JP4538955B2 - Photoelectric conversion device using ether compound electrolyte - Google Patents
Photoelectric conversion device using ether compound electrolyte Download PDFInfo
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- JP4538955B2 JP4538955B2 JP2000604485A JP2000604485A JP4538955B2 JP 4538955 B2 JP4538955 B2 JP 4538955B2 JP 2000604485 A JP2000604485 A JP 2000604485A JP 2000604485 A JP2000604485 A JP 2000604485A JP 4538955 B2 JP4538955 B2 JP 4538955B2
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- photoelectric conversion
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- conversion element
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- -1 ether compound Chemical class 0.000 title claims description 46
- 238000006243 chemical reaction Methods 0.000 title claims description 39
- 239000003792 electrolyte Substances 0.000 title claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 150000002497 iodine compounds Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 22
- 239000004065 semiconductor Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000975 dye Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- HQOKJWBWTJVHNJ-UHFFFAOYSA-N 1,3-bis[2-(2-methoxyethoxy)ethoxy]propan-2-ol Chemical compound COCCOCCOCC(O)COCCOCCOC HQOKJWBWTJVHNJ-UHFFFAOYSA-N 0.000 description 2
- XTIGGAHUZJWQMD-UHFFFAOYSA-N 1-chloro-2-methoxyethane Chemical compound COCCCl XTIGGAHUZJWQMD-UHFFFAOYSA-N 0.000 description 2
- ZZTDEFHCSZAWMD-UHFFFAOYSA-L 2-(4-carboxylatopyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+) Chemical compound [Ru+2].[O-]C(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 ZZTDEFHCSZAWMD-UHFFFAOYSA-L 0.000 description 2
- GWOGSJALVLHACY-UHFFFAOYSA-N 2-pyridin-2-ylpyridine;ruthenium Chemical class [Ru].N1=CC=CC=C1C1=CC=CC=N1 GWOGSJALVLHACY-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- SWJBITNFDYHWBU-UHFFFAOYSA-N [I].[I] Chemical compound [I].[I] SWJBITNFDYHWBU-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PJSOCBVWZJGTHW-UHFFFAOYSA-N n-(1h-indazol-5-yl)-5-[3-methoxy-4-[2-(2-methoxyethoxy)ethoxy]phenyl]-1,3-oxazol-2-amine Chemical compound C1=C(OC)C(OCCOCCOC)=CC=C1C(O1)=CN=C1NC1=CC=C(NN=C2)C2=C1 PJSOCBVWZJGTHW-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- UJPGTXMINFGYFB-UHFFFAOYSA-N 1,3-bis(2-methoxyethoxy)propan-2-ol Chemical compound COCCOCC(O)COCCOC UJPGTXMINFGYFB-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- DQBPICZFQWJEKL-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxymethyl]oxirane Chemical compound COCCOCCOCC1CO1 DQBPICZFQWJEKL-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DKNPRRRKHAEUMW-UHFFFAOYSA-N Iodine aqueous Chemical compound [K+].I[I-]I DKNPRRRKHAEUMW-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 1
- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Description
発明の分野
本発明は、高イオン伝導性を有するエーテル化合物の電解質を用いた光電変換素子に関する。
関連技術
従来、電気化学的な各種デバイスに有機溶剤のイオン伝導体が注目されている。特に太陽電池用に使われる光電変換素子用のイオン伝導体として、炭酸エステルやテトラヒドロフランなどの有機溶剤にヨウ素とヨウ化カリウムを添加した電解質などが提案されている。しかし、これらの電解液は蒸気圧が高く、光電変換素子の耐久性の阻害になっており、特に太陽電池分野では１０年以上の耐久性が必要であり、イオン伝導性、安全性およびシール安定性の優れた電解質が望まれている。
発明の要旨
本発明者らは、エーテル化合物（Ｉ）、（ＩＩ）、（ＩＩＩ）または（ＩＶ）：（Ａ）に、ヨウ素とヨウ素化合物の組み合わせあるいは臭素と臭素化合物の組み合わせからなる酸化還元対（Ｂ）を添加することにより所望の電解質が得られ、更にこの電解質は、太陽電池などの光電変換素子に応用するために有用であることを見出して本発明を完成した。すなわち、本発明は、充分なイオン伝導性と優れた安定性を有する電解質を用いることにより、長期安定性に優れた光電変換素子を提供する。
本発明者らは、エーテル化合物（Ｉ）、（ＩＩ）、（ＩＩＩ）または（ＩＶ）：（Ａ）に、ヨウ素とヨウ素化合物の組み合わせあるいは臭素と臭素化合物の組み合わせからなる酸化還元対（Ｂ）を添加することにより所望の電解質が得られ、更にこの電解質は、太陽電池などの光電変換素子に応用するために有用であることを見出して本発明を完成した。すなわち、本発明は、充分なイオン伝導性と優れた安定性を有する電解質を用いることにより、長期安定性に優れた光電変換素子を提供する。
本発明は、
（Ａ）式（Ｉ）、（ＩＩ）、（ＩＩＩ）または（ＩＶ）：
で示されるエーテル化合物、ならびに
（Ｂ）ヨウ素とヨウ素化合物の組み合わせまたは臭素と臭素化合物の組み合わせからなる酸化還元対
を含んでなる電解質を用いた光電変換素子を提供する。
発明の詳細な説明
式（Ｉ）、（ＩＩ）、（ＩＩＩ）および（ＩＶ）において、Ａ１の例は、メチル基、エチル基、プロピル基、エテニル基（ＣＨ２＝ＣＨ−）などである。
エーテル化合物におけるエチレンオキシド単位（−ＣＨ２ＣＨ２Ｏ−）の総数は、１〜２０、例えば、３〜１２であってよい。Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５は、同様または異なっていてよい。
式（Ｉ）の構造式が式（Ｉ−１）で表されるエーテル化合物の合成法は次のとおりである。
式（Ｉ−１）において、ｌ＋ｍ＋ｎの合計は、好ましくは２以上、更に好ましくは３以上である。
（Ｓｔｅｐ１）
（ａ）式のグリシジルエーテルに対し、３倍モル量の（ｂ）式のアルコールと１．１倍モル量のペレット状のＮａＯＨをフラスコに入れて攪拌し、７０℃でグリシジルエーテル（ａ）を滴下する。滴下終了後、約１時間攪拌した後、ＨＣｌ水溶液で反応液を中和する。ろ過、濃縮後、蒸留により中間体の（ｄ）式のアルコールを得る。
次に、中間体アルコール（ｄ）式と、その１．５倍モル量のペレット状のＮａＯＨをフラスコに入れ攪拌し、６０℃で、中間体アルコールの１．５倍モル量の（ｃ）式の化合物を滴下する。滴下終了後、約２時間攪拌し、ろ過後、精製し、（Ｉ−１）式の化合物を得る。
式（ＩＩＩ）の構造式が式（ＩＩＩ−１）で表されるエーテル化合物の合成法は次のとおりである。
上記式（ＩＩＩ−１）において、ｏ＋ｐ＋ｑ＋ｒ＋ｓの合計は、好ましくは２以上、更に好ましくは３以上、例えば４以上である。
（Ｉ−１）式の合成法のＳｔｅｐ１と同様の方法で、（ｅ）、（ｆ）式のアルコールを合成する。
Ｃｌ−（−ＣＨ２−ＣＨ２−Ｏ−）ｓ−１−ＣＨ２−ＣＨ２−Ｃｌ （ｇ）
滴下終了後、約２時間攪拌し、ろ過後、精製し、（ＩＩＩ−１）式の化合物を得る。
式（ＩＶ）の構造式が式（ＩＶ−１）で表されるエーテル化合物の合成法は次のとおりである。
上記式（ＩＶ−１）において、ｔ＋ｕ＋ｖ＋ｗの合計は、好ましくは２以上、更に好ましくは３以上、例えば４以上である。
（Ｓｔｅｐ１）
（Ｉ−１）式の合成法のＳｔｅｐ１と同様の方法で、（ｈ）式のアルコールを合成する。
グリシジルエーテル（ｉ）に対し、２倍モル量の（ｊ）式のアルコールと１．１倍モル量のペレット状のＮａＯＨをフラスコに入れ攪拌し、７０℃でグリシジルエーテル（ｉ）を滴下する。
滴下終了後、約１時間攪拌した後、ＨＣｌ水溶液で反応液を中和する。ろ過、濃縮後、蒸留により、中間体アルコール（ｋ）を得る。
次に、中間体アルコール（ｋ）と、その１．５倍モル量のペレット状のＮａＯＨをフラスコに入れ、攪拌し、６０℃で中間体アルコール（ｋ）の１．５倍モル量の（ｌ）式の化合物を滴下する。滴下終了後、約２時間攪拌し、ろ過後、精製し、（ＩＶ−１）式の化合物を得る。
Ｃｌ−（−ＣＨ２−ＣＨ２−Ｏ−）ｖ−Ｒ２６ （ｌ）
式（ＩＩ）のエーテル化合物も上記と同様の操作により、得ることができる。 本発明でいう酸化還元対（Ｂ）とは、可逆的酸化還元反応を行う一対の化合物で、酸化体・還元体を独立に系内に添加したとき、速やかに電気化学的平衡に達するような物質を意味する。酸化還元対は、ヨウ素−ヨウ素化合物の組み合わせまたは臭素−臭素化合物の組み合わせである。
ヨウ素−ヨウ素化合物の組み合わせの酸化還元対は、例えばＩ２とＬｉＩ、ＮａＩ、ＫＩ、ＣｓＩ、ＣａＩ２等の金属ヨウ化物の組み合わせ、またはＩ２とアルキルアンモニウムヨーダイド、ピリジニウムヨーダイドなど４級アンモニウム化合物のヨウ素塩もしくはそれらを側鎖に持つ高分子化合物等の組み合わせにより構成されることが好ましい。
臭素−臭素化合物の組み合わせの酸化還元対は、例えばＢｒ２とＬｉＢｒ、ＮａＢｒ、ＫＢｒ、ＣｓＢｒ、ＣａＢｒ２等の金属臭化物、あるいは、Ｂｒ２とアルキルアンモニウムブロマイド、ピリジニウムブロマイドなどの４級アンモニウム化合物の臭素塩またはそれらを側鎖に持つ高分子化合物等の組み合わせにより構成されることが好ましい。
酸化還元対の混合割合は、混合するエーテル化合物と任意に選択することが出来る。一般に酸化還元対の混合量が多いほど高いイオン伝導度を示す電解質を得ることが出来る。しかし、混合量が多すぎると、イオンの解離が起こりにくくなり、伝導度が低下してくる。また、酸化還元対の平衡電位が問題になる場合は、必要な平衡電位が得られるよう混合量を調整することができる。
本発明において、上記酸化還元対の使用量は、エーテル化合物１００重量部に対して１〜５０重量部、例えば５〜３５重量部であってよい。
酸化還元対におけるヨウ素：ヨウ素化合物（および臭素：臭素化合物）のモル比は、１：５〜５：１が好ましい。
本発明の電解質の製造方法は特に制約はないが、通常、エーテル化合物（Ａ）、酸化還元対（Ｂ）が混合できればよい。
酸化還元対（Ｂ）をエーテル化合物（Ａ）に混合する方法は特に制約されないが、酸化還元対（Ｂ）を直接、エーテル化合物（Ａ）に混合させる方法、酸化還元対（Ｂ）を含む有機溶媒にエーテル化合物（Ａ）を混合させる方法などがある。粘性の高いあるいは固体状のエーテル化合物の場合は、有機溶媒（例えば、アセトニトリル）を用いて電解質製造の後に有機溶媒を除去する。
本発明において光電変換素子とは、電極間の電気化学反応を利用して、光エネルギーを電気エネルギーに変換する素子である。この光電変換素子に光を照射すると、一方の電極で電子が発生し、電極間に設けられた電線を通って対電極に移動する。対電極に移動した電子は、本発明のエーテル化合物よりなる電解質中の酸化還元対を還元する。還元された酸化還元対は、エーテル化合物よりなる電解質中を陰イオンとして一方の電極から他方の電極へ移動して、他方の電極に達し自らは酸化体に戻ることで、電子を他方の電極に戻す。このようにして、本発明の光電変換素子は、光エネルギーを電気エネルギーに変換できる素子またはセンサーである。又、光に応答するところから光センサーとしての機能も有する。
光電変換素子は、エーテル化合物の電解質および一対（２つ）の電極を有してなる。
電極としては、ガラス板（光を透過する透明の保護材）に付着された導電体が挙げられる。電極を有するガラス板は、導電性材料（例えば、金属、酸化物半導体、特にインジウム−錫酸化物（ＩＴＯ）をコーティングしたガラス板であってよい。
透明電極に酸化チタン、酸化亜鉛、酸化タングステン、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カリウム、タンタル酸カリウム、酸化タングステン、酸化鉄などの酸化物半導体、硫化カドミウム、ＣｄＴｅ、ケイ素、フタロシアニン、ポリチエニレン、ポリピロール、ポリアニリンなどの半導体、または、前記の酸化物半導体や半導体を色素や他の無機物で増感したものなどを一層または二層以上担持させると、より好ましい光電変換素子が得られる。すなわち、本発明の光電変換素子は、エーテル化合物よりなる電解質、半導体（例えば、ｎ型半導体またはｐ型半導体）を含んでなる１つの電極、半導体（例えば、ｐ型半導体またはｎ型半導体）または金属である１つの対電極を有してなってよい。
電極に担持する半導体としては、酸化物半導体が好ましく、特に、酸化チタンまたは色素で増感した酸化チタンが、安定性、安全性、価格の点から好ましい。色素としては、有機金属錯体、例えばルテニウム−ビピリジン錯体、特にシス−ジ（チオシアナト）−Ｎ，Ｎ’−ビス（２，２’−ビピリジル−４，４’−ジカルボン酸）ルテニウム（ＩＩ）（ｃｉｓ−ｄｉ（ｔｈｉｏｃｙａｎａｔｏ）−Ｎ，Ｎ’−ｂｉｓ（２，２’−ｂｉｐｙｒｉｄｙｌ−４，４’−ｄｉｃａｒｂｏｘｙｌｉｃ ａｃｉｄ）ｒｕｔｈｅｎｉｕｍ（ＩＩ））を用いることができる。
電解質を電極上に設けるには、電解質を直接電極に含浸あるいは不織布に含浸する方法などを採用することが出来る。もしくは、電極間にスペーサーを設けても良い。このようにして電解質を電極上に設けた後、電解質上に対電極を設けて、本発明の光電変換素子を得ることが出来る。
光電変換素子に本発明のエーテル化合物の電解質を用いると、優れたイオン伝導性を有しかつ優れた安定性を有するものであるため、良好な変換効率を有する光電変換素子を得ることが出来る。
本発明の光電変換素子は、太陽電池、光センサー等として使用できる。
図１は、実施例４で得られた光電変換素子の断面図である。光電変換素子は、ガラス板１および６、電極２および５、半導体層３およびエーテル化合物の電解質層４を有する。
透明のガラス板１および６は、光電変換素子を保護し、かつ光を透過する。ガラス板１および６の厚さは０．１〜５ｍｍであって良い。電極２は、透明なＩＴＯ（インジウム−錫酸化物）であって良い。電極２の厚さは、２〜１００μｍであって良い。層３は、多孔質ＴｉＯ２からなり、光からホールと電子を発光させる。電解質層４は、エーテル化合物と電解質化合物から成り、イオンのキャリア層として機能する。電解質層４の厚さは５〜１０００μｍであって良い。電極５は、金属（例えば、金および白金）からできている事が好ましい。電極５の厚さは、２〜１００μｍであって良い。
光電変換素子の側面は、樹脂７で封止されていることが好ましい。樹脂７の例は、エポキシ樹脂、アクリル樹脂等である。電極２および電極５にはリード線８が接続されている。リード線８は、導電性ペースト（図示せず）によって電極２および５に取付られている。導電性ペーストの例は、銀ペースト、カーボンペースト等である。
実施例
以下、実施例により本発明を具体的に説明する。
エーテル化合物の特性を以下のとおり測定した。
イオン伝導度（導電率）
イオン伝導度（導伝率σ）は、複素インピーダンス測定により求めた。測定は４０℃、電圧１０ｍＶ、周波数５Ｈｚ〜１３ＭＨｚの交流法を用いた。
合成例１（エーテル化合物（ｉ）の合成）
（Ｓｔｅｐ１）
ジエチレングリコールモノメチルエーテル３６０ｇ（３．０モル）にペレット状のＮａＯＨ４４．０ｇ（１．１モル）を加え、７０℃で攪拌しながら、２−（２−メトキシエトキシ）エチルグリシジルエーテル１７６ｇ（１．０モル）を少量ずつ滴下した。滴下終了後、約１時間攪拌した後室温で放冷した。その後、塩酸で中和し、析出した塩をろ過し、濃縮した後、減圧蒸留により精製し、１，３−ビス［２−（２−メトキシエトキシ）エトキシ］−２−プロパノール２２２ｇ（収率７５％）を得た。蒸留温度は１７１〜１７５℃／０．８ｍｍＨｇであった。
（Ｓｔｅｐ２）
Ｓｔｅｐ１で得られた１，３−ビス［２−（２−メトキシエトキシ）エトキシ］−２−プロパノール１００ｇ（０．３４モル）にペレット状のＮａＯＨ２０．４ｇ（０．５１モル）を加え、６０℃で攪拌しながら、２−クロロエチルメチルエーテル４８．２ｇ（０．５１モル）を少量ずつ滴下した。滴下終了後、約２時間攪拌し、析出した塩をろ過し、濃縮した後、減圧蒸留により精製し、１，３−ビス［２−（２−メトキシエトキシ）エトキシ］−２−（２−メトキシエトキシ）プロパン（ｉ）１０２ｇ（収率８５％）を得た。蒸留温度は１５５〜１６１℃／０．２ｍｍＨｇであった。
合成例１のＳｔｅｐ１と同様の方法で合成した１，３−ビス（２−メトキシエトキシ）−２−プロパノール１００ｇ（０．４８モル）にペレット状のＮａＯＨ９．６ｇ（０．２４モル）を加え、７０℃で攪拌しながら２−クロロエチルエーテル１１．４ｇ（０．０８モル）を少量ずつ滴下した。滴下終了後、約２時間攪拌した後、室温で放冷した。その後、析出した塩をろ過し、濃縮した後、減圧下（１８０℃／０．１ｍｍＨｇ）で低沸物を除いて、（ｉｉ）式の化合物３１．２ｇ（収率８０％）を得た。
（Ｓｔｅｐ１）
エピクロロヒドリン５０６ｇ（５．５モル）にペレット状のＮａＯＨ６８．０ｇ（１．７モル）を加え、４０℃で攪拌しながら、合成例１のＳｔｅｐ１と同様の方法で合成した１−（２−メトキシエトキシ）−３−［２−（２−メトキシエトキシ）エトキシ］−２−プロパノール２７８ｇ（１．１モル）を少量ずつ滴下した。滴下終了後、約２時間攪拌した後室温で放冷した。その後、析出した塩をろ過し、濃縮した後、減圧蒸留により精製し、１−（２−メトキシエトキシ）−３−［２−（２−メトキシエトキシ）エトキシ］プロピル−２−グリシジルエーテル２３１ｇ（収率６８％）を得た。蒸留温度は１４３〜１４７℃／０．３ｍｍＨｇであった。
（Ｓｔｅｐ２）
次に、エトキシエタノール１１７ｇ（１．３モル）にペレット状のＮａＯＨ２８．８ｇ（０．７２モル）を加え、７０℃で攪拌しながら、Ｓｔｅｐ１で得られた１−（２−メトキシエトキシ）−３−［２−（２−メトキシエトキシ）エトキシ］プロピル−２−グリシジルエーテル２００ｇ（０．６５モル）を少量ずつ滴下した。滴下終了後約１時間攪拌した後、室温で放冷した。その後、塩酸で中和し、析出した塩をろ過し、濃縮した後、減圧蒸留により、精製し、（ｍ）式の化合物１８４ｇ（収率７１％）を得た。蒸留温度は１８５〜１９２℃／０．１ｍｍＨｇであった。
Ｓｔｅｐ２で合成した（ｍ）式の化合物１５０ｇ（０．３８モル）にペレット状のＮａＯＨ２２．８ｇ（０．５７モル）を加え、６０℃で攪拌しながら、２−クロロエチルメチルエーテル５３．９ｇ（０．５７モル）を少量ずつ滴下した。滴下終了後、約２時間攪拌し、析出した塩をろ過し、濃縮した後、減圧下（１８０℃／０．１ｍｍＨｇ）で低沸物を除いて、（ｉｉｉ）式の化合物１３４ｇ（収率７７％）を得た。
合成例１で製造したエーテル化合物（ｉ）１ｇ、オリゴエチレングリコールジメチルエーテル（分子量：４００）１ｇ、ヨウ化リチウム２００ｍｇおよびヨウ素５０ｍｇを混合した。この混合物のイオン伝導度を測定したところ７．４×１０−３Ｓ／ｃｍであった。
実施例２
合成例２で製造したエーテル化合物（ｉｉ）１ｇ、ヨウ化リチウム４００ｍｇ及びヨウ素１００ｍｇを混合し、イオン伝導度を測定したところ８．２×１０−３Ｓ／ｃｍであった。
実施例３
合成例３で製造したエーテル化合物（ｉｉｉ）を実施例２と同様にイオン伝導度を測定したところ、９．２×１０−３Ｓ／ｃｍであった。
実施例４
１）エーテル化合物の合成例で得たそれぞれの化合物（（ｉ）〜（ｉｉｉ））１ｇとヨウ化リチウム３００ｍｇを混合し電解質化合物を得た。スパッタ法により白金をコートした透明ガラス板（ガラス厚：２ｍｍ、白金厚：２０μｍ）に不織布（厚み５０μｍ）を被せ、不織布に電解質化合物を染み込ませた後、ヨウ素雰囲気下に２時間暴露させた。
２）対電極として、ＩＴＯ（インジウム−錫酸化物）をスパッタ法によりコーティングした透明ガラス板（ガラス板の厚さ：２ｍｍ、ＩＴＯ膜の厚さ：２０μｍ）に酸化チタンの懸濁液を塗布し、乾燥後、焼結して多孔質酸化チタン被膜（厚さ：１０μｍ）を形成した。得られた多孔質酸化チタン被膜１ｃｍ２当たり、増感色素として、シス−ジチオシアナト−Ｎ，Ｎ’−ビス（２、２−ビピリジル−４，４’−ジカルボン酸）ルテニウム（ＩＩ）のルテニウム−ビピリジン錯体を１００μｇ吸着させた。その後、１）と同様に作成した電解質化合物を酸化チタン層に含浸させた。
１）および２）で作製した電解質及び電極を貼り合わせながら側面をエポキシ樹脂で封止した後、導電性ペースト（銀ペースト）によりリード線（銅線）を白金電極およびＩＴＯ電極に取り付けて光電変換素子を得た。光電変換素子は、図１に示すようなものであった。
ＡＭ１．５のソーラーシミュレータを光源として、９６Ｗ／ｍ２の光を照射して、電流の光応答性を測定した。エーテル化合物（ｉ）を使用した半導体層３および電解質層４を有する光電変換素子、エーテル化合物（ｉｉ）を使用した半導体層３および電解質層４を有する光電変換素子、エーテル化合物（ｉｉｉ）を使用した半導体層３および電解質層４を有する光電変換素子において、それぞれ安定な一定の電流［１．０ｍＡ（化合物（ｉ）の場合）、１．２ｍＡ（化合物（ｉｉ）の場合）、１．１ｍＡ（化合物（ｉｉｉ）の場合）］を発生し続けた。
このことから、本発明の高分子固体電解質は、光照射により直流電流を継続して流し、光電変換素子が太陽電池として良好に機能していることがわかった。
発明の効果
安定性に優れた電解質を使用した本発明の光電変換素子は、光照射により直流電流を継続的に流し、効率よくイオンを輸送できる。本発明の光電変換素子は、太陽電池として良好に機能する。
【図面の簡単な説明】
図１は、実施例４で得られた光電変換素子の断面図である。 Field of the Invention The present invention relates to a photoelectric conversion element using an electrolyte of an ether compound having high ionic conductivity.
Related art Conventionally, ionic conductors of organic solvents have attracted attention in various electrochemical devices. In particular, as an ionic conductor for a photoelectric conversion element used for a solar cell, an electrolyte in which iodine and potassium iodide are added to an organic solvent such as carbonate ester or tetrahydrofuran has been proposed. However, these electrolytes have a high vapor pressure, which impedes the durability of the photoelectric conversion element. In particular, in the solar cell field, durability of 10 years or more is required, and ion conductivity, safety, and stability of the seal are required. An electrolyte having excellent properties is desired.
Summary of the invention The inventors of the present invention have obtained from ether compounds (I), (II), (III) or (IV): (A) a combination of iodine and iodine compound or a combination of bromine and bromine compound. The desired electrolyte was obtained by adding the redox couple (B), and the present invention was found to be useful for application to a photoelectric conversion element such as a solar cell, thereby completing the present invention. That is, this invention provides the photoelectric conversion element excellent in long-term stability by using the electrolyte which has sufficient ion conductivity and outstanding stability.
The present inventors provide an oxidation-reduction pair (B) comprising an ether compound (I), (II), (III) or (IV): (A) and a combination of iodine and an iodine compound or a combination of bromine and a bromine compound. As a result, it was found that this electrolyte is useful for application to a photoelectric conversion element such as a solar cell, thereby completing the present invention. That is, this invention provides the photoelectric conversion element excellent in long-term stability by using the electrolyte which has sufficient ion conductivity and outstanding stability.
The present invention
(A) Formula (I), (II), (III) or (IV):
And (B) a photoelectric conversion element using an electrolyte comprising an oxidation-reduction pair comprising a combination of iodine and an iodine compound or a combination of bromine and a bromine compound.
DETAILED DESCRIPTION <br/> formula invention (I), in (II), (III) and (IV), examples of A 1 include a methyl group, an ethyl group, a propyl group, an ethenyl group (CH 2 = CH- ) Etc.
The total number of ethylene oxide units (—CH 2 CH 2 O—) in the ether compound may be 1-20, such as 3-12. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 101 , R 102 , R 103 , R 104 , R 105 may be similar or different.
A method for synthesizing the ether compound in which the structural formula of the formula (I) is represented by the formula (I-1) is as follows.
In the formula (I-1), the sum of l + m + n is preferably 2 or more, more preferably 3 or more.
(Step 1)
3 times mole amount of alcohol of formula (b) and 1.1 times mole amount of NaOH in pellet form are stirred in a flask with respect to glycidyl ether of formula (a), and glycidyl ether (a) is stirred at 70 ° C. Dripping. After completion of the dropwise addition, the mixture is stirred for about 1 hour, and then the reaction solution is neutralized with an aqueous HCl solution. After filtration and concentration, an intermediate alcohol of formula (d) is obtained by distillation.
Next, the intermediate alcohol (d) formula and 1.5 times the molar amount of pelleted NaOH were placed in a flask and stirred, and at 60 ° C., the intermediate alcohol (1.5) molar amount (c) formula The compound is added dropwise. After completion of dropping, the mixture is stirred for about 2 hours, filtered and purified to obtain a compound of formula (I-1).
The synthesis method of the ether compound in which the structural formula of the formula (III) is represented by the formula (III-1) is as follows.
In the above formula (III-1), the sum of o + p + q + r + s is preferably 2 or more, more preferably 3 or more, for example 4 or more.
(I-1) The alcohols of the formulas (e) and (f) are synthesized by the same method as Step 1 of the synthesis method of the formula (I-1).
Cl - (- CH 2 -CH 2 -O-) s-1 -CH 2 -CH 2 -Cl (g)
After completion of dropping, the mixture is stirred for about 2 hours, filtered and purified to obtain a compound of formula (III-1).
The synthesis method of the ether compound in which the structural formula of the formula (IV) is represented by the formula (IV-1) is as follows.
In the above formula (IV-1), the total of t + u + v + w is preferably 2 or more, more preferably 3 or more, for example 4 or more.
(Step 1)
The alcohol of the formula (h) is synthesized by the same method as Step 1 of the synthesis method of the formula (I-1).
To the glycidyl ether (i), a 2-fold molar amount of the alcohol of the formula (j) and a 1.1-fold molar amount of pelleted NaOH are placed in a flask and stirred, and glycidyl ether (i) is added dropwise at 70 ° C.
After completion of dropping, the mixture is stirred for about 1 hour, and then the reaction solution is neutralized with an aqueous HCl solution. After filtration and concentration, an intermediate alcohol (k) is obtained by distillation.
Next, intermediate alcohol (k) and 1.5 times its molar amount of pelleted NaOH were placed in a flask, stirred, and 1.5 times the amount of intermediate alcohol (k) (l) at 60 ° C. ) The compound of formula is added dropwise. After completion of dropping, the mixture is stirred for about 2 hours, filtered and purified to obtain a compound of formula (IV-1).
Cl-(— CH 2 —CH 2 —O—) v —R 26 (l)
The ether compound of the formula (II) can also be obtained by the same operation as described above. The redox couple (B) referred to in the present invention is a pair of compounds that perform a reversible redox reaction. When an oxidant / reductant is independently added to the system, an electrochemical equilibrium is quickly reached. Means a substance. The redox couple is an iodine-iodine compound combination or a bromine-bromine compound combination.
The redox pair of the iodine-iodine compound combination includes, for example, a combination of I 2 and a metal iodide such as LiI, NaI, KI, CsI, and CaI 2 , or quaternary ammonium such as I 2 and alkylammonium iodide, pyridinium iodide. It is preferably constituted by a combination of an iodine salt of a compound or a polymer compound having them in the side chain.
Bromine - Bromine bromine compound combinations redox pairs, such Br 2 and LiBr, NaBr, KBr, CsBr, CaBr 2 , etc. of the metal bromide or,, Br 2 and alkyl bromide, quaternary ammonium compounds such as pyridinium bromide It is preferably constituted by a combination of a salt or a polymer compound having a side chain thereof.
The mixing ratio of the redox pair can be arbitrarily selected from the ether compound to be mixed. In general, an electrolyte having a higher ionic conductivity can be obtained as the mixing amount of the redox couple increases. However, when the mixing amount is too large, ion dissociation hardly occurs and the conductivity decreases. In addition, when the equilibrium potential of the redox couple becomes a problem, the mixing amount can be adjusted so as to obtain a necessary equilibrium potential.
In this invention, the usage-amount of the said oxidation reduction pair may be 1-50 weight part with respect to 100 weight part of ether compounds, for example, 5-35 weight part.
The molar ratio of iodine: iodine compound (and bromine: bromine compound) in the redox couple is preferably 1: 5 to 5: 1.
Although there is no restriction | limiting in particular in the manufacturing method of the electrolyte of this invention, Usually, what is necessary is just to be able to mix an ether compound (A) and a redox couple (B).
The method of mixing the redox couple (B) with the ether compound (A) is not particularly limited, but the method of mixing the redox couple (B) directly with the ether compound (A), the organic containing the redox couple (B) There is a method of mixing the ether compound (A) with a solvent. In the case of a highly viscous or solid ether compound, the organic solvent is removed after the electrolyte production using an organic solvent (for example, acetonitrile).
In the present invention, the photoelectric conversion element is an element that converts light energy into electric energy by utilizing an electrochemical reaction between electrodes. When this photoelectric conversion element is irradiated with light, electrons are generated at one of the electrodes, and move to a counter electrode through an electric wire provided between the electrodes. The electrons transferred to the counter electrode reduce the redox couple in the electrolyte made of the ether compound of the present invention. The reduced redox couple moves from one electrode to the other electrode as an anion in the electrolyte composed of an ether compound, reaches the other electrode, and returns to the oxidant itself, thereby transferring electrons to the other electrode. return. Thus, the photoelectric conversion element of the present invention is an element or sensor that can convert light energy into electric energy. It also has a function as an optical sensor because it responds to light.
The photoelectric conversion element includes an ether compound electrolyte and a pair (two) of electrodes.
As an electrode, the conductor attached to the glass plate (transparent protective material which permeate | transmits light) is mentioned. The glass plate having the electrodes may be a glass plate coated with a conductive material (for example, a metal, an oxide semiconductor, particularly indium-tin oxide (ITO)).
Titanium oxide, zinc oxide, tungsten oxide, barium titanate, strontium titanate, potassium titanate, potassium tantalate, tungsten oxide, iron oxide and other oxide semiconductors, cadmium sulfide, CdTe, silicon, phthalocyanine, polythienylene, When a semiconductor such as polypyrrole or polyaniline, or the above-described oxide semiconductor or semiconductor sensitized with a dye or another inorganic substance is supported in one or more layers, a more preferable photoelectric conversion element can be obtained. That is, the photoelectric conversion element of the present invention includes an electrolyte composed of an ether compound, one electrode including a semiconductor (for example, an n-type semiconductor or a p-type semiconductor), a semiconductor (for example, a p-type semiconductor or an n-type semiconductor), or a metal. May have one counter electrode.
As the semiconductor carried on the electrode, an oxide semiconductor is preferable, and in particular, titanium oxide or titanium oxide sensitized with a dye is preferable from the viewpoint of stability, safety, and cost. Examples of dyes include organometallic complexes such as ruthenium-bipyridine complexes, particularly cis-di (thiocyanato) -N, N′-bis (2,2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) (cis). -Di (thiocyanato) -N, N'-bis (2,2'-bipyridyl-4,4'-dicboxylic acid) ruthenium (II)) can be used.
In order to provide the electrolyte on the electrode, a method of directly impregnating the electrolyte with the electrode or impregnating the nonwoven fabric can be employed. Alternatively, a spacer may be provided between the electrodes. Thus, after providing electrolyte on an electrode, a counter electrode is provided on electrolyte and the photoelectric conversion element of this invention can be obtained.
When the ether compound electrolyte of the present invention is used for a photoelectric conversion element, it has excellent ionic conductivity and excellent stability, and therefore a photoelectric conversion element having good conversion efficiency can be obtained.
The photoelectric conversion element of this invention can be used as a solar cell, a photosensor, etc.
1 is a cross-sectional view of the photoelectric conversion element obtained in Example 4. FIG. The photoelectric conversion element has glass plates 1 and 6, electrodes 2 and 5, a semiconductor layer 3, and an electrolyte layer 4 of an ether compound.
Transparent glass plates 1 and 6 protect the photoelectric conversion element and transmit light. The thickness of the glass plates 1 and 6 may be 0.1-5 mm. The electrode 2 may be transparent ITO (indium-tin oxide). The thickness of the electrode 2 may be 2 to 100 μm. The layer 3 is made of porous TiO 2 and emits holes and electrons from the light. The electrolyte layer 4 includes an ether compound and an electrolyte compound, and functions as an ion carrier layer. The thickness of the electrolyte layer 4 may be 5 to 1000 μm. The electrode 5 is preferably made of metal (for example, gold and platinum). The thickness of the electrode 5 may be 2 to 100 μm.
The side surface of the photoelectric conversion element is preferably sealed with resin 7. Examples of the resin 7 are an epoxy resin, an acrylic resin, and the like.
Examples Hereinafter, the present invention will be described specifically by way of examples.
The properties of the ether compound were measured as follows.
Ionic conductivity (conductivity)
The ionic conductivity (conductivity σ) was determined by complex impedance measurement. The measurement used the alternating current method of 40 degreeC, voltage 10mV, and frequency 5Hz-13MHz.
Synthesis Example 1 (Synthesis of ether compound (i))
(Step 1)
While adding 44.0 g (1.1 mol) of pellet-like NaOH to 360 g (3.0 mol) of diethylene glycol monomethyl ether and stirring at 70 ° C., 176 g (1.0 mol) of 2- (2-methoxyethoxy) ethyl glycidyl ether was stirred. ) Was added dropwise in small portions. After completion of dropping, the mixture was stirred for about 1 hour and then allowed to cool at room temperature. Thereafter, the mixture was neutralized with hydrochloric acid, and the deposited salt was filtered and concentrated, and then purified by distillation under reduced pressure to obtain 222 g of 1,3-bis [2- (2-methoxyethoxy) ethoxy] -2-propanol (75% yield). %). The distillation temperature was 171 to 175 ° C./0.8 mmHg.
(Step 2)
To 100 g (0.34 mol) of 1,3-bis [2- (2-methoxyethoxy) ethoxy] -2-propanol obtained in Step 1, 20.4 g (0.51 mol) of NaOH in the form of pellets was added, and 60 ° C. While stirring, 48.2 g (0.51 mol) of 2-chloroethyl methyl ether was added dropwise little by little. After completion of the dropwise addition, the mixture was stirred for about 2 hours, and the deposited salt was filtered and concentrated, and then purified by distillation under reduced pressure to obtain 1,3-bis [2- (2-methoxyethoxy) ethoxy] -2- (2-methoxy 102 g (85% yield) of ethoxy) propane (i) were obtained. The distillation temperature was 155 to 161 ° C./0.2 mmHg.
To 1,3-bis (2-methoxyethoxy) -2-propanol 100 g (0.48 mol) synthesized by the same method as in Step 1 of Synthesis Example 1, 9.6 g (0.24 mol) of NaOH in pellet form was added, While stirring at 70 ° C., 11.4 g (0.08 mol) of 2-chloroethyl ether was added dropwise little by little. After completion of the dropwise addition, the mixture was stirred for about 2 hours and then allowed to cool at room temperature. Thereafter, the deposited salt was filtered and concentrated, and then the low-boiling substances were removed under reduced pressure (180 ° C./0.1 mmHg) to obtain 31.2 g (yield 80%) of the compound of formula (ii).
(Step 1)
1- (2) synthesized in the same manner as Step 1 of Synthesis Example 1 while adding 68.0 g (1.7 mol) of pellet-like NaOH to 506 g (5.5 mol) of epichlorohydrin and stirring at 40 ° C. -Methoxyethoxy) -3- [2- (2-methoxyethoxy) ethoxy] -2-propanol (278 g, 1.1 mol) was added dropwise in small portions. After completion of dropping, the mixture was stirred for about 2 hours and allowed to cool at room temperature. Thereafter, the precipitated salt was filtered and concentrated, and then purified by distillation under reduced pressure to obtain 231 g of 1- (2-methoxyethoxy) -3- [2- (2-methoxyethoxy) ethoxy] propyl-2-glycidyl ether (yield). 68%). The distillation temperature was 143 to 147 ° C./0.3 mmHg.
(Step 2)
Next, 18.8 g (0.72 mol) of pellet-like NaOH was added to 117 g (1.3 mol) of ethoxyethanol, and 1- (2-methoxyethoxy) -3 obtained in Step 1 was stirred at 70 ° C. -200 g (0.65 mol) of [2- (2-methoxyethoxy) ethoxy] propyl-2-glycidyl ether was added dropwise little by little. After completion of dropping, the mixture was stirred for about 1 hour and then allowed to cool at room temperature. Then, after neutralizing with hydrochloric acid, the deposited salt was filtered and concentrated, and then purified by distillation under reduced pressure to obtain 184 g (yield 71%) of the compound of formula (m). The distillation temperature was 185 to 192 ° C./0.1 mmHg.
2150 g (0.57 mol) of pellet-like NaOH was added to 150 g (0.38 mol) of the compound of the formula (m) synthesized in Step 2, and 53.9 g (2-chloroethyl methyl ether) was stirred at 60 ° C. 0.57 mol) was added dropwise in small portions. After completion of the dropwise addition, the mixture was stirred for about 2 hours, and the precipitated salt was filtered and concentrated, and then the low-boiling substances were removed under reduced pressure (180 ° C./0.1 mmHg) to obtain 134 g of a compound of the formula (iii) (yield 77). %).
1 g of the ether compound (i) produced in Synthesis Example 1, 1 g of oligoethylene glycol dimethyl ether (molecular weight: 400), 200 mg of lithium iodide and 50 mg of iodine were mixed. When the ionic conductivity of this mixture was measured, it was 7.4 × 10 −3 S / cm.
Example 2
When 1 g of the ether compound (ii) produced in Synthesis Example 2 was mixed with 400 mg of lithium iodide and 100 mg of iodine, and the ionic conductivity was measured, it was 8.2 × 10 −3 S / cm.
Example 3
When the ionic conductivity of the ether compound (iii) produced in Synthesis Example 3 was measured in the same manner as in Example 2, it was 9.2 × 10 −3 S / cm.
Example 4
1) 1 g of each compound ((i) to (iii)) obtained in the synthesis example of the ether compound and 300 mg of lithium iodide were mixed to obtain an electrolyte compound. A transparent glass plate (glass thickness: 2 mm, platinum thickness: 20 μm) coated with platinum by a sputtering method was covered with a nonwoven fabric (thickness 50 μm), and the nonwoven fabric was impregnated with an electrolyte compound, and then exposed to an iodine atmosphere for 2 hours.
2) As a counter electrode, a suspension of titanium oxide is applied to a transparent glass plate (thickness of glass plate: 2 mm, thickness of ITO film: 20 μm) coated with ITO (indium-tin oxide) by sputtering. After drying, it was sintered to form a porous titanium oxide film (thickness: 10 μm). Ruthenium-bipyridine of cis-dithiocyanato-N, N′-bis (2,2-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) as a sensitizing dye per 1 cm 2 of the obtained porous titanium oxide coating 100 μg of the complex was adsorbed. Thereafter, the titanium oxide layer was impregnated with the electrolyte compound prepared in the same manner as in 1).
After the electrolyte and electrodes produced in 1) and 2) are bonded together, the side surfaces are sealed with an epoxy resin, and then lead wires (copper wires) are attached to the platinum electrodes and ITO electrodes with a conductive paste (silver paste) for photoelectric conversion. An element was obtained. The photoelectric conversion element was as shown in FIG.
Using an AM1.5 solar simulator as a light source, light of 96 W / m 2 was irradiated to measure the photoresponsiveness of the current. Photoelectric conversion element having semiconductor layer 3 and electrolyte layer 4 using ether compound (i), photoelectric conversion element having semiconductor layer 3 and electrolyte layer 4 using ether compound (ii), and ether compound (iii) were used. In the photoelectric conversion element having the semiconductor layer 3 and the electrolyte layer 4, a stable constant current [1.0 mA (in the case of compound (i)), 1.2 mA (in the case of compound (ii)), 1.1 mA (compound) In the case of (iii))] continues to be generated.
From this, it was found that the polymer solid electrolyte of the present invention continuously passed a direct current by light irradiation, and the photoelectric conversion element functioned well as a solar cell.
Effect of the invention The photoelectric conversion element of the present invention using an electrolyte having excellent stability can efficiently transport ions by allowing a direct current to flow continuously by light irradiation. The photoelectric conversion element of the present invention functions well as a solar cell.
[Brief description of the drawings]
1 is a cross-sectional view of the photoelectric conversion element obtained in Example 4. FIG.
Claims (4)
で示されるエーテル化合物、ならびに
（Ｂ）ヨウ素とヨウ素化合物の組み合わせまたは臭素と臭素化合物の組み合わせからなる酸化還元対
を含んでなる電解質を用いた光電変換素子。(A) Formula (I), (II), (III) or (IV):
And (B) a photoelectric conversion element using an electrolyte comprising an oxidation-reduction pair comprising a combination of iodine and an iodine compound or a combination of bromine and a bromine compound.
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| PCT/JP2000/001379 WO2000054361A1 (en) | 1999-03-10 | 2000-03-08 | Photoelectric conversion devices made by using ethereal electrolytes |
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| CN102471417B (en) * | 2009-07-15 | 2015-08-19 | 巴斯夫欧洲公司 | Multipolymer, its purposes as thickening material and preparation method thereof |
| JP5524557B2 (en) | 2009-09-28 | 2014-06-18 | 富士フイルム株式会社 | Method for producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| JP5620081B2 (en) | 2009-09-28 | 2014-11-05 | 富士フイルム株式会社 | Method for manufacturing photoelectric conversion element |
| JP5756772B2 (en) | 2011-03-30 | 2015-07-29 | 富士フイルム株式会社 | Photoelectric conversion element and photoelectrochemical cell |
| JP5972811B2 (en) | 2013-02-22 | 2016-08-17 | 富士フイルム株式会社 | Photoelectric conversion element, method for producing photoelectric conversion element, and dye-sensitized solar cell |
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| JPH08236165A (en) * | 1994-12-29 | 1996-09-13 | Ishihara Sangyo Kaisha Ltd | High polymer solid electrolyte, and its manufacture, and photo-electric transfer element using it |
| JPH0927352A (en) * | 1994-12-29 | 1997-01-28 | Ishihara Sangyo Kaisha Ltd | Porous material-high polymer solid electrolyte complex, its manufacture, and photoelectric conversion element using it |
| JPH09245848A (en) * | 1996-03-14 | 1997-09-19 | Shin Etsu Chem Co Ltd | Photo charging type thin power source element |
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| JPH08236165A (en) * | 1994-12-29 | 1996-09-13 | Ishihara Sangyo Kaisha Ltd | High polymer solid electrolyte, and its manufacture, and photo-electric transfer element using it |
| JPH0927352A (en) * | 1994-12-29 | 1997-01-28 | Ishihara Sangyo Kaisha Ltd | Porous material-high polymer solid electrolyte complex, its manufacture, and photoelectric conversion element using it |
| JPH09245848A (en) * | 1996-03-14 | 1997-09-19 | Shin Etsu Chem Co Ltd | Photo charging type thin power source element |
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