WO2005104291A1 - 色素増感型太陽電池用電解液、色素増感型太陽電池用酸化物半導体電極及び色素増感型太陽電池 - Google Patents
色素増感型太陽電池用電解液、色素増感型太陽電池用酸化物半導体電極及び色素増感型太陽電池 Download PDFInfo
- Publication number
- WO2005104291A1 WO2005104291A1 PCT/JP2005/004993 JP2005004993W WO2005104291A1 WO 2005104291 A1 WO2005104291 A1 WO 2005104291A1 JP 2005004993 W JP2005004993 W JP 2005004993W WO 2005104291 A1 WO2005104291 A1 WO 2005104291A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dye
- solar cell
- oxide semiconductor
- sensitized solar
- semiconductor layer
- Prior art date
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 128
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 67
- -1 phosphazene compound Chemical class 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 41
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 35
- 239000003960 organic solvent Substances 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 11
- 229910052711 selenium Inorganic materials 0.000 claims description 11
- 239000011669 selenium Substances 0.000 claims description 11
- 125000005647 linker group Chemical group 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052699 polonium Inorganic materials 0.000 claims description 5
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 58
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 125000001424 substituent group Chemical group 0.000 description 21
- 229910052731 fluorine Inorganic materials 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 11
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229940021013 electrolyte solution Drugs 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 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
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- AFYNADDZULBEJA-UHFFFAOYSA-N bicinchoninic acid Chemical compound C1=CC=CC2=NC(C=3C=C(C4=CC=CC=C4N=3)C(=O)O)=CC(C(O)=O)=C21 AFYNADDZULBEJA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000015556 catabolic process 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
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JQVXMIPNQMYRPE-UHFFFAOYSA-N ethyl dimethyl phosphate Chemical compound CCOP(=O)(OC)OC JQVXMIPNQMYRPE-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 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 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229930192419 itoside Natural products 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052763 palladium 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
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 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
- 229910052703 rhodium Inorganic materials 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 125000003652 trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
- H01M14/005—Photoelectrochemical storage cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Definitions
- Electrolyte for dye-sensitized solar cell oxide semiconductor electrode for dye-sensitized solar cell, and dye-sensitized solar cell
- the present invention relates to an electrolyte for a dye-sensitized solar cell, an oxide semiconductor electrode for a dye-sensitized solar cell, and a dye-sensitized solar cell provided with the electrolyte and a Z or oxide semiconductor electrode.
- the present invention relates to a battery, and more particularly to an electrolyte for a dye-sensitized solar cell and an oxide semiconductor electrode for a dye-sensitized solar cell in which the risk of ignition is suppressed.
- a solar cell generally used is a pn junction type solar cell using crystalline silicon or amorphous silicon as a photoelectric conversion material.
- a photoelectric conversion material such as crystalline silicon
- the production of a photoelectric conversion material requires a large amount of energy, so that the above-mentioned objects such as energy saving cannot be achieved.
- a large amount of energy is required for the production of the photoelectric conversion material, and as a result, the pn junction type solar cell must be expensive.
- a dye-sensitized solar cell using an oxide semiconductor sensitized with an organic dye without using silicon or the like as a photoelectric conversion material is known. Since the dye-sensitized solar cell can be made of an oxide semiconductor and an organic dye which are mass-produced and relatively inexpensive, they can be compared with the pn junction solar cell using silicon or the like in terms of raw materials. There are many advantages.
- the dye-sensitized solar cell for example, a zinc oxide powder is compression-molded and sintered at 1300 ° C. for 1 hour to form a disc-shaped sintered body on a surface of Rosebenga as an organic dye.
- a dye-sensitized solar cell using an oxide semiconductor electrode obtained by adsorbing a metal has been proposed (see Neychar, 268 (1976), p. 402).
- the solar cell has a very low current value at an electromotive voltage of 0.2 V in the current Z voltage curve of about 25 ⁇ , which is extremely low. It was far from I-Dai!
- an oxide semiconductor has a spectral sensitizing dye layer such as a transition metal complex on the surface thereof (see Japanese Patent Application Laid-Open No. 220380/1990), and a titanium oxide semiconductor layer doped with metal ions has a surface.
- a spectral sensitizing dye layer such as a transition metal complex
- a dye-sensitized solar cell using an oxide semiconductor film consisting of a sintered product of an aggregate of oxide semiconductor fine particles Batteries see Japanese Patent Application Laid-Open No. Hei 10-92477) are known, and the photoelectric conversion efficiency of these dye-sensitized solar cells is greatly improved.
- the dye-sensitized solar cell may be heated by sunlight during use under sunlight, and the electrolyte of the dye-sensitized solar cell is generally organic. Since an electrolytic solution containing a solvent and a redox electrolyte is used, at high temperatures, the organic solvent in the electrolytic solution is vaporized and decomposed to generate gas, and the generated gas causes the battery to ignite and ignite. There was a possibility. In addition, since the oxide semiconductor layer on which the organic dye is adsorbed is formed by impregnating the oxide semiconductor layer with the organic dye solution, the solvent in the organic dye solution is the same as the solvent in the electrolytic solution.
- the gas is generated by being vaporized and decomposed, or the generated gas may ignite or ignite the battery.
- the wettability between the oxide semiconductor layer and the electrolytic solution is not good, so that the interface resistance is large and the electron transfer is hindered. There was a point.
- an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide an electrolyte and an oxide semiconductor electrode for a dye-sensitized solar cell that can prevent ignition and ignition of the battery even at a high temperature. It is in.
- Another object of the present invention is to provide a highly safe dye-sensitized solar cell comprising a powerful dye-sensitized solar cell electrolyte and a Z or oxide semiconductor electrode. .
- the inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, by adding a phosphazene conjugate to an electrolyte for a dye-sensitized solar cell, ignition and ignition of the electrolyte were prevented.
- the ignition and ignition of the oxide semiconductor electrode can be prevented by adding the phosphazene conjugate to the organic dye solution impregnating the oxide semiconductor layer.
- the electrolyte solution for a dye-sensitized solar cell of the present invention is characterized by containing a phosphazene compound and a redox electrolyte.
- the phosphazene compound has the following formula (I):
- R 1 each independently represents a monovalent substituent or a halogen element
- Y 1 each independently represents a divalent linking group, a divalent element or a single bond
- X represents a substituent containing at least one element selected from the group consisting of carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium, and polonium.
- R 2 each independently represents a monovalent substituent or a halogen element; n represents 3-15).
- the content of the phosphazene compound is 0.1% by volume or more.
- the content of the phosphazene compound is more preferably 3 to 30% by volume.
- the phosphazene conjugate is represented by the formula (I), and the content of the phosphazene conjugate is represented by the following formula: % By volume or more.
- the electrolyte for a dye-sensitized solar cell of the present invention may contain an organic solvent in addition to the phosphazene conjugate and the redox electrolyte.
- the oxidized semiconductor electrode for a dye-sensitized solar cell of the present invention comprises a conductive substrate
- the oxide semiconductor layer has It is characterized by containing a phosphazene ligature.
- the phosphazene compound contained in the oxide semiconductor layer is represented by the formula (I) or the formula (II). ).
- the oxide semiconductor electrode for a dye-sensitized solar cell according to the present invention is characterized in that an organic dye solution containing the organic dye and the phosphazene compound is added to the oxide semiconductor layer provided on the conductive substrate. It is preferable that the organic dye is impregnated to be adsorbed on the oxide semiconductor layer.
- the organic dye solution may further contain an organic solvent.
- the content of the phosphazene conjugate in the organic color solution is preferably in the range of 3 to 30% by volume.
- the phosphazene compound is represented by the formula (I)
- the content of the phosphazene conjugate is preferably in the range of 3% by volume or more.
- the dye-sensitized solar cell of the present invention comprises a conductive substrate, an oxide semiconductor layer provided on the conductive substrate, and an organic dye adsorbed on the oxide semiconductor layer.
- a dye-sensitized solar cell including an oxide semiconductor electrode, a counter electrode, and an electrolyte, wherein the electrolyte is the above-described electrolyte for a dye-sensitized solar cell.
- Another dye-sensitized solar cell according to the present invention is an oxidization method comprising a conductive substrate, an oxide semiconductor layer provided on the conductive substrate, and an organic dye adsorbed on the oxide semiconductor layer.
- a dye-sensitized solar cell comprising a compound semiconductor electrode, a counter electrode, and an electrolytic solution, wherein the oxide semiconductor electrode is the oxide semiconductor electrode for the dye-sensitized solar cell. I do.
- a dye-sensitized solar cell provides an oxide semiconductor comprising a conductive substrate, an oxide semiconductor layer provided on the conductive substrate, and an organic dye adsorbed on the oxide semiconductor layer.
- the electrolyte is the dye-sensitized solar cell electrolyte
- the oxide semiconductor electrode is the dye-sensitized solar cell. It is preferably an oxide semiconductor electrode for a sensitive solar cell.
- a phosphazene conjugate is added to an electrolyte for a dye-sensitized solar cell.
- This can provide an electrolyte for a dye-sensitized solar cell in which the possibility of ignition or ignition is reduced.
- a phosphazene conjugate is added to an organic dye solution impregnated in an oxide semiconductor layer to provide an oxide semiconductor electrode with a reduced possibility of ignition and ignition. can do.
- a dye-sensitized solar cell electrolytes and Z or oxide semiconductor electrodes a dye-sensitized solar cell with greatly improved safety can be provided.
- FIG. 1 is a partial cross-sectional view of one embodiment of the dye-sensitized solar cell of the present invention.
- the electrolyte for a dye-sensitized solar cell of the present invention is characterized by containing a phosphazene compound and a redox electrolyte, and may further contain an organic solvent and the like.
- the electrolyte for a dye-sensitized solar cell according to the present invention even if the organic solvent in the electrolyte is vaporized and decomposed to generate gas at a high temperature, the electrolyte is derived from the phosphazene conjugate. The risk of ignition and ignition of organic solvents is reduced by the action of nitrogen gas.
- phosphorus which constitutes the phosphazene compound, has the effect of generating phosphate esters and the like to suppress the chain decomposition of the polymer material constituting the battery, thereby reducing the risk of ignition and ignition of the battery. It can be reduced in total.
- the phosphazene compound contains a halogen, the halogen functions as a scavenger for active radicals in the event of burning, further reducing the danger of burning the electrolytic solution.
- the phosphazene conjugate used in the electrolyte solution for a dye-sensitized solar cell of the present invention includes a chain phosphazene conjugate represented by the above formula (I) and a phosphazene conjugate of the above formula (II)
- the cyclic phosphazene compound to be used is preferably exemplified. Further, among the phosphazene conjugates represented by the formula (I) or (II), those which are liquid at 25 ° C (room temperature) are preferable.
- the viscosity of the liquid phosphazene compound at 25 ° C is preferably 300 mPa's (300 cP) or less, more preferably 20 mPa's (20 cP) or less, and particularly preferably 5 mPa's (5 cP) or less.
- the viscosity was measured using a viscometer [R type viscometer Model RE500-SL, manufactured by Toki Sangyo Co., Ltd.] By measuring at each rotation speed of 3rpm, 5rpm, 7rpm, 10rpm, 20rpm and 50rpm for 120 seconds, the rotation speed when the indicated value becomes 50-60% is used as the analysis condition, and the viscosity at that time is measured. I asked.
- the viscosity force of the phosphazene compound at 25 ° C exceeds 3 ⁇ 400 mPa's (300 cP), the ionic conductivity of the electrolytic solution will be significantly reduced, and the performance will be insufficient especially under low temperature conditions such as below the freezing point.
- R 1 in the formula (I) is not particularly limited as long as it is a monovalent substituent or a halogen element.
- Each R 1 may be the same or different.
- the monovalent substituent include an alkoxy group, an alkyl group, a carboxyl group, an acyl group, an aryl group, and the like. Among them, an alkoxy group is preferable because the phosphazene compound has a low viscosity.
- preferred examples of the halogen element include fluorine, chlorine, and bromine.
- alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like, and an alkoxy-substituted alkoxy group such as a methoxyethoxy group, a methoxyethoxyethoxy group, and the like.
- a methoxy group, an ethoxy group, A methoxy group and an ethoxy group are more preferred from the viewpoints of low viscosity and high dielectric constant, which are preferred by a methoxyethoxy group and a methoxyethoxy ethoxy group.
- Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group.
- Examples of the acetyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutylyl group and a valeryl group.
- the aryl group includes a phenyl group, a tolyl group, a naphthyl group and the like.
- the hydrogen element in these monovalent substituents is preferably substituted with a halogen element.
- the halogen element fluorine, chlorine and bromine are preferred, fluorine is most preferred, and chlorine is more preferred. .
- all of the substituents may be substituted with a halogen element. In this case, for example, by changing the ratio of the number of substituents such as fluorine and chlorine, the boiling point of the phosphazene conjugate
- Formula (I) is a divalent linking group, each Y 1 to Nag particularly limited as long as it is a bivalent element or a single bond may be identical or different.
- the divalent linking group in addition to the CH group, oxygen,
- a divalent linking group containing at least one element selected from the group consisting of sulfur, selenium, and nitrogen is preferable.
- a divalent linking group containing elements of sulfur and Z or selenium is preferable because the risk of ignition and ignition of the electrolyte is significantly reduced.
- X in the formula (I) is a group power consisting of carbon, silicon, genolemanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium, and polonium. There is no particular limitation as long as it is a substituent containing at least one of them. From the viewpoint of harmfulness, environment, etc., X in the formula (I) is preferably a substituent containing at least one element selected from the group consisting of carbon, silicon, nitrogen, phosphorus, oxygen and sulfur.
- R 4 and R 5 each independently represent a monovalent substituent or a rho or a logen element; ⁇ 3 , ⁇ 4 and ⁇ 5 each independently represent a divalent linking group, a divalent element or a single bond Represents a divalent group or a divalent element.] Is more preferable.
- Formula (III) of Y 3 as the Upsilon 4 and Upsilon 5 of formula (V) of the formula (IV), 2 divalent linking group similar to that described in Upsilon 1 of formula (I) or 2 Any of the valence elements is preferably exemplified. Similarly, a divalent linking group containing elements of sulfur and ⁇ or selenium is particularly preferable because the risk of ignition and ignition of the electrolyte is greatly reduced. Further, Upsilon 3, as the Upsilon 4 and Upsilon 5, a single bond is also preferred. Two ⁇ 3 of the formula (III) and two ⁇ 5 of the formula (V) may be the same or different.
- ⁇ is not particularly limited as long as it is a divalent group or a divalent element.
- the divalent group includes a CH group and a CHR group (where R is an alkyl group, an alkoxy group, a phenyl group, etc.).
- NR group oxygen, sulfur, selenium, boron, aluminum, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, genoleum, zirconium, lead, phosphorus Group consisting of, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten, iron, cobalt, and nickel.
- the divalent element includes oxygen, sulfur, selenium and the like. Among these, as the ⁇ in formula (III), CH, CHR, and NR groups, as well as oxygen, sulfur, and selenium group strength
- a divalent group containing at least one is preferred.
- a divalent group containing elements of sulfur and ⁇ or selenium is preferable because the risk of ignition and ignition of the electrolyte is greatly reduced.
- a phosphorus-containing substituent represented by the formula (III) is particularly preferable in that the risk of ignition and ignition can be particularly effectively reduced. Further, when the substituent is a substituent containing sulfur as represented by the formula (IV), it is particularly preferable in terms of small interface resistance of the electrolytic solution.
- R 2 in the formula (II) is not particularly limited as long as it is a monovalent substituent or a halogen element.
- the monovalent substituent include an alkoxy group, an alkyl group, a carboxyl group, an acyl group, an aryl group and the like.
- the phosphazene conjugate has a low viscosity.
- Alkoxy groups are preferred.
- preferred examples of the halogen element include fluorine, chlorine, and bromine, and among them, fluorine is particularly preferred.
- the alkoxy group include a methoxy group, an ethoxy group, a methoxyethoxy group, a propoxy group, and a phenoxy group.
- a methoxy group, an ethoxy group, a methoxyethoxy group and a phenoxy group are particularly preferred.
- the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.
- the acetyl group include a formyl group, an acetyl group, a propioyl group, a butyryl group, and an isobutyryl group.
- the araryl group include a phenyl group, a tolyl group, and a naphthyl group.
- the hydrogen element in these monovalent substituents is preferably substituted with a halogen element.
- Preferred halogen elements include fluorine, chlorine, bromine and the like, and the substituent substituted with a fluorine atom is preferred. Examples thereof include a trifluoroethoxy group.
- R 1 — R 5 in the formula (I) and the formula (V) By appropriately selecting ⁇ 3 ⁇ 5 and ⁇ , a phosphazene compound having more suitable viscosity, solubility suitable for addition and mixing, and the like can be obtained. These phosphazene conjugates may be used alone or in combination of two or more.
- the content of the phosphazene conjugate in the electrolyte for a dye-sensitized solar cell is more preferably 0.1% by volume or more, and further preferably 3 to 30% by volume.
- the content of the phosphazene compound in the electrolytic solution is 0.1% by volume or more, wettability between the oxide semiconductor layer and the electrolytic solution is improved. Further, by setting the content of the phosphazene compound in the electrolytic solution to 3% by volume or more, the possibility of ignition or ignition of the electrolytic solution can be sufficiently reduced.
- the content of the phosphazene compound in the electrolyte is preferably 3 vol% or more. It is also preferred that only the phosphazene conjugate of formula (I) and the redox electrolyte also constitute power.
- the redox electrolyte used in the electrolyte for a dye-sensitized solar cell of the present invention includes 1/1 / 1-
- the quality can be obtained by known methods, for example, a 1 / 1-based redox electrolyte
- Ammonium salt or imidazoline salt of metal or metal such as Lil, Nal, KI, Cal
- Degradation can be prepared by using a bromide ammonium salt or imidazolym salt or a metal bromide such as LiBr, NaBr, KBr, or CaBr alone or by mixing with bromine.
- dox electrolytes ⁇ / ⁇ —-based redox electrolytes are preferred.
- the concentration of the redox electrolyte in the electrolyte for solar cells is preferably in the range of 0.1 to 2 mol / L ( ⁇ ). More preferably, the range of 0.5-1.5mol / L is even more preferred! /.
- the electrolyte for a dye-sensitized solar cell of the present invention may contain an organic solvent in addition to the phosphazene conjugate and the redox electrolyte.
- organic solvent include carbonates such as propylene carbonate, ethylene carbonate, dimethinolecarbonate, methinoolethinolecarbonate, and diethyl carbonate; esters such as methyl acetate and methyl propionate; tetrahydrofuran; Ethers such as dioxolane and 1,2-dimethoxyethane, alcohols such as methanol, ethanol, ethylene glycolone , propylene glycol and glycerin; ratatones such as ⁇ -butyrate rataton; amides such as dimethylformamide; 3 -Oxazolidinones such as methyl-2-oxazolidinone, phosphates such as trimethyl phosphate, triethyl phosphate, ethyl dimethyl
- An oxide semiconductor electrode for a dye-sensitized solar cell according to the present invention includes a conductive substrate, an oxide semiconductor layer provided on the conductive substrate, and an organic dye adsorbed on the oxide semiconductor layer. Wherein the oxide semiconductor layer further contains a phosphazene conjugate.
- An oxide semiconductor electrode for a dye-sensitized solar cell is formed, for example, by applying an organic dye solution containing an organic dye, a phosphazene conjugate, and an organic solvent to an oxide semiconductor layer provided on a conductive substrate. It is manufactured by impregnating and adsorbing an organic dye to the oxide semiconductor layer.
- the organic dye solution contains an organic solvent.
- the organic solvent is vaporized and decomposed to generate gas, and the generated gas may cause a battery to ignite or catch fire.
- the oxide semiconductor electrode for a dye-sensitized solar cell of the present invention the organic solvent used for the adsorption of the organic dye to the oxide semiconductor layer is decomposed at high temperatures to generate gas at high temperatures. Nevertheless, the danger of ignition and ignition of the organic solvent is reduced by the action of nitrogen gas and phosphate ester derived from the phosphazene compound present in the oxide semiconductor layer.
- the phosphazene conjugate contained in the oxide semiconductor layer is a phosphazene used in the above-described electrolyte for a dye-sensitized solar cell. It is the same as the conjugated product, and likewise preferably includes a chain phosphazene conjugated product represented by the formula (I) and a cyclic phosphazene conjugated product represented by the formula (II). Further, among the phosphazene compounds represented by the formula (I) or (II), those which are liquid at 25 ° C. (room temperature) are preferable.
- the viscosity of the liquid phosphazene compound at 25 ° C is preferably 300 mPa's (300 cP) or less, more preferably 20 mPa's (20 cP) or less, and particularly preferably 5 mPa's (5 cP) or less.
- the chain phosphazene compound represented by the formula (I) and the cyclic phosphazene conjugate represented by the formula (II) are the same as described in the section of the electrolytic solution.
- the phosphazene conjugate is suitable for adding to an organic dye solution.
- the conductive substrate used for the dye-sensitized solar cell oxide semiconductor electrode of the present invention has a conductive oxide layer formed on a transparent substrate having no conductivity, which is preferably transparent. It is preferable to be provided.
- the conductive oxide ITO, SnO, fluorine-doped SnO (
- FTO FTO
- transparent substrate 22 Generally called FTO
- transparent plastic plastic
- the material of the oxide semiconductor layer used in the oxide semiconductor electrode for a dye-sensitized solar cell of the present invention conventionally known materials can be used, and specifically, Ti, Sn Oxides of transition metals such as, Nb, Zn, In and perovskite oxides such as SrTiO
- TiO is particularly preferred.
- the oxide semiconductor is preferably fine particles.
- the average particle size is 5 ⁇ m or less, more preferably, 50 nm or less, more preferably, the specific surface area is 5 m 2 / g or more, preferably 5 m 2 / g or more. More preferred.
- the thickness of the oxide semiconductor layer is preferably in the range of 1 ⁇ m to 1 mm.
- organic dye used for the dye-sensitized solar cell oxide semiconductor electrode of the present invention conventionally known organic dyes can be used, and those capable of absorbing sunlight over a wide wavelength range are preferable.
- organic dye include Ru complexes such as biviridyl Ru complex, terpyridyl Ru complex, phenanthroline Ru complex, bicinchoninic acid Ru complex, chlorophyll, rhodamine, Olysin, phloxine, fluorescein, erythroxin, peranin, rose bengal and the like. These organic dyes may be used alone or in a combination of two or more.
- the organic dye solution used for producing the oxide semiconductor electrode for a dye-sensitized solar cell of the present invention contains at least the phosphazene conjugate and the organic dye, and may further contain an organic solvent.
- organic solvent examples include alcohols such as methanol and ethanol, -tolyls such as acetonitrile, amides such as dimethylformamide, and ethers such as dioxane. . These organic solvents may be used alone or as a mixture of two or more.
- the content of the phosphazene conjugate in the organic dye solution is preferably in the range of 3 to 30% by volume.
- the content of the phosphazene compound in the organic dye solution is preferably 3% by volume or more. It is also preferable that the organic dye solution is composed of only the phosphazene compound of the formula (I) and the organic dye.
- the concentration of the organic dye in the organic dye solution is more preferably 10 to 500 mg, preferably 11 to 100 mg of the organic dye, in 100 mL of the organic dye solution.
- a dye-sensitized solar cell according to the present invention includes a conductive substrate, an oxide semiconductor layer provided on the conductive substrate, and an oxide semiconductor electrode including an organic dye adsorbed on the oxide semiconductor layer. , A counter electrode, and an electrolytic solution, wherein at least the electrolytic solution for the dye-sensitized solar cell of the present invention described above is used as the electrolytic solution, or the dye-sensitized type of the present invention described above is used for the oxide semiconductor electrode.
- An oxide semiconductor for a solar cell is characterized in that a semiconductor electrode is used, and the dye-sensitized solar cell electrolyte of the present invention described above is used as an electrolytic solution, and an acid semiconductor of the present invention described above is used as an acid semiconductor electrode. It is preferable to use an oxide semiconductor electrode for a dye-sensitized solar cell.
- an oxide semiconductor electrode for a dye-sensitized solar cell since the above-described electrolyte for dye-sensitized solar cell and Z or an oxide semiconductor electrode for dye-sensitized solar cell are used, even at high temperature, The risk of ignition and ignition of the electrolyte and the organic solvent contained in the Z or oxide semiconductor layer is suppressed.
- oxide semiconductor electrode for a dye-sensitized solar cell of the present invention in the dye-sensitized solar cell of the present invention.
- a known oxide semiconductor electrode may be used as the oxide semiconductor electrode.
- the counter electrode used in the dye-sensitized solar cell of the present invention has a conductive oxide layer provided on a transparent substrate having no conductivity, and a redox electrolyte provided on the conductive oxide layer. It is preferable that a catalyst for promoting a reduction reaction of ions therein is arranged.
- the conductive oxide is preferably ITO, SnO, or the like.
- a material for transparent substrates that do not have conductivity As a material for transparent substrates that do not have conductivity,
- examples thereof include glass and transparent plastic.
- examples of the catalyst that promotes the reduction reaction of ions in the redox electrolyte include Pt, Ru, Rh, Pd and the like, and among them, Pt is preferable. These catalysts can be formed on the conductive oxide layer by sputtering or the like. Further, after the catalyst is attached by sputtering, an aqueous solution of chloroplatinic acid or the like may be further applied and calcined and reduced.
- the dye-sensitized solar cell of the present invention it is preferable to use the above-described electrolyte solution for a dye-sensitized solar cell of the present invention.
- a known electrolytic solution may be used as the electrolytic solution.
- FIG. 1 is a partial cross-sectional view of one embodiment of the dye-sensitized solar cell of the present invention.
- conductive oxide layers 2A and 2B are disposed on transparent substrates 1A and 1B, respectively.
- a catalyst 3 that promotes a reduction reaction of ions in the redox electrolyte is disposed on the conductive oxide layer 2A.
- the oxide semiconductor layer 4 is disposed on the conductive oxide layer 2B, and the organic dye is adsorbed on the oxide semiconductor layer 4.
- an opposing electrode 5 composed of the transparent substrate 1A, the conductive oxide layer 2A and the catalyst 3, and an oxide semiconductor electrode 6 composed of the transparent substrate 1B, the conductive oxide layer 2B and the oxide semiconductor layer 4,
- the catalyst 3 of the counter electrode 5 and the oxide semiconductor layer 4 of the oxide semiconductor electrode 6 are in contact with each other with the electrolyte 7 interposed therebetween.
- the phosphoric acid is contained in the oxide semiconductor layer 4 and Z or the electrolyte 7. Battery ignition, bow I fire danger reduced due to the inclusion of zen compounds! RU
- n 3 a cyclic phosphazene compound in which one of six R 2 , one is an ethoxy group and five is fluorine, viscosity at 25 ° C .: l. lcP, boiling point: 125. C] in a mixture consisting of 10 volume 0/0, Ru (2,2, - Bibirijiru 4,4 '- dicarboxylate) (NCS) was dissolved to be 3 X 10- 4 M complexes, Organic dye solution
- a liquid was prepared.
- the safety of the obtained organic dye solution was evaluated by the following method.
- the safety of the organic dye solution was evaluated based on the combustion behavior of a flame ignited in an atmospheric environment, using a method adapted from UL (Underwriting Laboratory) standard UL94HB method. At that time, ignitability, flammability, formation of carbides, and phenomena during secondary ignition were also observed. Specifically, based on the UL test standard, a non-combustible quartz fiber was impregnated with l.OmL of the above organic dye solution to prepare a 127 mm ⁇ 12.7 mm test piece.
- the case where the test flame does not ignite the test piece is “non-flammable”, and the case where the ignited flame does not reach the 25 mm line and no ignition is found on the falling object is “ Flame-retardant, self-extinguishing when the ignited flame is extinguished on the 25-100mm line and no ignition is found on falling objects, and flammable when the ignited flame exceeds the 100mm line. evaluated.
- TiO colloid solution TiO: 11% by mass
- tin oxide was applied to a glass substrate, and platinum was adhered to the surface of the tin oxide layer by a sputtering method without heating under an Ar atmosphere to produce a counter electrode.
- the oxide semiconductor electrode and the counter electrode were opposed to each other via a 25 m thick spacer film whose center was cut off in a square shape, and fixed in two places with clips to produce a dye-sensitized solar cell.
- the cell characteristics of the obtained dye-sensitized solar cell were measured by the following method. The results are shown in Table 1.
- AM1.5 Simulated sunlight (AM1.5, 198 mW / cm 2 ) was irradiated, and short-circuit photocurrent, photovoltage, form factor (fill factor), and conversion efficiency were measured.
- AM Air mass
- AMI.0 means light incident from directly above (incident angle of 90 degrees)
- AMI.5 means the amount of passing light Means light reaching 1.5 times (incident angle 41.8 degrees).
- phosphazene B is replaced with phosphazene B (in the formula (II), n is 3, a cyclic phosphazene compound in which two out of six R 2 are ethoxy groups and four are fluorine) , Viscosity at 25 ° C: 1.3 cP, boiling point: 194 ° C], phosphazene C [In the formula (II), n is 3, one of six R 2 is a phenoxy group, and five are fluorine.
- phosphazene D [In the formula (II), n is 3 and one of six R 2 is a propoxy group.
- oxide semiconductor was produced in the same manner as in Example 1. Further, a counter electrode was produced in the same manner as in Example 1. Furthermore, Asetonitoriru 45 volume 0/0, 3-methyl-2-Okisazorijinon 45 vol 0/0, and phosphazene A 10 vol% force becomes mixed solution, 30 mM iodine (mmol / L), potassium iodide 0.3 M (mol / L) to prepare an electrolytic solution.
- a dye-sensitized solar cell was produced in the same manner as in Example 7, except that phosphazene A was used instead of phosphazene A, phosphazene 0, phosphazene E, and phosphazene F in the preparation of the electrolyte solution.
- Table 2 shows the safety of the electrolyte used and the battery characteristics of the battery obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004-124307 | 2004-04-20 | ||
JP2004124307A JP2005310481A (ja) | 2004-04-20 | 2004-04-20 | 色素増感型太陽電池用電解液、色素増感型太陽電池用酸化物半導体電極及び色素増感型太陽電池 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005104291A1 true WO2005104291A1 (ja) | 2005-11-03 |
Family
ID=35197303
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/004993 WO2005104291A1 (ja) | 2004-04-20 | 2005-03-18 | 色素増感型太陽電池用電解液、色素増感型太陽電池用酸化物半導体電極及び色素増感型太陽電池 |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP2005310481A (ja) |
WO (1) | WO2005104291A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2432966A (en) * | 2005-11-25 | 2007-06-06 | Seiko Epson Corp | Dye-sensitised electrochemical cell |
JP2012243436A (ja) * | 2011-05-17 | 2012-12-10 | Sony Corp | 光電変換素子およびその製造方法ならびに電子機器 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000173619A (ja) * | 1998-09-29 | 2000-06-23 | Sanyo Electric Co Ltd | リチウムイオン電池 |
JP2000277182A (ja) * | 1999-03-29 | 2000-10-06 | Sanyo Chem Ind Ltd | 色素増感型太陽電池用非水電解液およびそれを用いた太陽電池 |
WO2002021630A1 (fr) * | 2000-09-07 | 2002-03-14 | Bridgestone Corporation | Additif pour batterie secondaire à électrolyte non aqueux |
JP2002075442A (ja) * | 2000-08-29 | 2002-03-15 | Fuji Photo Film Co Ltd | 電解質組成物及びそれを用いた電気化学電池 |
WO2002082575A1 (fr) * | 2001-03-30 | 2002-10-17 | Bridgestone Corporation | Additif pour pile et condensateur electrique double couche |
JP2003272643A (ja) * | 2002-03-20 | 2003-09-26 | Bridgestone Corp | リチウム1次電池 |
-
2004
- 2004-04-20 JP JP2004124307A patent/JP2005310481A/ja not_active Withdrawn
-
2005
- 2005-03-18 WO PCT/JP2005/004993 patent/WO2005104291A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000173619A (ja) * | 1998-09-29 | 2000-06-23 | Sanyo Electric Co Ltd | リチウムイオン電池 |
JP2000277182A (ja) * | 1999-03-29 | 2000-10-06 | Sanyo Chem Ind Ltd | 色素増感型太陽電池用非水電解液およびそれを用いた太陽電池 |
JP2002075442A (ja) * | 2000-08-29 | 2002-03-15 | Fuji Photo Film Co Ltd | 電解質組成物及びそれを用いた電気化学電池 |
WO2002021630A1 (fr) * | 2000-09-07 | 2002-03-14 | Bridgestone Corporation | Additif pour batterie secondaire à électrolyte non aqueux |
WO2002082575A1 (fr) * | 2001-03-30 | 2002-10-17 | Bridgestone Corporation | Additif pour pile et condensateur electrique double couche |
JP2003272643A (ja) * | 2002-03-20 | 2003-09-26 | Bridgestone Corp | リチウム1次電池 |
Also Published As
Publication number | Publication date |
---|---|
JP2005310481A (ja) | 2005-11-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10366842B2 (en) | Dye-sensitized solar cell and method for manufacturing thereof | |
JP4470370B2 (ja) | 光電変換素子の製造方法 | |
EP2296216B1 (en) | Dye-sensitized solar cell, method for manufacturing dye-sensitized solar cell, and dye-sensitized solar cell module | |
JP4674435B2 (ja) | 光電変換素子 | |
US20080210296A1 (en) | Dye-Sensitized Photovoltaic Device, Method for Making the Same, Electronic Device, Method for Making the Same, and Electronic Apparatus | |
JP2007311336A (ja) | リン酸塩を含有する半導体電極及びこれを採用した太陽電池 | |
JP5261068B2 (ja) | 光電変換素子用電解質組成物及びそれを用いた光電変換素子 | |
JP2012036237A (ja) | 金属錯体色素、光電変換素子及び光電気化学電池 | |
JP2004234988A (ja) | 光電変換素子およびその製造方法ならびに電子装置およびその製造方法ならびに半導体層およびその製造方法 | |
TWI449236B (zh) | 膠態電解液、其製法及其染料敏化太陽能電池 | |
JP3462115B2 (ja) | 色素増感型太陽電池用非水電解液およびそれを用いた太陽電池 | |
JP4716636B2 (ja) | 複合半導体 | |
KR20100115629A (ko) | 극소수성 화합물이 도입된 금속산화물 반도체 전극. 이를 포함하는 염료감응 태양전지 및 그 제조 방법 | |
WO2005104291A1 (ja) | 色素増感型太陽電池用電解液、色素増感型太陽電池用酸化物半導体電極及び色素増感型太陽電池 | |
JP2007188809A (ja) | ゲル電解質、光電変換素子及び太陽電池 | |
JP2005310482A (ja) | 色素増感型太陽電池用ポリマー電解質及びそれを用いた色素増感型太陽電池 | |
JP5770115B2 (ja) | 光電変換素子および色素増感太陽電池 | |
JP5566681B2 (ja) | 光電変換素子用電解質組成物及び光電変換素子 | |
JP2016207919A (ja) | 共吸着剤ならびにこの共吸着剤を用いた光電変換素子用光電極、光電変換素子および色素増感太陽電池 | |
JP5332114B2 (ja) | 光電変換素子及び太陽電池 | |
JP2004103374A (ja) | 光電変換素子 | |
KR101465454B1 (ko) | 염료감응 태양전지용 유기염료 및 이를 포함하는 염료감응 태양전지 | |
JP2007200833A (ja) | 色素増感型太陽電池用電解液、色素増感型太陽電池用酸化物半導体電極及び色素増感型太陽電池 | |
JP2011150883A (ja) | 光電変換素子、光センサ、および、太陽電池 | |
JP2012036239A (ja) | 金属錯体色素、光電変換素子及び光電気化学電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: DE |
|
122 | Ep: pct application non-entry in european phase |