JP4493921B2 - Dye-sensitized solar cell - Google Patents
Dye-sensitized solar cell Download PDFInfo
- Publication number
- JP4493921B2 JP4493921B2 JP2003035362A JP2003035362A JP4493921B2 JP 4493921 B2 JP4493921 B2 JP 4493921B2 JP 2003035362 A JP2003035362 A JP 2003035362A JP 2003035362 A JP2003035362 A JP 2003035362A JP 4493921 B2 JP4493921 B2 JP 4493921B2
- Authority
- JP
- Japan
- Prior art keywords
- dye
- sensitized solar
- solar cell
- electrolyte
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- 239000000919 ceramic Substances 0.000 claims description 6
- 239000007784 solid electrolyte Substances 0.000 claims description 6
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- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- FGYADSCZTQOAFK-UHFFFAOYSA-N 1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C=NC2=C1 FGYADSCZTQOAFK-UHFFFAOYSA-N 0.000 description 6
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- 238000007740 vapor deposition Methods 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 239000012327 Ruthenium complex Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- 239000000434 metal complex dye Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
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- 239000000049 pigment Substances 0.000 description 2
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- 238000010248 power generation Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 239000003570 air Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 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
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- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- BTIJJDXEELBZFS-QDUVMHSLSA-K hemin Chemical compound CC1=C(CCC(O)=O)C(C=C2C(CCC(O)=O)=C(C)\C(N2[Fe](Cl)N23)=C\4)=N\C1=C/C2=C(C)C(C=C)=C3\C=C/1C(C)=C(C=C)C/4=N\1 BTIJJDXEELBZFS-QDUVMHSLSA-K 0.000 description 1
- 229940025294 hemin Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SJHHDDDGXWOYOE-UHFFFAOYSA-N oxytitamium phthalocyanine Chemical compound [Ti+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 SJHHDDDGXWOYOE-UHFFFAOYSA-N 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 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
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- 238000010992 reflux Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は色素増感型太陽電池に関する。
【０００２】
【従来の技術】
近年、地球温暖化やエネルギー問題に対する関心の高まりとともに太陽電池の様々な開発が進められている。その太陽電池の中でも、色素増感型太陽電池はグレッツェルらにより提案されて以来、使用する材料が安価であること、比較的シンプルなプロセスで製造できること等の利点からその実用化が期待されている。
【０００３】
また、このような色素増感型太陽電池においては、変換効率（電池特性）の向上を図る一方で、電池寿命を実用レベルにまで向上させることが実用化に向けた重要な課題となっている。すなわち、色素増感型太陽電池の長期使用による変換効率の低下を抑制し、優れた変換効率を長期にわたり持続する耐久性を得ることである。
【０００４】
従来の色素増感型太陽電池では、Ｉ3 -／Ｉ-からなる酸化還元対を含む電解質（例えば、電解質溶液）を調製する際に、ヨウ化リチウムを添加すると光電流が増加し、光電変換効率が向上することが知られている（例えば、特許文献１参）。
【０００５】
電解液中においてヨウ化リチウムから生じるリチウムカチオンは、例えば、負に帯電した半導体電極（光電極）の表面に引き寄せられた際に、その正電荷により半導体電極表面のフェルミ準位を下げる働き（より正の電位の側にシフトさせる働き）があると考えられている。これにより、例えば、半導体電極表面のフェルミ準位と増感色素の励起準位との電位差が拡げられ、その結果、色素から酸化物半導体への電子移動が速やかに進行するようになり、光電流が増加すると考えられている。
【０００６】
しかし、上記従来の色素増感型太陽電池のようにヨウ化リチウムを使用すると、開放電圧（最大出力電圧）が低下するという問題があった。開放電圧が低下すると発電時に得られる出力電圧も低下し、充分な光電変換効率を得ることができなくなる。色素増感型太陽電池の開放電圧は半導体電極のフェルミ準位と電解液中の酸化還元対の酸化還元電位との差により決まるが、ヨウ化リチウムを使用すると、先に述べたリチウムカチオンの作用により半導体電極表面のフェルミ準位がシフト（開放電圧が減少する側にシフト）することが上記の問題の大きな要因の１つとして考えられている。
【０００７】
そして、上述のように半導体電極表面のフェルミ準位がシフトすると、開放電圧の低下に伴って半導体電極表面又は光励起された増感色素から電解質中へ電子が移動するいわゆる逆電子移動（「暗電流」又は「漏れ電流」ともいう）が発生し易くなっていた。この暗電流が発生すると、発電時に得られる出力電圧及び光電流密度が低下することになる。
【０００８】
そこで、上述の開放電圧の低下及びこれに伴う暗電流の発生を抑制する目的で、４−ｔｅｒｔ−ブチルピリジン、Ｎ−メチルベンズイミダゾールのような複素環状化合物かならなる塩基を電解質中に添加した構成の色素増感型太陽電池が提案されている（例えば、非特許文献１参照）。この複素環状化合物かならなる塩基には、半導体電極表面に配位して半導体電極表面から電解質中への暗電流の発生を抑制する働きがあると考えられている。
【０００９】
また、色素増感型太陽電池において色素｛例えば、ルテニウム錯体［cis-Di(thiocyanato)-N,N'-bis(2,2'-bipyridyl-4,4'dicarboxylic acid)-ruthenium(II)］等｝は光を捕捉する役割があり、色素の劣化を防止することが、電池寿命を伸ばして光電変換効率を長期にわたって安定的に得るためには重要であると考えられている。
【００１０】
【特許文献１】
特開２００１−５２７６６号公報
【非特許文献１】
Mohammad K. et al.，Journal of American Chemical Society，2001，123，p.1613-1624.
【００１１】
【発明が解決しようとする課題】
しかしながら、本発明者らは、４−ｔｅｒｔ−ブチルピリジン、Ｎ−メチルベンズイミダゾールのような複素環状化合物かならなる塩基を添加した電解質を有する構成の色素増感型太陽電池においては、電池を長期にわたり作動させた場合の光電変換効率の経時的な低下が著しく、作動耐久性において未だ不充分であることを見出した。また、電池を長期にわたり保存した後に起動させた場合の光電変換効率が充分ではなく、保存耐久性においても未だ不充分であることを見出した。
【００１２】
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、電池製造後の初期において高い光電変換効率を得ることができ、しかも長期にわたって作動させた場合、又は長期にわたって保存した後に作動させた場合であっても、充分な光電変換効率を得ることができる耐久性に優れた色素増感型太陽電池を提供することを目的とする。
【００１３】
【課題を解決するための手段】
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、４−ｔｅｒｔ−ブチルピリジン、Ｎ−メチルベンズイミダゾールのような複素環状化合物かならなる塩基が添加された電解質を有する構成の色素増感型太陽電池においては、上記塩基により光電極中の色素（この色素は電解質中にも含有されている場合もある）の劣化が進行することが先に述べたの問題の大きな原因の１つとなっていることを見出した。
【００１４】
そして、本発明者らは更に検討を重ねた結果、４−ｔｅｒｔ−ブチルピリジン、Ｎ−メチルベンズイミダゾールのような複素環状化合物かならなる塩基のかわりにピリミジン環を有する有機化合物を電解質に添加することにより、逆電子移動を充分に防止しつつ初期において高い光電変換効率を得ることができ、しかも長期にわたって作動させた場合、又は長期にわたって保存した後に作動させた場合であっても、充分な光電変換効率を維持することができる耐久性に優れた色素増感型太陽電池ができることを見出し、本発明に到達した。
【００１５】
すなわち、本発明は、受光面を有する多孔質の半導体電極と当該受光面上に隣接して配置された透明電極とを有する光電極と、対極とを有しており、半導体電極と対極とが電解質を介して対向配置された構成を有する色素増感型太陽電池であって、半導体電極には、色素が含有されており、電解質には、ピリミジン環を有する有機化合物が少なくとも含有されていること、を特徴とする色素増感型太陽電池を提供する。
【００１６】
本発明によれば、４−ｔｅｒｔ−ブチルピリジン、Ｎ−メチルベンズイミダゾールのような複素環状化合物かならなる塩基のかわりにピリミジン環を有する有機化合物を電解質中に含有させることにより、初期において高い光電変換効率を得ることができ、しかも長期にわたって作動させた場合、又は長期にわたって保存した後に作動させた場合であっても、初期に得られる光電変換効率の低下が充分に防止され、充分な光電変換効率を維持することができる耐久性に優れた色素増感型太陽電池を容易に構成することができる。
【００１７】
上述のように、ピリミジン環を有する有機化合物を電解質（例えば、電解液）中に含有させることにより、色素の劣化が十分に防止される理由については明確には解明されていない。しかしながら、本発明者らは、４−ｔｅｒｔ−ブチルピリジン、Ｎ−メチルベンズイミダゾールのような複素環状化合物かならなる塩基に比べてピリミジン環を有する有機化合物は、色素増感型太陽電池の寿命に大きく影響するとされている色素の分解反応や配位子の交換反応に対する反応活性が低いためであると考えている。
【００１８】
例えば、本発明者らは、従来の色素増感型太陽電池の電解質（例えば、電解液）中に添加されていた複素環状化合物かならなる塩基は、半導体電極中の色素（例えば、先に述べたルテニウム錯体等の有機金属錯体）の配位中心となる金属イオン（又は金属原子）に対するの求核性が高く、配位中心から配位子の脱離反応の進行に寄与している可能性があると考えている。例えば、４−ｔｅｒｔ−ブチルピリジンの場合、その窒素原子のサイトがルテニウムイオン（又はルテニウム原子）等の配位中心に対して反応し、配位子の脱離反応を促進させている可能性があると考えている。
【００１９】
これに対してピリミジン環を有する有機化合物は、上述の複素環状化合物かならなる塩基に比べて配位中心への求核性が低く色素を劣化させる能力が低いと本発明者らは考えている。そのため、色素増感型太陽電池は、初期において高い光電変換効率を得ることができ、しかも長期にわたって作動させた場合、又は長期にわたって保存した後に作動させた場合であっても、初期に得られる光電変換効率の低下が充分に防止され、充分な光電変換効率を維持することができる耐久性に優れた色素増感型太陽電池を得ることができると考えている。
【００２０】
また、本発明において、電解質（例えば電解液）中に酸が存在する場合、ピリミジン環を有する有機化合物は、この酸と中和反応して塩の状態で存在していてもよい。この場合でも上記の本発明の作用効果を得ることができる。例えば、光電極の多孔質の半導体電極中に色素としてルテニウム錯体［cis-Di(thiocyanato)-N,N'-bis(2,2'-bipyridyl-4,4'dicarboxylic acid)-ruthenium(II)］を含有させた場合、半導体電極の細孔内に含浸された電解質中に含まれるピリミジン環を有する有機化合物が、上記のルテニウム錯体からなる色素のカルボキシル基と中和反応して塩を形成した状態であってもよい。この場合でも、実験により得られた結果から、色素の光増感機能は劣化しないものと本発明者らは考えている。
【００２１】
ここで、本発明において、「色素」とは、金属錯体色素及び有機色素を示す。また、「電解質」とは、（ｉ）電解質溶液（以下、必要に応じて「電解液」という）、（ｉｉ）電解質溶液にゲル化剤を添加してゲル化したもの、及び、（ｉｉｉ）固体電解質、並びに、（ｉｖ）多孔体材料からなる多孔体層の細孔内に（ｉ）〜（ｉｉｉ）のうちの何れかを含浸させたものを示す。
【００２２】
【発明の実施の形態】
以下、図面を参照しながら本発明の光電極及び色素増感型太陽電池の好適な実施形態について詳細に説明する。なお、以下の説明では、同一または相当部分には同一符号を付し、重複する説明は省略する。
【００２３】
［第１実施形態］
図１は、本発明の色素増感型太陽電池の第１実施形態の基本構成を示す模式断面図である。
【００２４】
図１に示す色素増感型太陽電池２０は、主として、光電極１０と、対極ＣＥと、スペーサＳにより光電極１０と対極ＣＥとの間に形成される間隙に充填された電解液Ｅと、から構成されている。また、図１に示す光電極１０は、主として、受光面Ｆ２を有する半導体電極２と、当該半導体電極２の受光面Ｆ２上に隣接して配置された透明電極１と、から構成されている。そして、半導体電極２は、受光面Ｆ２と反対側の裏面Ｆ２２において電解液Ｅと接触している。
【００２５】
この色素増感型太陽電池２０は、透明電極１を透過して半導体電極２に照射される光Ｌ１０によって、半導体電極２内に吸着されている増感色素が励起され、この増感色素から半導体電極２へ電子が注入される。そして、半導体電極２において注入された電子は、透明電極１に集められて外部に取り出される。
【００２６】
透明電極１の構成は特に限定されるものではなく、通常の色素増感型太陽電池に搭載される透明電極を使用できる。例えば、図１に示す透明電極１は、ガラス基板等の透明基板４の半導体電極２の側にいわゆる透明導電膜３をコートした構成を有する。この透明導電膜３としては、液晶パネル等に用いられる透明電極を用いればよい。
【００２７】
例えば、フッ素ドープＳｎＯ2コートガラス、ＩＴＯコートガラス、ＺｎＯ：Ａｌコートガラス、アンチモンドープ酸化スズ（ＳｎＯ2−Ｓｂ）、等が挙げられる。また、酸化スズや酸化インジウムに原子価の異なる陽イオン若しくは陰イオンをドープした透明電極、メッシュ状、ストライプ状など光が透過できる構造にした金属電極をガラス基板等の基板上に設けたものでもよい。
【００２８】
透明基板４としては、液晶パネル等に用いられる透明基板を用いてよい。具体的には透明なガラス基板、ガラス基板表面を適当に荒らすなどして光の反射を防止したもの、すりガラス状の半透明のガラス基板など光を透過するものが透明基板材料として挙げられる。なお、光を透過するものであれば材質はガラスでなくてもよく、透明プラスチック板、透明プラスチック膜、無機物透明結晶体などでもよい。
【００２９】
図１に示す多孔質の半導体電極２は、酸化物半導体粒子を構成材料とする酸化物半導体層からなる。半導体電極２に含有される酸化物半導体粒子は特に限定されるものではなく、公知の酸化物半導体等を使用することができる。酸化物半導体としては、例えば、ＴｉＯ2，ＺｎＯ，ＳｎＯ2，Ｎｂ2Ｏ5，Ｉｎ2Ｏ3，ＷＯ3，ＺｒＯ2，Ｌａ2Ｏ3，Ｔａ2Ｏ5，ＳｒＴｉＯ3，ＢａＴｉＯ3等を用いることができる。これらの酸化物半導体の中でもアナターゼ型ＴｉＯ2が好ましい。そして、この半導体電極２中の細孔内には電解質（電解液Ｅ）が含浸される。
【００３０】
また、半導体電極２に含有される増感色素は、可視光領域および／または赤外光領域に吸収を持つ色素であれば特に限定されるものではない。より好ましくは、少なくとも２００ｎｍ〜２μｍの波長の光により励起されて電子を放出するものであればよい。このような増感色素としては、金属錯体や有機色素等を用いることができる。
【００３１】
金属錯体としては銅フタロシアニン、チタニルフタロシアニン等の金属フタロシアニン、クロロフィルまたはその誘導体、ヘミン、ルテニウム、オスミウム、鉄及び亜鉛の錯体（例えば、シス−ジシアネート−Ｎ，Ｎ’−ビス（２、２’−ビピリジル−４、４’−ジカルボキシレート）ルテニウム（ＩＩ））等が挙げられる。有機色素としては，メタルフリーフタロシアニン，シアニン系色素，メロシアニン系色素，キサンテン系色素，トリフェニルメタン系色素等を用いることができる。
【００３２】
また、対極ＣＥは、電解質（電解液Ｅ）中の酸化還元対（例えば、Ｉ3 -／Ｉ-等）に高効率で電子を渡すことができる材料から構成されるものであれば特に限定されるものではなく、例えば、シリコン太陽電池、液晶パネル等に通常用いられている対極と同じものを用いることが可能である。例えば、前述の透明電極１と同じ構成を有するものであってもよく、透明電極１と同様の透明導電膜３上にＰｔ等の金属薄膜電極を形成し、金属薄膜電極を電解液Ｅの側に向けて配置させるものであってもよい。また、透明電極１の透明導電膜３に白金を少量付着させたものであってもよく、白金などの金属薄膜、炭素などの導電性膜などであってもよい。
【００３３】
更に、電解液Ｅは、先に述べたピリミジン環を有する有機化合物を少なくとも含み、かつ、光励起され半導体への電子注入を果した後の色素を還元するための酸化還元種を含んでいれば特に限定されない。例えば、ピリミジン環を有する有機化合物を含む液状の電解質であってもよく、これに公知のゲル化剤（高分子或いは低分子のゲル化剤）を添加して得られるゲル状の電解質であってもよい。これらの電解液Ｅ又はゲル状の電解質は、多孔質の半導体電極２の細孔内にも充填されている。更に、対極ＣＥが多孔質の電子伝導性材料から構成されている場合には、この対極ＣＥの内部の細孔内にも充填されている。
【００３４】
また、電解液Ｅのかわりに、ピリミジン環を有する有機化合物を含む固体高分子電解質又はセラミック固体電解質からなる層を半導体電極２と対極ＣＥとの間に配置してもよい。この場合、多孔質の半導体電極２の細孔内には上述の固体高分子電解質又はセラミック固体電解質を充填してもよい。
【００３５】
また、多孔質の半導体電極２の細孔内には、上述の電解液Ｅ又は、別の電解液（但し、ピリミジン環を有する有機化合物、光励起され半導体への電子注入を果した後の色素を還元するための酸化還元種を含む）を充填してもよく、これらをゲル化したものを充填してもよい。更に、対極ＣＥが多孔質の電子伝導性材料から構成されている場合、この対極ＣＥの内部の細孔内にも上述の半導体電極２に用いることが可能な電解質と同様の電解質を充填してよい。
【００３６】
また、電解液Ｅに使用される溶媒としては、溶質成分を溶解できる化合物であれば特に制限はないが、電気化学的に不活性で、比誘電率が高くかつ粘度が低い溶媒（およびこれらの混合溶媒）が好ましく、例えば，メトキシアセトニトリル、メトキシプロピオニトリルやアセトニトリルのようなニトリル化合物，γ−ブチロラクトンやバレロラクトンのようなラクトン化合物，エチレンカーボネートやプロピレンカーボネートのようなカーボネート化合物、炭酸プロピレン等が挙げられる。
【００３７】
電解液Ｅに使用されるピリミジン環を有する有機化合物以外の溶質としては、半導体電極２に担持された色素や対極ＣＥと電子の受け渡しを行える酸化還元対（Ｉ3 -／Ｉ-系の電解質、Ｂｒ3 -／Ｂｒ-系の電解質、ハイドロキノン／キノン系の電解質などのレドックス電解質）や、この電子の受け渡しを助長する作用を有する化合物等が挙げられ、これらがそれぞれ単独あるいは複数組み合せて含まれていてもよい。
【００３８】
より具体的には、酸化還元対を構成する物質としては、例えば，ヨウ素，臭素，塩素などのハロゲン，ヨウ化−１，２−ジメチル−３−プロピルイミダゾリウム，ヨウ化テトラプロピルアンモニウムなどが挙げられる。なお、耐久性が大きく低下しない範囲の量（例えば、５ｍｍｏｌ／Ｌ以下）のヨウ化リチウムを含有させてもよいが、ヨウ化リチウムは含有させない方が好ましい。
【００３９】
また、この電解液Ｅには、電子の受け渡しを効率よく行うための添加剤として、従来の４−ｔ−ブチルピリジンのかわりに、ピリミジン環を有する有機化合物が含有されている。ピリミジン環を有する有機化合物は色素との反応性が低いと考えられる。
【００４０】
従って、ピリミジン環を有する有機化合物を含む電解質Ｅを採用することにより、初期において高い光電変換効率を得ることができ、しかも長期にわたって作動させた場合、又は長期にわたって保存した後に作動させた場合であっても、初期に得られる光電変換効率の低下が充分に防止され、充分な光電変換効率を維持することができる耐久性に優れた色素増感型太陽電池を得ることができる。
【００４１】
上述の本発明の効果をより確実に得る観点から、ピリミジン環を有する有機化合物は、下記一般式（１）で表される構造を有していることが好ましい。
【００４２】
【化９】
【００４３】
式（１）中、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ同一であっても異なっていてもよく、水素原子、ハロゲン原子、炭素数が１〜２０の炭化水素基、及び、炭素数が１〜２０のアルコキシ基からなる群より選択される１種の特性基を示す。但し、Ｒ １ 、Ｒ ２ 、Ｒ ３ 及びＲ ４ の少なくとも一つはハロゲン原子であり、Ｒ２及びＲ３は互いに結合して縮合環を形成していてもよい。
【００４４】
ここで、Ｒ1、Ｒ2、Ｒ3及びＲ4がそれぞれ炭化水素基の場合、この「炭化水素基」とは、炭素数が１〜２０のものであって、かつ、アルキル基、アルケニル基、アルキニル基、アリル基、アリール基、及び、複素環基からなる群から選択される少なくとも１種の特性基を示す。
【００４５】
また、Ｒ1、Ｒ2、Ｒ3及びＲ4がそれぞれアルコキシ基の場合、この「アルコキシ基」とは、一般式：Ｒ−Ｏ−で表される構造を有する特性基を示す。ここで、上記Ｒは、炭素数が１〜２０のものであって、かつ、アルキル基、アルケニル基、アルキニル基、アリル基、アリール基、及び、複素環基からなる群から選択される少なくとも１種の特性基を示す。
【００４６】
更に、Ｒ2及びＲ3が互いに結合して縮合環を形成する場合には、「縮合環」は、炭素原子及び水素原子からなる構造の環の他に、環の構成原子（即ち、Ｒ2及びＲ3の構成原子）として上述したもの以外に窒素原子が含まれた「縮合複素環」であってもよい。
【００４７】
上述の本発明の効果を更に確実に得る観点から、ピリミジン環を有する有機化合物が、下記一般式（５）及び（６）で表される化合物からなる群より選択される少なくとも１種であることが好ましい。
【００４８】
【化１０】
【００４９】
【化１１】
【００５０】
【化１２】
【００５１】
【化１３】
【００５２】
【化１４】
【００５３】
【化１５】
【００５４】
【化１６】
【００５５】
また、電解質Ｅ中におけるピリミジン環を有する有機化合物の濃度は、１０-4〜１０ｍｏｌ／Ｌであることが好ましく、１０-2〜１０ｍｏｌ／Ｌであることがより好ましい。ここで、ピリミジン環を有する有機化合物の濃度が１０-4ｍｏｌ／Ｌ未満であると、ピリミジン環を有する有機化合物の添加効果が不充分となり、充分な光電変換効率が得られない傾向があり、他方、ピリミジン環を有する有機化合物の濃度が１０ｍｏｌ／Ｌを超えると、短絡電流は増加するものの開放電圧及びＦ．Ｆ．が低下するため、光電変換効率が低下する傾向がある。
【００５６】
また、スペーサＳの構成材料は特に限定されるものではなく、例えば、シリカビーズ等を用いることができる。
【００５７】
また、電解液Ｅを密封する目的で光電極１０、対極ＣＥ及びスペーサＳを一体化するために使用する封止材としては、電解液Ｅの成分ができる限り外部に漏洩しないように封止できるものであればよく、特に制限されないが、例えば、エポキシ樹脂、シリコーン樹脂、エチレン／メタクリル酸共重合体、表面処理ポリエチレンからなる熱可塑性樹脂などを用いることができる。
【００５８】
次に、図１に示した色素増感型太陽電池２０の製造方法の一例について説明する。
【００５９】
透明電極１を製造する場合は、ガラス基板等の基板４上に先に述べたフッ素ドープＳｎＯ2等の透明導電膜３をスプレーコートする等の公知の薄膜製造技術を用いて形成することができる。例えば、この他にも、真空蒸着法、スパッタリング法、ＣＶＤ法及びゾルゲル法の公知の薄膜製造技術を用いて形成することができる。
【００６０】
透明電極１の透明導電膜３上に半導体電極２を形成する方法としては、例えば、以下の方法がある。すなわち、先ず、所定の大きさ（例えば粒子径が１０〜３０ｎｍ程度）を有する酸化物半導体粒子を分散させた分散液を調製する。この分散液の溶媒は水、有機溶媒、または両者の混合溶媒など酸化物半導体粒子を分散できるものなら特に限定されない。また、分散液中には必要に応じて界面活性剤、粘度調節剤を加えてもよい。
【００６１】
次に、分散液を透明電極１の透明導電膜３上に塗布し、次いで乾燥する。このときの塗布方法としてはバーコーター法、印刷法などを用いることができる。そして、乾燥した後、空気中、不活性ガス或いは窒素中で加熱、焼成して半導体電極２（多孔質半導体膜）を形成する。
【００６２】
次に、半導体電極２中に浸着法等の公知の技術により増感色素を含有させる。増感色素は半導体電極２に付着（化学吸着、物理吸着または堆積など）させることにより含有させる。この付着方法は、例えば色素を含む溶液中に半導体電極２を浸漬するなどの方法を用いることができる。この際、溶液を加熱し還流させるなどして増感色素の吸着、堆積を促進することができる。なお、このとき、色素の他に必要に応じて、銀等の金属やアルミナ等の金属酸化物を半導体電極２中に含有させてもよい。
【００６３】
なお、半導体電極２内に含まれる光電変換反応を阻害する不純物を除去する表面酸化処理を、各層それぞれの形成時毎、或いは、各層全てを形成した時などに公知の方法により適宜施してもよい。
【００６４】
また、透明電極１の透明導電膜３上に半導体電極２を形成する他の方法としては、以下の方法がある。すなわち、透明電極１の透明導電膜３上にＴｉＯ2等の半導体を膜状に蒸着させる方法を用いてもよい。透明導電膜３上に半導体を膜状に蒸着させる方法としては公知の薄膜製造技術を用いることができる。例えば、電子ビーム蒸着、抵抗加熱蒸着、スパッタ蒸着、クラスタイオンビーム蒸着等の物理蒸着法を用いてもよく、酸素等の反応性ガス中で金属等を蒸発させ、反応生成物を透明導電膜３上に堆積させる反応蒸着法を用いてもよい。更に、反応ガスの流れを制御する等してＣＶＤ等の化学蒸着法を用いることもできる。
【００６５】
このようにして光電極１０を作製した後は、例えば、光電極１０の作製に用いた方法と同様の公知の薄膜製造技術により対極ＣＥを作製し、図１に示すように、光電極１０と、対極ＣＥとを、スペーサＳを介して対向させるように組み上げる。このとき、スペーサＳにより光電極１０と対極ＣＥとの間に形成される空間にピリミジン環を有する有機化合物を含有する電解液Ｅを充填し、色素増感型太陽電池２０を完成させる。
【００６６】
［第２実施形態］
図２は、本発明の色素増感型太陽電池の第２実施形態を示す模式断面図である。以下、図２に示す色素増感型太陽電池３０について説明する。なお、上述の図１に示した色素増感型太陽電池２０に関して説明した要素と同一の要素については同一の符号を付し、重複する説明は省略する。
【００６７】
図２に示す色素増感型太陽電池３０は、図１に示した光電極１０を使用し、図１に示した対極ＣＥと同様の対極ＣＥを使用している。そして、図１に示した色素増感型太陽電池２０においてはスペーサＳにより光電極１０と対極ＣＥとの間に形成される空間に電解液Ｅを充填したのに比較して、図２に示す色素増感型太陽電池３０においては、光電極１０と対極ＣＥとの間に多孔体層ＰＳを配置している。
【００６８】
この多孔体層ＰＳは多数の細孔を有した構造を有しており、この多孔体層ＰＳの内部には、図１に示した色素増感型太陽電池２０に使用したものと同様のピリミジン環を有する有機化合物を含有する電解液Ｅが充填されて保持されている。
【００６９】
また、この電解液Ｅは半導体電極２内や、使用する構成材料（例えば、炭素等の多孔質の導電性膜）によっては対極ＣＥにも保持されている。そして、図２に示す色素増感型太陽電池３０の半導体電極２及び多孔体層ＰＳの側面は、電解液Ｅが、半導体電極２及び多孔体層ＰＳの側面から外部に漏れることを防止するためにシール材５により被覆されている。
【００７０】
多孔体層ＰＳは、電解液Ｅを保持可能であり、電子伝導性を有さない多孔体であれば特に限定されない。例えば、ルチル型の酸化チタン粒子により形成した多孔体を使用してもよい。また、ルチル型の酸化チタン以外の構成材料としては、ジルコニア、アルミナ、シリカ等が挙げられる。
【００７１】
また、シール材５としては、例えば、ポリエチレン等の熱可塑性樹脂フィルム、あるいはエポキシ系接着剤を使用することができる。
【００７２】
次に、図２に示す色素増感型太陽電池３０の製造方法の一例について説明する。先ず、図１に示した色素増感型太陽電池２０と同様にして光電極１０を作製する。次に、光電極１０の半導体電極２を作製する場合と同様の手順により、光電極１０の半導体電極２の面Ｆ２２上に多孔体層ＰＳを形成する。例えば、ルチル型の酸化チタン等の多孔体層ＰＳの構成材料を含む分散液（スラリー）を調製し、これを半導体電極２の面Ｆ２２上に塗布し乾燥させることにより形成してもよい。
【００７３】
また、対極ＣＥについても、例えば、炭素等の多孔質の導電性膜を対極ＣＥとする場合には、例えば、カーボンペーストを調製し、これを多孔体層ＰＳの面上に塗布し乾燥させることにより形成し、公知の薄膜製造技術により導電性膜の多孔体層ＰＳの側と反対の側の面上に基板を形成し対極ＣＥとしてもよい、そして半導体電極２及び多孔体層ＰＳの側面をシール材５で被覆して色素増感型太陽電池３０を完成する。なお、このような対極ＣＥの一部である基板としては、通常の基板を用いてもよく、透明基板でもよい。
【００７４】
なお、この色素増感型太陽電池３０においても、電解液Ｅは、先に述べたピリミジン環を有する有機化合物を少なくとも含み、かつ、光励起され半導体への電子注入を果した後の色素を還元するための酸化還元種を含んでいれば特に限定されない。例えば、ピリミジン環を有する有機化合物を含む液状の電解質であってもよく、これに公知のゲル化剤（高分子或いは低分子のゲル化剤）を添加して得られるゲル状の電解質であってもよい。また、電解液Ｅのかわりに、ピリミジン環を有する有機化合物を含む固体高分子電解質又はセラミック固体電解質を半導体電極２及び多孔体層ＰＳ中の細孔内（更に、対極ＣＥが多孔質の電子伝導性材料から構成されている場合には、この対極ＣＥの内部の細孔内）にそれぞれ充填してもよい。
【００７５】
［第３実施形態］
図３は、本発明の色素増感型太陽電池の第３実施形態を示す模式断面図である。以下、図３に示す色素増感型太陽電池４０について説明する。なお、上述の図１に示した色素増感型太陽電池２０又は図２に示した色素増感型太陽電池３０に関して説明した要素と同一の要素については同一の符号を付し、重複する説明は省略する。
【００７６】
図３に示す色素増感型太陽電池４０は、以下に示す多孔体層ＰＳの形状と対極ＣＥの構成以外は図２に示した色素増感型太陽電池３０と同様の構成を有している。すなわち、図３に示す色素増感型太陽電池４０の場合、多孔体層ＰＳが半導体電極２の裏面Ｆ２２を覆う部分の他に半導体電極２の側面を密着して覆う鍔状の縁部分を有している。この鍔状の縁部分は、光電極１０の透明電極１の受光面Ｆ１の法線方向に略平行となる方向にのびてその先端が透明電極１に接続されている。
【００７７】
この透明電極１と多孔体層ＰＳとの接続部についてより詳細に説明すると、この接続部において、透明電極１の透明導電膜３の部分は、例えばレーザスクライブ等の技術により完全に削りとられ、透明基板４の表面があらわれる深さの溝９が形成されている。そして、この溝９の部分に多孔体層ＰＳの鍔状に形成された縁部分が挿入されている。
【００７８】
また、対極ＣＥは多孔体層ＰＳに隣接して配置される炭素電極８と、この炭素電極８の多孔体層ＰＳと反対側の面上に隣接して配置される基板６とから構成されている。ここで炭素電極８は、カーボンブラック粒子と、グラファイト粒子と、アナターゼ型の酸化チタン粒子よりも電気抵抗率の低い導電性酸化物粒子とを少なくとも構成材料として形成された多孔質の電極であることが好ましい。そして、この対極ＣＥにも、多孔体層ＰＳの鍔状の縁部分を密着して覆うための鍔状の縁部分が形成されている。この対極ＣＥの鍔状の縁部分も、光電極１０の透明電極１の受光面Ｆ１の法線方向に略平行となる方向にのびてその先端が透明電極１の透明導電膜３の表面に密着するように接続されている。
【００７９】
また、半導体電極２の側面のうち多孔体層ＰＳの鍔状の縁部分で覆われていない部分、及び、多孔体層ＰＳの側面のうち、対極ＣＥの鍔状の縁部分で覆われていない部分は、図２に示した色素増感型太陽電池３０に使用されているものと同様のシール材５を密着させて配置することによりシールされている。更に、対極ＣＥの鍔状の縁部分の外表面に対しても図２に示した色素増感型太陽電池３０に使用されているものと同様のシール材５が密着するように配置されている。
【００８０】
基板６とシール材５とを配置することにより、半導体電極２及び多孔体層ＰＳのそれぞれの内部に含有されている電解質（例えば、先に述べた電解液Ｅ）の電池４０外部への逸散を充分に防止することができる。なお、必要に応じて、基板６と炭素電極８との間にもシール材５を密着させて配置しておいてもよい。これにより、対極ＣＥ内部に含有されている電解質（例えば、先に述べた電解液Ｅ）の電池４０外部への逸散をより充分に防止することができる。
【００８１】
以上のように、この色素増感型太陽電池４０は、光電極１０の透明電極１に多孔体層ＰＳと対極ＣＥとがそれぞれ一体化された構成を有している。そして、多孔体層ＰＳの鍔状の縁部分により、光電極１０と対極ＣＥとの電気的な接触が防止されている。
【００８２】
なお、光電極１０と対極ＣＥとの電気的な接触（光電極１０と対極ＣＥとの間での電子移動）が充分に防止されるのであれば、図３において、多孔体層ＰＳの鍔状の縁部分を設けずに、半導体電極２の側面と対極ＣＥの鍔状の縁部分の内側面とが見かけ接触している状態の構成としてもよい。この場合、溝９内には半導体電極２の構成材料が挿入される。
【００８３】
半導体電極２及び多孔体層ＰＳの内部の細孔内（更に、対極ＣＥが多孔質の電子伝導性材料から構成されている場合には、この対極ＣＥの内部の細孔内）に含浸される電解質は、先に述べたピリミジン環を有する有機化合物を少なくとも含み、かつ、光励起され半導体への電子注入を果した後の色素を還元するための酸化還元種を含んでいれば特に限定されない。例えば、先に述べた電解液Ｅであってもよい。
【００８４】
例えば、ピリミジン環を有する有機化合物を含む液状の電解質であってもよく、これに公知のゲル化剤（高分子或いは低分子のゲル化剤）を添加して得られるゲル状の電解質であってもよい。また、電解液のかわりに、ピリミジン環を有する有機化合物を含む固体高分子電解質又はセラミック固体電解質を多孔体層ＰＳ中の細孔内（更に、対極ＣＥが多孔質のそれぞれ）充填してもよい。
【００８５】
この色素増感型太陽電池４０は、光電極１０を形成する際に、上記の溝９をレーザスクライブ等の公知の技術により形成し、多孔体層ＰＳ及び対極ＣＥの形成時にそれぞれ上述の鍔状の縁部分が形成されるように原料となるスラリー（或いはペースト）を塗布し、その後基板６を公知の方法により形成させたこと以外は図２に示した色素増感型太陽電池３０と同様の製造方法により形成することができる。
【００８６】
以上、本発明の好適な実施形態について説明したが、本発明は上記実施形態に限定されるものではない。
【００８７】
例えば、本発明の色素増感型太陽電池は、例えば、図４に示す色素増感型太陽電池５０のように、複数の電池を併設したモジュールの形態を有していてもよい。図４に示す色素増感型太陽電池５０は、図２に示した色素増感型太陽電池３０又は図３に示した色素増感型太陽電池４０をそれぞれ複数個直列に併設する場合の一例を示している。
【００８８】
図２に示した色素増感型太陽電池３０に比較して、図４に示す色素増感型太陽電池５０は、隣り合う太陽電池の単セルの光電極１０間に設けられるシール材５と一方の単セル（以下、単セルＡという）の光電極１０との間に溝９が形成されている。
【００８９】
この溝９は、単セルＡの半導体電極２を、例えばレーザスクライブなどの技術により削りとることにより形成される。この溝９のうちのシール材５の近傍部分は、半導体電極２の部分を完全に除去して透明電極１の透明導電膜３の層があらわれる深さまで達している。また、この溝９のうちの単セルＡの半導体電極２の近傍部分は、半導体電極２の部分と透明導電膜３の部分を完全に除去して、透明電極１の透明基板４の層があらわれる深さまで達している。
【００９０】
そして、この溝のうちのシール材５の近傍部分には、隣り合う光電極１０の透明導電膜３及び該透明導電膜３上の半導体電極２の部分同士が電気的に接触しないように、これらの部分の間に単セルＡの多孔体層ＰＳの鍔状に形成された縁部分が透明電極１の透明基板４に接触するようにして挿入されている。
【００９１】
更に、この溝のうちの単セルＡの半導体電極２の近傍部分、すなわち、単セルＡの多孔体層ＰＳとシール材５との間の部分には、単セルＡの対極ＣＥの鍔状に形成された縁部分が、もう一方の単セルＡの透明電極１の透明導電膜３に接触するようにして挿入されている。この色素増感型太陽電池５０は、図３に示した色素増感型太陽電池４０と同様の製造方法により形成することができる。
【００９２】
【実施例】
以下、実施例及び比較例を挙げて本発明の色素増感型太陽電池について更に詳しく説明するが、本発明はこれらの実施例に何ら限定されるものではない。
【００９３】
【実施例】
以下、実施例及び比較例を挙げて本発明の色素増感型太陽電池について更に詳しく説明するが、本発明はこれらの実施例に何ら限定されるものではない。
【００９４】
（参考例１）
以下に示す手順により、図１に示した光電極１０と同様の構成を有する光電極を作製し、更に、この光電極を用いた以外は図１に示す色素増感型太陽電池２０と同様の構成を有する色素増感型太陽電池（受光面の面積：１ｃｍ２）を作製した。
【００９５】
先ず、オートクレーブの温度を２３０℃とした以外は、Journal of ceramic society （第８０巻、第３１５７〜３１７１頁、１９８７年）に記載のバルベらの方法に従い、アセチルアセトン、イオン交換水、界面活性剤（Ａｌｄｒｉｃｈ社製、商品名；「ｔｒｉｔｏｎＸ」）からなる液にＴｉＯ2粒子（Ｄｅｇｕｓｓａ社製、商品名；「Ｐ２５」）を分散した半導体電極形成用のスラリー（ＴｉＯ2粒子の含有量；１１質量％、ＴｉＯ2粒子の平均粒子径：約１０ｎｍ、「スラリー１」とする）を調製した。
【００９６】
次に、スラリー１中に増粘剤としてポリエチレングリコール（和光純薬社製、数平均分子量；２０００）を添加し混合することにより、半導体電極形成用のペースト（以下、ペースト１という）を調製した。なお、ペースト１中のＴｉＯ2粒子とポリエチレングリコールとの質量比はＴｉＯ2粒子：ポリエチレングリコール＝１０：３となるように調節した。
【００９７】
一方、ガラス基板４（透明導電性ガラス）上にフッ素ドープされたＳｎＯ2導電膜３（膜厚；６００ｎｍ）を形成した透明電極１（日本板ガラス社製、表面抵抗；約１０Ω／ｃｍ2、厚さ；１ｍｍ）を準備した。そして、このＳｎＯ2導電膜３上に、上述のペースト１をドクターブレードを用いて１００μｍの厚さとなるまで塗布し、次いで温度を２５℃に保持して３０分間乾燥させた。
【００９８】
その後、ペースト１を塗布した透明電極１を電気炉内に移して、大気中、４５０℃の条件のもとで３０分間焼成した。次に、電気炉から透明電極１を取り出し、冷却した。このようにして、ＳｎＯ2導電膜３上に図１に示す半導体電極２と同様の構成の半導体電極（受光面の面積；４ｃｍ2、半導体膜からなる層の厚さ；８μｍ、ＴｉＯ2の塗布量：１５ｇ／ｍ2）を形成し、色素（金属錯体色素及び有機色素）を含有していない状態の光電極を作製した。
【００９９】
その後、光電極の半導体電極の裏面に色素を以下のようにして吸着させた。先ず、増感色素として色素（Ｒｅｄ ｄｙｅ, Ｓｏｌｏｒｏｎｉｘ社製、商品名：「Ｎ７１９」）即ち、ルテニウム錯体［cis-Di(thiocyanato)-N,N'-bis(2,2'-bipyridyl-4,4'dicarboxylic acid)-ruthenium(II)］を用い、これをエタノールとＤＭＦ｛ＨＣＯＮ（ＣＨ3）2｝の混合溶媒（エタノールとＤＭＦの質量比；エタノール：ＤＭＦ＝１：１）に溶解させた溶液（増感色素の濃度；３×１０-4ｍｏｌ／Ｌ）を調製した。次に、この溶液に半導体電極を浸漬し、暗所、２５℃の温度条件のもとで１２時間放置した。次に、この溶液から半導体電極を取り出してエタノールで洗浄し、暗所にて自然乾燥させた。これにより、半導体電極２の内部に増感色素を約１．２×１０-7ｍｏｌ／ｍ2吸着させた光電極１２を完成させた。
【０１００】
次に、上記の光電極と同様の形状と大きさを有する対極として、電子ビーム蒸着法によりＰｔが蒸着された透明導電性ガラス電極（Ｐｔ薄膜の厚さ；３ｎｍ）を作製した。
【０１０１】
また、電解液Ｅとして、式（２）に示したピリミジン環を有する有機化合物を含むヨウ素系レドックス溶液（ヨウ化テトラブチルアンモニウムの濃度；０．６ｍｏｌ／Ｌ、ヨウ素の濃度；０．１ｍｏｌ／Ｌ、ピリミジン環を有する有機化合物の濃度；０．1ｍｏｌ／Ｌ、溶媒；メトキシプロピオニトリル）を調製した。
【０１０２】
更に、半導体電極の大きさに合わせた形状を有する三井デュポンポリケミカル社製のスペーサＳ（商品名：「ハイミラン」）を準備した。次に、図１に示すように、光電極１２と対極ＣＥとスペーサＳを介して対向させた。そして、毛細管現象を利用することにより、スペーサＳと光電極１２又は対極ＣＥとの間の隙間からスペーサＳ、光電極１２及び対極ＣＥによりに画成された空間に上記の電解液Ｅを充填し、エポキシ樹脂により各部材間をシールして、色素増感型太陽電池を完成させた。
【０１０３】
（参考例２）
電解液Ｅとして、式（３）に示したピリミジン環を有する有機化合物を含むヨウ素系レドックス溶液（ヨウ化テトラブチルアンモニウムの濃度；０．６ｍｏｌ／Ｌ、ヨウ素の濃度；０．１ｍｏｌ／Ｌ、ピリミジン環を有する有機化合物の濃度；０．1ｍｏｌ／Ｌ、溶媒；メトキシプロピオニトリル）を調製した。この電解液Ｅを用いたこと以外は、参考例１と同様の手順及び条件で色素増感型太陽電池を作製した。
【０１０４】
（参考例３）
電解液Ｅとして、式（４）に示したピリミジン環を有する有機化合物を含むヨウ素系レドックス溶液（ヨウ化テトラブチルアンモニウムの濃度；０．６ｍｏｌ／Ｌ、ヨウ素の濃度；０．１ｍｏｌ／Ｌ、ピリミジン環を有する有機化合物の濃度；０．1ｍｏｌ／Ｌ、溶媒；メトキシプロピオニトリル）を調製した。この電解液Ｅを用いたこと以外は、参考例１と同様の手順及び条件で色素増感型太陽電池を作製した。
【０１０５】
（実施例４）
電解液Ｅとして、式（５）に示したピリミジン環を有する有機化合物を含むヨウ素系レドックス溶液（ヨウ化テトラブチルアンモニウムの濃度；０．６ｍｏｌ／Ｌ、ヨウ素の濃度；０．１ｍｏｌ／Ｌ、ピリミジン環を有する有機化合物の濃度；０．1ｍｏｌ／Ｌ、溶媒；メトキシプロピオニトリル）を調製した。この電解液Ｅを用いたこと以外は、実施例１と同様の手順及び条件で色素増感型太陽電池を作製した。
【０１０６】
（実施例５）
電解液Ｅとして、式（６）に示したピリミジン環を有する有機化合物を含むヨウ素系レドックス溶液（ヨウ化テトラブチルアンモニウムの濃度；０．６ｍｏｌ／Ｌ、ヨウ素の濃度；０．１ｍｏｌ／Ｌ、ピリミジン環を有する有機化合物の濃度；０．1ｍｏｌ／Ｌ、溶媒；メトキシプロピオニトリル）を調製した。この電解液Ｅを用いたこと以外は、実施例１と同様の手順及び条件で色素増感型太陽電池を作製した。
【０１０７】
（参考例６）
電解液Ｅとして、式（７）に示したピリミジン環を有する有機化合物を含むヨウ素系レドックス溶液（ヨウ化テトラブチルアンモニウムの濃度；０．６ｍｏｌ／Ｌ、ヨウ素の濃度；０．１ｍｏｌ／Ｌ、ピリミジン環を有する有機化合物の濃度；０．1ｍｏｌ／Ｌ、溶媒；メトキシプロピオニトリル）を調製した。この電解液Ｅを用いたこと以外は、参考例１と同様の手順及び条件で色素増感型太陽電池を作製した。
【０１０８】
（参考例７）
電解液Ｅとして、式（８）に示したピリミジン環を有する有機化合物を含むヨウ素系レドックス溶液（ヨウ化テトラブチルアンモニウムの濃度；０．６ｍｏｌ／Ｌ、ヨウ素の濃度；０．１ｍｏｌ／Ｌ、ピリミジン環を有する有機化合物の濃度；０．1ｍｏｌ／Ｌ、溶媒；メトキシプロピオニトリル）を調製した。この電解液Ｅを用いたこと以外は、参考例１と同様の手順及び条件で色素増感型太陽電池を作製した。
【０１０９】
（比較例１）
電解液Ｅとして、ピリミジン環を有する有機化合物を含まないヨウ素系レドックス溶液（ヨウ化テトラブチルアンモニウムの濃度；０．６ｍｏｌ／Ｌ、ヨウ素の濃度；０．１ｍｏｌ／Ｌ、溶媒；メトキシプロピオニトリル）を調製した。この電解液Ｅを用いたこと以外は、参考例１と同様の手順及び条件で色素増感型太陽電池を作製した。
【０１１０】
（比較例２）
電解液Ｅとして、ピリミジン環を有する有機化合物のかわりに、従来の４−ｔｅｒｔ−ブチルピリジンを含むヨウ素系レドックス溶液（ヨウ化テトラブチルアンモニウムの濃度；０．６ｍｏｌ／Ｌ、ヨウ素の濃度；０．１ｍｏｌ／Ｌ、４−ｔｅｒｔ−ブチルピリジンの濃度；０．1ｍｏｌ／Ｌ、溶媒；メトキシプロピオニトリル）を調製した。この電解液Ｅを用いたこと以外は、参考例１と同様の手順及び条件で色素増感型太陽電池を作製した。
【０１１１】
［電池特性試験１］
以下の手順及び測定条件により電池特性試験を行ない、実施例４及び実施例５、参考例１〜参考例３、参考例６及び参考例７並びに比較例１及び比較例２の色素増感型太陽電池の光電変換効率ηを測定した。
【０１１２】
電池特性試験は、ソーラーシミュレータ（ワコム製、商品名；「ＷＸＳ−８５−Ｈ型」）を用い、ＡＭフィルター（ＡＭ１．５）を通したキセノンランプ光源から１０００ｍＷ／ｃｍ2の擬似太陽光を照射することにより行った。
【０１１３】
先ず、各色素増感型太陽電池について、Ｉ−Ｖテスターを用いて室温（２５℃）にて電流−電圧特性を測定し、開放電圧（Ｖｏｃ／Ｖ）、短絡電流（Ｉｓｃ／ｍＡ・ｃｍ-2）、曲線因子（F.F.）を求め、これらから起動初期の光電変換効率η［％］を求めた。
【０１１４】
その後、８５℃に保持した恒温槽に各色素増感型太陽電池を入れ、遮光状態でありかつ回路開放状態で保存し、３６０時間経過した後、恒温槽から取り出して、室温（２５℃）にて上記と同様の電流−電圧特性を測定し、３６０時間経過後の光電変換効率ηを求めた。その結果を表１に示す。
【０１１５】
【表１】
【０１１６】
表１に示した結果から明らかなように、本発明の色素増感型太陽電池に使用するピリミジン環を有する有機化合物を含有させた電解質を用いた実施例４及び実施例５並びに参考例１〜参考例３、参考例６及び参考例７の色素増感型太陽電池は、８５℃という色素増感型太陽電池が実用化された際に最も適用される可能性の高い比較的高温の作動環境下で長期にわたり保存された後においても優れた光電変換効率をほぼ維持できることが確認された。一方、比較例１及び比較例２の色素増感型太陽電池は、保存時間の経過とともに光電変換効率が大幅に低下していることが確認された。
【０１１７】
［電池特性試験２］
参考例１、比較例１及び比較例２の色素増感型太陽電池を別途作製し、以下に示す手順及び条件以外は上述の電池特性試験１と同様の手順及び測定条件により電池特性試験を行ない、参考例１と比較例１の色素増感型太陽電池の光電変換効率ηを測定した。
【０１１８】
すなわち、参考例１、比較例１及び比較例２の色素増感型太陽電池をそれぞれ短絡させ、電解液Ｅの温度を６０℃に保持した状態とし、これに先に述べた１０００ｍＷ／ｃｍ2の疑似太陽光を連続的に照射した。そして、疑似太陽光の照射開始から２４時間経過後、１２０時間経過後、２４０時間経過後の光電変換効率ηをそれぞれ測定した。その結果を表２に示す。
【０１１９】
【表２】
【０１２０】
表２に示した結果から明らかなように、参考例１の色素増感型太陽電池は、６０℃の作動環境下で長期にわたり疑似太陽光の照射を受けて連続的に作動させられた後においても優れた光電変換効率を維持できることが確認された。一方、参考例１の色素増感型太陽電池に比較して、比較例１及び比較例２の色素増感型太陽電池は、疑似太陽光の照射時間の経過とともに光電変換性能が大幅に低下していることが確認された。
【０１２１】
【発明の効果】
以上説明したように、本発明によれば、初期において高い光電変換効率を得ることができ、しかも長期にわたって作動させた場合、又は長期にわたって保存した後に作動させた場合であっても、充分な光電変換効率を得ることができる耐久性に優れた色素増感型太陽電池を得ることができる。
【図面の簡単な説明】
【図１】本発明の色素増感型太陽電池の第１実施形態の基本構成を示す模式断面図である。
【図２】本発明の色素増感型太陽電池の第２実施形態の基本構成を示す模式断面図である。
【図３】本発明の色素増感型太陽電池の第３実施形態の基本構成を示す模式断面図である。
【図４】図２又は図３に示した色素増感型太陽電池を複数併設する場合の一例を示す模式断面図である。
【符号の説明】
１…透明電極、２…半導体電極、３…透明導電膜、４…透明基板、５…シール材、６・・・基板、８・・・炭素電極、９・・・レーザスクライブにより形成された溝、１０…光電極、２０,３０，４０，５０…色素増感型太陽電池、ＣＥ…対極、Ｅ…電解質、Ｆ１，Ｆ２，Ｆ３…受光面、Ｆ２２…半導体電極２の裏面、Ｓ…スペーサ、ＰＳ…多孔体層。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dye-sensitized solar cell.
[0002]
[Prior art]
In recent years, various developments of solar cells have been promoted with increasing interest in global warming and energy problems. Among the solar cells, since the dye-sensitized solar cell was proposed by Gretzell et al., Its practical use is expected from the advantages such as the low cost of materials used and the fact that it can be manufactured by a relatively simple process. .
[0003]
In such a dye-sensitized solar cell, while improving conversion efficiency (battery characteristics), improving the battery life to a practical level is an important issue for practical use. . That is, it is to suppress the decrease in conversion efficiency due to long-term use of the dye-sensitized solar cell, and to obtain durability that maintains excellent conversion efficiency over a long period of time.
[0004]
In conventional dye-sensitized solar cells, IThree -/ I-It is known that when lithium iodide is added in preparing an electrolyte containing a redox couple consisting of (for example, an electrolyte solution), photocurrent increases and photoelectric conversion efficiency improves (for example, Patent Document 1). three).
[0005]
Lithium cations generated from lithium iodide in the electrolytic solution, for example, when attracted to the surface of a negatively charged semiconductor electrode (photoelectrode), lower the Fermi level on the surface of the semiconductor electrode by its positive charge (more It is considered that there is a shift to the positive potential side). As a result, for example, the potential difference between the Fermi level on the surface of the semiconductor electrode and the excitation level of the sensitizing dye is expanded, and as a result, the electron transfer from the dye to the oxide semiconductor proceeds rapidly, and the photocurrent Is believed to increase.
[0006]
However, when lithium iodide is used as in the conventional dye-sensitized solar cell, the open circuit voltage (maximum output voltage) is reduced. When the open circuit voltage decreases, the output voltage obtained during power generation also decreases, and sufficient photoelectric conversion efficiency cannot be obtained. The open-circuit voltage of a dye-sensitized solar cell is determined by the difference between the Fermi level of the semiconductor electrode and the redox potential of the redox couple in the electrolyte, but when lithium iodide is used, the action of the lithium cation described above As a result, the Fermi level on the surface of the semiconductor electrode is shifted (shifted to the side where the open-circuit voltage decreases) as one of the major causes of the above problem.
[0007]
When the Fermi level on the surface of the semiconductor electrode shifts as described above, so-called reverse electron transfer (“dark current”) in which electrons move from the semiconductor electrode surface or photoexcited sensitizing dye into the electrolyte as the open circuit voltage decreases. Or “leakage current”). When this dark current is generated, the output voltage and photocurrent density obtained during power generation are reduced.
[0008]
Therefore, a base made of a heterocyclic compound such as 4-tert-butylpyridine or N-methylbenzimidazole was added to the electrolyte for the purpose of suppressing the reduction of the open circuit voltage and the generation of dark current associated therewith. A dye-sensitized solar cell having a configuration has been proposed (see, for example, Non-Patent Document 1). The base made of this heterocyclic compound is considered to have a function of coordinating to the surface of the semiconductor electrode and suppressing the generation of dark current from the surface of the semiconductor electrode into the electrolyte.
[0009]
In dye-sensitized solar cells, dye {eg, ruthenium complex [cis-Di (thiocyanato) -N, N'-bis (2,2'-bipyridyl-4,4'dicarboxylic acid) -ruthenium (II)] Etc.} has a role of capturing light, and preventing the deterioration of the dye is considered to be important for extending the battery life and stably obtaining the photoelectric conversion efficiency over a long period of time.
[0010]
[Patent Document 1]
JP 2001-52766 A
[Non-Patent Document 1]
Mohammad K. et al., Journal of American Chemical Society, 2001, 123, p.1613-1624.
[0011]
[Problems to be solved by the invention]
However, in the dye-sensitized solar cell having a structure having an electrolyte added with a base consisting of a heterocyclic compound such as 4-tert-butylpyridine and N-methylbenzimidazole, the present inventors have long-lasted the battery. It has been found that the photoelectric conversion efficiency when operated for a long time is remarkably lowered with time, and the operation durability is still insufficient. Further, it has been found that the photoelectric conversion efficiency when the battery is started after being stored for a long period is not sufficient, and the storage durability is still insufficient.
[0012]
The present invention has been made in view of the above-described problems of the prior art, and can obtain high photoelectric conversion efficiency in the initial stage after battery manufacture, and can be operated after long-term operation or after long-term storage. It is an object of the present invention to provide a dye-sensitized solar cell with excellent durability capable of obtaining a sufficient photoelectric conversion efficiency even if it is used.
[0013]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the inventors of the present invention have an electrolyte to which a base made of a heterocyclic compound such as 4-tert-butylpyridine and N-methylbenzimidazole is added. In dye-sensitized solar cells, the above-mentioned base causes the deterioration of the dye in the photoelectrode (this dye may also be contained in the electrolyte), which is a major cause of the problem described above. I found out that it was one.
[0014]
As a result of further studies, the present inventors have added an organic compound having a pyrimidine ring to the electrolyte instead of a base made of a heterocyclic compound such as 4-tert-butylpyridine and N-methylbenzimidazole. Thus, high photoelectric conversion efficiency can be obtained in the initial stage while sufficiently preventing reverse electron transfer, and sufficient photoelectricity can be obtained even when operated for a long period of time or after being stored for a long period of time. The present inventors have found that a dye-sensitized solar cell having excellent durability capable of maintaining the conversion efficiency can be obtained, and has reached the present invention.
[0015]
That is, the present invention includes a porous semiconductor electrode having a light receiving surface, a photoelectrode having a transparent electrode disposed adjacent to the light receiving surface, and a counter electrode, and the semiconductor electrode and the counter electrode are A dye-sensitized solar cell having a configuration in which an electrolyte is disposed opposite to each other, the semiconductor electrode contains a dye, and the electrolyte contains at least an organic compound having a pyrimidine ring. A dye-sensitized solar cell characterized by the above is provided.
[0016]
According to the present invention, an organic compound having a pyrimidine ring instead of a base consisting of a heterocyclic compound such as 4-tert-butylpyridine and N-methylbenzimidazole is contained in the electrolyte, so that a high photoelectric property can be obtained in the initial stage. Conversion efficiency can be obtained, and even when operated for a long period of time, or when operated after storage for a long period of time, a decrease in the photoelectric conversion efficiency obtained at the initial stage is sufficiently prevented, and sufficient photoelectric conversion is achieved. A dye-sensitized solar cell excellent in durability capable of maintaining efficiency can be easily configured.
[0017]
As described above, the reason why the deterioration of the dye is sufficiently prevented by containing an organic compound having a pyrimidine ring in an electrolyte (for example, an electrolytic solution) has not been clearly clarified. However, the present inventors have found that organic compounds having a pyrimidine ring have a longer lifetime for dye-sensitized solar cells than bases made of heterocyclic compounds such as 4-tert-butylpyridine and N-methylbenzimidazole. This is thought to be due to the low reaction activity for the dye decomposition reaction and ligand exchange reaction, which are considered to have a large effect.
[0018]
For example, the inventors of the present invention have proposed that a base made of a heterocyclic compound added to an electrolyte (for example, an electrolytic solution) of a conventional dye-sensitized solar cell is a dye (for example, described above) in a semiconductor electrode. Highly nucleophilic with respect to the metal ion (or metal atom) that is the coordination center of organometallic complexes such as ruthenium complexes), and may contribute to the progress of the ligand elimination reaction from the coordination center I believe there is. For example, in the case of 4-tert-butylpyridine, there is a possibility that the site of the nitrogen atom reacts with a coordination center such as ruthenium ion (or ruthenium atom) to promote the elimination reaction of the ligand. I think there is.
[0019]
On the other hand, the present inventors consider that an organic compound having a pyrimidine ring has a low nucleophilicity to a coordination center and a low ability to deteriorate a dye as compared with a base made of the above-described heterocyclic compound. . Therefore, the dye-sensitized solar cell can obtain high photoelectric conversion efficiency in the initial stage, and even when operated for a long period of time or after being stored for a long period of time, It is believed that a dye-sensitized solar cell excellent in durability capable of sufficiently preventing a decrease in conversion efficiency and maintaining sufficient photoelectric conversion efficiency can be obtained.
[0020]
Moreover, in this invention, when an acid exists in electrolyte (for example, electrolyte solution), the organic compound which has a pyrimidine ring may neutralize with this acid, and may exist in the state of a salt. Even in this case, the above-described effects of the present invention can be obtained. For example, ruthenium complex [cis-Di (thiocyanato) -N, N'-bis (2,2'-bipyridyl-4,4'dicarboxylic acid) -ruthenium (II)] as a dye in the porous semiconductor electrode of the photoelectrode ], The organic compound having a pyrimidine ring contained in the electrolyte impregnated in the pores of the semiconductor electrode neutralized with the carboxyl group of the dye composed of the ruthenium complex to form a salt. It may be in a state. Even in this case, the present inventors consider that the photosensitization function of the dye does not deteriorate from the results obtained by experiments.
[0021]
Here, in the present invention, the “dye” refers to a metal complex dye and an organic dye. In addition, the “electrolyte” includes (i) an electrolyte solution (hereinafter referred to as “electrolyte” as necessary), (ii) a gel formed by adding a gelling agent to the electrolyte solution, and (iii) A solid electrolyte and (iv) a porous layer made of a porous material are impregnated with any one of (i) to (iii).
[0022]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the photoelectrode and the dye-sensitized solar cell of the present invention will be described in detail with reference to the drawings. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.
[0023]
[First Embodiment]
FIG. 1 is a schematic cross-sectional view showing the basic configuration of the first embodiment of the dye-sensitized solar cell of the present invention.
[0024]
A dye-sensitized solar cell 20 shown in FIG. 1 mainly includes a photoelectrode 10, a counter electrode CE, and an electrolyte E filled in a gap formed between the photoelectrode 10 and the counter electrode CE by a spacer S; It is composed of 1 mainly includes a semiconductor electrode 2 having a light receiving surface F2 and a transparent electrode 1 disposed adjacently on the light receiving surface F2 of the semiconductor electrode 2. The semiconductor electrode 2 is in contact with the electrolytic solution E on the back surface F22 opposite to the light receiving surface F2.
[0025]
In the dye-sensitized solar cell 20, the sensitizing dye adsorbed in the semiconductor electrode 2 is excited by the light L <b> 10 that passes through the transparent electrode 1 and is applied to the semiconductor electrode 2. Electrons are injected into the electrode 2. The electrons injected in the semiconductor electrode 2 are collected in the transparent electrode 1 and taken out to the outside.
[0026]
The structure of the transparent electrode 1 is not specifically limited, The transparent electrode mounted in a normal dye-sensitized solar cell can be used. For example, the transparent electrode 1 shown in FIG. 1 has a configuration in which a so-called transparent conductive film 3 is coated on the semiconductor electrode 2 side of a transparent substrate 4 such as a glass substrate. As the transparent conductive film 3, a transparent electrode used for a liquid crystal panel or the like may be used.
[0027]
For example, fluorine-doped SnO2Coated glass, ITO coated glass, ZnO: Al coated glass, antimony-doped tin oxide (SnO2-Sb), etc. In addition, a transparent electrode obtained by doping cations or anions with different valences into tin oxide or indium oxide, or a metal electrode having a structure capable of transmitting light, such as a mesh shape or a stripe shape, provided on a substrate such as a glass substrate Good.
[0028]
As the transparent substrate 4, a transparent substrate used for a liquid crystal panel or the like may be used. Specific examples of the transparent substrate material include transparent glass substrates, materials that prevent the reflection of light by appropriately roughening the surface of the glass substrate, and materials that transmit light, such as a ground glass-like translucent glass substrate. Note that the material may not be glass as long as it transmits light, and may be a transparent plastic plate, a transparent plastic film, an inorganic transparent crystal, or the like.
[0029]
A porous semiconductor electrode 2 shown in FIG. 1 includes an oxide semiconductor layer containing oxide semiconductor particles as a constituent material. The oxide semiconductor particles contained in the semiconductor electrode 2 are not particularly limited, and a known oxide semiconductor or the like can be used. As an oxide semiconductor, for example, TiO2, ZnO, SnO2, Nb2OFive, In2OThree, WOThree, ZrO2, La2OThree, Ta2OFive, SrTiOThree, BaTiOThreeEtc. can be used. Among these oxide semiconductors, anatase TiO2Is preferred. The pores in the semiconductor electrode 2 are impregnated with an electrolyte (electrolytic solution E).
[0030]
The sensitizing dye contained in the semiconductor electrode 2 is not particularly limited as long as it is a dye having absorption in the visible light region and / or the infrared light region. More preferably, any material that emits electrons when excited by light having a wavelength of at least 200 nm to 2 μm may be used. As such a sensitizing dye, a metal complex, an organic dye, or the like can be used.
[0031]
Examples of metal complexes include metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine, chlorophyll or derivatives thereof, hemin, ruthenium, osmium, iron and zinc complexes (eg, cis-dicyanate-N, N′-bis (2,2′-bipyridyl). -4,4'-dicarboxylate) ruthenium (II)) and the like. As the organic dye, metal-free phthalocyanine, cyanine dye, merocyanine dye, xanthene dye, triphenylmethane dye, and the like can be used.
[0032]
The counter electrode CE is a redox pair (for example, I) in the electrolyte (electrolytic solution E).Three -/ I-Etc.) is not particularly limited as long as it is made of a material that can pass electrons with high efficiency. For example, the same counter electrode as that normally used for a silicon solar cell, a liquid crystal panel, or the like is used. It is possible. For example, it may have the same configuration as that of the transparent electrode 1 described above. A metal thin film electrode such as Pt is formed on the transparent conductive film 3 similar to the transparent electrode 1, and the metal thin film electrode is disposed on the side of the electrolyte E You may arrange | position toward. Alternatively, a small amount of platinum may be attached to the transparent conductive film 3 of the transparent electrode 1, or a metal thin film such as platinum, a conductive film such as carbon, or the like may be used.
[0033]
Further, the electrolytic solution E particularly includes at least the organic compound having the pyrimidine ring described above, and if it contains a redox species for reducing the dye after photoexcitation and electron injection into the semiconductor. It is not limited. For example, it may be a liquid electrolyte containing an organic compound having a pyrimidine ring, and is a gel electrolyte obtained by adding a known gelling agent (polymer or low molecular weight gelling agent) to this. Also good. The electrolytic solution E or the gel electrolyte is also filled in the pores of the porous semiconductor electrode 2. Furthermore, when the counter electrode CE is made of a porous electron conductive material, the pores inside the counter electrode CE are also filled.
[0034]
Further, instead of the electrolytic solution E, a layer made of a solid polymer electrolyte or a ceramic solid electrolyte containing an organic compound having a pyrimidine ring may be disposed between the semiconductor electrode 2 and the counter electrode CE. In this case, the pores of the porous semiconductor electrode 2 may be filled with the above-described solid polymer electrolyte or ceramic solid electrolyte.
[0035]
In addition, in the pores of the porous semiconductor electrode 2, the above-described electrolytic solution E or another electrolytic solution (however, an organic compound having a pyrimidine ring, a dye after being photoexcited and injecting electrons into the semiconductor) (Including redox species for reduction) or a gelled product of these. Further, when the counter electrode CE is made of a porous electron conductive material, the same electrolyte as the electrolyte that can be used for the semiconductor electrode 2 is filled in the pores inside the counter electrode CE. Good.
[0036]
The solvent used in the electrolytic solution E is not particularly limited as long as it is a compound that can dissolve the solute component, but is electrochemically inert, has a high relative dielectric constant, and a low viscosity (and these solvents). Mixed solvents) are preferable, for example, nitrile compounds such as methoxyacetonitrile, methoxypropionitrile and acetonitrile, lactone compounds such as γ-butyrolactone and valerolactone, carbonate compounds such as ethylene carbonate and propylene carbonate, and propylene carbonate. Can be mentioned.
[0037]
As the solute other than the organic compound having a pyrimidine ring used in the electrolytic solution E, a redox pair (I) capable of transferring electrons to and from the dye supported on the semiconductor electrode 2 and the counter electrode CE.Three -/ I-System electrolyte, BrThree -/ Br-Based electrolytes, redox electrolytes such as hydroquinone / quinone based electrolytes), compounds having an effect of promoting the transfer of electrons, and the like. These may be included singly or in combination.
[0038]
More specifically, examples of the substance constituting the redox pair include halogens such as iodine, bromine, and chlorine, -1,2-dimethyl-3-propylimidazolium iodide, tetrapropylammonium iodide, and the like. It is done. Note that an amount of lithium iodide in an amount that does not greatly decrease the durability (for example, 5 mmol / L or less) may be included, but it is preferable not to include lithium iodide.
[0039]
In addition, the electrolytic solution E contains an organic compound having a pyrimidine ring instead of the conventional 4-t-butylpyridine as an additive for efficiently transferring electrons. An organic compound having a pyrimidine ring is considered to have low reactivity with a dye.
[0040]
Therefore, by adopting the electrolyte E containing an organic compound having a pyrimidine ring, high photoelectric conversion efficiency can be obtained in the initial stage, and when operated for a long period of time or after being stored for a long period of time. However, it is possible to obtain a dye-sensitized solar cell excellent in durability that can sufficiently prevent a decrease in the photoelectric conversion efficiency obtained in the initial stage and maintain a sufficient photoelectric conversion efficiency.
[0041]
From the viewpoint of obtaining the effects of the present invention more reliably, the organic compound having a pyrimidine ring preferably has a structure represented by the following general formula (1).
[0042]
[Chemical 9]
[0043]
In formula (1), R1, R2, R3And R4May be the same or different and are each selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. The characteristic group of is shown. However,R 1 , R 2 , R 3 And R 4 At least one of is a halogen atom,R2And R3May be bonded to each other to form a condensed ring.
[0044]
Where R1, R2, RThreeAnd RFourAre each a hydrocarbon group, the "hydrocarbon group" means one having 1 to 20 carbon atoms and an alkyl group, alkenyl group, alkynyl group, allyl group, aryl group, and heterocyclic ring. At least one characteristic group selected from the group consisting of groups;
[0045]
R1, R2, RThreeAnd RFourAre each an alkoxy group, the “alkoxy group” represents a characteristic group having a structure represented by the general formula: R—O—. Here, the R has 1 to 20 carbon atoms and is at least one selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an allyl group, an aryl group, and a heterocyclic group. Indicates the characteristic group of the species.
[0046]
In addition, R2And RThreeAre bonded to each other to form a condensed ring, the “condensed ring” means a ring-constituting atom (ie, R2And RThreeIn addition to the above-mentioned constituent atoms, a “fused heterocycle” containing a nitrogen atom may be used.
[0047]
From the viewpoint of more reliably obtaining the effects of the present invention described above, an organic compound having a pyrimidine ring is represented by the following general formula:(5) and (6)It is preferable that it is at least 1 sort (s) selected from the group which consists of a compound represented by these.
[0048]
[Chemical Formula 10]
[0049]
Embedded image
[0050]
Embedded image
[0051]
Embedded image
[0052]
Embedded image
[0053]
Embedded image
[0054]
Embedded image
[0055]
The concentration of the organic compound having a pyrimidine ring in the electrolyte E is 10-Four10 mol / L is preferred, 10-2More preferably, it is 10 mol / L. Here, the concentration of the organic compound having a pyrimidine ring is 10-FourIf it is less than mol / L, the effect of adding an organic compound having a pyrimidine ring tends to be insufficient, and sufficient photoelectric conversion efficiency tends not to be obtained. On the other hand, the concentration of the organic compound having a pyrimidine ring is 10 mol / L. Exceeding this will increase the short circuit current, but the open circuit voltage and F.I. F. Decreases, the photoelectric conversion efficiency tends to decrease.
[0056]
The constituent material of the spacer S is not particularly limited, and for example, silica beads or the like can be used.
[0057]
Moreover, as a sealing material used for integrating the photoelectrode 10, the counter electrode CE, and the spacer S for the purpose of sealing the electrolytic solution E, it can be sealed so that the components of the electrolytic solution E do not leak to the outside as much as possible. Any material can be used as long as it is not particularly limited. For example, an epoxy resin, a silicone resin, an ethylene / methacrylic acid copolymer, a thermoplastic resin made of surface-treated polyethylene, or the like can be used.
[0058]
Next, an example of a method for manufacturing the dye-sensitized solar cell 20 shown in FIG. 1 will be described.
[0059]
When the transparent electrode 1 is manufactured, the fluorine-doped SnO described above on the substrate 4 such as a glass substrate.2It can form using well-known thin film manufacturing techniques, such as spray-coating the transparent conductive films 3, such as. For example, in addition to this, it can be formed using a known thin film manufacturing technique such as a vacuum deposition method, a sputtering method, a CVD method, and a sol-gel method.
[0060]
Examples of a method for forming the semiconductor electrode 2 on the transparent conductive film 3 of the transparent electrode 1 include the following methods. That is, first, a dispersion liquid in which oxide semiconductor particles having a predetermined size (for example, a particle diameter of about 10 to 30 nm) is dispersed is prepared. The solvent of this dispersion liquid is not particularly limited as long as it can disperse oxide semiconductor particles such as water, an organic solvent, or a mixed solvent of both. Moreover, you may add surfactant and a viscosity modifier to a dispersion liquid as needed.
[0061]
Next, the dispersion is applied onto the transparent conductive film 3 of the transparent electrode 1 and then dried. As a coating method at this time, a bar coater method, a printing method, or the like can be used. Then, after drying, the semiconductor electrode 2 (porous semiconductor film) is formed by heating and firing in air, inert gas or nitrogen.
[0062]
Next, a sensitizing dye is contained in the semiconductor electrode 2 by a known technique such as an adhesion method. The sensitizing dye is contained by adhering to the semiconductor electrode 2 (chemical adsorption, physical adsorption or deposition). As this adhesion method, for example, a method of immersing the semiconductor electrode 2 in a solution containing a dye can be used. At this time, adsorption and deposition of the sensitizing dye can be promoted by heating and refluxing the solution. At this time, a metal such as silver or a metal oxide such as alumina may be contained in the semiconductor electrode 2 in addition to the pigment, if necessary.
[0063]
The surface oxidation treatment for removing impurities that inhibit the photoelectric conversion reaction contained in the semiconductor electrode 2 may be appropriately performed by a known method every time each layer is formed or when all the layers are formed. .
[0064]
Other methods for forming the semiconductor electrode 2 on the transparent conductive film 3 of the transparent electrode 1 include the following methods. That is, on the transparent conductive film 3 of the transparent electrode 1 TiO2A method of vapor-depositing a semiconductor such as a film may be used. As a method for depositing a semiconductor on the transparent conductive film 3, a known thin film manufacturing technique can be used. For example, a physical vapor deposition method such as electron beam vapor deposition, resistance heating vapor deposition, sputter vapor deposition, or cluster ion beam vapor deposition may be used. Metal or the like is evaporated in a reactive gas such as oxygen, and the reaction product is converted into the transparent conductive film 3. A reactive vapor deposition method may be used. Furthermore, chemical vapor deposition such as CVD can be used by controlling the flow of the reaction gas.
[0065]
After the photoelectrode 10 is produced in this manner, for example, a counter electrode CE is produced by a known thin film manufacturing technique similar to the method used for producing the photoelectrode 10, and as shown in FIG. The counter electrode CE is assembled so as to face the spacer S. At this time, the space formed between the photoelectrode 10 and the counter electrode CE by the spacer S is filled with the electrolytic solution E containing an organic compound having a pyrimidine ring, and the dye-sensitized solar cell 20 is completed.
[0066]
[Second Embodiment]
FIG. 2 is a schematic cross-sectional view showing a second embodiment of the dye-sensitized solar cell of the present invention. Hereinafter, the dye-sensitized solar cell 30 illustrated in FIG. 2 will be described. In addition, the same code | symbol is attached | subjected about the element same as the element demonstrated regarding the dye-sensitized solar cell 20 shown in the above-mentioned FIG. 1, and the overlapping description is abbreviate | omitted.
[0067]
A dye-sensitized solar cell 30 shown in FIG. 2 uses the photoelectrode 10 shown in FIG. 1 and a counter electrode CE similar to the counter electrode CE shown in FIG. In the dye-sensitized solar cell 20 shown in FIG. 1, the space formed between the photoelectrode 10 and the counter electrode CE is filled with the electrolytic solution E by the spacer S, as shown in FIG. In the dye-sensitized solar cell 30, the porous layer PS is disposed between the photoelectrode 10 and the counter electrode CE.
[0068]
This porous layer PS has a structure having a large number of pores, and inside this porous layer PS is a pyrimidine similar to that used in the dye-sensitized solar cell 20 shown in FIG. An electrolytic solution E containing an organic compound having a ring is filled and held.
[0069]
The electrolytic solution E is also held in the counter electrode CE in the semiconductor electrode 2 or depending on the constituent material used (for example, a porous conductive film such as carbon). The side surfaces of the semiconductor electrode 2 and the porous body layer PS of the dye-sensitized solar cell 30 shown in FIG. 2 prevent the electrolyte E from leaking outside from the side surfaces of the semiconductor electrode 2 and the porous body layer PS. Is covered with a sealing material 5.
[0070]
The porous body layer PS is not particularly limited as long as the porous body layer PS can hold the electrolytic solution E and does not have electron conductivity. For example, you may use the porous body formed with the rutile type titanium oxide particle. Examples of constituent materials other than rutile type titanium oxide include zirconia, alumina, and silica.
[0071]
Moreover, as the sealing material 5, for example, a thermoplastic resin film such as polyethylene or an epoxy adhesive can be used.
[0072]
Next, an example of a method for manufacturing the dye-sensitized solar cell 30 shown in FIG. 2 will be described. First, the photoelectrode 10 is produced in the same manner as the dye-sensitized solar cell 20 shown in FIG. Next, the porous layer PS is formed on the surface F22 of the semiconductor electrode 2 of the photoelectrode 10 by the same procedure as that for producing the semiconductor electrode 2 of the photoelectrode 10. For example, a dispersion (slurry) containing a constituent material of the porous layer PS such as rutile type titanium oxide may be prepared, and this may be applied to the surface F22 of the semiconductor electrode 2 and dried.
[0073]
For the counter electrode CE, for example, when a porous conductive film such as carbon is used as the counter electrode CE, for example, a carbon paste is prepared, and this is applied to the surface of the porous body layer PS and dried. The substrate may be formed on the surface opposite to the porous layer PS side of the conductive film by a known thin film manufacturing technique to form the counter electrode CE, and the side surfaces of the semiconductor electrode 2 and the porous layer PS may be Covering with the sealing material 5 completes the dye-sensitized solar cell 30. In addition, as a board | substrate which is a part of such a counter electrode CE, a normal board | substrate may be used and a transparent substrate may be used.
[0074]
In this dye-sensitized solar cell 30 as well, the electrolytic solution E contains at least the organic compound having the pyrimidine ring described above, and reduces the dye after being photoexcited and injecting electrons into the semiconductor. If it contains the oxidation reduction seed | species for, it will not specifically limit. For example, it may be a liquid electrolyte containing an organic compound having a pyrimidine ring, and is a gel electrolyte obtained by adding a known gelling agent (polymer or low molecular weight gelling agent) to this. Also good. Further, instead of the electrolytic solution E, a solid polymer electrolyte or a ceramic solid electrolyte containing an organic compound having a pyrimidine ring is placed in the pores in the semiconductor electrode 2 and the porous body layer PS (and the electron conduction in which the counter electrode CE is porous). In the case where it is made of a conductive material, it may be filled in the inside pores of the counter electrode CE).
[0075]
[Third Embodiment]
FIG. 3 is a schematic cross-sectional view showing a third embodiment of the dye-sensitized solar cell of the present invention. Hereinafter, the dye-sensitized solar cell 40 shown in FIG. 3 will be described. In addition, the same code | symbol is attached | subjected about the element same as the element demonstrated regarding the dye-sensitized solar cell 20 shown in the above-mentioned FIG. 1, or the dye-sensitized solar cell 30 shown in FIG. Omitted.
[0076]
The dye-sensitized solar cell 40 shown in FIG. 3 has the same configuration as the dye-sensitized solar cell 30 shown in FIG. 2 except for the shape of the porous layer PS and the configuration of the counter electrode CE shown below. . In other words, in the case of the dye-sensitized solar cell 40 shown in FIG. is doing. The flange-shaped edge portion extends in a direction substantially parallel to the normal direction of the light receiving surface F 1 of the transparent electrode 1 of the photoelectrode 10, and the tip thereof is connected to the transparent electrode 1.
[0077]
The connecting portion between the transparent electrode 1 and the porous layer PS will be described in more detail. In this connecting portion, the transparent conductive film 3 portion of the transparent electrode 1 is completely scraped off by a technique such as laser scribing, for example. A groove 9 having a depth at which the surface of the transparent substrate 4 appears is formed. And the edge part formed in the groove | channel shape of the porous body layer PS in the part of this groove | channel 9 is inserted.
[0078]
The counter electrode CE is composed of a carbon electrode 8 disposed adjacent to the porous body layer PS and a substrate 6 disposed adjacent to the surface of the carbon electrode 8 opposite to the porous body layer PS. Yes. Here, the carbon electrode 8 is a porous electrode formed of carbon black particles, graphite particles, and conductive oxide particles having an electric resistivity lower than that of anatase-type titanium oxide particles as at least constituent materials. Is preferred. The counter electrode CE is also formed with a bowl-shaped edge portion for closely covering and covering the bowl-shaped edge portion of the porous body layer PS. The saddle-shaped edge portion of the counter electrode CE also extends in a direction substantially parallel to the normal direction of the light receiving surface F1 of the transparent electrode 1 of the photoelectrode 10, and the tip thereof is in close contact with the surface of the transparent conductive film 3 of the transparent electrode 1. To be connected.
[0079]
Further, the portion of the side surface of the semiconductor electrode 2 not covered with the bowl-shaped edge portion of the porous body layer PS and the side surface of the porous body layer PS are not covered with the bowl-shaped edge portion of the counter electrode CE. The portion is sealed by disposing the same sealing material 5 as that used in the dye-sensitized solar cell 30 shown in FIG. Further, the same sealing material 5 as that used in the dye-sensitized solar cell 30 shown in FIG. 2 is arranged so as to be in close contact with the outer surface of the bowl-shaped edge portion of the counter electrode CE. .
[0080]
By disposing the substrate 6 and the sealing material 5, the electrolyte (for example, the electrolytic solution E described above) contained in each of the semiconductor electrode 2 and the porous body layer PS is diffused to the outside of the battery 40. Can be sufficiently prevented. If necessary, the sealing material 5 may be disposed in close contact between the substrate 6 and the carbon electrode 8. Thereby, it is possible to more sufficiently prevent the electrolyte (for example, the above-described electrolytic solution E) contained in the counter electrode CE from escaping to the outside of the battery 40.
[0081]
As described above, the dye-sensitized solar cell 40 has a configuration in which the porous layer PS and the counter electrode CE are integrated with the transparent electrode 1 of the photoelectrode 10. And the electrical contact with the photoelectrode 10 and the counter electrode CE is prevented by the bowl-shaped edge part of the porous body layer PS.
[0082]
If the electrical contact between the photoelectrode 10 and the counter electrode CE (electron transfer between the photoelectrode 10 and the counter electrode CE) is sufficiently prevented, the saddle-like shape of the porous layer PS in FIG. The side surface of the semiconductor electrode 2 and the inner side surface of the bowl-shaped edge portion of the counter electrode CE may be apparently in contact with each other without providing the edge portion. In this case, the constituent material of the semiconductor electrode 2 is inserted into the groove 9.
[0083]
Impregnated in the pores inside the semiconductor electrode 2 and the porous body layer PS (in addition, in the pores inside the counter electrode CE when the counter electrode CE is made of a porous electron conductive material). The electrolyte is not particularly limited as long as it contains at least the organic compound having the pyrimidine ring described above and contains a redox species for reducing the dye after photoexcitation and electron injection into the semiconductor. For example, the electrolyte solution E described above may be used.
[0084]
For example, it may be a liquid electrolyte containing an organic compound having a pyrimidine ring, and is a gel electrolyte obtained by adding a known gelling agent (polymer or low molecular weight gelling agent) to this. Also good. Further, instead of the electrolytic solution, a solid polymer electrolyte or a ceramic solid electrolyte containing an organic compound having a pyrimidine ring may be filled in the pores in the porous layer PS (and the counter electrode CE is porous). .
[0085]
In the dye-sensitized solar cell 40, when the photoelectrode 10 is formed, the groove 9 is formed by a known technique such as laser scribing, and when the porous body layer PS and the counter electrode CE are formed, respectively, The same as the dye-sensitized solar cell 30 shown in FIG. 2 except that a raw material slurry (or paste) is applied so that the edge portion of the substrate is formed, and then the substrate 6 is formed by a known method. It can be formed by a manufacturing method.
[0086]
The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.
[0087]
For example, the dye-sensitized solar cell of the present invention may have a module form in which a plurality of batteries are provided as in a dye-sensitized solar cell 50 shown in FIG. The dye-sensitized solar cell 50 shown in FIG. 4 is an example in which a plurality of the dye-sensitized solar cells 30 shown in FIG. 2 or the dye-sensitized solar cells 40 shown in FIG. Show.
[0088]
Compared to the dye-sensitized solar cell 30 shown in FIG. 2, the dye-sensitized solar cell 50 shown in FIG. 4 is different from the seal material 5 provided between the single-cell photoelectrodes 10 of adjacent solar cells. A groove 9 is formed between the photoelectrode 10 of a single cell (hereinafter referred to as a single cell A).
[0089]
The groove 9 is formed by scraping the semiconductor electrode 2 of the single cell A by a technique such as laser scribing. A portion of the groove 9 in the vicinity of the sealing material 5 reaches the depth at which the layer of the transparent conductive film 3 of the transparent electrode 1 appears by completely removing the portion of the semiconductor electrode 2. Further, in the vicinity of the semiconductor electrode 2 of the single cell A in the groove 9, the portion of the semiconductor electrode 2 and the portion of the transparent conductive film 3 are completely removed, and the layer of the transparent substrate 4 of the transparent electrode 1 appears. It has reached the depth.
[0090]
Further, in the vicinity of the sealing material 5 in the groove, the transparent conductive film 3 of the adjacent photoelectrode 10 and the portions of the semiconductor electrode 2 on the transparent conductive film 3 are not electrically contacted with each other. The edge part formed in the shape of a bowl of the porous body layer PS of the single cell A is inserted between these parts so as to contact the transparent substrate 4 of the transparent electrode 1.
[0091]
Further, in the vicinity of the semiconductor electrode 2 of the single cell A in the groove, that is, in the portion between the porous layer PS of the single cell A and the sealing material 5, the counter electrode CE of the single cell A has a bowl shape. The formed edge portion is inserted so as to contact the transparent conductive film 3 of the transparent electrode 1 of the other unit cell A. The dye-sensitized solar cell 50 can be formed by the same manufacturing method as the dye-sensitized solar cell 40 shown in FIG.
[0092]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and it demonstrates in more detail about the dye-sensitized solar cell of this invention, this invention is not limited to these Examples at all.
[0093]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and it demonstrates in more detail about the dye-sensitized solar cell of this invention, this invention is not limited to these Examples at all.
[0094]
(referenceExample 1)
A photoelectrode having the same configuration as that of the photoelectrode 10 shown in FIG. 1 is prepared by the following procedure, and the same as the dye-sensitized solar cell 20 shown in FIG. 1 except that this photoelectrode is used. Dye-sensitized solar cell having a structure (light receiving surface area: 1 cm2) Was produced.
[0095]
First, according to the method of Barbe et al. Described in Journal of ceramic society (Vol. 80, pages 3157-3171, 1987) except that the temperature of the autoclave was changed to 230 ° C., acetylacetone, ion-exchanged water, surfactant ( Aldrich, trade name: “tritonX”)2Slurry (TiO2) for forming a semiconductor electrode in which particles (Degussa, trade name: “P25”) are dispersed2Particle content: 11% by mass, TiO2The average particle size of the particles: about 10 nm, “Slurry 1”) was prepared.
[0096]
Next, a paste for forming a semiconductor electrode (hereinafter referred to as paste 1) was prepared by adding and mixing polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., number average molecular weight: 2000) as a thickener in slurry 1. . TiO in paste 12The mass ratio of particles to polyethylene glycol is TiO2Particle: Polyethylene glycol was adjusted to be 10: 3.
[0097]
On the other hand, SnO doped with fluorine on the glass substrate 4 (transparent conductive glass)2Transparent electrode 1 having a conductive film 3 (film thickness: 600 nm) (manufactured by Nippon Sheet Glass Co., Ltd., surface resistance: about 10Ω / cm)2, Thickness; 1 mm). And this SnO2On the conductive film 3, the above-mentioned paste 1 was applied to a thickness of 100 μm using a doctor blade, and then dried at a temperature of 25 ° C. for 30 minutes.
[0098]
Thereafter, the transparent electrode 1 to which the paste 1 was applied was transferred into an electric furnace and baked in the atmosphere at 450 ° C. for 30 minutes. Next, the transparent electrode 1 was taken out from the electric furnace and cooled. In this way, SnO2A semiconductor electrode having the same structure as the semiconductor electrode 2 shown in FIG. 1 on the conductive film 3 (light receiving surface area: 4 cm)2, Thickness of layer made of semiconductor film; 8 μm, TiO2Coating amount: 15 g / m2) Was formed, and a photoelectrode in a state containing no dye (metal complex dye and organic dye) was produced.
[0099]
Then, the pigment | dye was made to adsorb | suck to the back surface of the semiconductor electrode of a photoelectrode as follows. First, a dye (Red dye, manufactured by Sololonix, trade name: “N719”), that is, a ruthenium complex [cis-Di (thiocyanato) -N, N′-bis (2,2′-bipyridyl-4, 4'dicarboxylic acid) -ruthenium (II)], and ethanol and DMF {HCON (CHThree)2} In a mixed solvent (mass ratio of ethanol and DMF; ethanol: DMF = 1: 1) (concentration of sensitizing dye; 3 × 10-Fourmol / L) was prepared. Next, the semiconductor electrode was immersed in this solution and left for 12 hours in a dark place at 25 ° C. Next, the semiconductor electrode was taken out from this solution, washed with ethanol, and naturally dried in a dark place. As a result, a sensitizing dye is about 1.2 × 10 6 inside the semiconductor electrode 2.-7mol / m2The adsorbed photoelectrode 12 was completed.
[0100]
Next, as a counter electrode having the same shape and size as the above-described photoelectrode, a transparent conductive glass electrode (thickness of Pt thin film; 3 nm) on which Pt was deposited by an electron beam deposition method was produced.
[0101]
Further, as the electrolytic solution E, an iodine-based redox solution containing an organic compound having a pyrimidine ring represented by the formula (2) (tetrabutylammonium iodide concentration; 0.6 mol / L, iodine concentration; 0.1 mol / L) The concentration of the organic compound having a pyrimidine ring; 0.1 mol / L, solvent; methoxypropionitrile) was prepared.
[0102]
Furthermore, a spacer S (trade name: “High Milan”) manufactured by Mitsui DuPont Polychemical Co., Ltd. having a shape matched to the size of the semiconductor electrode was prepared. Next, as shown in FIG. 1, the photoelectrode 12, the counter electrode CE, and the spacer S were opposed to each other. Then, by using the capillary phenomenon, the space defined by the spacer S, the photoelectrode 12 and the counter electrode CE is filled with the above-described electrolytic solution E from the gap between the spacer S and the photoelectrode 12 or the counter electrode CE. Each member was sealed with an epoxy resin to complete a dye-sensitized solar cell.
[0103]
(referenceExample 2)
As an electrolytic solution E, an iodine-based redox solution containing an organic compound having a pyrimidine ring represented by the formula (3) (tetrabutylammonium iodide concentration; 0.6 mol / L, iodine concentration; 0.1 mol / L, pyrimidine) The concentration of the organic compound having a ring: 0.1 mol / L, solvent: methoxypropionitrile) was prepared. Except for using this electrolytic solution E,referenceA dye-sensitized solar cell was produced according to the same procedure and conditions as in Example 1.
[0104]
(referenceExample 3)
As an electrolytic solution E, an iodine-based redox solution containing an organic compound having a pyrimidine ring represented by Formula (4) (tetrabutylammonium iodide concentration; 0.6 mol / L, iodine concentration; 0.1 mol / L, pyrimidine) The concentration of the organic compound having a ring: 0.1 mol / L, solvent: methoxypropionitrile) was prepared. Except for using this electrolytic solution E,referenceA dye-sensitized solar cell was produced according to the same procedure and conditions as in Example 1.
[0105]
Example 4
As an electrolytic solution E, an iodine-based redox solution containing an organic compound having a pyrimidine ring represented by the formula (5) (tetrabutylammonium iodide concentration; 0.6 mol / L, iodine concentration; 0.1 mol / L, pyrimidine) The concentration of the organic compound having a ring: 0.1 mol / L, solvent: methoxypropionitrile) was prepared. A dye-sensitized solar cell was produced in the same procedure and conditions as in Example 1 except that this electrolytic solution E was used.
[0106]
(Example 5)
As an electrolytic solution E, an iodine-based redox solution containing an organic compound having a pyrimidine ring represented by the formula (6) (tetrabutylammonium iodide concentration; 0.6 mol / L, iodine concentration; 0.1 mol / L, pyrimidine) The concentration of the organic compound having a ring: 0.1 mol / L, solvent: methoxypropionitrile) was prepared. A dye-sensitized solar cell was produced in the same procedure and conditions as in Example 1 except that this electrolytic solution E was used.
[0107]
(referenceExample 6)
As an electrolytic solution E, an iodine-based redox solution containing an organic compound having a pyrimidine ring represented by the formula (7) (tetrabutylammonium iodide concentration; 0.6 mol / L, iodine concentration; 0.1 mol / L, pyrimidine) The concentration of the organic compound having a ring: 0.1 mol / L, solvent: methoxypropionitrile) was prepared. Except for using this electrolytic solution E,referenceA dye-sensitized solar cell was produced according to the same procedure and conditions as in Example 1.
[0108]
(referenceExample 7)
As an electrolytic solution E, an iodine-based redox solution containing an organic compound having a pyrimidine ring represented by the formula (8) (concentration of tetrabutylammonium iodide; 0.6 mol / L, iodine concentration; 0.1 mol / L, pyrimidine The concentration of the organic compound having a ring: 0.1 mol / L, solvent: methoxypropionitrile) was prepared. Except for using this electrolytic solution E,referenceA dye-sensitized solar cell was produced according to the same procedure and conditions as in Example 1.
[0109]
(Comparative Example 1)
As an electrolytic solution E, an iodine-based redox solution not containing an organic compound having a pyrimidine ring (tetrabutylammonium iodide concentration; 0.6 mol / L, iodine concentration; 0.1 mol / L, solvent; methoxypropionitrile) Was prepared. Except for using this electrolytic solution E,referenceA dye-sensitized solar cell was produced according to the same procedure and conditions as in Example 1.
[0110]
(Comparative Example 2)
Instead of an organic compound having a pyrimidine ring as the electrolyte E, an iodine-based redox solution containing 4-tert-butylpyridine (concentration of tetrabutylammonium iodide; 0.6 mol / L, iodine concentration; 1 mol / L, concentration of 4-tert-butylpyridine; 0.1 mol / L, solvent; methoxypropionitrile). Except for using this electrolytic solution E,referenceA dye-sensitized solar cell was produced according to the same procedure and conditions as in Example 1.
[0111]
[Battery characteristics test 1]
Perform battery characteristics test according to the following procedure and measurement conditions,Example 4 and Example 5, Reference Example 1 to Reference Example 3, Reference Example 6 and Reference Example 7And the photoelectric conversion efficiency (eta) of the dye-sensitized solar cell of the comparative example 1 and the comparative example 2 was measured.
[0112]
The battery characteristic test was performed using a solar simulator (trade name; “WXS-85-H type” manufactured by Wacom) and 1000 mW / cm from a xenon lamp light source that passed through an AM filter (AM1.5).2It was performed by irradiating simulated sunlight.
[0113]
First, for each dye-sensitized solar cell, current-voltage characteristics were measured at room temperature (25 ° C.) using an IV tester, and an open circuit voltage (Voc / V) and a short circuit current (Isc / mA · cm).-2), The fill factor (F.F.) was obtained, and the photoelectric conversion efficiency η [%] at the initial stage of starting was obtained from these.
[0114]
Thereafter, each dye-sensitized solar cell is placed in a thermostatic bath maintained at 85 ° C., stored in a light-shielded state and in an open circuit state, and after 360 hours, is taken out of the thermostatic bath and brought to room temperature (25 ° C.). The current-voltage characteristics similar to the above were measured, and the photoelectric conversion efficiency η after 360 hours was obtained. The results are shown in Table 1.
[0115]
[Table 1]
[0116]
As is clear from the results shown in Table 1, an electrolyte containing an organic compound having a pyrimidine ring used in the dye-sensitized solar cell of the present invention was used.Example 4 and Example 5, Reference Example 1 to Reference Example 3, Reference Example 6 and Reference Example 7This dye-sensitized solar cell is excellent even after being stored for a long time in a relatively high temperature operating environment that is most likely to be applied when a dye-sensitized solar cell at 85 ° C. is put into practical use. It was confirmed that the photoelectric conversion efficiency can be substantially maintained. On the other hand, it was confirmed that the photoelectric conversion efficiency of the dye-sensitized solar cells of Comparative Example 1 and Comparative Example 2 significantly decreased with the passage of storage time.
[0117]
[Battery characteristics test 2]
referenceA dye-sensitized solar cell of Example 1, Comparative Example 1 and Comparative Example 2 was separately prepared, and a battery characteristic test was performed according to the same procedure and measurement conditions as the above-described battery characteristic test 1 except for the procedure and conditions shown below.referenceThe photoelectric conversion efficiency η of the dye-sensitized solar cells of Example 1 and Comparative Example 1 was measured.
[0118]
That is,referenceThe dye-sensitized solar cells of Example 1, Comparative Example 1 and Comparative Example 2 were each short-circuited, and the temperature of the electrolytic solution E was maintained at 60 ° C., and 1000 mW / cm previously described2The simulated sunlight was continuously irradiated. The photoelectric conversion efficiency η after 24 hours, 120 hours, and 240 hours from the start of irradiation with pseudo sunlight was measured. The results are shown in Table 2.
[0119]
[Table 2]
[0120]
As is clear from the results shown in Table 2,referenceIt was confirmed that the dye-sensitized solar cell of Example 1 can maintain excellent photoelectric conversion efficiency even after being operated continuously by receiving irradiation of pseudo-sunlight for a long time in an operating environment of 60 ° C. . on the other hand,referenceCompared to the dye-sensitized solar cell of Example 1, the dye-sensitized solar cells of Comparative Example 1 and Comparative Example 2 have greatly reduced photoelectric conversion performance with the passage of pseudo-sunlight irradiation time. Was confirmed.
[0121]
【The invention's effect】
As described above, according to the present invention, high photoelectric conversion efficiency can be obtained in the initial stage, and sufficient photoelectricity can be obtained even when operated for a long period of time or after being stored for a long period of time. A dye-sensitized solar cell with excellent durability capable of obtaining conversion efficiency can be obtained.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing the basic configuration of a first embodiment of a dye-sensitized solar cell of the present invention.
FIG. 2 is a schematic cross-sectional view showing a basic configuration of a second embodiment of the dye-sensitized solar cell of the present invention.
FIG. 3 is a schematic cross-sectional view showing a basic configuration of a third embodiment of the dye-sensitized solar cell of the present invention.
4 is a schematic cross-sectional view showing an example in which a plurality of dye-sensitized solar cells shown in FIG. 2 or FIG. 3 are provided.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Transparent electrode, 2 ... Semiconductor electrode, 3 ... Transparent electrically conductive film, 4 ... Transparent substrate, 5 ... Sealing material, 6 ... Substrate, 8 ... Carbon electrode, 9 ... Groove formed by laser scribing DESCRIPTION OF SYMBOLS 10 ... Photoelectrode, 20, 30, 40, 50 ... Dye-sensitized solar cell, CE ... Counter electrode, E ... Electrolyte, F1, F2, F3 ... Light-receiving surface, F22 ... Back surface of semiconductor electrode 2, S ... Spacer, PS: porous layer.
Claims (7)
前記半導体電極には、色素が含有されており、
前記電解質には、ピリミジン環を有する有機化合物が少なくとも含有されており、
前記ピリミジン環を有する有機化合物が、下記一般式（１）で表されることを特徴とする色素増感型太陽電池。
The semiconductor electrode contains a dye,
Wherein the electrolyte is an organic compound having a pyrimidine ring are contained at least,
The organic compound having a pyrimidine ring is represented by the following general formula (1): A dye-sensitized solar cell.
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| JP2006236960A (en) * | 2005-01-28 | 2006-09-07 | Fujikura Ltd | Dye-sensitized solar cell and its manufacturing method |
| DE112006002294T5 (en) * | 2005-09-02 | 2008-10-30 | Kyocera Corp. | A photoelectric conversion device and a method of manufacturing the same, and a photoelectric power generation device |
| JP4856089B2 (en) * | 2005-10-11 | 2012-01-18 | 京セラ株式会社 | PHOTOELECTRIC CONVERSION DEVICE, MANUFACTURING METHOD THEREOF, AND PHOTOVOLTAIC GENERATION DEVICE |
| CA2655192A1 (en) | 2006-07-05 | 2008-01-10 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized solar cell |
| JP5273709B2 (en) | 2008-07-02 | 2013-08-28 | シャープ株式会社 | Dye-sensitized solar cell, method for producing the same, and dye-sensitized solar cell module |
| CN102265453B (en) | 2008-10-29 | 2014-10-01 | 富士胶片株式会社 | Dye, photoelectric conversion element and photoelectrochemical cell each comprising the dye, and process for producing dye |
| JP5320109B2 (en) * | 2009-02-27 | 2013-10-23 | 株式会社豊田中央研究所 | Dye-sensitized solar cell and method for producing the same |
| JP5620081B2 (en) | 2009-09-28 | 2014-11-05 | 富士フイルム株式会社 | Method for manufacturing photoelectric conversion element |
| 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 |
| 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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