JP5773351B2 - 燃料電池 - Google Patents
燃料電池 Download PDFInfo
- Publication number
- JP5773351B2 JP5773351B2 JP2009500940A JP2009500940A JP5773351B2 JP 5773351 B2 JP5773351 B2 JP 5773351B2 JP 2009500940 A JP2009500940 A JP 2009500940A JP 2009500940 A JP2009500940 A JP 2009500940A JP 5773351 B2 JP5773351 B2 JP 5773351B2
- Authority
- JP
- Japan
- Prior art keywords
- fuel cell
- cathode
- polyoxometalate
- redox
- cell according
- 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 - Fee Related
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- 239000000446 fuel Substances 0.000 title claims description 74
- 239000013460 polyoxometalate Substances 0.000 claims description 61
- 239000012528 membrane Substances 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000005518 polymer electrolyte Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000011733 molybdenum Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 32
- 239000003054 catalyst Substances 0.000 description 19
- 150000001768 cations Chemical class 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 241000894007 species Species 0.000 description 10
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- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010405 reoxidation reaction Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 101100286980 Daucus carota INV2 gene Proteins 0.000 description 5
- 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 5
- 101100397045 Xenopus laevis invs-b gene Proteins 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 101150110971 CIN7 gene Proteins 0.000 description 4
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- -1 alkali metal salt Chemical class 0.000 description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
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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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 2
- 150000004697 chelate complex Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- QWNCDHYYJATYOG-UHFFFAOYSA-N 2-phenylquinoxaline Chemical class C1=CC=CC=C1C1=CN=C(C=CC=C2)C2=N1 QWNCDHYYJATYOG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
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- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
-
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- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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Description
Xa[ZbMcOd]
ここで、
Xは、水素、アルカリ金属、アルカリ土類金属、アンモニウム、及びそれらの2以上の組合せから選択され;
Zは、B、P、S、As、Si、Ge、Ni、Rh、Sn、Al、Cu、I、Br、F、Fe、Co、Cr、Zn、H2、Te、Mn及びSe、並びにそれらの2以上の組合せから選択され;
Mは、Mo、W、V、Nb、Ta、Mn、Fe、Co、Cr、Ni、Zn、Rh、Ru、Tl、Al、Ga、In、並びに第一、第二、及び第三遷移金属系及びランタナイド系から選択される他の金属、並びにそれらの2以上の組合せから選択される金属であり;
aは、[McOd]アニオンを電荷バランスさせるために必要なXの数であり;
bは0から20であり;
cは1から40であり;及び
dは1から180である。
a)プロトン交換膜に隣接して置かれたアノードでH+イオンを形成させる段階;
b)酸化状態にある酸化還元対を伴う本発明のカソード液を、プロトン交換膜の反対側に隣接して置かれたカソードに供給する段階;及び
c)触媒を、膜を通り抜けるH+イオンと同時にカソードと接触させる際に、還元させて電荷をバランスさせる段階、
を含むプロトン交換膜燃料電池の操作方法が提供される。
d)カソード液を、カソードから再酸化区域に通し、触媒を再酸化させる段階、
を更に含んでよい。
e)カソード液を、再酸化区域からカソード液貯蔵槽に通過させる段階、
を含む。
O2+4Spred+4H+ → 2H2O+4Spox
本発明に係る2つのカソード溶液を調製した。第一の、H3Na2PMo10V2O40(INV1)は二個のバナジウム原子を包含し、第二の、H3Na2PMo9V3O40(INV2)は三個のバナジウム原子を包含した。
使用した電池は全ての実験で同じであり、100ppi RVC カソードと共にイオンパワーNafion 115 MEAを利用し、75℃で作動させた。
このデータは、バナジウム含量が異なる本発明に係るポリオキソメタレートの、電気化学的及び再生性能の比較を示す。使用したポリオキソメタレートは、以下の通りであった。
H3Na2V2ポリオキソメタレート:0.3M H3Na2PMo10V2O40
H3Na3V3ポリオキソメタレート:0.3M H3Na3PMo9V3O40
H3Na4V4ポリオキソメタレート:0.3M H3Na4PMo8V4O40
H3Na5V5ポリオキソメタレート:0.3M H3Na5PMo7V5O40
ナトリウムイオンをプロトンにイオン交換して、酸性化された型のV3及びV4ポリオキソメタレートを調製した。交換には、少し過剰のイオン交換樹脂(Dowex−50)を使用して、全てのNa+イオンをH+イオンに交換することを目指した。イオン交換を確実に有効なレベルにするため、この手順を二回行った。イオン交換のレベルを決定するために、交換されたポリオキソメタレートをNaOHで滴定して、ポリオキソメタレート溶液の中和に要するナトリウムを決定した。全てプロトン化された型のV2ポリオキソメタレートを、構成成分であるバナジウム及びモリブデン酸化物から直接合成した。全てナトリウム型のV4ポリオキソメタレートを、炭酸ナトリウムと共に、バナジウム及びモリブデン酸化物から直接合成した。
H3Na2V2ポリオキソメタレート:0.3M H3Na2PMo10V2O40
H5V2ポリオキソメタレート:0.3M H5PMo10V2O40
H3Na3V3ポリオキソメタレート:0.3M H3Na3PMo9V3O40
H4.5Na1.5V3ポリオキソメタレート:0.3M H4.5Na1.5PMo9V3O40
H3Na4V4ポリオキソメタレート:0.3M H3Na4PMo8V4O40
H5Na2V4ポリオキソメタレート:0.3M H5Na2PMo8V4O40
Na7V4ポリオキソメタレート:0.3M Na7PMo8V4O40
Claims (16)
- イオン選択性高分子電解質膜で分離されたアノードとカソード;電池のアノード領域への燃料の供給手段;電池のカソード領域への酸化剤の供給手段;アノードとカソードの間の電気回路の提供手段;カソードと流体連通して流れる非揮発性カソード溶液であって、電池の作動で、カソードで少なくとも部分的に還元され、カソードでのこの様な還元の後、酸化剤との反応で少なくとも部分的に再生されるポリオキソメタレートを含み、少なくとも0.1M(0.1×103mol/m3)の前記ポリオキソメタレートを含む前記カソード溶液;を含む酸化還元型燃料電池であって、
前記ポリオキソメタレートが下記式で表させる酸化還元型燃料電池:
X a [Z b M c O d ]
(ここで、
Xは、少なくとも一の水素、並びに、アルカリ金属、アルカリ土類金属、アンモニウム及びそれらの2以上の組合せから選択される少なくとも一の他の物質を含み;
Zは、B、P、S、As、Si、Ge、Ni、Rh、Sn、Al、Cu、I、Br、F、Fe、Co、Cr、Zn、Te、Mn及びSe、並びにそれらの2以上の組合せから選択され;
Mは、Mo、W、V、Nb、Ta、Mn、Fe、Co、Cr、Ni、Zn、Rh、Ru、Tl、Al、Ga、In、並びに第一、第二、及び第三遷移金属系及びランタノイド系から選択される他の金属、並びにそれらの2以上の組合せから選択される金属であり;
aは、[M c O d ]アニオンを電荷バランスさせるために必要なXの数であり;
bは0から20であり;
cは1から40であり;及び
dは1から180である。) - bが0から2である請求項1に記載の酸化還元型燃料電池。
- cが5から20である請求項1又は2に記載の酸化還元型燃料電池。
- dが30から70である請求項1−3のいずれか一項に記載の酸化還元型燃料電池。
- Mがバナジウム、モリブデン、及びそれらの組合せから選択させる請求項1−4のいずれか一項に記載の酸化還元型燃料電池。
- Zがリンである請求項1−5のいずれか一項に記載の酸化還元型燃料電池。
- Xが水素とアルカリ金属及び/又はアルカリ土類金属イオンとの組合せを含む請求項1−6のいずれか一項に記載の酸化還元型燃料電池。
- 前記ポリオキソメタレート中に中心金属として2−4のバナジウム金属を含有する請求項1−7のいずれか一項に記載の酸化還元型燃料電池。
- 前記ポリオキソメタレートがH3Na2PMo10V2O40を含む請求項8に記載の酸化還元型燃料電池。
- 前記ポリオキソメタレートがH3Na2PMo9V3O40を含む請求項8に記載の酸化還元型燃料電池。
- 前記ポリオキソメタレートがH3Na4PMo8V4O40を含む請求項8に記載の酸化還元型燃料電池。
- 前記カソード溶液が少なくとも一の付随的酸化還元種を含む請求項1−11のいずれか一項に記載の酸化還元型燃料電池。
- 前記付随的酸化還元種が、結紮された遷移金属錯体、請求項1で使用されるポリオキソメタレートとは異なるポリオキソメタレート種、及びそれらの組合せから選択される請求項12に記載の酸化還元型燃料電池。
- 前記遷移金属錯体中の単数又は複数の遷移金属が、酸化状態II−Vのマンガン、I−IVの鉄、I−IIIの銅、I−IIIのコバルト、I−IIIのニッケル、(II−VII)クロム、II−IVのチタン、IV−VIのタングステン、II−Vのバナジウム、及びII−VIのモリブデンから選択される請求項13に記載の酸化還元型燃料電池。
- 前記カソード溶液が、いかなる付随的酸化還元種も含まない請求項1−11のいずれか一項に記載の酸化還元型燃料電池。
- 前記カソード溶液中の前記ポリオキソメタレートの濃度が0.15M(0.15×103mol/m3)を超える請求項1−15のいずれか一項に記載の酸化還元型燃料電池。
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KR20170109085A (ko) | 2017-09-27 |
US9005828B2 (en) | 2015-04-14 |
EP1999811B8 (en) | 2014-06-25 |
KR20160106197A (ko) | 2016-09-09 |
KR20080110640A (ko) | 2008-12-18 |
KR101904461B1 (ko) | 2018-10-04 |
CN101405901A (zh) | 2009-04-08 |
JP2014160669A (ja) | 2014-09-04 |
EP1999811B1 (en) | 2014-03-12 |
WO2007110663A2 (en) | 2007-10-04 |
WO2007110663A3 (en) | 2007-12-06 |
CN104953136A (zh) | 2015-09-30 |
JP2009530784A (ja) | 2009-08-27 |
CN104953136B (zh) | 2018-09-04 |
KR20140084361A (ko) | 2014-07-04 |
EP1999811A2 (en) | 2008-12-10 |
IN266777B (ja) | 2015-06-01 |
BRPI0709089A2 (pt) | 2011-06-28 |
US20090317668A1 (en) | 2009-12-24 |
GB0605878D0 (en) | 2006-05-03 |
ES2466351T3 (es) | 2014-06-10 |
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