JP4676719B2 - Electrolyte for dye-sensitized solar cell and dye-sensitized solar cell using the same - Google Patents
Electrolyte for dye-sensitized solar cell and dye-sensitized solar cell using the same Download PDFInfo
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- JP4676719B2 JP4676719B2 JP2004167510A JP2004167510A JP4676719B2 JP 4676719 B2 JP4676719 B2 JP 4676719B2 JP 2004167510 A JP2004167510 A JP 2004167510A JP 2004167510 A JP2004167510 A JP 2004167510A JP 4676719 B2 JP4676719 B2 JP 4676719B2
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- JP
- Japan
- Prior art keywords
- dye
- solar cell
- sensitized solar
- group
- iodide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003792 electrolyte Substances 0.000 title description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 21
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 150000001408 amides Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical group C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 125000005156 substituted alkylene group Chemical group 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 57
- 230000000052 comparative effect Effects 0.000 description 29
- 238000005259 measurement Methods 0.000 description 29
- DWOWCUCDJIERQX-UHFFFAOYSA-M 5-azoniaspiro[4.4]nonane;iodide Chemical compound [I-].C1CCC[N+]21CCCC2 DWOWCUCDJIERQX-UHFFFAOYSA-M 0.000 description 19
- 125000003003 spiro group Chemical group 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 206010070834 Sensitisation Diseases 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000008313 sensitization Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- IVCMUVGRRDWTDK-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1 IVCMUVGRRDWTDK-UHFFFAOYSA-M 0.000 description 4
- SFPQDYSOPQHZAQ-UHFFFAOYSA-N 2-methoxypropanenitrile Chemical compound COC(C)C#N SFPQDYSOPQHZAQ-UHFFFAOYSA-N 0.000 description 4
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- -1 cyclic ester Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XTPRURKTXNFVQT-UHFFFAOYSA-N hexyl(trimethyl)azanium Chemical compound CCCCCC[N+](C)(C)C XTPRURKTXNFVQT-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ISHFYECQSXFODS-UHFFFAOYSA-M 1,2-dimethyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1C ISHFYECQSXFODS-UHFFFAOYSA-M 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- NZSICTQUKULOSA-UHFFFAOYSA-N 5-azoniaspiro[4.4]nonane Chemical compound C1CCC[N+]21CCCC2 NZSICTQUKULOSA-UHFFFAOYSA-N 0.000 description 2
- HOTNVZSJGHTWIU-UHFFFAOYSA-N 6-azoniaspiro[5.5]undecane Chemical compound C1CCCC[N+]21CCCCC2 HOTNVZSJGHTWIU-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- MKHFCTXNDRMIDR-UHFFFAOYSA-N cyanoiminomethylideneazanide;1-ethyl-3-methylimidazol-3-ium Chemical compound [N-]=C=NC#N.CCN1C=C[N+](C)=C1 MKHFCTXNDRMIDR-UHFFFAOYSA-N 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- XQTFNBQBERLQQH-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;fluoride Chemical compound [F-].CC[N+]=1C=CN(C)C=1 XQTFNBQBERLQQH-UHFFFAOYSA-M 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- CXBGUFGZFSPXJX-UHFFFAOYSA-N 4-azoniaspiro[3.3]heptane Chemical compound C1CC[N+]21CCC2 CXBGUFGZFSPXJX-UHFFFAOYSA-N 0.000 description 1
- XEYHFNNNWRPOHF-UHFFFAOYSA-N 5-azoniaspiro[4.5]decane Chemical compound C1CCC[N+]21CCCCC2 XEYHFNNNWRPOHF-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- UXJMNYUMTLTHQF-UHFFFAOYSA-M [I-].C1CCCC[N+]11CCCCC1 Chemical compound [I-].C1CCCC[N+]11CCCCC1 UXJMNYUMTLTHQF-UHFFFAOYSA-M 0.000 description 1
- ILYQODZMNNHWNB-UHFFFAOYSA-M [I-].C1CCC[N+]21CCCCC2 Chemical compound [I-].C1CCC[N+]21CCCCC2 ILYQODZMNNHWNB-UHFFFAOYSA-M 0.000 description 1
- HACFXITYQNEDSM-UHFFFAOYSA-M [I-].C1CC[N+]21CCC2 Chemical compound [I-].C1CC[N+]21CCC2 HACFXITYQNEDSM-UHFFFAOYSA-M 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
- 229940011411 erythrosine Drugs 0.000 description 1
- 235000012732 erythrosine Nutrition 0.000 description 1
- 239000004174 erythrosine Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OXRVSIYVKVCGEW-UHFFFAOYSA-M hexyl(trimethyl)azanium;iodide Chemical compound [I-].CCCCCC[N+](C)(C)C OXRVSIYVKVCGEW-UHFFFAOYSA-M 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- GVKCHTBDSMQENH-UHFFFAOYSA-L phloxine B Chemical compound [Na+].[Na+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 GVKCHTBDSMQENH-UHFFFAOYSA-L 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- LGFIKQWAHMGMEO-UHFFFAOYSA-N ruthenium(2+);diisothiocyanate Chemical compound [Ru+2].[N-]=C=S.[N-]=C=S LGFIKQWAHMGMEO-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Description
本発明は、新規な色素増感型太陽電池用非水電解液及びそれを用いた色素増感型太陽電池に関するものである。 The present invention relates to a novel non-aqueous electrolyte for dye-sensitized solar cells and a dye-sensitized solar cell using the same.
太陽電池は、太陽光などの光の照射を受けて、そのエネルギーを直接電気エネルギーに変換することのできる電池であって、光起電力効果を利用した光電変換素子の一種である。太陽電池には、シリコン系太陽電池の他に、最近脚光を浴びている色素増感型太陽電池がある。 A solar battery is a battery that can receive light such as sunlight and directly convert the energy into electric energy, and is a type of photoelectric conversion element that uses the photovoltaic effect. In addition to silicon-based solar cells, solar cells include dye-sensitized solar cells that have recently attracted attention.
この色素増感型太陽電池は、金属酸化物系半導体を光電極とし、対向電極との間に酸化還元対を有する電解質を挟み込んで形成される。近年、特許文献１に開示されるように、金属酸化物半導体を多孔質化してその表面に色素を吸着させることでエネルギー変換効率が著しく高まったため、本格的な実用化に向けてさらなる検討が行われている。 This dye-sensitized solar cell is formed by using a metal oxide semiconductor as a photoelectrode and sandwiching an electrolyte having a redox pair with a counter electrode. In recent years, as disclosed in Patent Document 1, energy conversion efficiency has been remarkably increased by making a metal oxide semiconductor porous and adsorbing a dye on the surface thereof. It has been broken.
色素増感型太陽電池における検討課題の一つに、エネルギー変換効率の向上という問題がある。例えば、色素増感型太陽電池の変換効率は、通常３〜７％程度あり、特に優れたものでも１０％程度である。ところが，シリコン型太陽電池のエネルギー変換効率は１０〜２０％を達成しており、特に優れたものでは２０％を超えるものがある。 One of the issues to be investigated in dye-sensitized solar cells is the problem of improving energy conversion efficiency. For example, the conversion efficiency of a dye-sensitized solar cell is usually about 3 to 7%, and even a particularly excellent one is about 10%. However, the energy conversion efficiency of silicon solar cells has achieved 10 to 20%, and particularly excellent ones exceed 20%.
このため、色素増感型太陽電池においてもエネルギー変換効率を向上させることが提案されており、特許文献２や特許文献３に見られるように電解液についての研究がなされている。しかしながら、未だ充分な成果が得られていない。
本発明の目的は、上記の従来の事情に鑑み、エネルギー変換効率に優れた色素増感型太陽電池用の新規な非水電解液及びそれを用いた色素増感型太陽電池を提供することにある。 An object of the present invention is to provide a novel non-aqueous electrolyte for a dye-sensitized solar cell excellent in energy conversion efficiency and a dye-sensitized solar cell using the same in view of the above-described conventional circumstances. is there.
本発明者は、鋭意研究の結果、色素増感型太陽電池用の電解液として、４級窒素原子をスピロ原子に持つ構造を有する特定の化合物を溶質とする非水電解液を使用することにより上記の課題を解決しうることを見出した。
かくして、本発明は、以下の要旨を有することを特徴とするものである。
As a result of diligent research, the inventor of the present invention uses a nonaqueous electrolytic solution containing a specific compound having a structure having a quaternary nitrogen atom as a spiro atom as a solute as an electrolytic solution for a dye-sensitized solar cell. It has been found that the above problems can be solved.
Thus, the present invention is characterized by having the following gist.
１．式（１）で表される４級窒素原子をスピロ原子に持つ構造を有する化合物（Ａ）と、その対イオンであるよう素イオンとからなる溶質を含有することを特徴とする色素増感太陽電池用の非水電解液。 1. Compounds having a structure having a quaternary nitrogen atom of formula (1) spiro atom (A) and a dye-sensitized, characterized in that it contains a solute consisting of iodine ion to be the the counterion Non-aqueous electrolyte for solar cells.
２．化合物（Ａ）が式（２）で示される（式中、ｍ、ｎはそれぞれ独立して２〜５である）化合物である請求項１に記載の色素増感型太陽電池用の非水電解液。
2. The non-aqueous electrolysis for a dye-sensitized solar cell according to claim 1, wherein the compound (A) is a compound represented by the formula (2) (wherein m and n are each independently 2 to 5). liquid.
４．溶媒が、環状カーボネート類、環状エステル類、鎖状エステル類、ニトリル類、アルコール類、エーテル類、又はアミド類であるである溶媒を含有する上記１〜３のいずれかに記載の色素増感型太陽電池用非水電解液。
５.イオン性液体である溶媒を含有する請求項１〜３のいずれかに記載の色素増感型太陽電池用非水電解液。
６．化合物（Ａ）の濃度が０．１〜４．０モル／リットルある上記１〜５のいずれかに記載の色素増感型太陽電池用非水電解液。
７．よう素と非水溶媒およびまたはイオン性液体を含有する上記１〜６のいずれかに記載の色素増感型太陽電池用の非水電解液。
８．上記１〜７のいずれかに記載の色素増感型太陽電池用非水電解液を用いる色素増感型太陽電池。
4 . The dye-sensitized type according to any one of 1 to 3 above, wherein the solvent contains a solvent which is a cyclic carbonate, a cyclic ester, a chain ester, a nitrile, an alcohol, an ether, or an amide. Nonaqueous electrolyte for solar cells.
5. The nonaqueous electrolytic solution for a dye-sensitized solar cell according to any one of claims 1 to 3, comprising a solvent which is an ionic liquid.
6 . 6. The nonaqueous electrolytic solution for a dye-sensitized solar cell according to any one of 1 to 5 above, wherein the concentration of the compound (A) is 0.1 to 4.0 mol / liter.
7 . 7. The nonaqueous electrolytic solution for a dye-sensitized solar cell according to any one of 1 to 6 above, containing iodine and a nonaqueous solvent and / or an ionic liquid.
8 . A dye-sensitized solar cell using the non-aqueous electrolyte for a dye-sensitized solar cell according to any one of 1 to 7 above.
本発明により提供される電解液した非水電解液を用いた色素増感型太陽電池は、優れた電流−電圧特性を示し、光エネルギー変換効率が高く、太陽光に対して長期間安定で安全性の高い色素増感型太陽電池を提供することができ、その工業価値の大なるものである。 The dye-sensitized solar cell using the non-aqueous electrolytic solution provided by the present invention exhibits excellent current-voltage characteristics, has high light energy conversion efficiency, is stable and safe for a long time against sunlight. A highly sensitive dye-sensitized solar cell can be provided, and its industrial value is great.
本発明の電解液が使用される色素増感型太陽電池の構成について説明する。色素増感型太陽電池における光電極の部分は透明電極付きガラス基板上に金属酸化物半導体（酸化チタン）の多孔質膜（半導体電極）を形成させ、四塩化チタン水溶液などで酸化チタン多孔質膜を処理し、その表面に増感色素を付着させたものである。これを一方の電極（光電極）とし、対向電極との間に電解液を置く。太陽電池の周囲は前記電解液が漏れないようにシール材でシールされている。 The structure of the dye-sensitized solar cell in which the electrolytic solution of the present invention is used will be described. In the dye-sensitized solar cell, the photoelectrode part is formed by forming a porous film (semiconductor electrode) of a metal oxide semiconductor (titanium oxide) on a glass substrate with a transparent electrode, and using a titanium tetrachloride aqueous solution, etc. And a sensitizing dye is attached to the surface. This is one electrode (photoelectrode), and an electrolytic solution is placed between the counter electrode. The periphery of the solar cell is sealed with a sealing material so that the electrolyte does not leak.
本発明の色素増感型太陽電池にでは、光電極と対向電極との間の電解液として、上記したように、下記の式（１）で表される４級窒素原子をスピロ原子に持つ構造を有する化合物（Ａ）を溶質として含有する電解液を用いることにより電子移動をスムーズにし、電池の性能を安定させ、電池性能が著しく改善される。 In the dye-sensitized solar cell of the present invention, as described above, the electrolyte solution between the photoelectrode and the counter electrode has a quaternary nitrogen atom represented by the following formula (1) as a spiro atom. By using an electrolytic solution containing the compound (A) having a solute as a solute, electron transfer is smoothed, battery performance is stabilized, and battery performance is remarkably improved.
本発明では、化合物（Ａ）は、式（２）で示される化合物を溶質とする電解液が性能上及び製造コストの点からして好適である。式（２）中、ｍ、ｎは。上記したとおりであるが、なかでも、４又は５が好ましく、特に４が好ましい。 In the present invention, as the compound (A), an electrolytic solution containing the compound represented by the formula (2) as a solute is preferable from the viewpoint of performance and production cost. M and n in formula (2). As described above, 4 or 5 is preferable, and 4 is particularly preferable.
上記の式（１）又は（２）で表される化合物から電解液の溶質を構成する場合、その対イオンとしては、好ましくはよう素イオンが使用される。電解液中のよう素の含有量はイオン導電性及び光エネルギー変換効率の観点から好ましくは０．００５〜０．５モル／リットル、特には０．０１〜０．１モル／リットルが好ましい。 When the solute of the electrolytic solution is composed of the compound represented by the above formula (1) or (2), iodine ion is preferably used as the counter ion. The iodine content in the electrolytic solution is preferably 0.005 to 0.5 mol / liter, particularly 0.01 to 0.1 mol / liter from the viewpoints of ionic conductivity and light energy conversion efficiency.
また、上記の式（１）又は（２）で表される化合物を電解液の溶質から電解液を形成する場合、有機溶媒としては、メタノール、エタノール、1-プロパノール、iso-プロパノール、n-ブタノール、iso-ブタノール、tert-ブタノールなどのアルコール類、１，２−ジメトキシエタン、１，２−ジブトキシエタン、テトラヒドロフランなどのエーテル類、プロピオン酸メチルなどのエステル類、ジメチルホルムアミドなどのアミド類など、アセトニトリル(ＡＮ)、プロピオニトリル(ＰＮ)、メトキシプロピオニトリル(ＭＯＰＮ)などのニトリル類、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、γ−ブチロラクトン(ＧＢＬ)などの環状カーボネート類が挙げられる。なかでも、アセトニトリル(ＡＮ)、メトキシプロピオニトリル(ＭＯＰＮ)、プロピレンカーボネート（ＰＣ）、γ−ブチロラクトン(ＧＢＬ)が好ましい。 In addition, when forming the electrolytic solution from the solute of the electrolytic solution of the compound represented by the above formula (1) or (2), as the organic solvent, methanol, ethanol, 1-propanol, iso-propanol, n-butanol Alcohols such as iso-butanol and tert-butanol, ethers such as 1,2-dimethoxyethane, 1,2-dibutoxyethane, tetrahydrofuran, esters such as methyl propionate, amides such as dimethylformamide, etc. Examples include nitriles such as acetonitrile (AN), propionitrile (PN), and methoxypropionitrile (MOPN), and cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and γ-butyrolactone (GBL). . Of these, acetonitrile (AN), methoxypropionitrile (MOPN), propylene carbonate (PC), and γ-butyrolactone (GBL) are preferable.
また、本発明の上記の式（１）又は（２）で表される化合物を溶質とする場合、溶媒は、上記有機溶媒の代わりに又は上記有機溶媒に加えて、イオン性液体を用いることもできる。イオン性液体の好ましい例としては、1-エチル-3-メチルイミダゾリウムホウフッ化物(EMI-BF4)、1-エチル-3-メチルイミダゾリウムフッ化物2.3フッ化水素酸錯体（EMI-F(HF)2.3）、1-エチル-3-メチルイミダゾリウムジシアナミド(EMI-DCA)、1-エチル-3-メチルイミダゾリウムトリフルオロメタンスルホニルイミド(EMI-TFSI)、1-メチル-3-プロピルイミダゾリウムよう化物(MPImI)、ヘキシルトリメチルアンモニウムトリフルオロメタンスルホニルイミド(HTMA-TFSI)などが挙げられる。 In addition, when the compound represented by the above formula (1) or (2) of the present invention is used as a solute, an ionic liquid may be used as the solvent instead of or in addition to the organic solvent. it can. Preferred examples of ionic liquids include 1-ethyl-3-methylimidazolium borofluoride (EMI-BF4), 1-ethyl-3-methylimidazolium fluoride 2.3 hydrofluoric acid complex (EMI-F (HF) 2.3), 1-ethyl-3-methylimidazolium dicyanamide (EMI-DCA), 1-ethyl-3-methylimidazolium trifluoromethanesulfonylimide (EMI-TFSI), 1-methyl-3-propylimidazolium iodide (MPImI), hexyltrimethylammonium trifluoromethanesulfonylimide (HTMA-TFSI) and the like.
本発明の電解液の形成使用される上記の有機溶媒又はイオン性液体は１種類で使用してもよく、又は２種類以上を組み合わせて使用してもよい。 The organic solvent or ionic liquid used for forming the electrolytic solution of the present invention may be used alone or in combination of two or more.
本発明の色素増感型太陽電池用の電解液における溶質としては、上記の式（１）又は（２）で表される化合物の１種または２種以上が使用され、電解液中のその濃度は、適宜選ばれる。なかでも、その濃度は、好ましくは０．１〜４モルモル／リットル、特に好ましくは０．５〜２モル／リットルが好適である。濃度が０．１モル／リットルより小さい場合には効果が小さくなり、一方、濃度が４モル／リットルより大きい場合には溶解しにくくなり、いずれも好ましくない。 As the solute in the electrolyte solution for the dye-sensitized solar cell of the present invention, one or more of the compounds represented by the above formula (1) or (2) is used, and its concentration in the electrolyte solution Is appropriately selected. Among them, the concentration is preferably 0.1 to 4 mol / liter, particularly preferably 0.5 to 2 mol / liter. When the concentration is less than 0.1 mol / liter, the effect is small, while when the concentration is more than 4 mol / liter, it is difficult to dissolve, both of which are not preferable.
また、本発明の色素増感型太陽電池用の電解液には、上記の式（１）又は（２）で表される化合物の溶質のほかに、他の溶質や添加剤を含有させ電解液の特性を向上させることができる。他の溶質の例としては、1,2-ジメチル-3-プロピルイミダゾリウムよう化物(DMPImI)、テトラプロピルアンモニウムよう化物(TPA-I)、1-メチル-3-プロピルイミダゾリウムよう化物(MPImI)などが挙げられる。また、添加剤の例としては、4-tert-ブチルピリジン(TBP)、よう化リチウム(LiI)などが挙げられる。 In addition to the solute of the compound represented by the above formula (1) or (2), the electrolyte solution for the dye-sensitized solar cell of the present invention contains other solutes and additives, and the electrolyte solution. The characteristics can be improved. Examples of other solutes include 1,2-dimethyl-3-propylimidazolium iodide (DMPImI), tetrapropylammonium iodide (TPA-I), 1-methyl-3-propylimidazolium iodide (MPImI) Etc. Examples of the additive include 4-tert-butylpyridine (TBP), lithium iodide (LiI) and the like.
本発明の色素増感型太陽電池用の電解液は、これにゲル化剤（高分子或いは低分子のゲル化剤）などを添加し、ゲル状乃至半固体の性状にして使用するころもできる。 The electrolyte solution for a dye-sensitized solar cell of the present invention can be used by adding a gelling agent (polymer or low-molecular gelling agent) to the gel-like or semi-solid property. .
以上、本発明の色素増感型太陽電池に用いる電解液についての説明をしたが、本発明の特徴は主に色素増感型太陽電池の電解液にあり、電解液以外の色素増感型太陽電池の構成は通常の一般的な色素増感型太陽電池の構造を使用することができる。 As mentioned above, although the electrolyte solution used for the dye-sensitized solar cell of the present invention has been described, the feature of the present invention is mainly the electrolyte solution of the dye-sensitized solar cell, and the dye-sensitized solar cell other than the electrolyte solution The structure of a battery can use the structure of a normal common dye-sensitized solar cell.
即ち、本発明の電解液を使用する色素増感型太陽電池に使用される、カソード電極は、導電性を有するものであれば特に問題はなく、任意の導電性材料を用いることができるが、Ｉ3 -などの還元反応を十分な速さで行わせる触媒能を持ったものが好ましく、たとえば、導電性ガラスなどの導電性材料に白金メッキや白金蒸着を施したものが好ましい。 That is, the cathode electrode used in the dye-sensitized solar cell using the electrolytic solution of the present invention has no particular problem as long as it has conductivity, and any conductive material can be used. I 3 - is preferably one having a catalytic ability to perform quickly enough a reduction reaction such as, for example, those subjected to platinum plating or platinum evaporation on a conductive material such as conductive glass is preferred.
また、アノード電極は、酸化物半導体の微少な結晶の表面に色素を吸着させた酸化物半導体層を有している導電性ガラスからなり、酸化物半導体としては、従来公知のものが使用できる。即ち、Ｔｉ、Ｎｂ、Ｚｎ、Ｓｎ、Ｚｒ、Ｙ、Ｌａ、Ｔａなどの遷移金属の酸化物の他、ＳｒＴｉＯ3、ＣａＴｉＯ3などのペロブスカイト系酸化物などがあげられる。また、この酸化物半導体はできるだけ微粒子であることが好ましく、その平均粒径は５０００ｎｍ以下、好ましくは５０ｎｍ以下である。また、その比表面積は５００ｃｍ2／ｃｍ以上、好ましくは１０００ｃｍ2／ｃｍ以上である。酸化物半導体を電極として用いるには、導電性ガラスなどの導電性基板上に固定して用いる。基板上の酸化物半導体の厚さは１０００ｎｍ以上が好ましい。 The anode electrode is made of conductive glass having an oxide semiconductor layer in which a dye is adsorbed on the surface of a minute crystal of an oxide semiconductor, and conventionally known oxide semiconductors can be used. That is, in addition to oxides of transition metals such as Ti, Nb, Zn, Sn, Zr, Y, La, and Ta, perovskite oxides such as SrTiO 3 and CaTiO 3 are exemplified. The oxide semiconductor is preferably as fine as possible, and its average particle size is 5000 nm or less, preferably 50 nm or less. The specific surface area is 500 cm 2 / cm or more, preferably 1000 cm 2 / cm or more. In order to use an oxide semiconductor as an electrode, it is used by being fixed on a conductive substrate such as conductive glass. The thickness of the oxide semiconductor on the substrate is preferably 1000 nm or more.
色素増感型太陽電池における酸化物半導体の微少な結晶の表面に吸着させる色素としては、従来公知のものが使用でき、太陽光を高波長範囲にわたって吸収できる能力を持つものであれば特に問題ない。このようなものとして、たとえばルテニウム錯体、クロロフィル、ローダミン、エオシン、フロキシン、フルオレセイン、エリスロシン、ウラニン、ローズベンガルなどがあげられる。 As a dye to be adsorbed on the surface of a minute crystal of an oxide semiconductor in a dye-sensitized solar cell, a conventionally known dye can be used, and there is no problem as long as it has an ability to absorb sunlight over a high wavelength range. . Examples of such compounds include ruthenium complexes, chlorophyll, rhodamine, eosin, phloxine, fluorescein, erythrosine, uranin, and rose bengal.
本発明の色素増感型太陽電池は、以上説明したカソード電極、アノード電極を組み合わせて用いることにより、高光電変換効率を有し、太陽光に対して長期間安定で、安全性の高い色素増感型太陽電池とすることができる。 The dye-sensitized solar cell of the present invention is a dye-sensitized solar cell having a high photoelectric conversion efficiency, stable for a long period of time, and high safety by using the cathode electrode and the anode electrode described above in combination. It can be set as a sensitive solar cell.
次に、実施例及び比較例を挙げて本発明を具体的に説明するが、これらは本発明を何ら限定するものではない。 EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated concretely, these do not limit this invention at all.
実施例１
酸化チタンゾル液して、チタンイソプロポキシドを以下のように加水分解することにより、酸化チタンゾル液を調製した。
Example 1
A titanium oxide sol solution was prepared by hydrolyzing titanium isopropoxide as follows.
１２５ｍｌのチタンイソプロポキシドを、０．１mol/l硝酸水溶液７５０ｍｌに攪拌しながら添加した。これを８０℃で２４時間激しく攪拌した。得られた液体をテフロン（登録商標）製の圧力容器内で２３０℃、２４時間オ−トクレ−ブ処理した。沈殿物を含むゾル液を攪拌により再懸濁させた。吸引濾過により、再懸濁しなかった沈殿物を除き、エバポレーターで酸化チタン濃度が１０ｗｔ％になるまでゾル液を濃縮した。基板への塗れ性を高めるため、Triton
X-100を1滴添加した。
125 ml of titanium isopropoxide was added to 750 ml of 0.1 mol / l aqueous nitric acid solution with stirring. This was stirred vigorously at 80 ° C. for 24 hours. The obtained liquid was autoclaved at 230 ° C. for 24 hours in a pressure vessel made of Teflon (registered trademark). The sol solution containing the precipitate was resuspended by stirring. The precipitate that was not resuspended was removed by suction filtration, and the sol solution was concentrated with an evaporator until the titanium oxide concentration reached 10 wt%. Triton to improve paintability on the substrate
One drop of X-100 was added.
次に、酸化チタン膜の焼成時におけるクラックの発生および導電性表面からの膜の剥離を防止するため以下のようにチタンアルコキシドをゾル液に添加した。すなわち、上記ゾル液を攪拌しながら、ジ−iso−プロポキシ・ビス（アセチルアセトナート）チタンとアセチルアセトンの８０：２０混合液を少しずつ添加した。添加終了後、１時間攪拌した。 Next, titanium alkoxide was added to the sol solution as follows in order to prevent generation of cracks during the firing of the titanium oxide film and peeling of the film from the conductive surface. That is, while stirring the sol solution, an 80:20 mixed solution of di-iso-propoxy bis (acetylacetonate) titanium and acetylacetone was added little by little. After completion of the addition, the mixture was stirred for 1 hour.
なお、ジ−iso−プロポキシ・ビス（アセチルアセトナート）チタンの添加量は３．４ｇ（酸化チタン微粒子重量に対し１０重量％）としてサンプルを作製した。 The sample was prepared with an addition amount of di-iso-propoxy bis (acetylacetonato) titanium of 3.4 g (10 wt% with respect to the titanium oxide fine particle weight).
色素結合電極（酸化チタン電極）の作製は上記のように調製したチタンアルコキシド添加ゾル液を用いて、以下の要領で酸化チタン電極を作製した。 The production of the dye-coupled electrode (titanium oxide electrode) was carried out using the titanium alkoxide-added sol solution prepared as described above, in the following manner.
縦２．０ｃｍ、横１．５ｃｍ、厚さ１ｍｍの導電性ガラス基板（Ｆ−ＳｎＯ2、シ−ト抵抗１０Ω／℃）の導電膜面側に、縦０．５ｃｍ、横０．５ｃｍの四角穴を設けた厚さ７０μｍのマスキングテ−プを貼り、穴の端部に前記チタンアルコキシド添加ゾル液３μLをピペットで添加した。このゾル液を縁が平らなガラス板を用いて引き延ばすことにより基板上に広げた。このように広げた膜を空気中で３０分間乾燥し、乾燥後マスキングテ−プを剥がし取った。次に、電気炉を用いて５００℃で３０分間焼成した。昇温速度は２℃／minとした。 A square of 0.5 cm in length and 0.5 cm in width on the conductive film side of a conductive glass substrate (F-SnO 2 , sheet resistance 10 Ω / ° C.) having a length of 2.0 cm, a width of 1.5 cm, and a thickness of 1 mm. A masking tape having a thickness of 70 μm provided with a hole was attached, and 3 μL of the titanium alkoxide-added sol solution was added to the end of the hole with a pipette. The sol solution was spread on a substrate by stretching using a glass plate having a flat edge. The film thus spread was dried in air for 30 minutes, and after drying, the masking tape was peeled off. Next, it baked for 30 minutes at 500 degreeC using the electric furnace. The heating rate was 2 ° C./min.
焼成後、基板温度が８０℃まで下がったところで、増感色素として（４，４’−ジカルボン酸−２，２’−ビピリジン）ルテニウム（II）ジイソチアネ−トを0.3mmol/l濃度で添加した無水エタノ−ル溶液２０ｍｌに浸漬し、２４時間放置した。 After firing, when the substrate temperature dropped to 80 ° C., anhydrous (4,4′-dicarboxylic acid-2,2′-bipyridine) ruthenium (II) diisothiocyanate was added as a sensitizing dye at a concentration of 0.3 mmol / l. It was immersed in 20 ml of ethanol solution and allowed to stand for 24 hours.
放置後、酸化チタン電極を取り出しアセトニトリルで洗浄した。基板上の酸化チタン膜は吸着されたルテニウム色素により深紅色となった。 After standing, the titanium oxide electrode was taken out and washed with acetonitrile. The titanium oxide film on the substrate became deep red due to the adsorbed ruthenium dye.
対向電極の準備として、対向電極は1mmφの穴が２ヶ所存在する導電性ガラス基板の導電膜面側に、白金を１００nmの厚さでスパッタリングしたものを用いた。 As a preparation of the counter electrode, a counter electrode was used in which platinum was sputtered to a thickness of 100 nm on the conductive film side of a conductive glass substrate having two 1 mmφ holes.
電解液として、1,1'-スピロビピロリジニウムよう化物0.6mol/l・4-tert-ブチルピリジン0.5mol/l・よう化リチウム0.1mol/l・よう素0.05mol/lの割合でアセトニトリルに溶解し試験溶液とした。 1,1'-spirobipyrrolidinium iodide 0.6 mol / l, 4-tert-butylpyridine 0.5 mol / l, lithium iodide 0.1 mol / l, iodine 0.05 mol / l as the electrolyte To give a test solution.
太陽電池の作製及び評価
上記の両電極および電解液を用いて、下記の要領で太陽電池サンプルの作製および評価を行った。
Production and Evaluation of Solar Cell A solar cell sample was produced and evaluated in the following manner using both the electrodes and the electrolytic solution.
作用電極である色素結合電極（酸化チタン電極）と対向電極を張り合わせるスペーサーとして、三井デュポンポリケミカル社製ハイミラン（厚さ５０μｍ）を使用した。なお、このスペーサーは、作用電極と張り合わせたときに、色素の吸着した酸化チタン膜と重なり合う中央部分が刳り貫くかれており、この刳り貫かれた空間部分に電解液が貯蔵できるようになっている。これを用いて、作用電極の色素の吸着した酸化チタン膜側と対向電極の白金をスパッタリングした側を張り合わせた。 High Milan (thickness 50 μm) manufactured by Mitsui DuPont Polychemical Co., Ltd. was used as a spacer for bonding the dye-bonded electrode (titanium oxide electrode) as the working electrode and the counter electrode. In addition, when this spacer is bonded to the working electrode, a central portion overlapping with the dye-adsorbed titanium oxide film is perforated, and the electrolyte can be stored in the perforated space portion. . Using this, the titanium oxide film side of the working electrode adsorbed with the dye and the platinum-sputtered side of the counter electrode were bonded together.
その後、対向電極に予め形成させておいた２つの穴のうち１方の穴から、電解液を導入した。電解液が電池内部に導入されるように充分な時間放置した。その後、対向電極の裏面側から封止板として１枚のハイミランと１枚のカバーガラスを順次積層して２つの穴を塞ぎ、電解液を封止した。 Thereafter, an electrolytic solution was introduced from one of the two holes previously formed in the counter electrode. It was left for a sufficient time so that the electrolyte was introduced into the battery. Thereafter, one Hi-Millan and one cover glass were sequentially laminated as a sealing plate from the back side of the counter electrode to close the two holes, and the electrolyte was sealed.
以上のようにして作成した色素増感型太陽電池に対し、ソーラーシュミレーターで照射強度100mW/cm2の光を照射して、光電変換効率をポテンシオスタットを用い測定した結果を表１に示す。 Table 1 shows the results obtained by irradiating the dye-sensitized solar cell produced as described above with light having an irradiation intensity of 100 mW / cm 2 using a solar simulator and measuring the photoelectric conversion efficiency using a potentiostat.
実施例２
実施例１において1,1'-スピロビピロリジニウムよう化物の濃度を1.5mol/lにする以外は実施例１と同様にして実施例２の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 2
A dye-sensitized solar cell of Example 2 was prepared in the same manner as in Example 1 except that the concentration of 1,1′-spirobipyrrolidinium iodide was changed to 1.5 mol / l in Example 1. Measurements were made. The results are shown in Table 1.
実施例３
実施例１において1,1'-スピロビピロリジニウムよう化物の濃度を4.0mol/lにする以外は実施例１と同様にして実施例３の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 3
A dye-sensitized solar cell of Example 3 was prepared in the same manner as in Example 1 except that the concentration of 1,1′-spirobipyrrolidinium iodide was 4.0 mol / l in Example 1. Measurements were made. The results are shown in Table 1.
実施例４
実施例１において1,1'-スピロビピロリジニウムよう化物の濃度を0.1mol/lにする以外は実施例１と同様にして実施例４の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 4
A dye-sensitized solar cell of Example 4 was prepared in the same manner as in Example 1 except that the concentration of 1,1′-spirobipyrrolidinium iodide in Example 1 was 0.1 mol / l. Measurements were made. The results are shown in Table 1.
実施例５
実施例１において1,1'-スピロビピロリジニウムよう化物の濃度を0.3mol/lにする以外は実施例１と同様にして実施例５の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 5
A dye-sensitized solar cell of Example 5 was prepared in the same manner as in Example 1 except that the concentration of 1,1′-spirobipyrrolidinium iodide was 0.3 mol / l in Example 1, and the same Measurements were made. The results are shown in Table 1.
実施例６
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりに1,1'-スピロビピペリジニウムよう化物を用いる以外は実施例１と同様にして実施例６の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 6
The dye-sensitized dye of Example 6 was used in the same manner as in Example 1 except that 1,1'-spirobipiperidinium iodide was used instead of 1,1'-spirobipyrrolidinium iodide in Example 1. A solar cell was prepared and the same measurement was performed. The results are shown in Table 1.
実施例７
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりに1,1'-スピロビアゼチジニウムよう化物を用いる以外は実施例１と同様にして実施例７の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 7
The dye-sensitized dye of Example 7 was used in the same manner as in Example 1 except that 1,1'-spirobiazetidinium iodide was used instead of 1,1'-spirobipyrrolidinium iodide in Example 1. A solar cell was prepared and the same measurement was performed. The results are shown in Table 1.
実施例８
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにスピロ[ピペリジン-1,1'-ピロリジニウム]よう化物を用いる以外は実施例１と同様にして実施例８の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 8
The dye sensitization of Example 8 was carried out in the same manner as in Example 1 except that spiro [piperidine-1,1'-pyrrolidinium] iodide was used instead of 1,1'-spirobipyrrolidinium iodide in Example 1. Type solar cell was prepared and the same measurement was performed. The results are shown in Table 1.
実施例９
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにスピロ[アゼチジン-1,1'-ピペリジン]よう化物を用いる以外は実施例１と同様にして実施例９の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 9
The dye sensitization of Example 9 was carried out in the same manner as in Example 1 except that spiro [azetidine-1,1'-piperidine] iodide was used instead of 1,1'-spirobipyrrolidinium iodide in Example 1. Type solar cell was prepared and the same measurement was performed. The results are shown in Table 1.
実施例１０
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにスピロ[アジリジン-1,1'-ピペリジン]よう化物を用いる以外は実施例１と同様にして実施例１０の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 10
The dye sensitization of Example 10 was performed in the same manner as in Example 1 except that spiro [aziridine-1,1′-piperidine] iodide was used in place of 1,1′-spirobipyrrolidinium iodide in Example 1. Type solar cell was prepared and the same measurement was performed. The results are shown in Table 1.
実施例１１
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにスピロ[アゼチジン-1,1'-ピロリジン]よう化物を用いる以外は実施例１と同様にして実施例１１の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 11
The dye sensitization of Example 11 was performed in the same manner as in Example 1 except that spiro [azetidine-1,1′-pyrrolidine] iodide was used instead of 1,1′-spirobipyrrolidinium iodide in Example 1. Type solar cell was prepared and the same measurement was performed. The results are shown in Table 1.
実施例１２
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにスピロ[アジリジン-1,1'-ピロリジン]よう化物を用いる以外は実施例１と同様にして実施例１２の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 12
The dye sensitization of Example 12 was performed in the same manner as in Example 1 except that spiro [aziridine-1,1′-pyrrolidine] iodide was used in place of 1,1′-spirobipyrrolidinium iodide in Example 1. Type solar cell was prepared and the same measurement was performed. The results are shown in Table 1.
実施例１３
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにスピロ[アゼチン-1,1'-ピロリジン]よう化物を用いる以外は実施例１と同様にして実施例１３の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 13
The dye sensitization of Example 13 was performed in the same manner as in Example 1 except that spiro [azetin-1,1′-pyrrolidine] iodide was used instead of 1,1′-spirobipyrrolidinium iodide in Example 1. Type solar cell was prepared and the same measurement was performed. The results are shown in Table 1.
実施例１４
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにスピロ[3-メチルピペリジン-1,1'-ピロリジニウム]よう化物を用いる以外は実施例１と同様にして実施例１４の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 14
In Example 1, except for using spiro [3-methylpiperidine-1,1′-pyrrolidinium] iodide instead of 1,1′-spirobipyrrolidinium iodide, Example 14 A dye-sensitized solar cell was prepared and subjected to the same measurement. The results are shown in Table 1.
実施例１５
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにスピロ[3-メチルピペリジン-1,1'-(3-エチルピロリジニウム)]よう化物を用いる以外は実施例１と同様にして実施例１５の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 15
Example 1 is different from Example 1 except that spiro [3-methylpiperidine-1,1 ′-(3-ethylpyrrolidinium)] iodide is used in place of 1,1′-spirobipyrrolidinium iodide. Similarly, the dye-sensitized solar cell of Example 15 was prepared and subjected to the same measurement. The results are shown in Table 1.
実施例１６
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにスピロ[3-アミノピペリジン-1,1'-ピロリジニウム]よう化物を用いる以外は実施例１と同様にして実施例１６の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 16
In Example 1, except that spiro [3-aminopiperidine-1,1′-pyrrolidinium] iodide is used instead of 1,1′-spirobipyrrolidinium iodide, the same procedure as in Example 1 is carried out. A dye-sensitized solar cell was prepared and subjected to the same measurement. The results are shown in Table 1.
実施例１７
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにスピロ[3-カルボキシルピペリジン-1,1'-ピロリジニウム]よう化物を用いる以外は実施例１と同様にして実施例１７の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 17
In Example 1, except for using spiro [3-carboxylpiperidine-1,1′-pyrrolidinium] iodide instead of 1,1′-spirobipyrrolidinium iodide, Example 17 A dye-sensitized solar cell was prepared and subjected to the same measurement. The results are shown in Table 1.
実施例１８
実施例１においてアセトニトリルの代わりにプロピレンカーボネートを用いる以外は実施例１と同様にして実施例１８の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 18
A dye-sensitized solar cell of Example 18 was prepared in the same manner as in Example 1 except that propylene carbonate was used instead of acetonitrile in Example 1, and the same measurement was performed. The results are shown in Table 1.
実施例１９
実施例１においてアセトニトリルの代わりに3-メトキシプロピオニトリルを用いる以外は実施例１と同様にして実施例１９の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 19
A dye-sensitized solar cell of Example 19 was made in the same manner as in Example 1 except that 3-methoxypropionitrile was used instead of acetonitrile in Example 1, and the same measurement was performed. The results are shown in Table 1.
実施例２０
実施例１においてアセトニトリルの代わりにγ-ブチロラクトンを用いる以外は実施例１と同様にして実施例２０の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 20
A dye-sensitized solar cell of Example 20 was made in the same manner as in Example 1 except that γ-butyrolactone was used instead of acetonitrile in Example 1, and the same measurement was performed. The results are shown in Table 1.
実施例２１
実施例１においてアセトニトリルの代わりにホウフッ化エチルメチルイミダゾリウム(EMI-BF)を用いる以外は実施例１と同様にして実施例２１の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 21
A dye-sensitized solar cell of Example 21 was prepared in the same manner as in Example 1 except that ethyl borofluoride (EMI-BF) was used instead of acetonitrile in Example 1, and the same measurement was performed. . The results are shown in Table 1.
実施例２２
実施例１においてアセトニトリルの代わりにヘキシルトリメチルアンモニウムトリフルオロメタンスルホニルイミド(HTMA-TFSI)を用いる以外は実施例１と同様にして実施例２２の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 22
A dye-sensitized solar cell of Example 22 was prepared in the same manner as in Example 1 except that hexyltrimethylammonium trifluoromethanesulfonylimide (HTMA-TFSI) was used instead of acetonitrile in Example 1, and the same measurement was performed. It was. The results are shown in Table 1.
実施例２３
実施例１においてアセトニトリルの代わりにアセトニトリル・3-メトキシプロピオニトリルを容量比１：１にした溶液を用いる以外は実施例１と同様にして実施例２３の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Example 23
A dye-sensitized solar cell of Example 23 was prepared in the same manner as in Example 1 except that a solution having a 1: 1 volume ratio of acetonitrile and 3-methoxypropionitrile was used instead of acetonitrile in Example 1, Similar measurements were made. The results are shown in Table 1.
比較例１
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりに1,2-ジメチル-3-プロピルイミダゾリウムよう化物を用いる以外は実施例１と同様にして比較例１の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Comparative Example 1
The dye sensitization of Comparative Example 1 was performed in the same manner as in Example 1 except that 1,2-dimethyl-3-propylimidazolium iodide was used in place of 1,1'-spirobipyrrolidinium iodide in Example 1. Type solar cell was prepared and the same measurement was performed. The results are shown in Table 1.
比較例２
実施例１において1,1'-スピロビピロリジニウムよう化物の代わりにヘキシルトリメチルアンモニウムよう化物を用いる以外は実施例１と同様にして比較例２の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Comparative Example 2
A dye-sensitized solar cell of Comparative Example 2 was prepared in the same manner as in Example 1 except that hexyltrimethylammonium iodide was used in place of 1,1′-spirobipyrrolidinium iodide in Example 1, and Was measured. The results are shown in Table 1.
比較例３
比較例１においてアセトニトリルの代わりにプロピレンカーボネートを用いる以外は比較例１と同様にして比較例３の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Comparative Example 3
A dye-sensitized solar cell of Comparative Example 3 was prepared in the same manner as in Comparative Example 1 except that propylene carbonate was used instead of acetonitrile in Comparative Example 1, and the same measurement was performed. The results are shown in Table 1.
比較例４
比較例１においてアセトニトリルの代わりに3-メトキシプロピオニトリルを用いる以外は比較例１と同様にして比較例４の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Comparative Example 4
A dye-sensitized solar cell of Comparative Example 4 was prepared in the same manner as in Comparative Example 1 except that 3-methoxypropionitrile was used instead of acetonitrile in Comparative Example 1, and the same measurement was performed. The results are shown in Table 1.
比較例５
比較例１においてアセトニトリルの代わりにγ-ブチロラクトンを用いる以外は比較例１と同様にして比較例５の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Comparative Example 5
A dye-sensitized solar cell of Comparative Example 5 was prepared in the same manner as in Comparative Example 1 except that γ-butyrolactone was used instead of acetonitrile in Comparative Example 1, and the same measurement was performed. The results are shown in Table 1.
比較例６
比較例１においてアセトニトリルの代わりにホウフッ化エチルメチルイミダゾリウム(EMI-BF)を用いる以外は比較例１と同様にして比較例６の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Comparative Example 6
A dye-sensitized solar cell of Comparative Example 6 was prepared in the same manner as in Comparative Example 1 except that ethyl borofluoride (EMI-BF) was used instead of acetonitrile in Comparative Example 1, and the same measurement was performed. . The results are shown in Table 1.
比較例７
比較例１においてアセトニトリルの代わりにヘキシルトリメチルアンモニウムトリフルオロメタンスルホニルイミド(HTMA-TFSI)を用いる以外は比較例１と同様にして比較例７の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Comparative Example 7
A dye-sensitized solar cell of Comparative Example 7 was prepared in the same manner as in Comparative Example 1 except that hexyltrimethylammonium trifluoromethanesulfonylimide (HTMA-TFSI) was used instead of acetonitrile in Comparative Example 1, and the same measurement was performed. It was. The results are shown in Table 1.
比較例８
比較例１においてアセトニトリルの代わりにアセトニトリル・3-メトキシプロピオニトリルを容量比１：１にした溶液を用いる以外は比較例１と同様にして比較例８の色素増感型太陽電池を作成し、同様の測定を行なった。この結果を表１に示す。
Comparative Example 8
A dye-sensitized solar cell of Comparative Example 8 was prepared in the same manner as Comparative Example 1 except that a solution in which acetonitrile and 3-methoxypropionitrile were used in a volume ratio of 1: 1 instead of acetonitrile in Comparative Example 1 was prepared. Similar measurements were made. The results are shown in Table 1.
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| KR20080079894A (en) * | 2007-02-28 | 2008-09-02 | 삼성에스디아이 주식회사 | Dye-sensitized solar cell and preparing method thereof |
| US8088917B2 (en) * | 2007-06-01 | 2012-01-03 | Invista North America S.A R.L. | Ionic liquids |
| JP5189869B2 (en) * | 2008-03-21 | 2013-04-24 | 株式会社豊田中央研究所 | Electrolytic solution and dye-sensitized solar cell |
| JP5189870B2 (en) * | 2008-03-21 | 2013-04-24 | 株式会社豊田中央研究所 | Electrolytic solution and dye-sensitized solar cell |
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| JP5679541B2 (en) | 2010-01-26 | 2015-03-04 | 株式会社デルタツーリング | Biological signal detection device |
| KR101781062B1 (en) | 2010-01-28 | 2017-09-25 | 카릿토 홀딩스 가부시키가이샤 | Electrolyte solution for dye sensitized solar cell, and dye sensitized solar cell using same, method for producing a dye sensitized solar cell, and method for improving a photoelectric conversion efficiency of an electrolyte solution for a dye sensitized solar cell |
| JP5701633B2 (en) * | 2011-02-07 | 2015-04-15 | 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 |
| JP2014088361A (en) * | 2012-04-27 | 2014-05-15 | Semiconductor Energy Lab Co Ltd | Cyclic quaternary ammonium salt, nonaqueous solvent, nonaqueous electrolyte, and power storage device |
| JP6370449B2 (en) * | 2012-04-27 | 2018-08-08 | 株式会社半導体エネルギー研究所 | Non-aqueous solvent, power storage device |
| CN106117217B (en) * | 2016-06-08 | 2018-07-10 | 南京远淑医药科技有限公司 | A kind of preparation method of fluozirconate |
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