JP5673344B2 - 色素増感太陽電池 - Google Patents
色素増感太陽電池 Download PDFInfo
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- JP5673344B2 JP5673344B2 JP2011112129A JP2011112129A JP5673344B2 JP 5673344 B2 JP5673344 B2 JP 5673344B2 JP 2011112129 A JP2011112129 A JP 2011112129A JP 2011112129 A JP2011112129 A JP 2011112129A JP 5673344 B2 JP5673344 B2 JP 5673344B2
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- Prior art keywords
- layer
- dye
- group
- hole transport
- semiconductor
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- 239000004065 semiconductor Substances 0.000 claims description 78
- 230000005525 hole transport Effects 0.000 claims description 76
- 239000002608 ionic liquid Substances 0.000 claims description 34
- 230000001235 sensitizing effect Effects 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- -1 phosphonium ion Chemical class 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000005452 bending Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 5
- 229920001940 conductive polymer Polymers 0.000 claims description 5
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- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 46
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- 239000000975 dye Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 29
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
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- 239000000539 dimer Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- 229910006404 SnO 2 Inorganic materials 0.000 description 6
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- 125000003545 alkoxy group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
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- 230000000694 effects Effects 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
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- 239000011701 zinc Substances 0.000 description 6
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- 230000001590 oxidative effect Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 4
- 150000004770 chalcogenides Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- JQEJJSKHXVZRNM-UHFFFAOYSA-K 4-ethylbenzenesulfonate;iron(3+) Chemical compound [Fe+3].CCC1=CC=C(S([O-])(=O)=O)C=C1.CCC1=CC=C(S([O-])(=O)=O)C=C1.CCC1=CC=C(S([O-])(=O)=O)C=C1 JQEJJSKHXVZRNM-UHFFFAOYSA-K 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 3
- UMXAKWDYSKLYBU-UHFFFAOYSA-K [Fe+3].[O-]S(=O)(=O)c1cccc2ccccc12.[O-]S(=O)(=O)c1cccc2ccccc12.[O-]S(=O)(=O)c1cccc2ccccc12 Chemical compound [Fe+3].[O-]S(=O)(=O)c1cccc2ccccc12.[O-]S(=O)(=O)c1cccc2ccccc12.[O-]S(=O)(=O)c1cccc2ccccc12 UMXAKWDYSKLYBU-UHFFFAOYSA-K 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
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- 125000001153 fluoro group Chemical group F* 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- ACQYKVVPCCAWBZ-UHFFFAOYSA-K iron(3+);methanesulfonate Chemical compound [Fe+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O ACQYKVVPCCAWBZ-UHFFFAOYSA-K 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- 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
- Y02E10/549—Organic PV cells
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Description
可とう性を有する支持体、導電層、整流層、少なくとも増感色素を半導体に担持してなる半導体層、正孔輸送剤を含有する固体の正孔輸送層、対極を設置してなる色素増感太陽電池において、前記正孔輸送層が分子量450以上710以下のイオン液体を含有することを特徴とする色素増感太陽電池。
前記正孔輸送剤が、導電性高分子であることを特徴とする(1)に記載の色素増感太陽電池。
特に限定されるものではなく、これまでに知られている非液体系の色素増感太陽電池の構成を有するものである。
本発明の色素増感太陽電池を構成する光電変換素子は、例えば図1に示される構成を有する。
即ち、例えば下記に示す如きものである。
電解重合法により重合体を得る場合は、重合体の合成がそのまま前記正孔輸送層の形成につながる。即ち、以下のような電解重合法が行われる。
本発明に係る光電変換素子10(図1参照)を構成する導電性支持体11は、透光性基板11a上に透明導電層などからなる第1電極層11bが形成されてなるものであって、この導電性支持体11は実質的に透明である。ここに、実質的に透明であるとは、光の透過率が50%以上であることが好ましく、80%以上であることが特に好ましい。
本発明の色素増感太陽電池においては、整流層13が、親水性樹脂中にn型半導体粒子が分散されてなるものであることが好ましい。
本発明の整流層13を構成する親水性樹脂は、ポリビニルアルコール、アルギン酸ナトリウム、などが挙げられ、これらの中でもポリ(ジアリルジメチルアンモニウムクロライド)などのカチオン性樹脂、およびアルギン酸ナトリウムなどのアニオン性樹脂が好ましい。
本発明の整流層13を構成するn型半導体粒子は、電子伝達作用を発揮するものであって、このような半導体物質を構成する半導体としては、周期表の第3族〜第5族、第13族〜第15族系の元素を有する化合物、例えば酸化物、硫化物、セレン化物などの金属のカルコゲニド、金属窒化物などを用いることができる。
整流層13は、例えば、第1電極層11bが形成されてなる導電性支持体11の当該第1電極層11b上に、水系媒体中に親水性樹脂が溶解されると共にn型半導体粒子が分散されてなる分散液を塗布して乾燥処理を施すことにより、形成することができる。
光電変換層14は、半導体物質に増感色素が担持されてなるものであり、電子輸送能を有するものである。
光電変換層14を構成する半導体物質は、電子伝達作用を発揮するものであって、このような半導体物質を構成する半導体としては、周期表の第3族〜第5族、第13族〜第15族系の元素を有する化合物、例えば酸化物、硫化物、セレン化物などの金属のカルコゲニド、金属窒化物などを用いることができる。
光電変換層14において半導体物質に担持される増感色素としては、増感作用を示すものであれば特に限定されず、公知の種々のものを用いることができるが、電荷の半導体物質への効率的な注入の観点から、増感色素としては、カルボキシル基を有するものを用いることが好ましい。
上記光電変換層14は、第1電極層11bと整流層13上に、半導体物質からなる半導体層を形成した後、当該半導体層の表面に増感色素を吸着させることにより、形成することができる。
半導体層は、例えば焼成により形成することができる。
半導体層に対する増感色素の吸着は、増感色素を適宜の溶媒に溶解させた浸漬液に、上記の半導体層を形成した構造物を浸漬することによって行われる。
第2電極層16は、対向電極であって、第2電極層16を構成する材料としては、導電性を有するものであればよく、白金、金、銀、銅、黒鉛などの任意の導電性材料を挙げることができる。第2電極層16は、正孔輸送層15との接触性の高い金属薄膜であることが好ましく、特に、正孔輸送層15との仕事関数の差が小さく、化学的に安定である金属である金を用いた薄膜であることが好ましい。
光電変換素子10は、導電性支持体11上に整流層13を形成し、この整流層13上に光電変換層14を形成し、その後、この光電変換層14の上に正孔輸送層15を形成し、さらに、この正孔輸送層15上に第2電極層16を形成することにより、得られる。
1.第1の基板作製
多孔質チタニア層の作製
抵抗が13Ω/□であるITO/PEN(ポリエチレンナフタレート;ペクセルテクノロジーズ社製)(導電性支持体)(フィルム厚さ200μm)の切り取りを行い、次に、図2−aの網掛け部相当について、YAGレーザー(波長1064nm)を搭載したレーザーマーカーを用いて、連続的にレーザー光を走査してエッチングを行い、ITO層のみの除去を行った。
次に、下記の前吸着化合物1(4−tert−ブチルシクロヘキシルカルボン酸)をアセトニトリル:t−ブチルアルコール=1:1(体積比)の混合溶媒に溶解し、5×10−4mol/L(リットル)の溶液を調製した。上記酸化チタンを塗布焼結した第1の基板を、この溶液に室温で3時間浸漬して前吸着化合物1の吸着処理を行った。
前記半導体電極1を、3,4−エチレンジオキシチオフェンの二量体(例示化合物M1−1)を1×10−2(モル/L)の割合で含有し、Li[(CF3SO2)2N]を0.1(モル/L)の割合で含有するアセトニトリル溶液(電解重合溶液)に浸漬した。作用極を前記半導体電極、対極を白金線、参照電極をAg/Ag+(AgNO3;0.01M)、保持電圧を−0.20Vとした。半導体層方向から光を照射(キセノンランプ使用、光強度24mW/cm2、430nm以下の波長をカット)しながら30分間電圧を保持して、正孔輸送層を前記半導体電極表面に形成した。得られた半導体電極/正孔輸送層をアセトニトリルで洗浄、乾燥した。
以下の図(図2−d)に従って、シート抵抗が13Ω/□であるITO/PEN(ポリエチレンナフタレート;ペクセルテクノロジーズ社製)(導電性支持体)(フィルム厚さ200μm)の切り取りを行い、図中の網掛け部相当について、YAGレーザー(波長1064nm)を搭載したレーザーマーカーを用いて、連続的にレーザー光を走査してエッチングを行い、ITO層のみの除去を行った。続いてITO層が残存している部分に、膜厚が100nmになるように金の蒸着を行った。
以下の構造のイオン液体を用いて、次の組成の溶液を調製した。
同様にして表1に示したイオン液体を用いて色素増感太陽電池(電池)2〜10を電池1と同様にして作製した。
作製し、ソーラーシミュレータ(英弘精機製)を用い、AMフィルター(AM−1.5)を通したキセノンランプから100mW・cm−2の擬似太陽光を照射することにより評価を行った。
ここで、Pは入射光強度[mW・cm−2]、Vocは開放電圧[V]、Jscは短絡電流密度[mA・cm−2]、F.F.は形状因子を示す。
11a 透光性基板
11b 第1電極層
11 導電性支持体
12 半導体電極
13 整流層
14 光電変換層
15 正孔輸送層
16 第2電極層
Claims (4)
- 可とう性を有する支持体、導電層、整流層、少なくとも増感色素を半導体に担持してなる半導体層、正孔輸送剤を含有する固体の正孔輸送層、対極を設置してなる色素増感太陽電池において、前記正孔輸送層が分子量450以上710以下のイオン液体を含有し、
前記イオン液体のカチオンが、長鎖アルキルを持つイミダゾリウムイオン、長鎖アルキルを持つ非対称アンモニウムイオンまたは長鎖アルキルを持つ非対称ホスホニウムイオンであり、
前記長鎖アルキルを持つイミダゾリウムイオンが、以下のいずれか:
長鎖アルキルを持つ非対称アンモニウムイオンが、以下のいずれか:
長鎖アルキルを持つ非対称ホスホニウムイオンが、以下のいずれか:
- 前記正孔輸送剤が、導電性高分子であることを特徴とする請求項1に記載の色素増感太陽電池。
- 可とう性を有する支持体、導電層、整流層、少なくとも増感色素を半導体に担持してなる半導体層、正孔輸送剤を含有する固体の正孔輸送層、対極を設置してなる色素増感太陽電池の耐屈曲性の向上方法であって、
前記正孔輸送層に、分子量450以上710以下のイオン液体を含有し、
前記イオン液体の分子量の調整は、置換基の導入、カチオン、アニオンの選択により行い、
前記イオン液体のカチオンが、長鎖アルキルを持つイミダゾリウムイオン、長鎖アルキルを持つ非対称アンモニウムイオンまたは長鎖アルキルを持つ非対称ホスホニウムイオンであり、
前記長鎖アルキルを持つイミダゾリウムイオンが、以下のいずれか:
長鎖アルキルを持つ非対称アンモニウムイオンが、以下のいずれか:
長鎖アルキルを持つ非対称ホスホニウムイオンが、以下のいずれか:
- 前記正孔輸送剤が、導電性高分子であることを特徴とする請求項3に記載の色素増感太陽電池の耐屈曲性の向上方法。
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