JP2005346963A - 光電気化学電池 - Google Patents
光電気化学電池 Download PDFInfo
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- JP2005346963A JP2005346963A JP2004162195A JP2004162195A JP2005346963A JP 2005346963 A JP2005346963 A JP 2005346963A JP 2004162195 A JP2004162195 A JP 2004162195A JP 2004162195 A JP2004162195 A JP 2004162195A JP 2005346963 A JP2005346963 A JP 2005346963A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 219
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 109
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 107
- 239000002608 ionic liquid Substances 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 239000011941 photocatalyst Substances 0.000 claims description 38
- 239000008151 electrolyte solution Substances 0.000 claims description 36
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000032258 transport Effects 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000013626 chemical specie Substances 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000013461 intermediate chemical Substances 0.000 claims 3
- 230000001172 regenerating effect Effects 0.000 claims 3
- 206010034972 Photosensitivity reaction Diseases 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 40
- 229910052799 carbon Inorganic materials 0.000 abstract description 39
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 14
- 239000012528 membrane Substances 0.000 abstract description 11
- 238000000638 solvent extraction Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 44
- 239000000463 material Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 239000011521 glass Substances 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000000274 adsorptive effect Effects 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- -1 1-butyl-3-methylimidazolium hexafluorophosphate Chemical compound 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
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Abstract
【解決手段】 イオン性液体2を入れた電解液容器3と、この電解液容器3内を、CO2捕獲室7とCO2放出室8とに二分する隔膜4とを有し、隔膜4を隔てて対向する側壁の一方をカーボン電極5、他方を光電極6とした。CO2放出室10の上部には上壁部10が形成され、この上壁部10にCO2取り出し口10Aを形成して、酸化還元メディエータの酸化、還元を利用して、太陽光の光エネルギーを電力に変換しながら二酸化炭素の分離濃縮を行う。
【選択図】 図1
Description
CO2Bred→CO2Box+e (2)
Bred→Box+e (3)
このように酸化された酸化還元メディエータは、CO2を放出する。放出されたCO2は、下記の式(4)のように、排ガスから分離濃縮されたCO2として取り出される。
また、酸化還元メディエータの酸化体Boxは、隔膜を透過してCO2捕獲室に戻って、下記の式(5)のように再度還元されてCO2の捕獲に供されるようになっている。
この方法では、二酸化炭素が電気化学的にCO2放出室へ向けてポンピングされて分離濃縮が達成されるようになっている。また、この方法では、純粋な二酸化炭素として分離濃縮することができ、しかも低濃度の二酸化炭素を含むガスからの分離濃縮も可能であるため、従来の分離濃縮手法はもちろん、溶融炭酸塩型燃料電池を用いた二酸化炭素の分離濃縮に対しても有利となっている。
KASAI,H.,:CO2 electrochemical separation by molten carbonate technology,Prepr Pap Am Chem Soc Div Fuel Chem.,Vol.47,No.1,pp.69-70 (2002) 竹信秀則,溶融炭酸塩形燃料電池を用いた石炭火力発電所排ガスからのCO2回収システムに関する研究,中国電力株式会社技研時報,No.98,pp.55-65(2002) Scovazzo, P., Koval, C., Noble, R., "Electrochemical Separation and Concentration of <1% Carbon Dioxide from Nitrogen," J. Electrochem. Soc., vol.150, no.5, pp.D91-D98, 2003
本発明の第1の実施の形態に係る光電気化学電池について、図1を用いて説明する。図1に示すように、本実施の形態に係る光電気化学電池1は、電解液としてのイオン性液体2を入れた電解液容器3と、電解液容器3内を左右に二分する隔膜4とを有している。
(ロ)そして、生成された電子−正孔対が、光触媒表面近傍に電解液(イオン性液体2)との接触によって形成されているバンドベンディングにより電荷分離され、伝導帯の電子は表面近傍からバルクへと輸送され、集電体層15を通って、カーボン電極5に移動する。また、正孔は光触媒表面に輸送され、下記の式(7)および(8)に示すように、二酸化炭素と結合している酸化還元メディエータの還元体ならびに二酸化炭素と結合していない酸化還元メディエータの還元体を酸化して酸化体にする。
Bred+h→Box (8)
(ハ)そして、酸化体となった、二酸化炭素と結合している酸化還元メディエータからは、下記の式(9)に示すように、二酸化炭素が放出される。
(ニ)二酸化炭素の酸化還元メディエータの酸化体は、カーボン電極5へイオン性液体2中を拡散して移動する。
(ヘ)そして、下記の式(11)に示すように、イオン性液体2中に取り込まれた二酸化炭素と二酸化炭素のキャリアである酸化還元メディエータの還元体とが結合する。
(ト)二酸化炭素と結合した酸化還元メディエータの還元体ならびに二酸化炭素と結合していない酸化還元メディエータの還元体が、光電極6へとイオン性液体中を拡散して移動する。
Box+e→Bred (13)
(第2の実施の形態)
次に、本発明の第2の実施の形態に係る光電気化学電池について図2〜図4を用いて説明する。
次に、本発明の第3の実施の形態に係る光電気化学電池について、図5および図6を用いて説明する。本実施の形態に係る光電気化学電池30は、上記した第2の実施の形態に係る光電気化学電池20において多孔質カーボン電極を筒状化した構成であり、筒状の多孔質カーボン電極の筒孔内に排ガスを通すようにしたものである。
次に、本発明の第4の実施の形態に係る光電気化学電池について、図7を用いて説明する。本実施の形態は、上述した第1の実施の形態に係る光電気化学電池1をCO2捕獲室7とCO2放出室8とに分断した構成であり、隔膜4を用いずにCO2捕獲室7内のイオン性液体2をポンプでCO2放出室8内に搬送駆動するようにした構成である。
次に、本発明の第5の実施の形態に係る光電気化学電池60について、図8を用いて説明する。本実施の形態に係る光電気化学電池60は、上記した第1の実施の形態に係る光電気化学電池1におけるカーボン電極5を、光電極に置き換えた構成である。
上述した実施の形態の開示の一部をなす論述および図面はこの発明を限定するものであると理解すべきではない。この開示から当業者には様々な代替実施の形態、実施例および運用技術が明らかとなろう。
2 イオン性液体
3,21,31 電解液容器
4 隔膜
5,48 カーボン電極
6,22,32,51 光電極
7 CO2捕獲室
8 CO2放出室
9A 排出口
10A 取り出し口
12 排ガス導入部
13,23A 電極触媒層
14,24,35,52 光触媒層
15,25、36,53 集電体層
16,26,37,54 ガラス板
17 外部負荷
33 多孔質カーボン電極
33A,49 電極触媒層
34 排ガス流路
41 第1電解液容器
42 第2電解液容器
43 ポンプ
44 搬送パイプ
45 オーバーフローパイプ
46,47 フィルタ
101 太陽電池
Claims (12)
- 酸化還元メディエータを含む電解液中に互いに離間する少なくとも一対の電極を配置し、前記電極のうち少なくとも一方の電極が、光照射されて励起電子を生成する光触媒を備えた光電極であり、該光電極によって電解液中の前記酸化還元メディエータの酸化もしくは還元を行って光エネルギーを電力に変換する光電気化学電池であって、
前記酸化還元メディエータは、酸化体と還元体とで二酸化炭素との結合力が異なり、結合力の大きい方が、前記一対の電極のいずれか一方に二酸化炭素を搬送する媒介化学種であることを特徴とする光電気化学電池。 - 前記電解液の溶媒は、非水溶媒であることを特徴とする請求項1記載の光電気化学電池。
- 前記電解液の溶媒は、イオン性液体であることを特徴とする請求項1記載の光電気化学電池。
- 前記媒介化学種を再生させる電極側の電解液中に二酸化炭素を含むガスを供給することを特徴とする請求項1乃至請求項3のいずれか一項に記載された光電気化学電池。
- 前記媒介化学種が再生される電極側の電解液と、前記媒介化学種が二酸化炭素を搬送する電極側の電解液と分離してイオン伝導する隔膜を備えることを特徴とする請求項1乃至請求項4のいずれか一項に記載された光電気化学電池。
- 前記媒介化学種を再生させる電極は、液体の透過を防止すると共に気体を透過させる多孔質構造であることを特徴とする請求項1乃至請求項4のいずれか一項に記載された光電気化学電池。
- 前記媒介化学種を再生させる電極は、一方の主面が前記電解液に接触し、他方の主面が二酸化炭素を含むガスに接触することを特徴とする請求項6記載の光電気化学電池。
- 前記光電極は、前記光触媒への紫外光の入射を遮ることを特徴とする請求項1乃至請求項7のいずれか一項に記載された光電気化学電池。
- 前記光電極は、電解液に接触する光触媒膜と、該光触媒膜が設けられた透明な集電膜とを備えてなり、前記光触媒膜もしくは集電膜が紫外光に対する遮光性を有することを特徴とする請求項1乃至請求項8のいずれか一項に記載された光電気化学電池。
- 前記光電極は、光を吸収する色素で光増感されていることを特徴とする請求項1乃至請求項9のいずれか一項に記載された光電気化学電池。
- 前記一対の電極に、太陽電池が電気的に直列に接続されていることを特徴とする請求項1乃至請求項10のいずれか一項に記載された光電気化学電池。
- 前記太陽電池が積層されていることを特徴とする請求項11記載の光電気化学電池。
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US11/569,836 US8791354B2 (en) | 2004-05-31 | 2005-05-13 | Photoelectrochemical cell |
PCT/JP2005/008767 WO2005117137A1 (ja) | 2004-05-31 | 2005-05-13 | 光電気化学電池 |
CNB2005800177299A CN100505327C (zh) | 2004-05-31 | 2005-05-13 | 光电化学电池 |
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US8791354B2 (en) | 2014-07-29 |
EP1768190A4 (en) | 2010-05-05 |
CN100505327C (zh) | 2009-06-24 |
JP5114823B2 (ja) | 2013-01-09 |
CN1981383A (zh) | 2007-06-13 |
US20080286643A1 (en) | 2008-11-20 |
EP1768190A1 (en) | 2007-03-28 |
WO2005117137A1 (ja) | 2005-12-08 |
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