WO2010050964A1 - Catalyseur d'alliage quaternaire pour pile à combustible - Google Patents
Catalyseur d'alliage quaternaire pour pile à combustible Download PDFInfo
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- WO2010050964A1 WO2010050964A1 PCT/US2008/081919 US2008081919W WO2010050964A1 WO 2010050964 A1 WO2010050964 A1 WO 2010050964A1 US 2008081919 W US2008081919 W US 2008081919W WO 2010050964 A1 WO2010050964 A1 WO 2010050964A1
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- WIPO (PCT)
- Prior art keywords
- mol
- recited
- transition metal
- catalytic alloy
- quaternary catalytic
- Prior art date
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- 239000000446 fuel Substances 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims description 33
- 229910002059 quaternary alloy Inorganic materials 0.000 title description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 35
- 239000000956 alloy Substances 0.000 claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 27
- 150000003624 transition metals Chemical class 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 11
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 239000011651 chromium Chemical group 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 239000010936 titanium Chemical group 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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 abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- ICTAZHZJEOVXOW-UHFFFAOYSA-N platinum vanadium Chemical compound [V].[Pt].[Pt].[Pt] ICTAZHZJEOVXOW-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- 229910052720 vanadium Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910002835 Pt–Ir Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
Classifications
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- 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
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- 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 disclosure relates to catalytic alloys and, more particularly, to a stable, high activity quaternary alloy catalyst for use in fuel cells.
- Fuel cells are commonly known and used for generating electric current.
- a single fuel cell typically includes an anode catalyst layer, a cathode catalyst layer, and an electrolyte between the anode catalyst layer and the cathode catalyst layer for generating an electric current in a known electrochemical reaction between a fuel and an oxidant.
- One problem associated with fuel cells is the operational efficiency of the catalysts.
- chemical activity at the cathode catalyst is one parameter that controls the efficiency.
- An indication of the chemical activity is the rate of electrochemical reduction of the oxidant at the cathode catalyst.
- Platinum has been used for the cathode catalyst.
- platinum is expensive and has a high over-potential for the cathodic oxygen reduction reaction.
- platinum is not stable in the harsh environment of the fuel cell. For instance, the elevated temperature and potential cycling may cause degradation of the chemical activity of platinum over time due to particle migration and dissolution.
- An exemplary quaternary catalytic alloy composition for use in a fuel cell includes platinum, vanadium, a transition metal M, and iridium in a molar ratio of Pt w V x M y Ir z , where 30 ⁇ w ⁇ 75 mol%, 5 ⁇ x ⁇ 50 mol%, 5 ⁇ y ⁇ 50 mol%, and 5 ⁇ z ⁇ 30 mol%, and the transition metal M is selected from cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.
- An exemplary fuel cell includes a quaternary catalytic alloy comprising platinum, vanadium, a transition metal M, and iridium in a molar ratio of Pt w V x M y Ir z , where 30 ⁇ w ⁇ 75 mol%, 5 ⁇ x ⁇ 50 mol%, 5 ⁇ y ⁇ 50 mol%, and 5 ⁇ z ⁇ 30 mol%, and the transition metal M is selected from cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.
- Figure 1 illustrates an example fuel cell.
- Figure 2 illustrates an example of a supported cathode catalyst.
- FIG. 1 illustrates selected portions of an example fuel cell 10.
- a single fuel cell unit 12 is shown; however, it is to be understood that multiple fuel cell units 12 may be stacked in a known manner in the fuel cell 10 to generate a desired amount of electric current. It is also to be understood that this disclosure is not limited to the arrangement of the example fuel cell 10, and the concepts disclosed herein may be applied to other fuel cell arrangements.
- the fuel cell 10 includes an electrode assembly 14 located between an anode interconnect 16 and a cathode interconnect 18.
- the anode interconnect 16 may deliver fuel, such as hydrogen gas, to the electrode assembly 14.
- the cathode interconnect 18 may deliver an oxidant, such as oxygen gas, to the electrode assembly 14.
- the anode interconnect 16 and the cathode interconnect 18 are not limited to any particular structure, but may include channels or the like for delivering the reactant gases to the electrode assembly 14.
- the electrode assembly 14 includes an anode catalyst layer 20, a cathode catalyst layer 22, and an electrolyte 24 located between the anode catalyst layer 20 and the cathode catalyst layer 22.
- the electrolyte 24 may be any suitable type of electrolyte for conducting ions between the anode catalyst layer 20 and the cathode catalyst layer 22 in the electrochemical reaction, to generate the electric current.
- the electrolyte 24 may be a polymer electrolyte membrane, phosphoric acid, a solid oxide electrolyte, or other type of electrolyte.
- the hydrogen at the anode catalyst 20 disassociates into protons that are conducted through the electrolyte 24 to the cathode catalyst 22 and electrons that flow through an external circuit 26 to power a load 28, for example.
- the electrons from the external circuit 26 combine with the protons and oxygen at the cathode catalyst 22 to form water as a product.
- the cathode catalyst 22, and optionally also the anode catalyst 20, is a supported catalyst 40.
- the example supported catalyst 40 is not necessarily shown to scale.
- the supported catalyst 40 includes a quaternary catalytic alloy 42 in the form of particles 44 disposed on a carbon support material 46.
- the particles 44 may have an average particle size of about 2-20 nanometers.
- the support material may be carbon black or other type of conductive material, and the quaternary catalytic alloy 42 may be about 10-70 wt% of the total weight of the supported catalyst 40.
- the quaternary catalytic alloy 42 includes a composition of platinum, vanadium, a transition metal M, and iridium in a molar ratio of Pt w V x M y Ir z .
- the transition metal M is selected from cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.
- the sum of w, x, y, and z equals 100 mol%.
- the quaternary catalytic alloy 42 is highly active and stable under typical fuel cell operating conditions. For instance, vanadium and the transition metal M enhance the activity of the quaternary catalytic alloy 42 and the iridium enhances the durability of the quaternary catalytic alloy 42 under elevated temperatures and potential cycling. Thus, the quaternary catalytic alloy 42 provides a desirable balance of activity and durability while also reducing costs by reducing the amount of platinum. In a further example, a composition where 30 ⁇ w ⁇ 60 mol%, 5 ⁇ x ⁇ 20 mol%, 20 ⁇ y ⁇ 40 mol%, and 5 ⁇ z ⁇ 15 mol% provides a desirable balance of activity and durability.
- a composition where w equals about 40 mol%, x equals about 20 mol%, y equals about 30 mol%, and z equals about 10 mol% may provide an even more desirable balance of activity and durability.
- the term "about” as used in this description relative to compositions or other values refers to possible variation in the given value, such as normally accepted variations or tolerances.
- the quaternary catalytic alloy compositions may include impurity elements. Additionally, the quaternary catalytic alloy compositions may include only the given elements, or the given elements and any impurities. Any elements other than the listed elements are considered to be impurities.
- the transition metal M may be cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.
- One composition that may be particularly useful includes cobalt as the transition metal M such that the composition is Pt w V x Co y Ir z .
- the combination of cobalt and vanadium enhances the activity of the quaternary catalytic alloy 42.
- the composition consists only of platinum, vanadium, cobalt, and iridium in a composition where 30 ⁇ w ⁇ 60 mol%, 5 ⁇ x ⁇ 20 mol%, 20 ⁇ y ⁇ 40 mol%, and 5 ⁇ z ⁇ 15 mol%.
- w equals about 40 mol%
- x equals about 20 mol%
- y equals about 30 mol%
- z equals about 10 mol%.
- the supported catalyst 40 may be formed according to known methods. The following examples are based on the composition Pt w V x Co y Ir z ; however, it is to be understood that, given this description, one of ordinary skill in the art will recognize that the methods may be modified for other transition metals to meet their particular needs.
- the supported catalyst 40 may be formed by preparing a solution from 5 grams of Ketjen Black, 7.3 mmol of IrCl 4 and 29.3 mmol chloroplatanic acid in 600 ml water by ultrasonically blending for 30 minutes. The solution is then boiled and 40 ml of 37% HCHO is added into the solution to reduce the Pt and Ir. The Pt-Ir/C products are then filtered and rinsed with distilled water.
- the Pt-Ir/KB is dispersed in 200 ml water and ultrasonically blended for 20 minutes, and 22 mmol Co(NOs) 2 -OH 2 O and 14.6 mmol NH 4 VO 3 are dissolved into the Pt-Ir/C slurry and stirred for 10 min.
- the slurry is then dried in a vacuum oven at 80 0 C and heat treated at 900 0 C for 60 minutes.
- the supported catalyst 40 may be formed by preparing a solution from 1.45 mmol of Ir(CO)s and 2.9 mmol of Pt (acetylacetonate, acac) 2 , 1.45 mmol of V (acac) 2 and 1.45 mmol of Co (CO)s in 100 ml ethyl glycol with 8 mmol of oleylamine and 8 mmol of oleic acid. The mixture is then be heated to boiling for 30 min with flux. 10 ml of 10 mmol NaBH 4 solution is added into the mixture to reduce all the metals. The mixture is then precipitated using centrifugation.
- the solid is re-dispersed in 100 ml hexane with 500 mg Ketjen Black. The slurry is then stirred overnight and allowed to dry. The solid is collected and heated in N 2 at 260 0 C for 30 minutes and then annealed at 900 0 C for 60 min.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
La présente invention concerne un catalyseur d'alliage quaternaire destiné à être utilisé dans une pile à combustible, comportant du platine-vanadium, un métal de transition M, et de l'iridium dans un rapport molaire PtwVxMyIrz, où 30 ≤ w ≤ 75 pour cent molaire, 5 ≤ x ≤ 50 pour cent molaire 5 ≤y ≤ 50 pour cent molaire, et 5 ≤ z ≤ 30 pour cent molaire, et le métal de transition M est cobalt, titane, chrome, manganèse, fer, nickel, cuivre, zinc, molybdène, tungstène, ou des combinaisons de ceux-ci.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2008/081919 WO2010050964A1 (fr) | 2008-10-31 | 2008-10-31 | Catalyseur d'alliage quaternaire pour pile à combustible |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US11355761B2 (en) | 2019-12-31 | 2022-06-07 | Robert Bosch Gmbh | Polyelemental catalyst structures for fuel cells |
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US5024905A (en) * | 1989-03-09 | 1991-06-18 | N. E. Chemcat Corporation | Platinum alloy electrocatalyst |
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US6916764B2 (en) * | 2002-02-19 | 2005-07-12 | Samsung Sdi Co., Ltd. | Pt-Ru-M1-M2 quaternary metal catalyst based on Pt-Ru for direct methanol fuel cell |
US7351444B2 (en) * | 2003-09-08 | 2008-04-01 | Intematix Corporation | Low platinum fuel cell catalysts and method for preparing the same |
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US4447506A (en) * | 1983-01-17 | 1984-05-08 | United Technologies Corporation | Ternary fuel cell catalysts containing platinum, cobalt and chromium |
US5024905A (en) * | 1989-03-09 | 1991-06-18 | N. E. Chemcat Corporation | Platinum alloy electrocatalyst |
US5013618A (en) * | 1989-09-05 | 1991-05-07 | International Fuel Cells Corporation | Ternary alloy fuel cell catalysts and phosphoric acid fuel cell containing the catalysts |
US5178971A (en) * | 1990-07-31 | 1993-01-12 | N.E. Chemcat Corporation | Supported platinum quaternary alloy electrocatalyst |
US6916764B2 (en) * | 2002-02-19 | 2005-07-12 | Samsung Sdi Co., Ltd. | Pt-Ru-M1-M2 quaternary metal catalyst based on Pt-Ru for direct methanol fuel cell |
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US11355761B2 (en) | 2019-12-31 | 2022-06-07 | Robert Bosch Gmbh | Polyelemental catalyst structures for fuel cells |
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