JP2005135782A - Photoelectric conversion element and dye-sensitized solar cell using it - Google Patents
Photoelectric conversion element and dye-sensitized solar cell using it Download PDFInfo
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- JP2005135782A JP2005135782A JP2003371525A JP2003371525A JP2005135782A JP 2005135782 A JP2005135782 A JP 2005135782A JP 2003371525 A JP2003371525 A JP 2003371525A JP 2003371525 A JP2003371525 A JP 2003371525A JP 2005135782 A JP2005135782 A JP 2005135782A
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- Prior art keywords
- photoelectric conversion
- dye
- conversion element
- mol
- compound
- Prior art date
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- Granted
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 84
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 44
- 239000004065 semiconductor Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- -1 quinoline compound Chemical class 0.000 claims description 27
- 239000003792 electrolyte Substances 0.000 claims description 20
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 150000002366 halogen compounds Chemical class 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 239000011630 iodine Substances 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000002497 iodine compounds Chemical class 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 230000001235 sensitizing effect Effects 0.000 claims description 2
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- 239000000049 pigment Substances 0.000 abstract 1
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- 239000000975 dye Substances 0.000 description 30
- 239000002904 solvent Substances 0.000 description 28
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- 239000003504 photosensitizing agent Substances 0.000 description 8
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- 239000002184 metal Substances 0.000 description 5
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- GCMNJUJAKQGROZ-UHFFFAOYSA-N 1,2-Dihydroquinolin-2-imine Chemical compound C1=CC=CC2=NC(N)=CC=C21 GCMNJUJAKQGROZ-UHFFFAOYSA-N 0.000 description 4
- ZTNANFDSJRRZRJ-UHFFFAOYSA-N 2,4-dimethylquinoline Chemical group C1=CC=CC2=NC(C)=CC(C)=C21 ZTNANFDSJRRZRJ-UHFFFAOYSA-N 0.000 description 4
- JJPSZKIOGBRMHK-UHFFFAOYSA-N 2,6-dimethylquinoline Chemical compound N1=C(C)C=CC2=CC(C)=CC=C21 JJPSZKIOGBRMHK-UHFFFAOYSA-N 0.000 description 4
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- MUDSDYNRBDKLGK-UHFFFAOYSA-N 4-methylquinoline Chemical group C1=CC=C2C(C)=CC=NC2=C1 MUDSDYNRBDKLGK-UHFFFAOYSA-N 0.000 description 4
- LUYISICIYVKBTA-UHFFFAOYSA-N 6-methylquinoline Chemical group N1=CC=CC2=CC(C)=CC=C21 LUYISICIYVKBTA-UHFFFAOYSA-N 0.000 description 4
- KDYVCOSVYOSHOL-UHFFFAOYSA-N 7-methylquinoline Chemical group C1=CC=NC2=CC(C)=CC=C21 KDYVCOSVYOSHOL-UHFFFAOYSA-N 0.000 description 4
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
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- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical group C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 4
- 150000003248 quinolines Chemical class 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000434 metal complex dye Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- RJSRSRITMWVIQT-UHFFFAOYSA-N quinolin-6-amine Chemical compound N1=CC=CC2=CC(N)=CC=C21 RJSRSRITMWVIQT-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- VWUCIBOKNZGWLX-UHFFFAOYSA-N 1h-imidazol-1-ium;bromide Chemical compound [Br-].C1=C[NH+]=CN1 VWUCIBOKNZGWLX-UHFFFAOYSA-N 0.000 description 2
- JBOIAZWJIACNJF-UHFFFAOYSA-N 1h-imidazole;hydroiodide Chemical compound [I-].[NH2+]1C=CN=C1 JBOIAZWJIACNJF-UHFFFAOYSA-N 0.000 description 2
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 2
- SVNCRRZKBNSMIV-UHFFFAOYSA-N 3-Aminoquinoline Chemical compound C1=CC=CC2=CC(N)=CN=C21 SVNCRRZKBNSMIV-UHFFFAOYSA-N 0.000 description 2
- ZGIKWINFUGEQEO-UHFFFAOYSA-N 3-bromoquinoline Chemical compound C1=CC=CC2=CC(Br)=CN=C21 ZGIKWINFUGEQEO-UHFFFAOYSA-N 0.000 description 2
- HNCYZWOTJQPKTQ-UHFFFAOYSA-N 4,6,8-trimethylquinoline Chemical compound N1=CC=C(C)C2=CC(C)=CC(C)=C21 HNCYZWOTJQPKTQ-UHFFFAOYSA-N 0.000 description 2
- DZXKOXPAULZIGL-UHFFFAOYSA-N 6,8-dimethoxy-4-methylquinoline Chemical compound N1=CC=C(C)C2=CC(OC)=CC(OC)=C21 DZXKOXPAULZIGL-UHFFFAOYSA-N 0.000 description 2
- GKJSZXGYFJBYRQ-UHFFFAOYSA-N 6-chloroquinoline Chemical compound N1=CC=CC2=CC(Cl)=CC=C21 GKJSZXGYFJBYRQ-UHFFFAOYSA-N 0.000 description 2
- NAGJQQFMJKMXJQ-UHFFFAOYSA-N 6-methoxy-2-methylquinoline Chemical compound N1=C(C)C=CC2=CC(OC)=CC=C21 NAGJQQFMJKMXJQ-UHFFFAOYSA-N 0.000 description 2
- NKCQEIXYLHACJC-UHFFFAOYSA-N 6-propan-2-ylquinoline Chemical group N1=CC=CC2=CC(C(C)C)=CC=C21 NKCQEIXYLHACJC-UHFFFAOYSA-N 0.000 description 2
- WQZQFYRSYLXBGP-UHFFFAOYSA-N 7-chloro-2-methylquinoline Chemical compound C1=CC(Cl)=CC2=NC(C)=CC=C21 WQZQFYRSYLXBGP-UHFFFAOYSA-N 0.000 description 2
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical compound C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000001983 dialkylethers Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
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- 239000012046 mixed solvent Substances 0.000 description 2
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- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000001007 phthalocyanine dye Substances 0.000 description 2
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
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- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- XMIAFAKRAAMSGX-UHFFFAOYSA-N quinolin-5-amine Chemical compound C1=CC=C2C(N)=CC=CC2=N1 XMIAFAKRAAMSGX-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
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- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
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- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
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- 229910052771 Terbium Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- PWIDFFRKCKLPNI-UHFFFAOYSA-M [I+].[I-] Chemical compound [I+].[I-] PWIDFFRKCKLPNI-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- WVMYSOZCZHQCSG-UHFFFAOYSA-N bis(sulfanylidene)zirconium Chemical compound S=[Zr]=S WVMYSOZCZHQCSG-UHFFFAOYSA-N 0.000 description 1
- HITXEXPSQXNMAN-UHFFFAOYSA-N bis(tellanylidene)molybdenum Chemical compound [Te]=[Mo]=[Te] HITXEXPSQXNMAN-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- HPQRSQFZILKRDH-UHFFFAOYSA-M chloro(trimethyl)plumbane Chemical compound C[Pb](C)(C)Cl HPQRSQFZILKRDH-UHFFFAOYSA-M 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 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
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- OMEPJWROJCQMMU-UHFFFAOYSA-N selanylidenebismuth;selenium Chemical compound [Se].[Bi]=[Se].[Bi]=[Se] OMEPJWROJCQMMU-UHFFFAOYSA-N 0.000 description 1
- HQASLXJEKYYFNY-UHFFFAOYSA-N selenium(2-);titanium(4+) Chemical compound [Ti+4].[Se-2].[Se-2] HQASLXJEKYYFNY-UHFFFAOYSA-N 0.000 description 1
- HVEIXSLGUCQTMP-UHFFFAOYSA-N selenium(2-);zirconium(4+) Chemical compound [Se-2].[Se-2].[Zr+4] HVEIXSLGUCQTMP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- FAWYJKSBSAKOFP-UHFFFAOYSA-N tantalum(iv) sulfide Chemical compound S=[Ta]=S FAWYJKSBSAKOFP-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- 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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- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
Description
本発明は、高い開放電圧を有する電解質溶液およびそれを用いた光電変換素子に関する。 The present invention relates to an electrolyte solution having a high open circuit voltage and a photoelectric conversion element using the same.
太陽光発電に使用する太陽電池として、単結晶シリコン、多結晶シリコン、アモルファスシリコン、テルル化カドミウム、セレン化インジウム銅等の化合物を用いた太陽電池が実用化若しくは主な研究開発の対象となっているが、家庭用電源等に広く普及させる上では製造コストが高いこと、原材料の確保が困難であること、エネルギーペイバックタイムが長いこと等の問題点があり、これらを克服する必要がある。一方、電池の大面積化や低価格化を目的として有機材料を用いた太陽電池が多く提案されているが、一般にこのような太陽電池は光電変換効率が低く、耐久性も悪いという問題がある。
ルテニウム錯体色素により分光増感された二酸化チタン多孔質薄膜を作用電極とする色素増感半導体型の光電変換素子及び太陽電池、並びにこれを作製するための材料及び製造技術を開示している（非特許文献１、特許文献１及び特許文献２参照）。
これらの色素増感半導体型太陽電池は、半導体層電極、対電極、およびそれらの電極間に挟持された電解質層とから構成される。光電変換材料である半導体層電極において、半導体層表面には、可視光領域に吸収スペクトルを有する光増感色素が吸着されている。
Solar cells that use compounds such as single crystal silicon, polycrystalline silicon, amorphous silicon, cadmium telluride, and indium copper selenide have been put into practical use or are the subject of major research and development. However, there are problems such as high manufacturing cost, difficulty in securing raw materials, and long energy payback time in order to spread widely in household power sources and the like, and these need to be overcome. On the other hand, many solar cells using organic materials have been proposed for the purpose of increasing the area of the battery and reducing the price, but in general, such solar cells have a problem of low photoelectric conversion efficiency and poor durability. .
Disclosed is a dye-sensitized semiconductor type photoelectric conversion element and solar cell having a titanium dioxide porous thin film spectrally sensitized with a ruthenium complex dye as a working electrode, and a material and a manufacturing technique for producing the same Patent Document 1, Patent Document 1 and Patent Document 2).
These dye-sensitized semiconductor solar cells are composed of a semiconductor layer electrode, a counter electrode, and an electrolyte layer sandwiched between these electrodes. In a semiconductor layer electrode that is a photoelectric conversion material, a photosensitizing dye having an absorption spectrum in the visible light region is adsorbed on the surface of the semiconductor layer.
これらの電池において、半導体層電極に光を照射すると、この電極側で電子が発生し、該電子は電気回路を通って対電極に移動する。対電極に移動した電子は、電解質中のイオンによって運ばれ、半導体層電極にもどる。このような過程が繰返されて電気エネルギーが取出される。
この色素増感半導体型光電変換素子の第一の利点は、二酸化チタン等の安価な酸化物半導体を高純度に精製することなく用いることができるため安価な光電変換素子を提供できる点であり、第二の利点は、用いる色素の吸収がブロードなため可視光線のほぼ全ての波長領域の光を電気に変換できることである。しかし、取り出し電圧が十分に得られないという問題があった。これは、電極から電荷輸送材料へ、光の照射とは関係なく逆電流が流れることに起因しており、この逆電流を十分に防止する手段はなかった。
The first advantage of this dye-sensitized semiconductor type photoelectric conversion element is that an inexpensive photoelectric conversion element can be provided because an inexpensive oxide semiconductor such as titanium dioxide can be used without being highly purified. A second advantage is that light in almost all wavelength regions of visible light can be converted into electricity because absorption of the dye used is broad. However, there is a problem that a sufficient extraction voltage cannot be obtained. This is because a reverse current flows from the electrode to the charge transport material regardless of light irradiation, and there was no means for sufficiently preventing this reverse current.
そこで、電極から電荷輸送材料へ、光の照射とは関係なく流れる逆電流を防止しつつ、取り出し電圧が十分に得られる色素増感半導体型光電変換素子及びこれを用いた太陽電池を提供すべく本発明者は鋭意研究を続けた。 Accordingly, to provide a dye-sensitized semiconductor photoelectric conversion element capable of obtaining a sufficient extraction voltage while preventing reverse current flowing from the electrode to the charge transport material regardless of light irradiation, and a solar cell using the same. The inventor has continued intensive research.
その結果、表面に色素を有する半導体層電極、対電極、電解質溶液からなる色素増感型光電変換素子であって、キノリン系化合物からなる電解質溶液を用いることにより、高い開放電圧、及び高い光電変換効率を発現する色素増感型光電変換素子の開発に成功した。
より具体的には、本発明は、一般式（I）
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７はそれぞれ独立して水素原子、アルキル基、アミノ基、アルコキシ基、ハロゲン基から選ばれる基であり、かつ、同一の基であってもよい。)で表される化合物の１種、又は２種以上を、含有してなる電解質溶液を用いたことを特徴とする色素増感型光電変換素子である。
また、さらに本発明においては、電解質溶液に、酸化還元系電解質を含むことを特徴としている。
さらに、本発明においては、酸化還元系電解質としてハロゲンイオンを対イオンとするハロゲン化合物及びハロゲン分子を用いることができる。
また、ハロゲン化合物がヨウ素化合物で、ハロゲン分子がヨウ素であることが好ましい。とくに、ハロゲン化合物がヨウ素の無機塩及び／または有機塩であるのがより好ましい。
また、ハロゲン化合物が臭素化合物で、ハロゲン分子が臭素であることが好ましい。とくに、ハロゲン化合物が臭素の無機塩及び／または有機塩であるのがより好ましい。
本願発明の色素増感型光電変換素子の典型的な例が、色素増感型太陽電池であり、半導体層電極として半導体酸化物を用い、その表面を色素で覆った電極を用いるものであり、当業者はこのような構成を熟知している。
本発明は、当然、このような多様な色素増感型光電変換素子を用いた色素増感型太陽電池を提供することもできる。
As a result, a dye-sensitized photoelectric conversion element comprising a semiconductor layer electrode having a dye on the surface, a counter electrode, and an electrolyte solution, and by using an electrolyte solution comprising a quinoline compound, a high open-circuit voltage and a high photoelectric conversion We have succeeded in developing a dye-sensitized photoelectric conversion device that exhibits high efficiency.
More specifically, the present invention relates to the general formula (I)
(Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are each independently a group selected from a hydrogen atom, an alkyl group, an amino group, an alkoxy group, and a halogen group; And a dye-sensitized photoelectric conversion element characterized by using an electrolyte solution containing one or two or more of the compounds represented by formula (1). .
Furthermore, the present invention is characterized in that the electrolyte solution contains a redox electrolyte.
Furthermore, in the present invention, halogen compounds and halogen molecules having halogen ions as counter ions can be used as the redox electrolyte.
Further, it is preferable that the halogen compound is an iodine compound and the halogen molecule is iodine. In particular, the halogen compound is more preferably an inorganic salt and / or organic salt of iodine.
Further, it is preferable that the halogen compound is a bromine compound and the halogen molecule is bromine. In particular, the halogen compound is more preferably an inorganic salt and / or organic salt of bromine.
A typical example of the dye-sensitized photoelectric conversion element of the present invention is a dye-sensitized solar cell, which uses a semiconductor oxide as a semiconductor layer electrode and uses an electrode whose surface is covered with a dye, Those skilled in the art are familiar with such a configuration.
Naturally, the present invention can also provide a dye-sensitized solar cell using such various dye-sensitized photoelectric conversion elements.
キノリン系化合物を含有する電解質溶液を用いることにより、非常に高い開放電圧を示す光電変換素子を得ることができ、光電変換効率の高い太陽電池を提供することができる。 By using an electrolyte solution containing a quinoline-based compound, a photoelectric conversion element exhibiting a very high open circuit voltage can be obtained, and a solar cell with high photoelectric conversion efficiency can be provided.
本発明のキノリン系化合物を含有する電解質溶液は、電解質と溶媒からなる。
本発明に好ましく用いることのできるキノリン系化合物としては、下記一般式（I）により表されるものであることが好ましい。
以下に一般式（I）で表される本発明のキノリン系化合物について詳しく説明する。式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７はそれぞれ独立して水素原子、アルキル基、アミノ基、アルコキシ基、ハロゲン基から選ばれる基であり、かつ、同一の基であってもよい。
具体的名化合物を挙げると、２−メチルキノリン、３−メチルキノリン、４−メチルキノリン、６−メチルキノリン、７−メチルキノリン、８−メチルキノリン、６−イソプロピルキノリン、２，４−ジメチルキノリン、２，６−ジメチルキノリン、４，６，８−トリメチルキノリン、等のアルキル置換キノリン化合物、２−アミノキノリン、３−アミノキノリン、５−アミノキノリン、６−アミノキノリン、８−アミノキノリン、６−アミノ−２−メチルキノリン、等のアミノ基置換キノリン化合物、６−メトキシ−２−メチルキノリン、６，８−ジメトキシ−４−メチルキノリン、等のアルコキシ基置換キノリン化合物、６−クロロキノリン、４、７−ジクロロキノリン、３−ブロモキノリン、７−クロロ−２−メチルキノリン、等のハロゲン基置換キノリン化合物等を挙げることができる。
電解質溶液に対するキノリン系化合物の濃度は０．００１ｍｏｌ／ｌ〜１０ｍｏｌ／ｌの範囲内であり、一層好ましい範囲は０．００５ｍｏｌ／ｌ〜５ｍｏｌ／ｌであり、特に好ましい範囲は０．０１ｍｏｌ／ｌ〜２ｍｏｌ／ｌであり、最も好ましい範囲は０．０５ｍｏｌ／ｌ〜１ｍｏｌ／ｌである。また、これらは単独または２種以上を組み合わせて用いることが出来る。
The electrolyte solution containing the quinoline compound of the present invention comprises an electrolyte and a solvent.
The quinoline compound that can be preferably used in the present invention is preferably one represented by the following general formula (I).
The quinoline compound of the present invention represented by the general formula (I) will be described in detail below. In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are each independently a group selected from a hydrogen atom, an alkyl group, an amino group, an alkoxy group, and a halogen group, and May be the same group.
Specific examples of the compound include 2-methylquinoline, 3-methylquinoline, 4-methylquinoline, 6-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-isopropylquinoline, 2,4-dimethylquinoline, Alkyl substituted quinoline compounds such as 2,6-dimethylquinoline, 4,6,8-trimethylquinoline, 2-aminoquinoline, 3-aminoquinoline, 5-aminoquinoline, 6-aminoquinoline, 8-aminoquinoline, 6-aminoquinoline, Amino group-substituted quinoline compounds such as amino-2-methylquinoline, alkoxy group-substituted quinoline compounds such as 6-methoxy-2-methylquinoline, 6,8-dimethoxy-4-methylquinoline, 6-chloroquinoline, 4, 7-dichloroquinoline, 3-bromoquinoline, 7-chloro-2-methylquinoline, etc. And the like Gen group substituted quinoline compounds.
The concentration of the quinoline compound with respect to the electrolyte solution is in the range of 0.001 mol / l to 10 mol / l, a more preferable range is 0.005 mol / l to 5 mol / l, and a particularly preferable range is 0.01 mol / l to 2 mol / l, and the most preferable range is 0.05 mol / l to 1 mol / l. Moreover, these can be used individually or in combination of 2 or more types.
本発明で使用する酸化還元系電解質にはハロゲンイオンを対イオンとするハロゲン化合物及びハロゲン分子からなるハロゲン系酸化還元系電解質、フェロシアン酸塩−フェリシアン酸塩やフェロセン−フェリシアニウムイオンなどの金属錯体等の金属酸化還元系電解質、アルキルチオール−アルキルジスルフィド、ビオロゲン色素、ヒドロキノン−キノン等の芳香族酸化還元系電解質などをあげることができるが、ハロゲン系酸化還元系電解質が好ましい。
本発明で用いる電解質はヨウ素分子とヨウ化物の組み合わせ（ヨウ化物としてはＬｉＩ、ＮａＩ、ＫＩ、ＣｓＩ、ＣａＩ2 などの金属ヨウ化物、あるいはテトラアルキルアンモニウムヨーダイド、ピリジニウムヨーダイド、イミダゾリウムヨーダイドなど４級アンモニウム化合物のヨウ素塩など）、臭素分子と臭化物の組み合わせ（臭化物としてはＬｉＢｒ、ＮａＢｒ、ＫＢｒ、ＣｓＢｒ、ＣａＢｒ2 などの金属臭化物、あるいはテトラアルキルアンモニウムブロマイド、ピリジニウムブロマイド、イミダゾリウムブロマイドなど４級アンモニウム化合物の臭素塩など）のほか、フェロシアン酸塩−フェリシアン酸塩やフェロセン−フェリシニウムイオンなどの金属錯体、ポリ硫化ナトリウム、アルキルチオール−アルキルジスルフィドなどのイオウ化合物、ビオロゲン色素、ヒドロキノン−キノンなどを用いることができる。
この中でもヨウ素分子とＬｉＩやピリジニウムヨーダイド、イミダゾリウムヨーダイドなど４級アンモニウム化合物のヨウ素塩を組み合わせた電解質、もしくは臭素分子とＢｒＩやピリジニウムブロマイド、イミダゾリウムブロマイドなど４級アンモニウム化合物の臭素塩を組み合わせた電解質が好ましい。上述した電解質は混合して用いてもよい。
電解質の好ましい濃度は０．１ｍｏｌ／ｌ〜１０ｍｏｌ／ｌであり、さらに好ましくは０．２ｍｏｌ／ｌ〜４ｍｏｌ／ｌである。また、電解液にヨウ素もしくは臭素を添加する場合の好ましいヨウ素もしくは臭素の添加濃度は０．０１ｍｏｌ／ｌ〜０．５ｍｏｌ／ｌである。
The oxidation-reduction electrolyte used in the present invention includes halogen compounds having halogen ions as counter ions and halogen-based oxidation-reduction electrolytes composed of halogen molecules, metals such as ferrocyanate-ferricyanate and ferrocene-ferricyanium ions. Examples include metal redox electrolytes such as complexes, and aromatic redox electrolytes such as alkylthiol-alkyl disulfides, viologen dyes, and hydroquinone-quinones, and halogen redox electrolytes are preferred.
The electrolyte used in the present invention is LiI as a combination (iodide iodine molecule and an iodide, NaI, KI, CsI, metal iodide such as CaI 2, or tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide, etc. Quaternary ammonium compound iodine salt), bromine molecule and bromide combination (bromide is metal bromide such as LiBr, NaBr, KBr, CsBr, CaBr 2 , or quaternary ammonium bromide, pyridinium bromide, imidazolium bromide, etc. Bromine salts of ammonium compounds), metal complexes such as ferrocyanate-ferricyanate and ferrocene-ferricinium ions, sodium polysulfide, alkylthiol-alkyl disulfides, etc. Sulfur compounds, viologen dyes, hydroquinone-quinones, and the like can be used.
Among these, electrolytes that combine iodine molecules with iodine salts of quaternary ammonium compounds such as LiI, pyridinium iodide, and imidazolium iodide, or bromine molecules and bromine salts of quaternary ammonium compounds such as BrI, pyridinium bromide, and imidazolium bromide. An electrolyte is preferred. The electrolytes described above may be used in combination.
The preferable concentration of the electrolyte is 0.1 mol / l to 10 mol / l, more preferably 0.2 mol / l to 4 mol / l. Further, when iodine or bromine is added to the electrolytic solution, a preferable concentration of iodine or bromine is 0.01 mol / l to 0.5 mol / l.
酸化還元電解質を溶解するために用いる溶媒としては、キノリン系化合物および酸化還元系電解質を溶解し、イオン伝導性に優れた化合物が望ましい。
溶媒としては水性溶媒および有機溶媒のいずれも使用できるが、キノリン系化合物および酸化還元系電解質をより安定化するため、有機溶媒が好ましい。
例えばこのような溶媒としては、エチレンカーボネート、プロピレンカーボネートなどのカーボネート化合物、３−メチル−２−オキサゾリジノンなどの複素環化合物、ジオキサン、ジエチルエーテルなどのエーテル化合物、エチレングリコールジアルキルエーテル、プロピレングリコールジアルキルエーテル、ポリエチレングリコールジアルキルエーテル、ポリプロピレングリコールジアルキルエーテルなどの鎖状エーテル類、メタノール、エタノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、ポリエチレングリコールモノアルキルエーテル、ポリプロピレングリコールモノアルキルエーテルなどのアルコール類、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリンなどの多価アルコール類、アセトニトリル、グルタロジニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリルなどのニトリル化合物、ジメチルスルフォキシド、スルフォランなど非プロトン性の極性物質等の有機溶剤等が挙げられる。
このなかでも、エチレンカーボネート、プロピレンカーボネートなどのカーボネート化合物、アセトニトリル、グルタロジニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリルなどのニトリル化合物が特に好ましい。これらは、単独または２種以上を組み合わせて用いることが出来る。
The solvent used for dissolving the redox electrolyte is preferably a compound that dissolves the quinoline compound and the redox electrolyte and has excellent ion conductivity.
As the solvent, any of an aqueous solvent and an organic solvent can be used, but an organic solvent is preferable in order to further stabilize the quinoline compound and the redox electrolyte.
Examples of such solvents include carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether compounds such as dioxane and diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, Chain ethers such as polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether, alcohols such as methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether and polypropylene glycol monoalkyl ether, ethylene glycol , Propylene glycol, polyethylene glycol, Polyhydric alcohols such as propylene glycol and glycerin, nitrile compounds such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, and benzonitrile, organic solvents such as aprotic polar substances such as dimethyl sulfoxide and sulfolane, etc. Is mentioned.
Among these, carbonate compounds such as ethylene carbonate and propylene carbonate, and nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, and benzonitrile are particularly preferable. These can be used alone or in combination of two or more.
本発明で用いるキノリン系化合物を含有する電解質溶液を用いた光電変換素子は負極、正極及び電荷分離層から成る。光電変換素子としては一般的に光エネルギーを電気エネルギーに変換する素子全体を指す。
本発明で用いるキノリン系化合物を含有する電解質溶液を用いた光電変換素子は、種々の材料に使用可能であるが、色素増感型太陽電池に特に最適である。
色素増感型太陽電池は半導体層電極、対極、電解質溶液で構成される。
半導体層電極は酸化チタン、酸化亜鉛などの金属酸化物半導体を導電性ガラスなどの導電性材料表面に薄膜化させて、その酸化物半導体薄膜に光増感色素を吸着担持することにより得られる。
対極は導電性ガラスなどの導電性材料表面に白金などを蒸着して得られる。得られた半導体電極と対峙するように対極を配置する。その隙間に電解質溶液を充填して光電変換素子の周囲を樹脂で封止して色素増感型太陽電池となる。
前記導電性材料としては、導電性を有するものであればどのようなものでもよく、例えば、透明ないし半透明のガラス基板やプラスチック板上に、例えば、フッ素あるいはアンチモンドープの酸化スズ（ＮＥＳＡ）、スズドープの酸化インジウム（ＩＴＯ）、酸化亜鉛などの導電性透明酸化物半導体薄膜をコートしたもの、好ましくは、フッ素ドープの酸化スズ薄膜をコートしたもの等が用いられる。
A photoelectric conversion element using an electrolyte solution containing a quinoline compound used in the present invention includes a negative electrode, a positive electrode, and a charge separation layer. A photoelectric conversion element generally refers to the entire element that converts light energy into electrical energy.
Although the photoelectric conversion element using the electrolyte solution containing the quinoline-type compound used by this invention can be used for various materials, it is especially optimal for a dye-sensitized solar cell.
The dye-sensitized solar cell includes a semiconductor layer electrode, a counter electrode, and an electrolyte solution.
The semiconductor layer electrode is obtained by thinning a metal oxide semiconductor such as titanium oxide or zinc oxide on the surface of a conductive material such as conductive glass and adsorbing and supporting a photosensitizing dye on the oxide semiconductor thin film.
The counter electrode is obtained by depositing platinum or the like on the surface of a conductive material such as conductive glass. A counter electrode is disposed so as to face the obtained semiconductor electrode. The gap is filled with an electrolyte solution, and the periphery of the photoelectric conversion element is sealed with a resin to obtain a dye-sensitized solar cell.
The conductive material may be anything as long as it has conductivity. For example, on a transparent or translucent glass substrate or plastic plate, for example, fluorine or antimony-doped tin oxide (NESA), Those coated with a conductive transparent oxide semiconductor thin film such as tin-doped indium oxide (ITO) or zinc oxide, preferably those coated with a fluorine-doped tin oxide thin film are used.
本発明で用いられる半導体薄膜は、ナノ粒子（粒子径５〜２０００ｎｍ）からなるナノポーラス構造を有する化合物半導体で構成することができる。
その材料としては、例えば、酸化チタン、酸化インジウム、酸化スズ、酸化ビスマス、酸化ジルコニウム、酸化タンタル、酸化ニオブ、酸化タングステン、酸化鉄、酸化ガリウム、酸化ニッケルなどの単一金属酸化物、チタン酸ストロンチウム、チタン酸バリウム、ニオブ酸カリウム、タンタル酸ナトリウムなどの複合酸化物、ヨウ化銀、臭化銀、ヨウ化銅、臭化銅などの金属ハロゲン化物、硫化亜鉛、硫化チタン、硫化インジウム、硫化ビスマス、硫化カドミウム、硫化ジルコニウム、硫化タンタル、硫化銀、硫化銅、硫化スズ、硫化タングステン、硫化モリブデン、セレン化カドミウム、セレン化ジルコニウム、セレン化亜鉛、セレン化チタン、セレン化インジウム、セレン化タングステン、セレン化モリブデン、セレン化ビスマス、テルル化カドミウム、テルル化タングステン、テルル化モリブデン、テルル化亜鉛、テルル化ビスマスなどのカルコゲナイド化合物、さらには、これらの化合物を二種類以上含む混合化合物半導体材料（例えば、酸化スズ／酸化亜鉛、酸化スズ／酸化チタン）が挙げられるが、これらに限定されない。
前記した半導体薄膜の膜厚は、０．１〜１００μｍであり、好ましくは、１〜３０μｍである。
The semiconductor thin film used in the present invention can be composed of a compound semiconductor having a nanoporous structure composed of nanoparticles (particle diameter of 5 to 2000 nm).
Examples of the material include single metal oxides such as titanium oxide, indium oxide, tin oxide, bismuth oxide, zirconium oxide, tantalum oxide, niobium oxide, tungsten oxide, iron oxide, gallium oxide, nickel oxide, and strontium titanate. , Composite oxides such as barium titanate, potassium niobate, sodium tantalate, metal halides such as silver iodide, silver bromide, copper iodide, copper bromide, zinc sulfide, titanium sulfide, indium sulfide, bismuth sulfide , Cadmium sulfide, zirconium sulfide, tantalum sulfide, silver sulfide, copper sulfide, tin sulfide, tungsten sulfide, molybdenum sulfide, cadmium selenide, zirconium selenide, zinc selenide, titanium selenide, indium selenide, tungsten selenide, selenide Molybdenum fluoride, bismuth selenide, Chalcogenide compounds such as cadmium bromide, tungsten telluride, molybdenum telluride, zinc telluride, bismuth telluride, and mixed compound semiconductor materials containing two or more of these compounds (for example, tin oxide / zinc oxide, tin oxide) / Titanium oxide), but is not limited thereto.
The film thickness of the semiconductor thin film described above is 0.1 to 100 μm, and preferably 1 to 30 μm.
本発明で用いる光増感色素としては、種々の可視光領域および／または赤外光領域に吸収を持つものを用いることができる。
このような光増感色素には、構造上の制限は特になく、たとえば、アゾ系色素、キノン系色素、キノンイミン系色素、キナクリドン系色素、スクアリリウム系色素、シアニン系色素、メロシアニン系色素、トリフェニルメタン系色素、キサンテン系色素、ポルフィリン系色素、フタロシアニン系色素、ペリレン系色素、インジゴ系色素、ナフタロシアニン系色素、および中心金属としてルテニウムなどを有するビピリジル錯体など、種々の色素が使用できる。
その中でも、フタロシアニン系色素、ナフタロシアニン系色素、およびビピリジル錯体のような金属錯体色素は、高い量子収率を有し、光に対する耐久性がよいため、光電変換材料には適している。
なお、金属錯体色素の場合においては、Ｃｕ、Ｎｉ、Ｆｅ、Ｃｏ、Ｖ、Ｓｎ、Ｓｉ、Ｔｉ、Ｇｅ、Ｃｒ、Ｚｎ、Ｒｕ、Ｍｇ、Ａｌ、Ｐｂ、Ｍｎ、Ｉｎ、Ｍｏ、Ｙ、Ｚｒ、Ｎｂ、Ｓｂ、Ｌａ、Ｗ、Ｐｔ、Ｔａ、Ｉｒ、Ｐｄ、Ｏｓ、Ｇａ、Ｔｂ、Ｅｕ、Ｒｂ、Ｂｉ、Ｓｅ、Ａｓ、Ｓｃ、Ａｇ、Ｃｄ、Ｈｆ、Ｒｅ、Ａｕ、Ａｃ、Ｔｃ、Ｔｅ、Ｒｈなどの金属が用いられる。この中でも、Ｃｕ、Ｔｉ、Ｚｎ、Ａｌ、Ｆｅ、Ｖ、Ｓｉ、Ｒｕ等の金属錯体色素は高い量子効率を有する。
本発明においては、半導体薄膜表面と強固に吸着するために、該色素は分子中にカルボキシル基、アルコキシ基、ヒドロキシル基、スルホン酸基、エステル基、メルカプト基、ホスホニル基などの置換基を有するものが好ましい。
As the photosensitizing dye used in the present invention, those having absorption in various visible light regions and / or infrared light regions can be used.
Such photosensitizing dyes are not particularly limited in structure. For example, azo dyes, quinone dyes, quinone imine dyes, quinacridone dyes, squarylium dyes, cyanine dyes, merocyanine dyes, triphenyl Various dyes such as methane dyes, xanthene dyes, porphyrin dyes, phthalocyanine dyes, perylene dyes, indigo dyes, naphthalocyanine dyes, and bipyridyl complexes having ruthenium as a central metal can be used.
Among these, metal complex dyes such as phthalocyanine dyes, naphthalocyanine dyes, and bipyridyl complexes are suitable for photoelectric conversion materials because they have a high quantum yield and good durability against light.
In the case of a metal complex dye, Cu, Ni, Fe, Co, V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, Y, Zr, Nb, Sb, La, W, Pt, Ta, Ir, Pd, Os, Ga, Tb, Eu, Rb, Bi, Se, As, Sc, Ag, Cd, Hf, Re, Au, Ac, Tc, Te, A metal such as Rh is used. Among these, metal complex dyes such as Cu, Ti, Zn, Al, Fe, V, Si, and Ru have high quantum efficiency.
In the present invention, the dye has a substituent such as a carboxyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, an ester group, a mercapto group, or a phosphonyl group in the molecule in order to strongly adsorb to the semiconductor thin film surface. Is preferred.
光増感色素の半導体薄膜上への吸着は、色素溶液中に半導体薄膜を浸し、室温で１分〜１０日、あるいは加熱条件下で１分から２４時間放置することによりおこなう。
好ましくは、室温で１２時間以上放置する方法である。光増感色素を半導体薄膜上に吸着させる場合に用いる溶媒は、光増感色素を溶解する溶媒なら何でも良い。例えば、メタノール、エタノール、イソプロパノール、t−ブタノール等のアルコール溶媒、ベンゼン等の炭化水素溶媒の他、テトラヒドロフラン、アセトニトリルなどの有機溶媒、さらには、それらの混合溶媒である。好ましくは、エタノール又はｔ−ブタノールとアセトニトリルの混合溶媒である。
光増感色素を半導体薄膜上に吸着させる場合の色素溶液の濃度は、０．０１ｍｍｏｌ／ｌから飽和量であり、好ましくは、０．１〜０．５ｍｍｏｌ／ｌである。
次に、実施例を挙げて本発明を具体的に説明するが、本発明はそれらの実施例のみに限定されるものではない。
Adsorption of the photosensitizing dye onto the semiconductor thin film is carried out by immersing the semiconductor thin film in a dye solution and allowing it to stand at room temperature for 1 minute to 10 days or under heating conditions for 1 minute to 24 hours.
The method is preferably left at room temperature for 12 hours or more. The solvent used for adsorbing the photosensitizing dye on the semiconductor thin film may be any solvent that dissolves the photosensitizing dye. For example, an alcohol solvent such as methanol, ethanol, isopropanol and t-butanol, a hydrocarbon solvent such as benzene, an organic solvent such as tetrahydrofuran and acetonitrile, and a mixed solvent thereof. Preferred is a mixed solvent of ethanol or t-butanol and acetonitrile.
When the photosensitizing dye is adsorbed on the semiconductor thin film, the concentration of the dye solution is from 0.01 mmol / l to a saturated amount, and preferably from 0.1 to 0.5 mmol / l.
Next, although an Example is given and this invention is demonstrated concretely, this invention is not limited only to those Examples.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、２−メチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた。
上記電解質溶液を、次の化学式
で表わされる増感色素を担持した導電性ガラス付き多孔質酸化チタン半導体薄膜（厚さ１５μｍ）に滴下した。ここにポリエチレンフィルム製のフレーム型スペーサー（厚さ２５μｍ）をのせ、白金対電極でこれを覆い、光電変換素子を構成した。
得られた光電変換素子に、Ｘｅランプを光源として強度１００ｍＷ／ｃｍ２の光を照射したところ、開放電圧は０．７１Ｖ、光電変換効率は７．１％であった。
As the electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 2-methylquinoline is dissolved in acetonitrile is used. It was.
The electrolyte solution has the following chemical formula:
It was dripped at the porous titanium oxide semiconductor thin film (thickness 15 micrometers) with the electrically conductive glass which carry | supported the sensitizing dye represented by these. A frame type spacer (thickness: 25 μm) made of polyethylene film was placed thereon, and this was covered with a platinum counter electrode to constitute a photoelectric conversion element.
When the obtained photoelectric conversion element was irradiated with light having an intensity of 100 mW / cm 2 using a Xe lamp as a light source, the open circuit voltage was 0.71 V and the photoelectric conversion efficiency was 7.1%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、３−メチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６７Ｖ、光電変換効率は６．９％であった。 As the electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 3-methylquinoline is dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.67 V and the photoelectric conversion efficiency was 6.9%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、４−メチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．７０Ｖ、光電変換効率は７．１％であった。 As the electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 4-methylquinoline is dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.70 V and the photoelectric conversion efficiency was 7.1%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、６−メチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６９Ｖ、光電変換効率は６．９％であった。 As the electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 6-methylquinoline is dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.69 V and the photoelectric conversion efficiency was 6.9%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、７−メチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６９Ｖ、光電変換効率は７．１％であった。 As the electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 7-methylquinoline is dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.69 V and the photoelectric conversion efficiency was 7.1%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、８−メチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６４Ｖ、光電変換効率は６．６％であった。 As the electrolyte solution, a solvent in which 0.1 mol / l of lithium iodide, 0.05 mol / l of iodine, 0.6 mol / l of dimethylpropylimidazolium iodide and 0.5 mol / l of 8-methylquinoline are dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.64 V and the photoelectric conversion efficiency was 6.6%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、６−イソプロピルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６８Ｖ、光電変換効率は６．９％であった。 As an electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 6-isopropylquinoline is dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.68 V and the photoelectric conversion efficiency was 6.9%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、２，４−ジメチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．７４Ｖ、光電変換効率は７．５％であった。 A solution in which 0.1 mol / l of lithium iodide, 0.05 mol / l of iodine, 0.6 mol / l of dimethylpropylimidazolium iodide, 0.5 mol / l of 2,4-dimethylquinoline are dissolved in acetonitrile as a solvent as an electrolyte solution When a photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that was used, the open circuit voltage was 0.74 V and the photoelectric conversion efficiency was 7.5%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、２，６−ジメチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．７３Ｖ、光電変換効率は７．１％であった。 A solution in which 0.1 mol / l of lithium iodide, 0.05 mol / l of iodine, 0.6 mol / l of dimethylpropylimidazolium iodide, 0.5 mol / l of 2,6-dimethylquinoline are dissolved as an electrolyte solution in acetonitrile. When a photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that was used, the open circuit voltage was 0.73 V and the photoelectric conversion efficiency was 7.1%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、４，６，８−トリメチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．７２Ｖ、光電変換効率は７．１％であった。
As an electrolyte solution, 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol /
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、２−アミノキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．８２Ｖ、光電変換効率は６．５％であった。 As an electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 2-aminoquinoline is dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.82 V and the photoelectric conversion efficiency was 6.5%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、３−アミノキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．７１Ｖ、光電変換効率は７．０％であった。 As an electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, and 0.5 mol / l 3-aminoquinoline are dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.71 V and the photoelectric conversion efficiency was 7.0%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、５−アミノキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６８Ｖ、光電変換効率は６．２％であった。 As the electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 5-aminoquinoline is dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.68 V and the photoelectric conversion efficiency was 6.2%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、６−アミノキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．７０Ｖ、光電変換効率は６．４％であった。 As an electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 6-aminoquinoline is dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.70 V and the photoelectric conversion efficiency was 6.4%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、８−アミノキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６４Ｖ、光電変換効率は６．２％であった。 As the electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 8-aminoquinoline is dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.64 V and the photoelectric conversion efficiency was 6.2%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、６−アミノ−２−メチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．７５Ｖ、光電変換効率は６．４％であった。 As an electrolyte solution, 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 6-amino-2-methylquinoline are dissolved in acetonitrile as a solvent. A photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the obtained one was used. The open circuit voltage was 0.75 V and the photoelectric conversion efficiency was 6.4%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、６−メトキシ−２−メチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．７４Ｖ、光電変換効率は７．２％であった。 As an electrolyte solution, 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 6-methoxy-2-methylquinoline are dissolved in acetonitrile as a solvent. A photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the obtained one was used. The open circuit voltage was 0.74 V and the photoelectric conversion efficiency was 7.2%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、６，８−ジメトキシ−４−メチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．７６Ｖ、光電変換効率は６．７％であった。 As an electrolyte solution, the solvent is acetonitrile, lithium iodide 0.1 mol / l, iodine 0.05 mol / l, dimethylpropylimidazolium iodide 0.6 mol / l, 6,8-dimethoxy-4-methylquinoline 0.5 mol / l When a photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that a solution obtained by dissolving was used, the open circuit voltage was 0.76 V and the photoelectric conversion efficiency was 6.7%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、６−クロロキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６５Ｖ、光電変換効率は６．５％であった。 As an electrolyte solution, a solvent in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 6-chloroquinoline is dissolved in acetonitrile is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.65 V and the photoelectric conversion efficiency was 6.5%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、４，７−ジクロロキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６１Ｖ、光電変換効率は６．３％であった。 A solution in which 0.1 mol / l of lithium iodide, 0.05 mol / l of iodine, 0.6 mol / l of dimethylpropylimidazolium iodide, and 0.5 mol / l of 4,7-dichloroquinoline are dissolved as an electrolyte solution in acetonitrile. When a photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that was used, the open circuit voltage was 0.61 V and the photoelectric conversion efficiency was 6.3%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、３−ブロモキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６７Ｖ、光電変換効率は６．７％であった。 As an electrolyte solution, a solvent in which acetonitrile is dissolved in 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, and 0.5 mol / l 3-bromoquinoline is used. The photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the open circuit voltage was 0.67 V and the photoelectric conversion efficiency was 6.7%.
電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌ、７−クロロ−２−メチルキノリン０．５ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．６５Ｖ、光電変換効率は６．７％であった。 As an electrolyte solution, 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.6 mol / l dimethylpropylimidazolium iodide, 0.5 mol / l 7-chloro-2-methylquinoline are dissolved in acetonitrile as a solvent. A photoelectric conversion element was constructed and evaluated in the same manner as in Example 1 except that the obtained one was used. The open circuit voltage was 0.65 V and the photoelectric conversion efficiency was 6.7%.
（比較例）電解質溶液として溶媒がアセトニトリルでヨウ化リチウム０．１ｍｏｌ／ｌ、ヨウ素０．０５ｍｏｌ／ｌ、ヨウ化ジメチルプロピルイミダゾリウム０．６ｍｏｌ／ｌを溶解したものを用いた以外は実施例１と同様にして光電変換素子を構成し評価したところ、開放電圧は０．５８Ｖ、光電変換効率は６．０％であった。
以上の結果から、キノリン系化合物を電解液に添加すると、開放電圧と光電変換効率が上昇することが明らかである。
(Comparative Example) Example 1 except that the electrolyte solution used was an acetonitrile solution in which 0.1 mol / l lithium iodide, 0.05 mol / l iodine, and 0.6 mol / l dimethylpropylimidazolium iodide were dissolved. When the photoelectric conversion element was constructed and evaluated in the same manner as described above, the open circuit voltage was 0.58 V, and the photoelectric conversion efficiency was 6.0%.
From the above results, it is clear that when the quinoline compound is added to the electrolytic solution, the open-circuit voltage and the photoelectric conversion efficiency are increased.
本発明によれば、電極から電荷輸送材料へ、光の照射とは関係なく流れる逆電流を防止しつつ、取り出し電圧が十分に得られる色素増感半導体型光電変換素子及びこれを用いた太陽電池を安価に提供することが出来る。また、これを用いた発電効率の良い太陽電池を提供することが出来き、この分野における産業に与える影響は大きい。
According to the present invention, a dye-sensitized semiconductor photoelectric conversion element capable of obtaining a sufficient extraction voltage while preventing a reverse current flowing from an electrode to a charge transport material regardless of light irradiation, and a solar cell using the same Can be provided at low cost. Moreover, it is possible to provide a solar cell with good power generation efficiency using this, which has a great influence on the industry in this field.
Claims (9)
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７はそれぞれ独立して水素原子、アルキル基、アミノ基、アルコキシ基、ハロゲン基から選ばれる基であり、かつ、同一の基であってもよい。)で表される化合物の１種、又は２種以上であることを特徴とする請求項１に記載した色素増感型光電変換素子。 The quinoline-based compound is represented by the following general formula (I)
(Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are each independently a group selected from a hydrogen atom, an alkyl group, an amino group, an alkoxy group, and a halogen group; The dye-sensitized photoelectric conversion element according to claim 1, wherein the dye-sensitized photoelectric conversion element is one type or two or more types of compounds represented by:
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| JP4370398B2 JP4370398B2 (en) | 2009-11-25 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010050575A1 (en) | 2008-10-29 | 2010-05-06 | 富士フイルム株式会社 | Dye, photoelectric conversion element and photoelectrochemical cell each comprising the dye, and process for producing dye |
| EP2302650A2 (en) | 2009-09-28 | 2011-03-30 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| EP2306479A2 (en) | 2009-09-28 | 2011-04-06 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| CN102898366A (en) * | 2012-03-30 | 2013-01-30 | 浙江工业大学 | Method for one-step preparation of 2-methylquinoline |
| WO2014129575A1 (en) | 2013-02-22 | 2014-08-28 | 富士フイルム株式会社 | Photoelectric conversion element, method for manufacturing photoelectric conversion element and dye-sensitized solar cell |
-
2003
- 2003-10-31 JP JP2003371525A patent/JP4370398B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010050575A1 (en) | 2008-10-29 | 2010-05-06 | 富士フイルム株式会社 | Dye, photoelectric conversion element and photoelectrochemical cell each comprising the dye, and process for producing dye |
| EP2845882A2 (en) | 2008-10-29 | 2015-03-11 | Fujifilm Corporation | Dye, Photoelectric Conversion Element and Photoelectrochemical Cell |
| EP2302650A2 (en) | 2009-09-28 | 2011-03-30 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| EP2306479A2 (en) | 2009-09-28 | 2011-04-06 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| CN102898366A (en) * | 2012-03-30 | 2013-01-30 | 浙江工业大学 | Method for one-step preparation of 2-methylquinoline |
| CN102898366B (en) * | 2012-03-30 | 2014-07-02 | 浙江工业大学 | Method for one-step preparation of 2-methylquinoline |
| WO2014129575A1 (en) | 2013-02-22 | 2014-08-28 | 富士フイルム株式会社 | Photoelectric conversion element, method for manufacturing photoelectric conversion element and dye-sensitized solar cell |
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| JP4370398B2 (en) | 2009-11-25 |
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