US20120107724A1 - Electrode catalyst for fuel cell, method for producing the same, and polymer electrolyte fuel cell using the same - Google Patents
Electrode catalyst for fuel cell, method for producing the same, and polymer electrolyte fuel cell using the same Download PDFInfo
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- US20120107724A1 US20120107724A1 US13/379,713 US201013379713A US2012107724A1 US 20120107724 A1 US20120107724 A1 US 20120107724A1 US 201013379713 A US201013379713 A US 201013379713A US 2012107724 A1 US2012107724 A1 US 2012107724A1
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- catalyst
- platinum
- acid
- carbon support
- alloy
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- 239000003054 catalyst Substances 0.000 title claims abstract description 208
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 239000005518 polymer electrolyte Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002253 acid Substances 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 46
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 34
- 239000010941 cobalt Substances 0.000 claims description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-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
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 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
- 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
- 238000004448 titration Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 60
- 239000000843 powder Substances 0.000 description 52
- 238000004140 cleaning Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910001873 dinitrogen Inorganic materials 0.000 description 14
- 229910000531 Co alloy Inorganic materials 0.000 description 13
- 238000011946 reduction process Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 238000010306 acid treatment Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UYXRCZUOJAYSQR-UHFFFAOYSA-N nitric acid;platinum Chemical compound [Pt].O[N+]([O-])=O UYXRCZUOJAYSQR-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- 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
-
- 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
-
- 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
- the invention relates to an electrode catalyst for a fuel cell, a method for producing the electrode catalyst, and a polymer electrolyte fuel cell using the electrode catalyst, which are developed so as to improve the performance of a platinum catalyst or platinum-alloy catalyst.
- the cell characteristics of polymer electrolyte fuel cells have remarkably improved for some reasons including the following reasons: 1) polymer electrolyte membranes having a high ion conductivity have been developed, and 2) catalyst-carrying carbon that is coated with a polymer electrolyte of the same type as or a different type from the polymer electrolyte membrane is used as a material that forms an electrode catalyst layer, so that three-dimensional reaction sites are provided in the catalyst layer.
- the polymer electrolyte fuel cells which exhibit the improved cell performance, can be easily made compact and lightweight; therefore, it has been expected to put the polymer electrolyte fuel cells to practical use in mobile vehicles, such as electric automobiles, or as a power source of a compact cogeneration system, for example.
- a gas-diffusible electrode used in a polymer electrolyte fuel cell consists of a catalyst layer containing the catalyst-carrying carbon coated with the polymer electrolyte as described above, and a gas diffusion layer that supplies reaction gas to the catalyst layer and collects electrons.
- a catalyst layer porous portions are present in which micropores are formed among secondary particles or tertiary particles of carbon as a constituent material of the catalyst layer, and the porous portions function as diffusion channels for the reaction gas.
- a catalyst formed of a noble metal, such as platinum or platinum alloy, which is stable in the polymer electrolyte is generally used as the above-mentioned catalyst.
- a catalyst having a noble metal, such as platinum or platinum alloy, supported on carbon black has been used as cathode and anode catalysts (electrode catalysts) of polymer electrolyte fuel cells.
- the platinum-carrying carbon black is prepared by adding sodium hydrogen sulfite to an aqueous acidic platinum-chloride solution, which is then caused to react with hydrogen peroxide to form platinum colloid, supporting the platinum colloid on carbon black, cleaning, and then subjecting the platinum-carrying carbon black to heat treatment as needed.
- an electrode catalyst for fuel cells as disclosed in Japanese Patent Application Publication 2002-289208 is composed of an electrically conductive carbon material, metal particles that are supported on the conductive carbon material and are less likely be oxidized than platinum under acidic conditions, and platinum that covers outer surfaces of the metal particles.
- the thus formed electrode catalyst has high durability, and the growth of platinum particles during operation of the fuel cell is suppressed or restricted.
- the metal particles include, for example, alloys comprised of platinum and at least one metal selected from gold, chromium, iron, nickel, cobalt, titanium, vanadium, copper, and manganese.
- an electrode catalyst as disclosed in Japanese Patent Application Publication No. 2005-25947 is prepared by subjecting highly dispersed carbon having a highly complex structure and a low specific surface area to a process selected from an activation process, oxidation process using nitric acid, a process for making the carbon hydrophilic, and a hydroxyl addition process, so as to activate the surface of the carbon, and then depositing metal on the carbon.
- the platinum catalyst or platinum-alloy catalyst of the related art is still insufficient in terms of the oxygen reduction capability, and it has been desired to develop higher-performance catalysts.
- the invention provides an electrode catalyst for a fuel cell, which offers higher performance than the platinum catalyst or platinum-alloy catalyst of the related art, a method for producing the electrode catalyst, and a polymer electrolyte fuel cell using the electrode catalyst.
- a first aspect of the invention is concerned with an electrode catalyst for a fuel cell, which includes: a carbon support, a platinum catalyst or a platinum-alloy catalyst supported on the carbon support, and at least 0.7 mmol of an acid per gram of the electrode catalyst, which is present on the carbon support.
- the electrode catalyst As described above, an acid treatment is conducted on the carbon support carrying platinum or platinum alloy, so that 0.7 mmol/g or more of acid per gram of the catalyst remains on the carbon support. As a result, the catalyst becomes hydrophilic, and the water-hold property around the catalyst is improved, resulting in a reduction in the resistance to proton shift in the catalyst layer, and improved power generation performance at low humidity.
- the platinum-alloy catalyst may consist of an alloy of platinum and at least one metal selected from ruthenium, molybdenum, osmium, cobalt, rhodium, iridium, iron, nickel, titanium, tungsten, palladium, rhenium, chromium, manganese, niobium, and tantalum.
- the carbon support on which the acid is present and the platinum catalyst or the platinum-alloy catalyst is supported may be hydrophilic.
- the acid may be present on the carbon support in an amount equal to or greater than 1.0 mmol per gram of the electrode catalyst, or may be present on the carbon support in an amount equal to or greater than 1.31 mmol per gram of the electrode catalyst.
- a second aspect of the invention is concerned with a method for producing an electrode catalyst for a fuel cell, which comprises a carbon support and a platinum catalyst or a platinum-alloy catalyst supported on the carbon support.
- the method includes the steps of: supporting the platinum catalyst or the platinum-alloy catalyst on the carbon support, and treating the carbon support carrying the platinum catalyst or the platinum-alloy catalyst with an acid, so that at least 0.7 mmol of the acid per gram of the electrode catalyst is present on the carbon support treated with the acid.
- the carbon support carrying the platinum catalyst or the platinum-alloy catalyst and treated with the acid may be cleaned.
- the platinum-alloy catalyst may consist of an alloy of platinum and at least one metal selected from ruthenium, molybdenum, osmium, cobalt, rhodium, iridium, iron, nickel, titanium, tungsten, palladium, rhenium, chromium, manganese, niobium, and tantalum.
- the carbon support on which the acid is present and the platinum catalyst or the platinum-alloy catalyst is supported may be hydrophilic.
- the acid may be present on the carbon support in an amount equal to or greater than 1.0 mmol per gram of the electrode catalyst, or may be present on the carbon support in an amount equal to or greater than 1.31 mmol per gram of the electrode catalyst.
- a third aspect of the invention is concerned with a polymer electrolyte fuel cell including the electrode catalyst according to the first aspect of the invention.
- FIG. 1 is a graph showing the relationship between the catalyst acid amount and the low-humidity efficiency point performance (at 0.2 A/cm 2 ) with regard to Examples 1, 2 and Comparative Examples 1-3;
- FIG. 2 is a graph showing the relationship between the catalyst acid amount and the low-humidity output point performance (at 1.02 A/cm 2 ) with regard to Examples 1, 2 and Comparative Examples 1-3;
- FIG. 3 is a graph showing the relationship between the catalyst acid amount and the low-humidity efficiency point performance (at 0.2 A/cm 2 ) with regard to Examples 3-7 and Comparative Examples 4-14;
- FIG. 4 is a graph showing the relationship between the catalyst acid amount and the low-humidity output point performance (at 1.02 A/cm 2 ) with regard to Examples 3-7 and Comparative Examples 4-14.
- the inventors reached the present invention by subjecting carbon carrying a platinum catalyst or platinum-alloy catalyst to a particular treatment so as to bring it into a particular carbon state.
- a single cell for use in a polymer electrolyte fuel cell was formed in the following manner, using a catalyst powder obtained in each example or comparative example.
- the catalyst powder was dispersed in an organic solvent, and the resulting dispersion liquid was applied by coating to a Teflon sheet to form catalyst layers (i.e., electrodes).
- the amount of Pt catalyst per 1 cm 2 of electrode area was 0.4 mg.
- the electrodes formed from the catalyst powder were attached to each other via a polymer electrolyte membrane by hot press, to provide a membrane-electrode assembly, and diffusion layers were mounted on the opposite sides of the membrane-electrode assembly, to form a single-cell electrode.
- the method of evaluating the catalyst performance will be described.
- the initial voltage measurement was conducted in the following manner.
- the temperature of the single cell was set to 80° C., and moisturized air that passed a bubbler heated to 60° C. was supplied to the cathode-side electrode at a rate of 2.0 L/min., while moisturized hydrogen that passed a bubbler heated to 60° C. was supplied to the anode-side electrode at a rate of 0.5 L/min.
- current voltage characteristics were measured. Comparisons of the performance among the catalysts of the respective examples were made through measurements of voltage values at current densities of 0.2 A/cm 2 and 1.0 A/cm 2 .
- Example 1 will be described. Initially, 4.2 g of Ketjen EC (manufactured by Ketjen Black International Company, JAPAN), which is commercially available, and 5.0 g of platinum were added to and dispersed in 0.5 L of pure water. About 100 mL of 0.1N ammonia was then added to the resulting liquid to make PH equal to about 10, so that a hydroxide was formed and deposited on carbon. The resulting dispersion liquid was subjected to filtration, and the obtained powder was dried at 100° C. in a vacuum for 10 hours. Then, the powder was held at 400° C. for 2 hours in hydrogen gas so as to be reduced, and then held at 1000° C. for 10 hours in nitrogen gas so as to provide a catalyst powder.
- Ketjen EC manufactured by Ketjen Black International Company, JAPAN
- platinum platinum were added to and dispersed in 0.5 L of pure water. About 100 mL of 0.1N ammonia was then added to the resulting liquid to make
- the obtained catalyst was thrown into 1 L of 0.5N nitric acid, heated to 80° C., and was stirred for 30 min. Then, the catalyst was isolated by filtration, and was dried in a blowing drier at 80° C. for 15 hours or longer, to provide a catalyst powder. The acid amount in the catalyst was measured, and the result of the measurement was 1.020 mmol/g-cat.
- Example 2 will be described.
- a catalyst powder as Example 2 was obtained by preparing a catalyst in the same manner as in Example 1, except that, after the catalyst powder was treated with the acid, it was dried in a vacuum drier at 60° C. for 15 hours or longer.
- the amount of acid in the catalyst was 1.156 mmol/g-cat.
- Comparative Example 1 will be described.
- a catalyst powder as Comparative Example 1 was obtained by preparing a catalyst in the same manner as in Example 1, except that the acid treatment (i.e., a process of treating the catalyst powder with an acid) was not conducted.
- the amount of acid in the catalyst was 0.52 mmol/g-cat.
- Comparative Example 2 will be described.
- a catalyst powder as Comparative Example 2 was obtained by preparing a catalyst in the same manner as in Example 1, except that, after the acid treatment was conducted, the catalyst was filtered and cleaned with 1 L of pure water, and the filtration and cleaning were repeated until the conductivity of drainage or waste liquid became equal to or lower than 20 ⁇ S/cm.
- the amount of acid in the catalyst was 0.628 mmol/g-cat.
- Comparative Example 3 will be described.
- a catalyst power as Comparative Example 3 was obtained by preparing a catalyst in the same manner as in Example 1, except that, after the acid treatment was conducted, the catalyst was filtered and cleaned with 1 L of pure water only once. The amount of acid in the catalyst was 0.996 mmol/g-cat.
- FIG. 1 shows the relationship between the catalyst acid amount and the low-humidity efficiency point performance (at 0.2 A/cm 2 ) with regard to Examples 1, 2 and Comparative Examples 1-3 as described above.
- FIG. 2 shows the relationship between the catalyst acid amount and the low-humidity output point performance (at 1.02 A/cm 2 ) with regard to Examples 1, 2 and Comparative Examples 1-3.
- Examples of the invention showed high voltage values at both of the current densities, 0.2 A/cm 2 and 1.02 A/cm 2 , since the catalysts of these Examples had an acid that can be hydrophilic.
- Comparative Examples showed low voltage values at both of the current densities, 0.2 A/cm 2 and 1.02 A/cm 2 . It is concluded from these results that the catalyst becomes hydrophilic when it contains an acid that can be hydrophilic, and the water-hold property around the catalyst is improved, resulting in a reduction in the resistance to proton shift in the catalyst layer.
- Comparative Example 4 will be described. Initially, 4.71 g of a commercially available carbon powder having a high specific surface area was added to and dispersed in 0.5 L of pure water, to provide a dispersion liquid. A hexahydroxo platinum nitric acid solution containing 4.71 g of platinum and an aqueous solution of cobalt nitrate containing 0.592 g of cobalt were dropped in this order into the dispersion liquid, to be sufficiently brought into contact with carbon. Then, about 5 mL of 0.01N ammonia was added to the resulting liquid to make PH equal to about 9, so that a hydroxide was formed and deposited on the carbon.
- the resulting dispersion liquid was repeatedly filtered and cleaned until the conductivity of filtration drainage became equal to or lower than 50 ⁇ S/cm, and the obtained powder was dried in a vacuum at 100° C. for 10 hours. Then, after the dried powder was held in hydrogen gas at 500° C. for 2 hours so as to be reduced, it was held in nitrogen gas at 700° C. for 0.5 hour and held in the same gas at 600° C. for 6 hours, to provide an alloy of platinum and cobalt.
- the catalyst powder was thrown into 0.5 L of 0.5N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning. Then, the catalyst was filtered and cleaned with 1 L of pure water, and the filtration and cleaning were repeated until the conductivity of the cleaning drainage became equal to or lower than 20 ⁇ S/cm. Then, the catalyst was isolated by filtration, and was dried in a vacuum drier at 100° C. for 12 hours or longer, to provide a catalyst powder as Comparative Example 4.
- Comparative Example 5 will be described.
- a catalyst powder as Comparative Example 5 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour and held in the same gas at 600° C. for 12 hours, to provide an alloy of platinum and cobalt.
- Comparative Example 6 will be described.
- a catalyst powder as Comparative Example 6 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour and held in the same gas at 600° C. for 18 hours, to provide an alloy of platinum and cobalt.
- Comparative Example 7 will be described.
- a catalyst powder as Comparative Example 7 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 6.5 hours, to provide an alloy of platinum and cobalt.
- Comparative Example 8 will be described.
- a catalyst powder as Comparative Example 8 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 800° C. for 6.5 hours, to provide an alloy of platinum and cobalt.
- Comparative Example 9 will be described.
- a catalyst powder as Comparative Example 9 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour, to provide an alloy of platinum and cobalt.
- Comparative Example 10 A catalyst powder as Comparative Example 10 was obtained in the same manner as in Comparative Example 4, except for the following steps.
- the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour, to provide an alloy of platinum and cobalt. Furthermore, the catalyst powder was thrown into 0.5 L of 0.5N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning. Then, in Comparative Example 10, the catalyst was isolated by filtration but not cleaned with pure water, and was dried in a vacuum drier at 100° C. for 12 hours or longer.
- Comparative Example 11 A catalyst powder as Comparative Example 11 was obtained in the same manner as in Comparative Example 4, except for the following steps.
- Comparative Example 11 after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour, to provide an alloy of platinum and cobalt. Furthermore, the catalyst powder was thrown into 0.5 L of 0.5N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning. Then, in Comparative Example 11, the catalyst was isolated by filtration but not cleaned with pure water, and was dried in a blowing drier at 80° C. for 12 hours or longer.
- Example 3 A catalyst powder as Example 3 was obtained in the same manner as in Comparative Example 4, except that, after the alloying process, the catalyst powder was thrown into 0.5 L of 2N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning. Then, in Example 3, the catalyst was isolated by filtration but not cleaned with pure water, and was dried in a vacuum drier at 100° C. for 12 hours or longer.
- Example 4 A catalyst powder as Example 4 was obtained in the same manner as in Comparative Example 4, except for the following steps.
- the catalyst powder was thrown into 0.5 L of 2N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning.
- the catalyst was filtered and cleaned with 1 L of pure water, and the filtration and cleaning were repeatedly conducted until the conductivity of the cleaning drainage became equal to or lower than 20 ⁇ S/cm.
- the catalyst was isolated by filtration, and was further thrown into 0.5 L of 0.5N nitric acid and stirred for 30 min. at room temperature. Thereafter, the catalyst was isolated by filtration but not cleaned with pure water, and was dried in a vacuum drier at 100° C. for 12 hours or longer.
- Example 5 A catalyst powder as Example 5 was obtained in the same manner as in Comparative Example 4, except for the following steps.
- the catalyst powder was thrown into 0.5 L of 2N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning.
- the catalyst was filtered and cleaned with 1 L of pure water, and the filtration and cleaning were repeatedly conducted until the conductivity of the cleaning drainage became equal to or lower than 20 ⁇ S/cm.
- the catalyst was isolated by filtration, and was further thrown into 0.5 L of 0.5N nitric acid and stirred for 30 min. at room temperature. Thereafter, the catalyst was isolated by filtration but not cleaned with pure water, and was dried in a blowing drier at 80° C. for 12 hours or longer.
- Example 6 A catalyst powder as Example 6 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour, to provide an alloy of platinum and cobalt, and the catalyst powder was thrown into 0.5 L of 0.5N nitric acid, heated to 80° C., and was stirred for 48 hours, so that cobalt that had not been alloyed was removed by acid cleaning.
- Comparative Example 12 will be described.
- a catalyst powder as Comparative Example 12 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 800° C. for 0.5 hour, to provide an alloy of platinum and cobalt.
- Comparative Example 13 will be described.
- a catalyst powder as Comparative Example 13 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.05 hour, to provide an alloy of platinum and cobalt.
- Example 7 A catalyst powder as Example 7 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 800° C. for 0.5 hour, to provide an alloy of platinum and cobalt, and that the catalyst powder was thrown into 0.5 L of 0.5N nitric acid, heated to 80° C., and was stirred for 48 hours, so that cobalt that had not been alloyed was removed by acid cleaning.
- Comparative Example 14 will be described.
- a catalyst powder as Comparative Example 14 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 800° C. for 0.5 hour, to provide an alloy of platinum and cobalt, and the catalyst powder was thrown into 0.5 L of 0.05N nitric acid, heated to 80° C., and was stirred for 48 hours, so that cobalt that had not been alloyed was removed by acid cleaning.
- FIG. 3 shows the relationship between the amount of acid in the catalyst and the low-humidity efficiency point performance (at 0.2 A/cm 2 ), with regard to Examples 3-7 and Comparative Examples 4-14.
- FIG. 4 shows the relationship between the amount of acid in the catalyst and the low-humidity output point performance (at 1.02 A/cm 2 ), with regard to Examples 3-7 and Comparative Examples 4-14.
- Example 3 1.01 0.765 0.514
- Example 4 1.05 0.764 0.528
- Example 5 1.31 0.758 0.525
- Example 6 0.80 0.772 0.548 Com.
- Ex. 12 0.43 0.730 0.457
- Ex. 13 0.46 0.729 0.438
- Example 7 0.73 0.763 0.532 Com.
- Ex. 14 0.55 0.760 0.521
- the platinum-alloy catalysts (Examples 3-7) according to the invention showed high voltage values at both of the current densities, 0.2 A/cm 2 and 1.02 A/cm 2 , since the catalysts of these examples had an acid that can be hydrophilic.
- Comparative Examples showed low voltage values at both of the current densities, 0.2 A/cm 2 and 1.02 A/cm 2 . It is concluded from these results that the catalyst becomes hydrophilic when it contains an acid that can be hydrophilic, and the water-hold property around the catalyst is improved, resulting in a reduction in the resistance to proton shift in the catalyst layer.
- carbon carrying a known platinum catalyst or known platinum-alloy catalyst may be used.
- various types of acids may be used in an acid treatment performed on the platinum or platinum-alloy carrying carbon, and nitric acid may be preferably used.
- the electrode catalyst for fuel cells according to the invention has a higher activity than the platinum catalyst or platinum-alloy catalyst of the related art, thus making it possible to reduce the amount of expensive platinum used in the catalyst.
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Abstract
Description
- This application is a national phase application of International Application No. PCT/IB2010/001019, filed May 4, 2010, and claims the priority of Japanese Application No. 2009-147429, filed Jun. 22, 2009, the contents of both of which are incorporated herein by reference.
- 1. Field of the Invention
- The invention relates to an electrode catalyst for a fuel cell, a method for producing the electrode catalyst, and a polymer electrolyte fuel cell using the electrode catalyst, which are developed so as to improve the performance of a platinum catalyst or platinum-alloy catalyst.
- 2. Description of the Related Art
- The cell characteristics of polymer electrolyte fuel cells have remarkably improved for some reasons including the following reasons: 1) polymer electrolyte membranes having a high ion conductivity have been developed, and 2) catalyst-carrying carbon that is coated with a polymer electrolyte of the same type as or a different type from the polymer electrolyte membrane is used as a material that forms an electrode catalyst layer, so that three-dimensional reaction sites are provided in the catalyst layer. The polymer electrolyte fuel cells, which exhibit the improved cell performance, can be easily made compact and lightweight; therefore, it has been expected to put the polymer electrolyte fuel cells to practical use in mobile vehicles, such as electric automobiles, or as a power source of a compact cogeneration system, for example.
- Generally, a gas-diffusible electrode used in a polymer electrolyte fuel cell consists of a catalyst layer containing the catalyst-carrying carbon coated with the polymer electrolyte as described above, and a gas diffusion layer that supplies reaction gas to the catalyst layer and collects electrons. In the catalyst layer, porous portions are present in which micropores are formed among secondary particles or tertiary particles of carbon as a constituent material of the catalyst layer, and the porous portions function as diffusion channels for the reaction gas. A catalyst formed of a noble metal, such as platinum or platinum alloy, which is stable in the polymer electrolyte is generally used as the above-mentioned catalyst.
- For example, a catalyst having a noble metal, such as platinum or platinum alloy, supported on carbon black has been used as cathode and anode catalysts (electrode catalysts) of polymer electrolyte fuel cells. Generally, the platinum-carrying carbon black is prepared by adding sodium hydrogen sulfite to an aqueous acidic platinum-chloride solution, which is then caused to react with hydrogen peroxide to form platinum colloid, supporting the platinum colloid on carbon black, cleaning, and then subjecting the platinum-carrying carbon black to heat treatment as needed.
- Platinum, which is an expensive noble metal, has been desired to exhibit sufficient performance even where a small amount of platinum is carried on a carbon support. Therefore, technologies for enhancing the catalyst activity with a reduced amount of platinum used have been studied. For example, an electrode catalyst for fuel cells as disclosed in Japanese Patent Application Publication 2002-289208 (JP-A-2002-289208) is composed of an electrically conductive carbon material, metal particles that are supported on the conductive carbon material and are less likely be oxidized than platinum under acidic conditions, and platinum that covers outer surfaces of the metal particles. The thus formed electrode catalyst has high durability, and the growth of platinum particles during operation of the fuel cell is suppressed or restricted. More specifically, examples of the metal particles include, for example, alloys comprised of platinum and at least one metal selected from gold, chromium, iron, nickel, cobalt, titanium, vanadium, copper, and manganese.
- In order to improve the utilization factor of noble metal and reduce the amount of noble metal used so as to reduce the cost of manufacture of electrode catalysts, an electrode catalyst as disclosed in Japanese Patent Application Publication No. 2005-25947 (JP-A-2005-25947) is prepared by subjecting highly dispersed carbon having a highly complex structure and a low specific surface area to a process selected from an activation process, oxidation process using nitric acid, a process for making the carbon hydrophilic, and a hydroxyl addition process, so as to activate the surface of the carbon, and then depositing metal on the carbon.
- However, the platinum catalyst or platinum-alloy catalyst of the related art is still insufficient in terms of the oxygen reduction capability, and it has been desired to develop higher-performance catalysts.
- The invention provides an electrode catalyst for a fuel cell, which offers higher performance than the platinum catalyst or platinum-alloy catalyst of the related art, a method for producing the electrode catalyst, and a polymer electrolyte fuel cell using the electrode catalyst.
- A first aspect of the invention is concerned with an electrode catalyst for a fuel cell, which includes: a carbon support, a platinum catalyst or a platinum-alloy catalyst supported on the carbon support, and at least 0.7 mmol of an acid per gram of the electrode catalyst, which is present on the carbon support.
- To form the electrode catalyst as described above, an acid treatment is conducted on the carbon support carrying platinum or platinum alloy, so that 0.7 mmol/g or more of acid per gram of the catalyst remains on the carbon support. As a result, the catalyst becomes hydrophilic, and the water-hold property around the catalyst is improved, resulting in a reduction in the resistance to proton shift in the catalyst layer, and improved power generation performance at low humidity.
- In the electrode catalyst according to the first aspect of the invention, the platinum-alloy catalyst may consist of an alloy of platinum and at least one metal selected from ruthenium, molybdenum, osmium, cobalt, rhodium, iridium, iron, nickel, titanium, tungsten, palladium, rhenium, chromium, manganese, niobium, and tantalum.
- In the electrode catalyst according to the first aspect of the invention, the carbon support on which the acid is present and the platinum catalyst or the platinum-alloy catalyst is supported may be hydrophilic.
- In the electrode catalyst according to first aspect of the invention, the acid may be present on the carbon support in an amount equal to or greater than 1.0 mmol per gram of the electrode catalyst, or may be present on the carbon support in an amount equal to or greater than 1.31 mmol per gram of the electrode catalyst.
- A second aspect of the invention is concerned with a method for producing an electrode catalyst for a fuel cell, which comprises a carbon support and a platinum catalyst or a platinum-alloy catalyst supported on the carbon support. The method includes the steps of: supporting the platinum catalyst or the platinum-alloy catalyst on the carbon support, and treating the carbon support carrying the platinum catalyst or the platinum-alloy catalyst with an acid, so that at least 0.7 mmol of the acid per gram of the electrode catalyst is present on the carbon support treated with the acid.
- In the method according to the second aspect of the invention, after the carbon support carrying the platinum catalyst or the platinum-alloy catalyst is treated with the acid, the carbon support carrying the platinum catalyst or the platinum-alloy catalyst and treated with the acid may be cleaned.
- In the method according to the second aspect of the invention, the platinum-alloy catalyst may consist of an alloy of platinum and at least one metal selected from ruthenium, molybdenum, osmium, cobalt, rhodium, iridium, iron, nickel, titanium, tungsten, palladium, rhenium, chromium, manganese, niobium, and tantalum.
- In the method according to the second aspect of the invention, the carbon support on which the acid is present and the platinum catalyst or the platinum-alloy catalyst is supported may be hydrophilic.
- In the method according to the second aspect of the invention, the acid may be present on the carbon support in an amount equal to or greater than 1.0 mmol per gram of the electrode catalyst, or may be present on the carbon support in an amount equal to or greater than 1.31 mmol per gram of the electrode catalyst.
- A third aspect of the invention is concerned with a polymer electrolyte fuel cell including the electrode catalyst according to the first aspect of the invention.
- The foregoing and further objects, features and advantages of the invention will become apparent from the following description of example embodiments with reference to the accompanying drawings, wherein:
-
FIG. 1 is a graph showing the relationship between the catalyst acid amount and the low-humidity efficiency point performance (at 0.2 A/cm2) with regard to Examples 1, 2 and Comparative Examples 1-3; -
FIG. 2 is a graph showing the relationship between the catalyst acid amount and the low-humidity output point performance (at 1.02 A/cm2) with regard to Examples 1, 2 and Comparative Examples 1-3; -
FIG. 3 is a graph showing the relationship between the catalyst acid amount and the low-humidity efficiency point performance (at 0.2 A/cm2) with regard to Examples 3-7 and Comparative Examples 4-14; and -
FIG. 4 is a graph showing the relationship between the catalyst acid amount and the low-humidity output point performance (at 1.02 A/cm2) with regard to Examples 3-7 and Comparative Examples 4-14. - The inventors reached the present invention by subjecting carbon carrying a platinum catalyst or platinum-alloy catalyst to a particular treatment so as to bring it into a particular carbon state.
- In the following, some examples of this invention and comparative examples will be described in detail. A process for producing a single cell used for evaluation, a method of evaluating the performance of a catalyst of each example, and a method of determining the amount of acid in the catalyst will be described below.
- The process for producing a single cell used for evaluation will be described. A single cell for use in a polymer electrolyte fuel cell was formed in the following manner, using a catalyst powder obtained in each example or comparative example. The catalyst powder was dispersed in an organic solvent, and the resulting dispersion liquid was applied by coating to a Teflon sheet to form catalyst layers (i.e., electrodes). The amount of Pt catalyst per 1 cm2 of electrode area was 0.4 mg. The electrodes formed from the catalyst powder were attached to each other via a polymer electrolyte membrane by hot press, to provide a membrane-electrode assembly, and diffusion layers were mounted on the opposite sides of the membrane-electrode assembly, to form a single-cell electrode.
- The method of evaluating the catalyst performance will be described. To evaluate the catalyst performance, the initial voltage measurement was conducted in the following manner. The temperature of the single cell was set to 80° C., and moisturized air that passed a bubbler heated to 60° C. was supplied to the cathode-side electrode at a rate of 2.0 L/min., while moisturized hydrogen that passed a bubbler heated to 60° C. was supplied to the anode-side electrode at a rate of 0.5 L/min. In this condition, current voltage characteristics were measured. Comparisons of the performance among the catalysts of the respective examples were made through measurements of voltage values at current densities of 0.2 A/cm2 and 1.0 A/cm2.
- The method of determining the acid amount in the catalyst will be described. After 0.5 g of catalyst was added to 20 ml of 0.1N sodium hydroxide, which was then ultrasonically stirred for 20 min., the resulting liquid was subjected to filtration. Then, 0.05 ml of Methyl Orange as an indicator was added to 5 ml of filtrate while it was being stirred, and titration was conducted with 0.05N hydrochloric acid.
- Example 1 will be described. Initially, 4.2 g of Ketjen EC (manufactured by Ketjen Black International Company, JAPAN), which is commercially available, and 5.0 g of platinum were added to and dispersed in 0.5 L of pure water. About 100 mL of 0.1N ammonia was then added to the resulting liquid to make PH equal to about 10, so that a hydroxide was formed and deposited on carbon. The resulting dispersion liquid was subjected to filtration, and the obtained powder was dried at 100° C. in a vacuum for 10 hours. Then, the powder was held at 400° C. for 2 hours in hydrogen gas so as to be reduced, and then held at 1000° C. for 10 hours in nitrogen gas so as to provide a catalyst powder. The obtained catalyst was thrown into 1 L of 0.5N nitric acid, heated to 80° C., and was stirred for 30 min. Then, the catalyst was isolated by filtration, and was dried in a blowing drier at 80° C. for 15 hours or longer, to provide a catalyst powder. The acid amount in the catalyst was measured, and the result of the measurement was 1.020 mmol/g-cat.
- Example 2 will be described. A catalyst powder as Example 2 was obtained by preparing a catalyst in the same manner as in Example 1, except that, after the catalyst powder was treated with the acid, it was dried in a vacuum drier at 60° C. for 15 hours or longer. The amount of acid in the catalyst was 1.156 mmol/g-cat.
- Comparative Example 1 will be described. A catalyst powder as Comparative Example 1 was obtained by preparing a catalyst in the same manner as in Example 1, except that the acid treatment (i.e., a process of treating the catalyst powder with an acid) was not conducted. The amount of acid in the catalyst was 0.52 mmol/g-cat.
- Comparative Example 2 will be described. A catalyst powder as Comparative Example 2 was obtained by preparing a catalyst in the same manner as in Example 1, except that, after the acid treatment was conducted, the catalyst was filtered and cleaned with 1 L of pure water, and the filtration and cleaning were repeated until the conductivity of drainage or waste liquid became equal to or lower than 20 μS/cm. The amount of acid in the catalyst was 0.628 mmol/g-cat.
- Comparative Example 3 will be described. A catalyst power as Comparative Example 3 was obtained by preparing a catalyst in the same manner as in Example 1, except that, after the acid treatment was conducted, the catalyst was filtered and cleaned with 1 L of pure water only once. The amount of acid in the catalyst was 0.996 mmol/g-cat.
-
FIG. 1 shows the relationship between the catalyst acid amount and the low-humidity efficiency point performance (at 0.2 A/cm2) with regard to Examples 1, 2 and Comparative Examples 1-3 as described above.FIG. 2 shows the relationship between the catalyst acid amount and the low-humidity output point performance (at 1.02 A/cm2) with regard to Examples 1, 2 and Comparative Examples 1-3. - As is understood from
FIG. 1 andFIG. 2 , Examples of the invention showed high voltage values at both of the current densities, 0.2 A/cm2 and 1.02 A/cm2, since the catalysts of these Examples had an acid that can be hydrophilic. On the other hand, Comparative Examples showed low voltage values at both of the current densities, 0.2 A/cm2 and 1.02 A/cm2. It is concluded from these results that the catalyst becomes hydrophilic when it contains an acid that can be hydrophilic, and the water-hold property around the catalyst is improved, resulting in a reduction in the resistance to proton shift in the catalyst layer. - Comparative Example 4 will be described. Initially, 4.71 g of a commercially available carbon powder having a high specific surface area was added to and dispersed in 0.5 L of pure water, to provide a dispersion liquid. A hexahydroxo platinum nitric acid solution containing 4.71 g of platinum and an aqueous solution of cobalt nitrate containing 0.592 g of cobalt were dropped in this order into the dispersion liquid, to be sufficiently brought into contact with carbon. Then, about 5 mL of 0.01N ammonia was added to the resulting liquid to make PH equal to about 9, so that a hydroxide was formed and deposited on the carbon. The resulting dispersion liquid was repeatedly filtered and cleaned until the conductivity of filtration drainage became equal to or lower than 50 μS/cm, and the obtained powder was dried in a vacuum at 100° C. for 10 hours. Then, after the dried powder was held in hydrogen gas at 500° C. for 2 hours so as to be reduced, it was held in nitrogen gas at 700° C. for 0.5 hour and held in the same gas at 600° C. for 6 hours, to provide an alloy of platinum and cobalt.
- Furthermore, the catalyst powder was thrown into 0.5 L of 0.5N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning. Then, the catalyst was filtered and cleaned with 1 L of pure water, and the filtration and cleaning were repeated until the conductivity of the cleaning drainage became equal to or lower than 20 μS/cm. Then, the catalyst was isolated by filtration, and was dried in a vacuum drier at 100° C. for 12 hours or longer, to provide a catalyst powder as Comparative Example 4.
- Comparative Example 5 will be described. A catalyst powder as Comparative Example 5 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour and held in the same gas at 600° C. for 12 hours, to provide an alloy of platinum and cobalt.
- Comparative Example 6 will be described. A catalyst powder as Comparative Example 6 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour and held in the same gas at 600° C. for 18 hours, to provide an alloy of platinum and cobalt.
- Comparative Example 7 will be described. A catalyst powder as Comparative Example 7 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 6.5 hours, to provide an alloy of platinum and cobalt.
- Comparative Example 8 will be described. A catalyst powder as Comparative Example 8 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 800° C. for 6.5 hours, to provide an alloy of platinum and cobalt.
- Comparative Example 9 will be described. A catalyst powder as Comparative Example 9 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour, to provide an alloy of platinum and cobalt.
- Comparative Example 10 will be described. A catalyst powder as Comparative Example 10 was obtained in the same manner as in Comparative Example 4, except for the following steps. In Comparative Example 10, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour, to provide an alloy of platinum and cobalt. Furthermore, the catalyst powder was thrown into 0.5 L of 0.5N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning. Then, in Comparative Example 10, the catalyst was isolated by filtration but not cleaned with pure water, and was dried in a vacuum drier at 100° C. for 12 hours or longer.
- Comparative Example 11 will be described. A catalyst powder as Comparative Example 11 was obtained in the same manner as in Comparative Example 4, except for the following steps. In Comparative Example 11, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour, to provide an alloy of platinum and cobalt. Furthermore, the catalyst powder was thrown into 0.5 L of 0.5N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning. Then, in Comparative Example 11, the catalyst was isolated by filtration but not cleaned with pure water, and was dried in a blowing drier at 80° C. for 12 hours or longer.
- Example 3 will be described. A catalyst powder as Example 3 was obtained in the same manner as in Comparative Example 4, except that, after the alloying process, the catalyst powder was thrown into 0.5 L of 2N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning. Then, in Example 3, the catalyst was isolated by filtration but not cleaned with pure water, and was dried in a vacuum drier at 100° C. for 12 hours or longer.
- Example 4 will be described. A catalyst powder as Example 4 was obtained in the same manner as in Comparative Example 4, except for the following steps. In Example 4, after the alloying process, the catalyst powder was thrown into 0.5 L of 2N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning. Then, the catalyst was filtered and cleaned with 1 L of pure water, and the filtration and cleaning were repeatedly conducted until the conductivity of the cleaning drainage became equal to or lower than 20 μS/cm. The catalyst was isolated by filtration, and was further thrown into 0.5 L of 0.5N nitric acid and stirred for 30 min. at room temperature. Thereafter, the catalyst was isolated by filtration but not cleaned with pure water, and was dried in a vacuum drier at 100° C. for 12 hours or longer.
- Example 5 will be described. A catalyst powder as Example 5 was obtained in the same manner as in Comparative Example 4, except for the following steps. In Example 5, after the alloying process, the catalyst powder was thrown into 0.5 L of 2N nitric acid, heated to 80° C., and was stirred for 30 min., so that cobalt that had not been alloyed was removed by acid cleaning. Then, the catalyst was filtered and cleaned with 1 L of pure water, and the filtration and cleaning were repeatedly conducted until the conductivity of the cleaning drainage became equal to or lower than 20 μS/cm. The catalyst was isolated by filtration, and was further thrown into 0.5 L of 0.5N nitric acid and stirred for 30 min. at room temperature. Thereafter, the catalyst was isolated by filtration but not cleaned with pure water, and was dried in a blowing drier at 80° C. for 12 hours or longer.
- Example 6 will be described. A catalyst powder as Example 6 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.5 hour, to provide an alloy of platinum and cobalt, and the catalyst powder was thrown into 0.5 L of 0.5N nitric acid, heated to 80° C., and was stirred for 48 hours, so that cobalt that had not been alloyed was removed by acid cleaning.
- Comparative Example 12 will be described. A catalyst powder as Comparative Example 12 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 800° C. for 0.5 hour, to provide an alloy of platinum and cobalt.
- Comparative Example 13 will be described. A catalyst powder as Comparative Example 13 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 700° C. for 0.05 hour, to provide an alloy of platinum and cobalt.
- Example 7 will be described. A catalyst powder as Example 7 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 800° C. for 0.5 hour, to provide an alloy of platinum and cobalt, and that the catalyst powder was thrown into 0.5 L of 0.5N nitric acid, heated to 80° C., and was stirred for 48 hours, so that cobalt that had not been alloyed was removed by acid cleaning.
- Comparative Example 14 will be described. A catalyst powder as Comparative Example 14 was obtained in the same manner as in Comparative Example 4, except that, after the reduction process, the catalyst powder was held in nitrogen gas at 800° C. for 0.5 hour, to provide an alloy of platinum and cobalt, and the catalyst powder was thrown into 0.5 L of 0.05N nitric acid, heated to 80° C., and was stirred for 48 hours, so that cobalt that had not been alloyed was removed by acid cleaning.
- TABLE 1 below shows, in list form, the remaining acid amount and the power generation performance with regard to Examples 3-7 and Comparative Examples 4-14.
FIG. 3 shows the relationship between the amount of acid in the catalyst and the low-humidity efficiency point performance (at 0.2 A/cm2), with regard to Examples 3-7 and Comparative Examples 4-14.FIG. 4 shows the relationship between the amount of acid in the catalyst and the low-humidity output point performance (at 1.02 A/cm2), with regard to Examples 3-7 and Comparative Examples 4-14. -
TABLE 1 Initial Cell Performance Low Humidity Catalyst Powder (Both Electrodes RH = 40) Acid Amount by Efficiency-point Output-point Back Titration Voltage at 0.2 Voltage mmol/g A/cm2(V) at 1.0 A/cm2(V) Com. Ex. 4 0.40 0.708 0.476 Com. Ex. 5 0.56 0.716 0.402 Com. Ex. 6 0.52 0.713 0.408 Com. Ex. 7 0.44 0.724 0.421 Com. Ex. 8 0.44 0.690 0.378 Com. Ex. 9 0.47 0.729 0.436 Com. Ex. 10 0.56 0.735 0.444 Com. Ex. 11 0.63 0.761 0.508 Example 3 1.01 0.765 0.514 Example 4 1.05 0.764 0.528 Example 5 1.31 0.758 0.525 Example 6 0.80 0.772 0.548 Com. Ex. 12 0.43 0.730 0.457 Com. Ex. 13 0.46 0.729 0.438 Example 7 0.73 0.763 0.532 Com. Ex. 14 0.55 0.760 0.521 - As is understood from
FIG. 3 andFIG. 4 , the platinum-alloy catalysts (Examples 3-7) according to the invention showed high voltage values at both of the current densities, 0.2 A/cm2 and 1.02 A/cm2, since the catalysts of these examples had an acid that can be hydrophilic. On the other hand, Comparative Examples showed low voltage values at both of the current densities, 0.2 A/cm2 and 1.02 A/cm2. It is concluded from these results that the catalyst becomes hydrophilic when it contains an acid that can be hydrophilic, and the water-hold property around the catalyst is improved, resulting in a reduction in the resistance to proton shift in the catalyst layer. - In practicing the present invention, carbon carrying a known platinum catalyst or known platinum-alloy catalyst may be used. Also, in practicing the present invention, various types of acids may be used in an acid treatment performed on the platinum or platinum-alloy carrying carbon, and nitric acid may be preferably used.
- While some embodiments of the invention have been illustrated above, it is to be understood that the invention is not limited to details of the illustrated embodiments, but may be embodied with various changes, modifications or improvements, which may occur to those skilled in the art, without departing from the scope of the invention.
- The electrode catalyst for fuel cells according to the invention has a higher activity than the platinum catalyst or platinum-alloy catalyst of the related art, thus making it possible to reduce the amount of expensive platinum used in the catalyst.
Claims (14)
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JP2009-147429 | 2009-06-22 | ||
JP2009147429A JP5270468B2 (en) | 2009-06-22 | 2009-06-22 | ELECTRODE CATALYST FOR FUEL CELL, ITS MANUFACTURING METHOD, AND SOLID POLYMER TYPE FUEL CELL USING THE SAME |
PCT/IB2010/001019 WO2010150058A1 (en) | 2009-06-22 | 2010-05-04 | Electrode catalyst for fuel cell, method for producing the same, and polymer electrolyte fuel cell using the same |
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US15/212,787 Active 2030-06-09 US10263260B2 (en) | 2009-06-22 | 2016-07-18 | Electrode catalyst for fuel cell, method for producing the same, and polymer electrolyte fuel cell using the same |
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US20130035228A1 (en) * | 2010-03-31 | 2013-02-07 | Kabushikikaisha Equos Research | Catalyst production method and catalyst production apparatus, and method for controlling characteristics of reaction layer for fuel cell using the catalyst |
US10263260B2 (en) | 2009-06-22 | 2019-04-16 | Toyota Jidosha Kabushiki Kaisha | Electrode catalyst for fuel cell, method for producing the same, and polymer electrolyte fuel cell using the same |
US10950869B2 (en) | 2014-10-24 | 2021-03-16 | Cataler Corporation | Fuel cell electrode catalyst and method for producing the same |
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KR20130141272A (en) * | 2012-06-15 | 2013-12-26 | 한라비스테온공조 주식회사 | Electric compressor |
KR101720886B1 (en) * | 2012-07-11 | 2017-03-28 | 쇼와 덴코 가부시키가이샤 | Method for operating fuel cell, and electric-power generating device |
GB201302016D0 (en) | 2013-02-05 | 2013-03-20 | Johnson Matthey Fuel Cells Ltd | Catalyst |
KR101697981B1 (en) | 2014-03-28 | 2017-01-19 | 엔.이. 켐캣 가부시키가이샤 | Electrode catalyst, composition for forming gas diffusion electrode, gas diffusion electrode, membrane-electrode assembly, and fuel cell stack |
EP3035426B1 (en) | 2014-03-28 | 2018-07-04 | N.E. Chemcat Corporation | Catalyst for electrode, composition for forming gas diffusion electrode, gas diffusion electrode, film-electrode assembly, and fuel cell stack |
KR101849154B1 (en) | 2015-09-18 | 2018-04-16 | 엔.이. 켐캣 가부시키가이샤 | Electrode catalyst, gas diffusion electrode-forming composition, gas diffusion electrode, membrane electrode assembly, and fuel cell stack |
JP6347259B2 (en) * | 2016-01-15 | 2018-06-27 | トヨタ自動車株式会社 | Method for producing catalyst layer for fuel cell |
CN109411772A (en) * | 2018-10-17 | 2019-03-01 | 无锡威孚高科技集团股份有限公司 | A kind of processing method for catalyst of fuel batter with proton exchange film |
JP7072040B1 (en) | 2020-12-10 | 2022-05-19 | 株式会社キャタラー | Fuel cell catalyst and its manufacturing method |
KR20230089613A (en) * | 2021-12-13 | 2023-06-21 | 희성촉매 주식회사 | Catalyst for fuel cell and method for preparing the same |
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CN102804467B (en) | 2016-12-28 |
US10263260B2 (en) | 2019-04-16 |
JP5270468B2 (en) | 2013-08-21 |
US20170012295A1 (en) | 2017-01-12 |
WO2010150058A8 (en) | 2011-03-03 |
EP2446495B1 (en) | 2013-10-30 |
WO2010150058A1 (en) | 2010-12-29 |
JP2011003492A (en) | 2011-01-06 |
EP2446495A1 (en) | 2012-05-02 |
CN102804467A (en) | 2012-11-28 |
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