ji phosphonium salt and the represented imidazole salts of general formula (2) of general formula (1) with special ratios.Particularly,, use Si Ji phosphonium salt 20mol%～80mol%, be preferably 40mol%～60mol%, use imidazole salts 20mol%～80mol%, be preferably 40mol%～60mol% with respect to both total amounts.By using both, can make electrolyte constituent of the present invention that higher photoelectric conversion efficiency is provided with aforesaid ratio.In addition, this constituent has fine solubility, and is rich in thermal endurance and anti-flammability.Specifically, the electrolyte constituent of the application of the invention, the redox efficient of redox couple improves, and the charge migration efficient in the electrolyte constituent improves, and short-circuit photocurrent density improves, its photoelectric conversion efficiency raising as a result.In addition, because of also the chemical stability of electrolyte constituent and thermal endurance being improved with Si Ji phosphonium salt and imidazole salts.In addition, four grades of represented Phosphonium ions of general formula (1) are compared with corresponding nitrogen cationoid, and are higher to the dissolubility of solvent, improve the particularly concentration of halide ion of anion easily, with regard to this viewpoint, also comparatively favourable.
In electrolyte constituent of the present invention, the ratio of Si Ji phosphonium salt is less than 20mol%, and when perhaps the ratio of imidazole salts exceeded 80mol%, short-circuit photocurrent density reduced, and photoelectric conversion efficiency reduces, and is derived from the chemical stability and the thermal endurance reduction of Si Ji phosphonium salt.Otherwise the ratio of Si Ji phosphonium salt exceeds 80mol%, and when perhaps the ratio of imidazole salts was less than 20mol%, open circuit voltage and form factor reduced, its photoelectric conversion efficiency reduction as a result.
Constituent of the present invention since contain as phosphorus containing components with the represented Si Ji phosphonium salt of general formula (1), therefore show anti-flammability and self-extinguishment.Particularly in the represented Si Ji phosphonium salt of general formula (1), because alkyl is lacked (carbon number is 1～6), molecular weight is less, thereby the ratio of phosphorus atoms is higher, and has the anti-flammability and the self-extinguishment of appropriateness.
Can understand according to above explanation, electrolyte constituent of the present invention improves the redox efficient of redox couple, and its result can obtain higher photoelectric conversion efficiency, in addition, electrolyte constituent of the present invention has fine solubility, and chemical stability, thermal endurance and anti-flammability are higher.Therefore, electrolyte constituent of the present invention can be advantageously used for the electrolyte constituent of photo-electric conversion element.
Electrolyte constituent of the present invention can only be made of general formula (1) represented Si Ji phosphonium salt and the represented imidazole salts of general formula (2), perhaps also contains other compositions except these compositions and constitutes.Aforesaid other compositions remake elaboration hereinafter.Contain at the electrolyte constituent under the situation of these other compositions, with regard to the viewpoint of reaching sufficiently high photoelectric conversion efficiency, the ratio of the total amount of the imidazole salts that Si Ji phosphonium salt that the general formula in the electrolyte constituent (1) is represented and general formula (2) are represented, be preferably 0.05mol/L～3.0mol/L with respect to electrolyte constituent integral body, be preferably 0.1mol/L～1.5mol/L especially.
Photo-electric conversion element with electrolyte constituent of the present invention comprises: the element that light is converted to the element of electric energy and converts electric energy to light on the contrary.The former typical example can be enumerated Blast Furnace Top Gas Recovery Turbine Unit (TRT) such as dye-sensitized solar cell and photodiode.The latter's typical example can be enumerated light-emitting devices such as light-emitting diode and other semiconductor lasers.No matter photo-electric conversion element is that Blast Furnace Top Gas Recovery Turbine Unit (TRT) still is light-emitting device, all as shown in Figure 1, photo-electric conversion element 10 possesses: semiconductor layer 11, be arranged at uvea 12 on the face of semiconductor layer 11, be arranged at transparent electrode layer 13 on another face of semiconductor layer 11, and the comparative electrode 14 of uvea 12 subtends configuration and be disposed at uvea 12 and comparative electrode 14 between dielectric substrate 15.Dielectric substrate 15 comprises and contains the represented halid constituent of Si Ji Phosphonium of general formula (1).With photo-electric conversion element shown in Figure 1 10 during, by from transparent electrode layer 13 sides irradiation sunlight (visible light), and between transparent electrode layer 13 and comparative electrode 14, produce electromotive force (electromotive force) as Blast Furnace Top Gas Recovery Turbine Unit (TRT).With the photo-electric conversion element shown in this figure 10 during as light-emitting device, by applying voltage between transparent electrode layer 13 and comparative electrode 14, and generation is luminous between semiconductor layer 11 and uvea 12.In addition, in Fig. 1, on transparent electrode layer 13 and comparative electrode 14, be connected with lead, also can substitute transparent electrode layer 13, and on semiconductor layer 11, connect lead.In the case, need not transparent electrode layer 13.
Using the photo-electric conversion element 10 of electrolyte constituent of the present invention is dye-sensitized solar cell as a kind of of Blast Furnace Top Gas Recovery Turbine Unit (TRT) especially effectively.Particularly contain the electrolyte constituent of three-normal-butyl methyl phosphonium iodide as four grades of represented phosphonium salts of general formula (1), can expect as inferior superiority and preferred, promptly improve the redox efficient of redox couple, its result can obtain higher photoelectric conversion efficiency.In addition,, then compare, can obtain higher chemistry and thermal stability with using the halid situation of nitrogen cationoid if this electrolyte constituent is used for dye-sensitized solar cell, thus preferred.
The photo-electric conversion element that uses electrolyte constituent of the present invention is during as dye-sensitized solar cell, the concrete formation of this dye-sensitized solar cell one for example described down.Be dye-sensitized solar cell be by transparent electrode layer, be coated be located on the transparent electrode layer and nanoporous (nanoporous) oxide semiconductor layer, the comparative electrode of carrying sensitizing coloring matter and be disposed at transparent electrode layer and comparative electrode between at least a portion and the dielectric substrate that contains redox couple constituted.If the sunlight (for example visible light) that is shone from the transparency electrode side excites the pigment on the oxide semiconductor, the pigment that then is excited is injected into electronics the conduction band of oxide semiconductor.Its result, the go back substance of the pigment oxidation body that is produced from dielectric substrate accepted electronics, and gets back to ground state state pigment, goes back substance and becomes oxysome.Be injected into electronics in the oxide semiconductor layer via external circuit, utilize comparative electrode that electronics is supplied to oxysome in the dielectric substrate.Utilization is with cocycle, and makes the constant photoelectric current of circuit circulation.
Described transparent electrode layer is good as if light transmittance, and comprises the layer of electric conducting material and have conductivity in surface formation, and then there is no particular restriction for its kind.Preferably, use or make up for example tin indium oxide (ITO), tin oxide (SnO separately
2), fluorine tin oxide (FTO), zinc oxide transparent oxide semiconductors such as (ZnO), be formed at glass, polyethylene terephthalate (PET with film like, polyethyleneterephthalate), Polyethylene Naphthalate (PEN, polyethylene naphthalate), (PC is on polycarbonate) etc. the non-conductive and transparent substrate for Merlon.The nanoporous oxide semiconductor layer is to be used singly or in combination titanium oxide (TiO
2), tin oxide (SnO
2), tungsten oxide (WO
3), zinc oxide (ZnO), niobium oxide (Nb
2O
5) the oxide semiconductor particulate that waits is as the porous membrane of principal component.The atomic average grain diameter of employed oxide semiconductor is preferably 1nm～200nm, is more preferably 3nm～100nm, and then is preferably 5nm～50nm.Oxide semiconductor is generally the n type, but is not limited thereto, and also can be the p type.Be carried on the sensitizing coloring matter on the nanoporous oxide semiconductor if absorb sunlight (for example visible light) effectively, then there is no particular restriction.With regard to the viewpoint that under the solar light irradiation condition, realizes photoexcitation (photoexcitation), preferably have containing metal misfit things such as the ruthenium misfit thing that contains the ligand of bipyridine (bipyridine) structure, terpyridyl structure etc. for example and iron misfit thing, the containing metal misfit thing of porphyrin (porphyrin) class or phthalocyanine (phthalocyanine) class, eosin (eosin), rhodamine (rhodamine), merocyanine (merocyanine), cumarin organic pigments such as (coumarin) etc.If produce the electrode of electromotive force between comparative electrode and the described transparency electrode, then be not particularly limited, the preferred electrode made from following method that uses: utilize behind the platiniferous solution such as sputtering method (sputter method) or vapour deposition method equal vacuum system embrane method, rubbing method, coating platinum acid chloride solution methods such as the heat treated film by wet method of enforcement, conductive materials such as gold, platinum, carbon class material, conductive polymer material are formed on the electrode that forms on the substrate with electrode form.
Under with the situation of electrolyte constituent of the present invention as the dielectric substrate of dye-sensitized solar cell, preferably except the represented imidazole salts of the represented Si Ji Phosphonium of general formula (1) and general formula (2), also in this electrolyte constituent, add redox couple.About redox couple, if the oxidation-reduction potential of this redox couple is between the oxidizing potential of the reduction potential that excites pigment and comparative electrode, then be not particularly limited, preferably use comprises iodide ion (I
-), bromide ion (Br
-), chloride ion (Cl
-) wait halide ion, with Br
3 -, I
3 -, I
5 -, I
7 -, Cl
2I
-, ClI
2 -, Br
2I
-, BrI
2 -Halogen-containing class redox couple in the polyhalide ion.Redox couple with molar concentration meter, is preferably 0.05mol/L～4.0mol/L with respect to the concentration of this electrolyte constituent integral body, is more preferably 0.1mol/L～3.0mol/L, and then is preferably 0.5mol/L～2.0mol/L.This halogen-containing class redox couple can obtain by halide ions such as halogenic molecule and iodide ion, bromide ion, chloride ion are reacted.Halogenic molecule is not particularly limited with respect to the ratio of halide ion, with molar ratio computing, is preferably 1%～100%, is more preferably 2%～50%, and then is preferably 3%～30%.
Si Ji phosphonium salt contained in the electrolyte constituent of the present invention has not only been given play to as electrolytical function, but also has given play to the function as the supply source of the halide ion that constitutes redox couple.Certainly, also can in the electrolyte constituent, add the supply source of this Si Ji phosphonium salt material in addition in addition as halide ion.For example can be used singly or in combination lithium halide, sodium halide, level Four ammonium halide, pyridinium halide, pyrrolidines halide, piperidines halide, sulfonium halide etc.
Under with the situation of electrolyte constituent of the present invention as the dielectric substrate of dye-sensitized solar cell, in order to improve photoelectric conversion efficiency, preferably in this electrolyte constituent, add organonitrogen compounds such as 4-tert .-butylpyridine (TBP), 2-vinylpyridine, N-vinyl-2-Pyrrolidone, lithium salts, sodium salt, magnesium salts, iodide, rhodanate, various additives such as water.As institute's illustration in the following example, if use TBP or be used in combination TBP with lithium iodide as additive, then can further improve photoelectric conversion efficiency, thereby preferably.There is no particular restriction for the addition of these additives, and the concentration of each additive in the electrolyte constituent is preferably 0.01mol/L～4.0mol/L, is more preferably 0.05mol/L～3.0mol/L, and then be preferably 0.1mol/L～2.0mol/L.
In electrolyte constituent of the present invention, optionally also can add solvent.Solvent preferably uses low viscosity and ionic mobility higher, and can show the solvent of excellent ionic conductivity.Aforesaid solvent for example can be enumerated: carbonate products such as ethylene carbonate, propylene carbonate; 3-methyl-heterocyclic compounds such as 2-oxazolidone; Ether compound such as dioxanes, Anaesthetie Ether; Chain ethers such as ethylene glycol bisthioglycolate alkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether; Alcohols such as methyl alcohol, ethanol, ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, polyalkylene glycol monoalkyl ether, polypropylene glycol monoalky lether; Polyalcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerine; Nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile; Dimethyl sulfoxide (DMSO) (DMSO, dimethyl sulfoxide), sulfolane non-proton property polar solvents such as (sulfolane); Water; Ionic liquid (normal temperature fuse salt) etc.These solvents can mix and use two or more.The use amount of solvent is preferably 5wt%～95wt% (percentage by weight) with respect to electrolyte constituent integral body.
Below, utilize example that the present invention is illustrated in further detail.Yet scope of the present invention is not limited thereto example.
[example 1 and comparative example 1 and 2]
Manufacturing has the electrolyte constituent of the composition shown in the following table 1.
Table 1
(unit: mol/L)
| Example 1 | Comparative example 1 | Comparative example 2 | |
| ??P4441-I *1 | ??0.3 | ??0.6 | ??- |
| ??DMPI-I *2 | ??0.3 | ??- | ??0.6 |
| Example 1 | Comparative example 1 | Comparative example 2 | |
| Methoxyacetonitrile | ??61 *4 | ??59 *4 | ??63 *4 |
| ??I 2 | ??0.5 | ??0.5 | ??0.5 |
| ??TBP *3 | ??0.5 | ??0.5 | ??0.5 |
| ??LiI | ??0.1 | ??0.1 | ??0.1 |
* (Nippon Chemical Ind makes 1: three-normal-butyl methyl phosphonium iodide; ProductName Hishicolin PX-4MI)
* 2: iodate 1,2-dimethyl-3-propyl imidazole (four countries change into Industries, Inc and make)
* 3:4-tert .-butylpyridine
*4：wt％
Use the electrolyte constituent of gained, make dye-sensitized solar cell in the following order, and it is estimated according to following method.Its result is shown in the table 2.
The light anode is to use as bottom electrode: will utilize scraper (doctor blade), and become the mode of 15 μ m with thickness, the fluorine tin oxide transparency electrode (FTO of coating TiOx nano particle (Solaronix D) gained; Asahi Glass limited company makes, 10.8 Ω cm
-2), calcine the electrode that formed in 30 minutes down at 450 ℃.With this light anode the N3 of 0.3mmol/l pigment (suitable-two (thiocyanogen)-N, N-two (2,2 '-bipyridine-4,4 '-dioctyl phthalate) ruthenium (II) misfit thing) in the ethanolic solution, with 40 ℃ of dipping a few hours, and the carrying pigment.The light anode of carrying pigment is clamped with the comparative electrode of carrying platinum, and (at interval: 300 μ m), between is filled the electrolyte constituent of gained in example and the comparative example to component units (cell).The active area of light anode is 0.283cm
3, and cover acting surface face in addition.In addition, make dye-sensitized solar cell according to well-established law.For the dye-sensitized solar cell of gained in this way, use AM 1.5 solar simulators (PeccellPEC-L10N) that Keithley-2400 type high voltage source and 500W xenon lamp are installed, measure photoelectric current-electromotive force characteristic.Luminous intensity is to use the ND filter and adjusts (100mWcm
-2).All mensuration is all carried out under the condition of normal temperature and pressure.In addition, form factor is the index of the electric internal losses of expression, and numerical value is big more, means that the performance of battery is high more.
Table 2
| Open circuit voltage (V) | Short-circuit photocurrent density (mA cm -2) | Form factor (%) | Photoelectric conversion efficiency (%) | |
| Example 1 | ??0.699 | ??18.8 | ??0.59 | ??7.8 |
| Comparative example 1 | ??0.698 | ??19.2 | ??0.55 | ??7.4 |
| Comparative example 2 | ??0.714 | ??16.4 | ??0.61 | ??7.1 |
Can judge by the result shown in the table 2, used the solar cell of the electrolyte constituent of the example of also using Si Ji phosphonium salt and imidazole salts, compare with the solar cell of the electrolyte constituent of the comparative example 1 that has used independent use Si Ji phosphonium salt, show higher photoelectric conversion efficiency.In addition, can judge, compare, show higher short-circuit photocurrent density and higher photoelectric conversion efficiency with the solar cell of the electrolyte constituent of the comparative example 2 that has used independent use imidazole salts.
Claims (7)
1. photo-electric conversion element electrolyte constituent, it is characterized in that: contain represented Si Ji phosphonium salt of following general formula (1) and the represented imidazole salts of following formula (2), and with respect to both total amounts, described Si Ji phosphonium salt contains 20mol%～80mol%, and described imidazole salts contains 20mol%～80mol%:
[changing 1]
In the formula, R
1, R
2, R
3, R
4The alkyl of expression carbon number 1～6 can be the same or different R
1With R
2Can form ring; X
1-expression univalent anion;
In the formula, R
5～R
9The alkyl of expression hydrogen or carbon number 1～8 can be the same or different; X
2-expression univalent anion.
2. photo-electric conversion element electrolyte constituent according to claim 1 is characterized in that: in described general formula (1), and R
1, R
2And R
3All be identical alkyl, R
4Carbon number be less than R
1, R
2And R
3Each carbon number.
3. photo-electric conversion element electrolyte constituent according to claim 2 is characterized in that: in described general formula (1), and R
1, R
2And R
3Be butyl, R
4Be methyl.
4. according to each described photo-electric conversion element electrolyte constituent in the claim 1 to 3, it is characterized in that: in described general formula (1), X
1-be iodide ion.
5. according to each described photo-electric conversion element electrolyte constituent in the claim 1 to 3, it is characterized in that:, contain the halogen-containing class redox couple that comprises halide ion and polyhalide ion of 0.05mol/L～4.0mol/L with respect to constituent integral body.
6. photo-electric conversion element is characterized in that: possess:
Semiconductor layer;
Uvea, it is arranged on the face of this semiconductor layer;
Comparative electrode, its uvea subtend configuration therewith; And
Dielectric substrate, it is disposed at this uvea therewith between the comparative electrode, and comprises electrolyte constituent according to claim 1.
7. photo-electric conversion element according to claim 6 is characterized in that: it is a dye-sensitized solar cell.
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|---|---|---|---|
| JP2009076604A JP5350851B2 (en) | 2009-03-26 | 2009-03-26 | Composition for photoelectric conversion element and photoelectric conversion element using the same |
| JP2009-076604 | 2009-03-26 |
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|---|---|
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|---|---|---|---|
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|---|---|
| JP (1) | JP5350851B2 (en) |
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|---|---|---|---|---|
| CN103299478A (en) * | 2011-01-13 | 2013-09-11 | 第一工业制药株式会社 | Photoelectric conversion element |
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| JP5709462B2 (en) * | 2010-10-28 | 2015-04-30 | 大阪瓦斯株式会社 | Electrolytic solution and photoelectric conversion element |
| JP5614807B2 (en) * | 2010-12-16 | 2014-10-29 | 日本化学工業株式会社 | Electrolyte composition for photoelectric conversion element and photoelectric conversion element |
| TW201238967A (en) * | 2011-01-31 | 2012-10-01 | Ube Industries | Photochemical cell including semiconductor fine particles sensitized by binuclear ruthenium complex dye, and electrolyte solution that contains tetraaryl borate compound, or electrolyte solution that contains plural kinds of onium salt |
| JP5991885B2 (en) * | 2012-08-24 | 2016-09-14 | 大阪瓦斯株式会社 | Electrolytic solution and photoelectric conversion element |
| JP5960033B2 (en) * | 2012-11-15 | 2016-08-02 | 国立大学法人岐阜大学 | Redox couple and photoelectric conversion device using the same |
| JP6315796B2 (en) * | 2014-06-18 | 2018-04-25 | カーリットホールディングス株式会社 | Electrolyte for dye-sensitized solar cell and dye-sensitized solar cell using the same |
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| JP2000299139A (en) * | 1999-04-14 | 2000-10-24 | Fuji Photo Film Co Ltd | Photoelectric conversion element and photoelectrochemical battery |
| JP2001035253A (en) * | 1999-07-19 | 2001-02-09 | Fuji Photo Film Co Ltd | Electrolyte composition, photoelectric transfer element and photo-electrochemical battery |
| JP2003092153A (en) * | 2001-09-18 | 2003-03-28 | Fuji Photo Film Co Ltd | Electrolyte composition, photoelectric transducing element and photovoltaic cell |
-
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| CN103299478A (en) * | 2011-01-13 | 2013-09-11 | 第一工业制药株式会社 | Photoelectric conversion element |
| CN103299478B (en) * | 2011-01-13 | 2015-05-20 | 第一工业制药株式会社 | Photoelectric conversion element |
Also Published As
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|---|---|
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| JP5350851B2 (en) | 2013-11-27 |
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