US20070037041A1 - Electrocatalyst Supports for Fuel Cells - Google Patents
Electrocatalyst Supports for Fuel Cells Download PDFInfo
- Publication number
- US20070037041A1 US20070037041A1 US11/462,739 US46273906A US2007037041A1 US 20070037041 A1 US20070037041 A1 US 20070037041A1 US 46273906 A US46273906 A US 46273906A US 2007037041 A1 US2007037041 A1 US 2007037041A1
- Authority
- US
- United States
- Prior art keywords
- particles
- electrode
- recited
- titanium
- dopant element
- 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.)
- Abandoned
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- 239000000446 fuel Substances 0.000 title claims abstract description 29
- 239000010411 electrocatalyst Substances 0.000 title description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000002245 particle Substances 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 239000002019 doping agent Substances 0.000 claims abstract description 23
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 71
- 229910052697 platinum Inorganic materials 0.000 claims description 26
- 239000010955 niobium Substances 0.000 claims description 20
- 229910052758 niobium Inorganic materials 0.000 claims description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- -1 titanium (IV) alkoxide compounds Chemical class 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000002244 precipitate Substances 0.000 abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- 230000008021 deposition Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910003191 Nb-TiO2 Inorganic materials 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002822 niobium compounds Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IXNCIJOVUPPCOF-UHFFFAOYSA-N 2-ethylhexan-1-ol;titanium Chemical compound [Ti].CCCCC(CC)CO.CCCCC(CC)CO.CCCCC(CC)CO.CCCCC(CC)CO IXNCIJOVUPPCOF-UHFFFAOYSA-N 0.000 description 1
- DMLWITSKISPJIJ-UHFFFAOYSA-N 2-ethylhexan-1-olate Chemical compound CCCCC(CC)C[O-] DMLWITSKISPJIJ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229920003936 perfluorinated ionomer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- H01M4/92—Metals of platinum group
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- 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
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- This invention pertains to electrode catalysts for fuel cells. More specifically, this invention pertains to corrosion resistant catalyst supports for fuel cells, especially for cells having a cathode at which oxygen is reduced in air.
- Fuel cells are electrochemical cells that are being developed for mobile and stationary electric power generation.
- One fuel cell design uses a solid polymer electrolyte (SPE) membrane or proton exchange membrane (PEM), to provide ion transport between the anode and cathode.
- SPE solid polymer electrolyte
- PEM proton exchange membrane
- Gaseous and liquid fuels capable of providing protons are used. Examples include hydrogen and methanol, with hydrogen being favored.
- Hydrogen is supplied to the fuel cell anode.
- Oxygen (as air) is the cell oxidant and is supplied to the cell's cathode.
- the fuel cell electrodes are formed of porous conductive materials, such as woven graphite, graphitized sheets, or carbon paper to enable the fuel to disperse over the surface of the membrane facing the fuel supply electrode.
- Each electrode comprises finely divided catalyst particles (for example, platinum particles), supported on carbon particles, to promote ionization of hydrogen at the anode and reduction of oxygen at the cathode.
- catalyst particles for example, platinum particles
- Protons flow from the anode through the ionically conductive polymer membrane to the cathode where they combine with oxygen to form water, which is discharged from the cell.
- Conductor plates carry away the electrons formed at the anode.
- PEM fuel cells utilize a membrane made of perfluorinated ionomers such as Dupont Nafion TM .
- the ionomer carries pendant ionizable groups (e.g. sulfonate groups) for transport of protons through the membrane from the anode to the cathode.
- This invention uses a porous form of titanium dioxide (sometimes called “titania”) as a high surface area support for platinum, or other suitable catalyst.
- titanium dioxide is mixed or doped with an element such as niobium to enhance the electrical conductivity of the support material.
- the titanium oxide is formed around removable filler particles (particulate templates), such as silica particles, that are chemically dissolved (etched) from the titanium dioxide particles to yield highly porous catalyst particle carriers. Particles of noble metal or other catalyst material are then deposited on the porous carrier material.
- a titanium dioxide carrier material is particularly useful in a catalytic electrode material in association with a proton exchange membrane in a fuel cell in which oxygen is electrochemically reduced.
- a titanium alkoxide compound is formed as a solution or sol in an alcohol or aqueous/alcohol medium.
- a solution or sol of titanium (IV) isopropoxide or titanium (IV) 2-ethylhexyloxide may be formed.
- a salt or alkoxide of a suitable dopant element may also be dissolved or dispersed in the medium.
- suitable dopant elements include lanthanum, manganese, molybdenum, niobium, tantalum, tungsten, strontium, vanadium, and yttrium.
- Also dispersed in the liquid medium are suitably sized particles (e.g. less than twenty nanometers in greatest dimension) of silica, polymer beads, or the like (preferably with the aid of ultrasonic energy).
- the titanium and dopant element compounds are then precipitated or gelled on the dispersed particles.
- the gelled or precipitated composite material is separated from the liquid medium and dried as necessary.
- the composite material is heated to a suitable temperature in a controlled atmosphere, for example of hydrogen or ammonia, to form very small particles (nanometer size) of titanium dioxide doped with a suitable quantity of niobium, or the like.
- the template particles consist of an organic polymer they may be removed by heating to leave pores in the agglomerated particles of titania.
- the template particles are inorganic, like silica, they may be chemically dissolved from the titanium dioxide particles leaving internal and external surface pores for receiving and dispersing fine particles of catalyst metal.
- the porous and doped titanium dioxide particles provide ample surface for the effective dispersion of platinum particles for use as cathodic electrode material on a Nafion TM proton exchange membrane in a hydrogen/ oxygen fuel cell environment.
- the titania carrier resists oxidative weight loss in a high temperature air environment and displays electrical conductivity.
- the titanium dioxide catalyst support materials of this invention have general utility in catalyst applications. Their utility includes applications as catalyst supports for catalyst particles in fuel cell electrodes. For example, these durable catalyst supports may be useful in an electrochemical fuel cell assembly including a solid polymer electrolyte membrane and a cathode that is exposed to oxygen or air.
- Many United States patents assigned to the assignee of this invention describe electrochemical fuel cell assemblies having an assembly of a solid polymer electrolyte membrane and electrode assembly.
- FIGS. 1-4 of U.S. Pat. No. 6,277,513 include such a description, and the specification and drawings of that patent are incorporated into this specification by reference.
- carbon particles are used to carry or support catalyst particles for electrode (anode or cathode) operation.
- porous and doped titanium dioxide particles are used to carry the catalyst for the electrode function.
- titanium (IV) alkoxides such as titanium (isopropoxide) 4 or titanium (2-ethylhexyloxide) 4
- titanium (isopropoxide) 4 or titanium (2-ethylhexyloxide) 4 are readily available and are, therefore, suitable and even preferred for use in the practice of this invention. These compounds have suitable solubility in alcohol (ethanol) for use in this method.
- suitable dopant elements include lanthanum, manganese, molybdenum, niobium, tantalum, tungsten, strontium, vanadium, and yttrium. Atoms of the dopant element(s) may be added to promote electronic conductivity by introducing defects in the crystalline titanium oxide support material.
- the dopant(s) is suitably added in an amount up to about half of the atoms of titanium in the support material.
- Alkoxide compounds or salts of these dopant elements are available and may be used for introducing one or more dopant element (s) into the titanium oxide catalyst support particles.
- titanium (IV) isopropoxide and niobium (V) chloride, or niobium (V) ethoxide are dissolved in ethanol in proportions of two atomic parts titanium per atom of niobium.
- Silica particles (10-15 nm in largest dimension) are dispersed in the alcohol solution or sol of titanium and niobium compounds. Silica is suitably added to the sol in an amount to provide about 1.2 parts by weight of silicon per part of titanium.
- nanometer size particles of nylon or vinyl chloride may be used as pore-forming templates in the dispersion. The uniformity of mixing of the constituents of the dispersion may be enhanced by sonic vibration of the dispersion.
- the solution (sol) is then acidified with aqueous hydrochloric acid to hydrolyze the titanium and niobium compounds and form a gel or precipitate of titanium-containing and niobium-containing material entraining the silica particles.
- the titanium containing material contains sufficient oxygen for the formation of titanium dioxide.
- the precipitate or gel is separated from the liquid medium and dried.
- the solid material is then heated to about 1000° C. in an atmosphere of hydrogen (or suitably, ammonia) so as to form crystalline titanium dioxide doped with elemental niobium.
- the particles of titanium dioxide are very small, nanometer size, and the particles of silica are dispersed in the doped titanium dioxide.
- the niobium doped oxide particles are chemically etched with aqueous sodium hydroxide or hydrogen fluoride to remove the pore-forming silica particles.
- the residue of the chemical etching is a mass of very small, pore containing, Nb-doped, TiO 2 particles where the pores are formed principally by the removal of the silica particles.
- the resulting porous TiO 2 was crystalline, contained Ti/Nb in an atomic ratio of 2, and had a BET surface area of 125 m 2 /g.
- Pt was deposited on this Nb-doped TiO 2 using an aqueous solution of diamineplatinum (II) nitrite, Pt (NO 2 ) 2 (NH 3 ) 2 , as a precursor.
- the Nb-doped TiO 2 was dispersed in water at 80° C. using ultrasonic energy.
- the platinum precursor was also separately dissolved in 70-80° C. water with stirring.
- the TiO 2 dispersion and the platinum precursor solution were mixed.
- the pH of the resulting platinum deposition medium was adjusted to 3.0 using acetic acid and carbon monoxide gas was diffused through the medium at a rate of two liters per minute.
- the reaction medium was stirred at 90° C.
- Hydrazine hydrate was used for reduction of the platinum and its deposition as very small particles on the niobium-doped TiO 2 particles. Hydrazine hydrate was added drop wise with stirring to the platinum deposition medium (at 90° C., pH 3, and with CO diffusion) over a period of one hour. Then the TiO 2 -containing medium with deposited platinum was cooled to room temperature. The reaction product of platinum deposited on niobium-doped titanium dioxide particles was filtered through a 0.45 micrometer pore-size cellulose nitrate membrane, washed with distilled water, and dried overnight in a vacuum oven at 50° C.
- platinum was deposited at 72 weight percent on porous niobium doped titanium dioxide and the resulting catalyst was tested with a gas phase accelerated thermal sintering method intended to induce oxidative corrosion of the catalyst.
- the test was conducted at 250° C. for 30 hours under an atmosphere, by volume, of 0.7% O 2, 8% H 2 O, and the balance helium.
- Two commercial platinum-on-carbon catalysts were subjected to the same corrosion testing for comparison.
- Table 1 records the mass loss resulting from the platinum-on-titanium dioxide catalyst produced in accordance with this invention and the two comparison carbon supported platinum catalysts.
- titanium oxide supported catalysts survives an oxidizing environment better than the carbon supported catalyst.
- the above porous, niobium-doped titanium oxide supported platinum catalyst was further tested for its oxygen reduction activity.
- the catalyst sample was prepared for electrochemical measurement by a special method (mixing and sonication in a suspension) to form an ink for application to a rotating disk electrode (RDE).
- the suspension contained the platinum on doped-titanium dioxide support (designated 41305 TJ) and a commercial electrically conductive particulate carbon dispersed in isopropanol and water.
- the dispersion also contained a 5% solution of Nafion TM ionomer in water.
- the supported platinum and carbon containing mixture was put into a sealed 60 ml glass bottle. The content was subsequently mixed by shaking and sonicated for 2-4 hours. Once a homogeneous ink suspension was formed, 10-20 micro liters of the suspension were dispensed on a glassy carbon electrode surface. After drying at room temperature, the electrode was put on the Rotating Disk Electrode (RDE) device for activity measurement (in micro-amperes per square centimeter of platinum at 0.9V). The resulting dried catalyst on the electrode contained 52.6 wt. % Pt.
- RDE Rotating Disk Electrode
- a sample of platinum on non-doped TiO 2 was prepared for comparison testing.
- the platinum on non-doped TiO 2 (sample 0131005TJ) was applied as in ink to a RCE for comparative electrode activity measurement by the technique described above.
- a second platinum on niobium-doped TiO 2 catalyst was prepared (sample 061705KV). This sample contained niobium in an amount of 5% of the titanium and the platinum loading on the electrode was lower (33.4%) than sample 131005TJ.
- the electrode was rotated at 1600 RPM in the 0.1 M HClO 4 electrolyte at 60° C. with a flowing, saturated oxygen atmosphere at one atmosphere.
- the electrode voltage scan rate was 5mV/s over a voltage range of 0-1V.
- Table 2 summarizes the specific oxygen reduction activities of two illustrative platinum-on-doped titanium dioxide support catalysts and like data obtained using the non-doped TiO 2 sample and two commercial platinum-on-carbon comparison catalysts.
- Specific activity (uA/cm 2 Pt at Catalyst Pt (wt %) Type 0.90 V) 0131005TJ 27.8 Pt/TiO 2 (no Nb) 153 041305TJ 52.6 Pt/Nb—TiO 2 (1:2) 548 061705KV 33.4 Pt/Nb—TiO 2 (5%) 494 Pt/C (3) 46.4 Pt Co/C 298 Pt/C (4) 46.5 Pt/HSC 172
- niobium-doped titanium support particles with platinum catalyst provided highly suitable specific electrode activity in the tests.
- the specific activities of the tow samples in uA/cm 2 Pt at 0.90V were higher than either of the platinum on carbon electrocatalysts or the platinum on non-doped TiO 2 electrode material.
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Abstract
Description
- This application claims priority based on provisional application Ser. No. 60/707,937, filed Aug. 12, 2005 and titled “Electrocatalyst Supports for Fuel Cells”, which is incorporated herein by reference.
- This invention pertains to electrode catalysts for fuel cells. More specifically, this invention pertains to corrosion resistant catalyst supports for fuel cells, especially for cells having a cathode at which oxygen is reduced in air.
- Fuel cells are electrochemical cells that are being developed for mobile and stationary electric power generation. One fuel cell design uses a solid polymer electrolyte (SPE) membrane or proton exchange membrane (PEM), to provide ion transport between the anode and cathode. Gaseous and liquid fuels capable of providing protons are used. Examples include hydrogen and methanol, with hydrogen being favored. Hydrogen is supplied to the fuel cell anode. Oxygen (as air) is the cell oxidant and is supplied to the cell's cathode. The fuel cell electrodes are formed of porous conductive materials, such as woven graphite, graphitized sheets, or carbon paper to enable the fuel to disperse over the surface of the membrane facing the fuel supply electrode. Each electrode comprises finely divided catalyst particles (for example, platinum particles), supported on carbon particles, to promote ionization of hydrogen at the anode and reduction of oxygen at the cathode. Protons flow from the anode through the ionically conductive polymer membrane to the cathode where they combine with oxygen to form water, which is discharged from the cell. Conductor plates carry away the electrons formed at the anode.
- Currently, state of the art PEM fuel cells utilize a membrane made of perfluorinated ionomers such as Dupont NafionTM. The ionomer carries pendant ionizable groups (e.g. sulfonate groups) for transport of protons through the membrane from the anode to the cathode.
- Currently, platinum (Pt) supported on a high surface area carbon is the most effective electrocatalyst for PEM fuel cell systems. However, a significant problem hindering large-scale implementation of proton exchange membrane (PEM) fuel cell technology is the loss of performance during extended operation and automotive cycling. Recent investigations of the deterioration of cell performance have revealed that a considerable part of the performance loss is due to the degradation of the electrocatalyst. Although carbon has been considered as the most favorable catalyst support because of its low cost, good electron conductivity, high surface area, and chemical stability, corrosion of carbon supports on the cathode side of PEM fuel cells is emerging as a challenging issue for long-term stability of PEM fuel cells.
- It is an object of this invention to provide a porous titanium oxide electrocatalyst support having suitable properties for a PEM fuel cell environment including suitable surface area, electrical conductivity and chemical stability.
- This invention uses a porous form of titanium dioxide (sometimes called “titania”) as a high surface area support for platinum, or other suitable catalyst. Preferably, the titanium dioxide is mixed or doped with an element such as niobium to enhance the electrical conductivity of the support material. The titanium oxide is formed around removable filler particles (particulate templates), such as silica particles, that are chemically dissolved (etched) from the titanium dioxide particles to yield highly porous catalyst particle carriers. Particles of noble metal or other catalyst material are then deposited on the porous carrier material. Such a titanium dioxide carrier material is particularly useful in a catalytic electrode material in association with a proton exchange membrane in a fuel cell in which oxygen is electrochemically reduced.
- In accordance with a preferred embodiment of the invention, a titanium alkoxide compound is formed as a solution or sol in an alcohol or aqueous/alcohol medium. For example, a solution or sol of titanium (IV) isopropoxide or titanium (IV) 2-ethylhexyloxide may be formed. A salt or alkoxide of a suitable dopant element may also be dissolved or dispersed in the medium. Examples of suitable dopant elements include lanthanum, manganese, molybdenum, niobium, tantalum, tungsten, strontium, vanadium, and yttrium. Also dispersed in the liquid medium are suitably sized particles (e.g. less than twenty nanometers in greatest dimension) of silica, polymer beads, or the like (preferably with the aid of ultrasonic energy). The titanium and dopant element compounds are then precipitated or gelled on the dispersed particles.
- The gelled or precipitated composite material is separated from the liquid medium and dried as necessary. The composite material is heated to a suitable temperature in a controlled atmosphere, for example of hydrogen or ammonia, to form very small particles (nanometer size) of titanium dioxide doped with a suitable quantity of niobium, or the like. When the template particles consist of an organic polymer they may be removed by heating to leave pores in the agglomerated particles of titania. When the template particles are inorganic, like silica, they may be chemically dissolved from the titanium dioxide particles leaving internal and external surface pores for receiving and dispersing fine particles of catalyst metal.
- The porous and doped titanium dioxide particles provide ample surface for the effective dispersion of platinum particles for use as cathodic electrode material on a NafionTM proton exchange membrane in a hydrogen/ oxygen fuel cell environment. The titania carrier resists oxidative weight loss in a high temperature air environment and displays electrical conductivity.
- Other objects and advantages of the invention will be apparent from a detailed description of illustrative preferred embodiments.
- The titanium dioxide catalyst support materials of this invention have general utility in catalyst applications. Their utility includes applications as catalyst supports for catalyst particles in fuel cell electrodes. For example, these durable catalyst supports may be useful in an electrochemical fuel cell assembly including a solid polymer electrolyte membrane and a cathode that is exposed to oxygen or air. Many United States patents assigned to the assignee of this invention describe electrochemical fuel cell assemblies having an assembly of a solid polymer electrolyte membrane and electrode assembly. For example, FIGS. 1-4 of U.S. Pat. No. 6,277,513 include such a description, and the specification and drawings of that patent are incorporated into this specification by reference. In the '513 patent, carbon particles are used to carry or support catalyst particles for electrode (anode or cathode) operation. In this invention, porous and doped titanium dioxide particles are used to carry the catalyst for the electrode function.
- Compounds of titanium (IV) alkoxides, such as titanium (isopropoxide)4 or titanium (2-ethylhexyloxide)4, are readily available and are, therefore, suitable and even preferred for use in the practice of this invention. These compounds have suitable solubility in alcohol (ethanol) for use in this method. As summarized above, suitable dopant elements include lanthanum, manganese, molybdenum, niobium, tantalum, tungsten, strontium, vanadium, and yttrium. Atoms of the dopant element(s) may be added to promote electronic conductivity by introducing defects in the crystalline titanium oxide support material. The dopant(s) is suitably added in an amount up to about half of the atoms of titanium in the support material. Alkoxide compounds or salts of these dopant elements are available and may be used for introducing one or more dopant element (s) into the titanium oxide catalyst support particles.
- For example, titanium (IV) isopropoxide and niobium (V) chloride, or niobium (V) ethoxide, are dissolved in ethanol in proportions of two atomic parts titanium per atom of niobium. Silica particles (10-15 nm in largest dimension) are dispersed in the alcohol solution or sol of titanium and niobium compounds. Silica is suitably added to the sol in an amount to provide about 1.2 parts by weight of silicon per part of titanium. As an alternative nanometer size particles of nylon or vinyl chloride may be used as pore-forming templates in the dispersion. The uniformity of mixing of the constituents of the dispersion may be enhanced by sonic vibration of the dispersion.
- The solution (sol) is then acidified with aqueous hydrochloric acid to hydrolyze the titanium and niobium compounds and form a gel or precipitate of titanium-containing and niobium-containing material entraining the silica particles. The titanium containing material contains sufficient oxygen for the formation of titanium dioxide.
- The precipitate or gel is separated from the liquid medium and dried. The solid material is then heated to about 1000° C. in an atmosphere of hydrogen (or suitably, ammonia) so as to form crystalline titanium dioxide doped with elemental niobium. The particles of titanium dioxide are very small, nanometer size, and the particles of silica are dispersed in the doped titanium dioxide.
- The niobium doped oxide particles are chemically etched with aqueous sodium hydroxide or hydrogen fluoride to remove the pore-forming silica particles. The residue of the chemical etching is a mass of very small, pore containing, Nb-doped, TiO2 particles where the pores are formed principally by the removal of the silica particles.
- In a specific experimental example, the resulting porous TiO2 was crystalline, contained Ti/Nb in an atomic ratio of 2, and had a BET surface area of 125 m2/g.
- In a continuation of the experimental illustration, Pt was deposited on this Nb-doped TiO2 using an aqueous solution of diamineplatinum (II) nitrite, Pt (NO2)2 (NH3)2, as a precursor. The Nb-doped TiO2 was dispersed in water at 80° C. using ultrasonic energy. The platinum precursor was also separately dissolved in 70-80° C. water with stirring. The TiO2 dispersion and the platinum precursor solution were mixed. The pH of the resulting platinum deposition medium was adjusted to 3.0 using acetic acid and carbon monoxide gas was diffused through the medium at a rate of two liters per minute. The reaction medium was stirred at 90° C.
- Hydrazine hydrate was used for reduction of the platinum and its deposition as very small particles on the niobium-doped TiO2 particles. Hydrazine hydrate was added drop wise with stirring to the platinum deposition medium (at 90° C., pH 3, and with CO diffusion) over a period of one hour. Then the TiO2-containing medium with deposited platinum was cooled to room temperature. The reaction product of platinum deposited on niobium-doped titanium dioxide particles was filtered through a 0.45 micrometer pore-size cellulose nitrate membrane, washed with distilled water, and dried overnight in a vacuum oven at 50° C.
- In this example platinum was deposited at 72 weight percent on porous niobium doped titanium dioxide and the resulting catalyst was tested with a gas phase accelerated thermal sintering method intended to induce oxidative corrosion of the catalyst. The test was conducted at 250° C. for 30 hours under an atmosphere, by volume, of 0.7% O2, 8% H2O, and the balance helium. Two commercial platinum-on-carbon catalysts were subjected to the same corrosion testing for comparison. Table 1 records the mass loss resulting from the platinum-on-titanium dioxide catalyst produced in accordance with this invention and the two comparison carbon supported platinum catalysts.
TABLE 1 Mass Loss Comparison Catalysts Pt loading Mass Loss Pt/TiO2 (no Nb) 42% −1.1% Pt/TiO2 (Nb/Ti = 1/2) 72% −4.4% Pt on carbon (1) 46.6% −55.8% Pt on carbon (2) 45.9% −76.2% - It is seen that the titanium oxide supported catalysts survives an oxidizing environment better than the carbon supported catalyst.
- The above porous, niobium-doped titanium oxide supported platinum catalyst was further tested for its oxygen reduction activity. The catalyst sample was prepared for electrochemical measurement by a special method (mixing and sonication in a suspension) to form an ink for application to a rotating disk electrode (RDE). The suspension contained the platinum on doped-titanium dioxide support (designated 41305 TJ) and a commercial electrically conductive particulate carbon dispersed in isopropanol and water. The dispersion also contained a 5% solution of NafionTM ionomer in water.
- The supported platinum and carbon containing mixture was put into a sealed 60 ml glass bottle. The content was subsequently mixed by shaking and sonicated for 2-4 hours. Once a homogeneous ink suspension was formed, 10-20 micro liters of the suspension were dispensed on a glassy carbon electrode surface. After drying at room temperature, the electrode was put on the Rotating Disk Electrode (RDE) device for activity measurement (in micro-amperes per square centimeter of platinum at 0.9V). The resulting dried catalyst on the electrode contained 52.6 wt. % Pt.
- A sample of platinum on non-doped TiO2 was prepared for comparison testing. The platinum on non-doped TiO2 (sample 0131005TJ) was applied as in ink to a RCE for comparative electrode activity measurement by the technique described above. Also, a second platinum on niobium-doped TiO2 catalyst was prepared (sample 061705KV). This sample contained niobium in an amount of 5% of the titanium and the platinum loading on the electrode was lower (33.4%) than sample 131005TJ.
- In the electrode activity tests the electrode was rotated at 1600 RPM in the 0.1 M HClO4 electrolyte at 60° C. with a flowing, saturated oxygen atmosphere at one atmosphere. The electrode voltage scan rate was 5mV/s over a voltage range of 0-1V.
- Table 2 summarizes the specific oxygen reduction activities of two illustrative platinum-on-doped titanium dioxide support catalysts and like data obtained using the non-doped TiO2 sample and two commercial platinum-on-carbon comparison catalysts.
TABLE 2 Specific activity (uA/cm2 Pt at Catalyst Pt (wt %) Type 0.90 V) 0131005TJ 27.8 Pt/TiO2 (no Nb) 153 041305TJ 52.6 Pt/Nb—TiO2 (1:2) 548 061705KV 33.4 Pt/Nb—TiO2 (5%) 494 Pt/C (3) 46.4 Pt Co/C 298 Pt/C (4) 46.5 Pt/HSC 172 - It is seen that the niobium-doped titanium support particles with platinum catalyst provided highly suitable specific electrode activity in the tests. The specific activities of the tow samples in uA/cm2 Pt at 0.90V were higher than either of the platinum on carbon electrocatalysts or the platinum on non-doped TiO2 electrode material.
- While the invention has been illustrated by certain preferred embodiment, these illustrations are intended to be non-limiting.
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Also Published As
Publication number | Publication date |
---|---|
WO2007021695A3 (en) | 2008-07-24 |
CN101365537B (en) | 2012-08-15 |
DE112006002287T5 (en) | 2008-07-03 |
CN101365537A (en) | 2009-02-11 |
US8025861B2 (en) | 2011-09-27 |
KR20080037709A (en) | 2008-04-30 |
US20100160153A1 (en) | 2010-06-24 |
WO2007021695A2 (en) | 2007-02-22 |
KR100982648B1 (en) | 2010-09-17 |
DE112006002287B4 (en) | 2009-12-17 |
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