WO2022158395A1 - 燃料電池電極触媒 - Google Patents
燃料電池電極触媒 Download PDFInfo
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- WO2022158395A1 WO2022158395A1 PCT/JP2022/001183 JP2022001183W WO2022158395A1 WO 2022158395 A1 WO2022158395 A1 WO 2022158395A1 JP 2022001183 W JP2022001183 W JP 2022001183W WO 2022158395 A1 WO2022158395 A1 WO 2022158395A1
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- fuel cell
- cell electrode
- catalyst
- carbon support
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- 239000000446 fuel Substances 0.000 title claims abstract description 116
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 61
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- 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
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J35/392—Metal surface area
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
-
- 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 present invention relates to a fuel cell electrode catalyst.
- Fuel cells are expected to be the next generation of batteries.
- polymer electrolyte fuel cells have advantages such as a low operating temperature, a short start-up time, and a compact size.
- a polymer electrolyte fuel cell has a structure in which a cathode (air electrode), a solid polymer electrolyte membrane, and an anode (fuel electrode) are stacked in this order.
- a cathode air electrode
- a solid polymer electrolyte membrane solid polymer electrolyte membrane
- an anode fuel electrode
- oxidation and reduction reactions occur at each electrode to generate electric power.
- the electrode contains a fuel cell catalyst for promoting the above oxidation/reduction reaction.
- fuel cell catalysts those having a structure in which catalyst particles are carried on a carbon powder carrier are widely used.
- Pt particles and Pt alloy particles are known as catalyst particles for fuel cell catalysts.
- Patent Document 1 describes a method for producing a Pt-supported catalyst in which a Pt precursor compound is reduced in the liquid phase in the presence of carrier particles.
- Patent Document 2 describes the use of Pt alloy particles as catalyst particles in order to improve the activity of the cathode of a polymer electrolyte fuel cell.
- Patent Document 3 describes that an anode catalyst in which Pt or a Pt alloy is supported on a carbon support and a water electrolysis catalyst such as IrO 2 are used together in the catalyst layer on the anode side of the fuel cell. ing.
- JP-A-08-084930 Japanese Patent Application Laid-Open No. 2003-142112 JP 2009-152143 A
- a fuel cell particularly a polymer electrolyte fuel cell, as described above
- oxygen or air is supplied to the cathode
- fuel such as hydrogen
- oxidation/reduction reactions occur at both electrodes to generate electric power. do.
- the fuel supplied to the anode may be depleted, for example, due to the effect of nitrogen permeating from the cathode or due to the effect of water condensate generated by the fuel cell reaction. can occur.
- the power generation voltage of the fuel cell is maintained as long as protons are supplemented by the above reaction. Therefore, deterioration of the carbon support is difficult to detect in the initial stage. If the initial deterioration of the carbon support is overlooked and the deterioration of the carbon support progresses further, the catalyst metal particles will drop off from the carbon support, resulting in a rapid decrease in the activity of the fuel cell electrode catalyst.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fuel cell electrode catalyst that suppresses deterioration of the carbon support during fuel starvation and is excellent in maintaining ECSA (electrochemically active area). to provide.
- ECSA electrochemically active area
- the present invention is as follows.
- the fuel cell electrode catalyst according to aspect 1 or 2 wherein the catalyst metal particles have an average particle size of 5.0 nm or less.
- a fuel cell electrode catalyst that suppresses the deterioration of the carbon support during fuel starvation and is excellent in maintaining the ECSA (electrochemically active area).
- FIG. 1 is a graph showing the relationship between the number of Pt particles per unit specific surface area of the carbon support (particles/100 nm 2 ) and the ECSA after the endurance test in the catalysts obtained in Examples.
- FIG. 2 is a graph showing the relationship between the number of Pt particles per unit specific surface area of the carbon support (particles/100 nm 2 ) and the ECSA retention rate after the endurance test in the catalysts obtained in Examples.
- the fuel cell electrode catalyst of the present invention is A fuel cell electrode catalyst in which catalyst metal particles made of Pt or a Pt alloy are supported on a carbon support, The number of catalyst metal particles per unit surface area of the carbon support is 4.3/100 nm2 or more and 16.0/100 nm2 or less. It is a fuel cell electrode catalyst.
- the number of catalytic metal particles per unit surface area of the carbon support is limited within a predetermined range.
- the catalyst metal particles when the catalyst metal particles are supported on the adsorption active sites of the carbon support, it is believed that they strongly adsorb to the carbon support and exhibit high catalytic activity.
- the catalyst metal particles weakly adsorbed to the carbon support are increased without being held by the adsorption active sites of the carbon support, resulting in coarse catalyst metal particles. It is considered that the catalytic activity is lowered due to the quenching. As the mechanism of this coarsening, coarsening due to dissolution and reprecipitation of the catalytic metal particles, coarsening due to migration and agglomeration of the catalytic metal particles on the carrier, and the like are assumed.
- the number of catalytic metal particles per unit surface area of the carbon support is limited to a predetermined range, thereby preventing deterioration of the carbon support during fuel starvation. is suppressed, and the maintenance of ECSA (electrochemically active area) is excellent.
- the carbon support in the fuel cell electrode catalyst of the present invention may be, for example, carbon black, graphite, carbon fiber, activated carbon, amorphous carbon, nanocarbon material, or the like.
- Nanocarbon materials include carbon nanotubes, graphene, fullerenes, and the like.
- Graphite may be used as the carbon carrier in the present invention.
- Graphite may be natural graphite or artificial graphite.
- Natural graphite includes massive graphite, earthy graphite, flake graphite, and the like.
- Artificial graphite includes graphitized carbon obtained by graphitizing any carbon material.
- the carbon support in the present invention may be particles of graphitized carbon.
- the carbon support in the present invention has a specific surface area measured by the BET method using nitrogen as an adsorbate of 10 m 2 /g or more, 20 m 2 /g or more, 30 m 2 /g or more, 40 m 2 /g or more, or 50 m 2 /g. 100 m 2 /g or less, 90 m 2 /g or less, 80 m 2 /g or less, 70 m 2 /g or less, or 60 m 2 /g or less.
- the specific surface area of the carbon support may be, for example, 10 m 2 /g or more and 100 m 2 /g or less, or 20 m 2 /g or more and 70 m 2 /g or less.
- the particle size of the carbon support may be 5 nm or more, 10 nm or more, 20 nm or more, 30 nm or more, or 50 nm or more, and may be 500 nm or less, 300 nm or less, or 200 nm or less as a number-average primary particle size measured by electron microscope observation. , or 100 nm or less.
- the particle size of the carbon support can be calculated as the number average equivalent diameter based on the electron microscope image taken for the fuel cell electrode catalyst.
- equivalent diameter refers to the diameter of a perfect circle having an outer circumference equal to the outer circumference of the figure to be measured.
- the catalytic metal particles are made of Pt or a Pt alloy and supported on a carbon support.
- the catalytic metal particles consist of a Pt alloy
- the Pt alloy may typically be a Pt--Fe alloy, a Pt--Co alloy, or a Pt--Ni alloy.
- the ratio of the Pt atoms in the Pt alloy is 50 mol% or more, 60 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, or 85 mol% or more, and 99 mol% or less, 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 75 mol% or less It's okay.
- the average particle size of the catalyst metal particles may be 5.0 nm or less, 4.5 nm or less, 4.0 nm or less, 3.5 nm or less, 3.0 nm or less, or 2.5 nm or less, 1.0 nm or more, 1 0.5 nm or greater, 2.0 nm or greater, or 2.5 nm or greater.
- Catalyst metal particles having an average particle size of 5.0 nm or less have the advantage of high ECSA.
- Catalyst metal particles having an average particle size of 1.0 nm or more have the advantage of being excellent in maintaining ECSA when the fuel cell is operated for a long period of time.
- the average particle diameter of the catalyst metal particles may be, for example, 2.0 nm or more and 3.5 nm or less.
- the average particle size of the catalytic metal particles in the fuel cell electrode catalyst of the present invention can be calculated by the Scherrer formula from the line width of the diffraction peak in the powder XRD measurement of the fuel cell electrode catalyst.
- the average particle size of the catalytic metal particles is calculated by the Scherrer formula from the line width of the diffraction peak of the (220) plane of Pt in the powder XRD measurement of the fuel cell electrode catalyst. good.
- the average particle size of the catalytic metal particles may be calculated by small-angle X-ray scattering or transmission electron microscopy (TEM).
- the number of catalytic metal particles per unit surface area of the carbon support is 4.3/100 nm 2 or more and 16.0/100 nm 2 or less. As described above, if there are too many catalyst metal particles per unit surface area of the carbon support, the catalyst metal particles are not retained by the adsorption active sites of the carbon support and are weakly adsorbed to the carbon support. It is considered that the catalyst activity is lowered due to the coarsening of the grains. On the other hand, if the amount of catalytic metal particles per unit surface area of the carbon support is too small, many adsorption active sites that are not protected by the catalytic metal particles remain on the carbon support, and the carbon support is likely to be decomposed. It is considered that the carbon support is likely to deteriorate when it is deficient.
- the number of catalyst metal particles per unit surface area of the carbon support is 4.4/100 nm 2 or more, 4.5/100 nm 2 or more, 5.0/100 nm 2 or more, 6.0/ 100 nm 2 or more, 80.0/100 nm 2 or more, 10.0/100 nm 2 or more, or 12.0/100 nm 2 or more, 15.0/100 nm 2 or less, 13.0/ It may be 100 nm 2 or less, 11.0/100 nm 2 or less, 10.0/100 nm 2 or less, 8.0/100 nm 2 or less, or 6.0/100 nm 2 or less.
- the number of catalytic metal particles per unit surface area of the carbon support may typically be 6.0/100 nm 2 or more and 10.0/100 nm 2 or less.
- the number of catalytic metal particles per unit surface area of the carbon support may be a value calculated from the average particle diameter of the catalytic metal particles and the specific surface area of the carbon support.
- the loading density of the catalytic metal particles that is, the loading amount (mass) of the catalytic metal particles per unit surface area of the carbon support is 6.0 mg/m 2 or more, 6.5 mg/m 2 or more, 7.0 mg/m 2 or more. , 8.0 mg/m 2 or more, 10 mg/m 2 or more, 12 mg/m 2 or more, or 15 mg/m 2 or more, 25 mg/m 2 or less, 22 mg/m 2 or less, 20 mg/m 2 or less, It may be 18 mg/m 2 or less, 15 mg/m 2 or less, 12 mg/m 2 or less, or 10 mg/m 2 or less.
- the loading density of the catalyst metal particles may typically be 6.5 mg/m 2 or more and 25.0 mg/m 2 or less.
- the loading ratio of the catalytic metal particles that is, the loading amount (mass) of the catalytic metal particles per unit mass of the catalytic metal particles is 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, and 20% by mass. % or more, or 25 mass % or more, and may be 75 mass % or less, 60 mass % or less, 50 mass % or less, 40 mass % or less, or 35 mass % or less.
- the fuel cell electrode catalyst of the present invention may contain optional components other than the carbon carrier and the catalytic metal particles.
- the optional component that may be contained in the fuel cell electrode catalyst of the present invention is, for example, one or two selected from carbon materials other than carbon supports, Ir particles, Ir-Ru alloy particles, Ir oxides, etc.
- the above ingredients may be used.
- the carbon material other than the carbon support is a carbon material that does not support catalyst metal particles, and may be selected from, for example, graphite, carbon fiber, graphitized carbon black, carbon nanotubes, and the like.
- the fuel cell electrode catalyst of the present invention can be prepared, for example, by contacting a carbon support and a catalyst metal precursor (precursor contacting step), and reducing the catalyst metal precursor to support catalyst metal particles on the carbon support. (supporting step).
- a Pt precursor is used as the catalytic metal precursor, the carbon support and the Pt precursor are brought into contact with each other in an appropriate solvent, and then the Pt precursor is reduced to obtain carbon.
- a fuel cell electrode catalyst can be obtained by supporting Pt particles on a carrier.
- the carbon carrier to be used may be appropriately selected and used according to the carbon carrier in the desired fuel cell electrode catalyst.
- the Pt precursor may be appropriately selected from solvent-soluble Pt compounds and used.
- Pt precursor for example, PtCl 2 , PtCl 4 , PtBr 2 , PtS, Pt(CN) 2 , PtCl 2 (NH 3 ) 2 (dinitrodiammineplatinum) and the like may be appropriately selected and used.
- the solvent may be selected from those capable of dissolving the Pt precursor used.
- the Pt precursor is PtCl2
- hydrochloric acid may be used
- PtBr2 aqueous hydrobromic acid
- PtCl2 (NH3)2 aqueous nitric acid may be used.
- water may be used when PtCl 4 , PtS, or Pt(CN) 2 .
- Reduction of the Pt precursor may be performed using a suitable reducing agent.
- Reducing agents may be, for example, ethanol, acetic acid, acetaldehyde, sodium borohydride, hydrazine, and the like.
- the reduction may be performed at a temperature of 10° C. or higher and 100° C. or lower for 0.5 hours or more and 8 hours or less.
- the reduction temperature is preferably 10° C. or higher and 50° C. or lower when sodium borohydride is used as the reducing agent, and 60° C. or higher when ethanol, acetic acid, acetaldehyde, or hydrazine is used as the reducing agent.
- the temperature is preferably 100° C. or lower.
- the fuel cell electrode catalyst can be obtained, for example, by any of the following methods.
- a method of sequentially reducing and supporting Pt and an alloy metal (Method 1): Contacting the carbon support and the Pt precursor in a suitable solvent, then reducing the Pt precursor, and supporting Pt particles on the carbon support to obtain Pt-supported carbon; After contacting the Pt-supported carbon and the alloy metal precursor in an appropriate solvent, the alloy metal precursor is reduced to obtain the Pt-alloy metal-supported carbon in which the alloy metal particles are supported on the Pt-supported carbon. and obtaining a fuel cell electrode catalyst in which Pt alloy particles are supported on a carbon support by heating the Pt-alloy metal-supporting carbon and alloying the Pt with the alloy metal.
- Method 2 A method of simultaneously reducing and supporting Pt and an alloy metal (Method 2): After contacting the carbon support with the Pt precursor and the alloy metal precursor in a suitable solvent, the Pt precursor and the alloy metal precursor are reduced to form Pt particles and alloy metal particles supported on the carbon support. obtaining a Pt-alloy metal-supported carbon; Obtaining a fuel cell electrode catalyst in which Pt alloy particles are supported on a carbon support by heating the Pt-alloy metal-supporting carbon to alloy the Pt with the alloy metal.
- alloy metal means a metal other than Pt in the Pt alloy that constitutes the catalyst metal particles.
- Method 1 A method of sequentially supporting Pt and an alloy metal on a carbon support (Method 1) In Method 1, first, a carbon support and a Pt precursor are brought into contact with each other in an appropriate solvent, and then the Pt precursor is reduced to support Pt particles on the carbon support to obtain Pt-supported carbon. This step may be carried out similarly to the production of fuel cell electrocatalysts when the catalytic metal particles are Pt particles.
- the alloy metal precursor is reduced to obtain a Pt-alloy in which the alloy metal particles are supported on the Pt-supported carbon.
- a metal-supported carbon is obtained.
- the alloy metal precursor may be appropriately selected and used according to the type of alloy metal in the desired fuel cell electrode catalyst.
- the alloy metal precursor may be appropriately selected from solvent-soluble compounds containing the desired alloy metal and used. For example, they may be hydroxides, chlorides, sulfides, nitrates, sulfates, acetates, etc. of the desired alloy metals.
- the solvent may be selected from those capable of dissolving the alloy metal precursor to be used.
- the solvent can be, for example, water.
- Reduction of the alloy metal precursor may be performed using a suitable reducing agent or neutralizing agent.
- the reducing agent can be, for example, sodium borohydride, hydrazine, hydrogen gas, formic acid, and the like.
- Neutralizing agents can be, for example, sodium metaborate, sodium hydroxide, sodium carbonate, ammonia, and the like.
- the reduction using a reducing agent may be performed at a temperature of 10°C or higher and 100°C or lower for 0.5 hours or longer and 8 hours or shorter.
- the reduction temperature is preferably 10° C. or higher and 50° C. or lower when sodium borohydride is used as the reducing agent, and 60° C. or higher when ethanol, acetic acid, acetaldehyde, or hydrazine is used as the reducing agent.
- the temperature is preferably 100° C. or lower.
- the alloy metal is once supported on the Pt-supporting carbon in a state of having a valence of 1 or higher, and then heated to reduce the alloy metal. It is considered that the alloy forms an alloy with Pt.
- the reduction using the neutralizing agent may be performed at a temperature of 60° C. or higher and 100° C. or lower for 0.5 hour or longer and 8 hours or shorter.
- the obtained Pt-alloy metal-supported carbon is heated to alloy the Pt with the alloy metal, thereby obtaining a fuel cell electrode catalyst in which the Pt alloy particles are supported on the carbon powder support.
- the heating conditions for alloying Pt and the alloy metal the description of heating in method (1) may be applied as is.
- the fuel cell electrode catalyst medium of the present invention may be produced, for example, by the above method or by a method obtained by appropriately modifying the above method by those skilled in the art.
- a fuel cell anode having a catalyst layer comprising the fuel cell electrocatalyst of the invention.
- the anode may have a suitable substrate layer and a catalyst layer on the substrate layer, the catalyst layer comprising the fuel cell electrode catalyst of the present invention.
- the base material layer may be appropriately selected and used from fuel cell electrode catalysts and solvents, as well as those having chemical and mechanical stability that can withstand heat treatment, pressure treatment, etc. that are preferably performed during electrode formation. .
- a sheet of polyimide, polyethylene, polypropylene, polysulfone, polytetrafluoroethylene, or the like may be used.
- the catalyst layer contains the fuel cell electrode catalyst of the present invention, but in addition to this, it may contain an ionomer, and may further contain optional components such as a binder.
- the ionomer may be, for example, Nafion (sulfonated tetrafluoroethylene-based (co)polymer).
- a fuel cell electrode assembly may have a structure in which an anode, a solid polymer electrolyte membrane, and a cathode are laminated in this order, and the anode may be an electrode containing the fuel cell electrode catalyst of the present invention.
- the solid polymer electrolyte membrane and the cathode in this fuel cell electrode assembly may be known solid polymer electrolyte membranes and cathodes, respectively.
- the fuel cell electrode assembly of the present invention may be produced by a known method, except that an electrode containing the fuel cell electrode catalyst of the present invention is used as the anode.
- Fuel cell Yet another aspect of the present invention provides a fuel cell including the fuel cell electrode assembly described above.
- the fuel cell of the present invention may be a polymer electrolyte fuel cell.
- the fuel cell of the present invention includes the fuel cell electrode assembly of the present invention.
- the fuel cell of the present invention may be produced by a known method, except that an electrode containing the fuel cell electrode catalyst of the present invention is used as the anode.
- reaction system was allowed to cool while stirring until the temperature of the reaction system reached 40°C or lower, and then the solid content was collected by filtration.
- the collected solid content was repeatedly washed with 1 L of pure water at 60°C. Washing was repeated until the conductivity of the filtrate was 5 ⁇ S/cm or less.
- the washed solid content was dried at 80°C for 15 hours and then pulverized to obtain a catalyst powder.
- the average particle size of the Pt particles calculated by the Scherrer formula from the line width of the diffraction peak of the (220) plane of Pt was 2.3 nm. Also, the number of Pt particles per unit area of the support was calculated from this average particle size and the specific surface area of the carbon support.
- a catalyst powder in which Pt is supported on Ketzen Black manufactured by Ketjen Black International Co., Ltd., product name "EC300" was used.
- a cathode catalyst layer-forming coating liquid was prepared in the same manner as in the preparation, and a cathode catalyst layer was formed on a sheet using this.
- the amount of Pt supported in the catalyst powder used for this cathode catalyst layer was 30 mass % based on the mass of the catalyst powder.
- the Teflon sheets having the anode catalyst layer and the cathode catalyst layer obtained above are laminated with the catalyst layer forming surfaces facing each other, transferred by hot pressing, and then the Teflon sheets are peeled off. , an anode catalyst layer, a polymer electrolyte membrane, and a cathode catalyst layer were laminated in this order to obtain a laminate. Then, a single cell for high voltage endurance test was manufactured by placing a diffusion layer on the surface of each catalyst layer.
- Examples 2 to 7, and Comparative Examples 1 to 4>> A catalyst powder was prepared and used in the same manner as in Example 1, except that the type of carbon support and the amount of dinitrodiammine platinum used (equivalent to metal Pt) were as shown in Table 1.
- a single cell for high voltage endurance test was manufactured by the same method, and a high voltage endurance test was conducted.
- the heat treatment conditions were 250° C. and 2 hours in Example 8, and 300° C. and 2 hours in Comparative Example 5.
- FIG. 1 shows a graph showing the relationship between the number of Pt particles per unit specific surface area of the carbon support (particles/100 nm 2 ) and the ECSA after the endurance test for each catalyst.
- FIG. 2 shows a graph showing the relationship between the number of Pt particles per unit specific surface area of the carbon support (particles/100 nm 2 ) and the ECSA retention rate after the endurance test for each catalyst.
- the catalysts of Comparative Examples 1-4 with a Pt loading density of less than 6.0 mg/m 2 did not have ECSA after the high voltage endurance test.
- the catalysts of Examples 1 to 8 having a Pt loading density of 6.0 mg/m 2 or more and 16.0 pieces/100 nm 2 or less exhibited significant ECSA even after the high voltage endurance test, and the ECSA retention rate was was verified to be high and exhibit excellent durability.
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Abstract
Description
C+2H2O→CO2+4H++4e-
カーボン担体に、Pt又はPt合金から成る触媒金属粒子が担持されている、燃料電池電極触媒であって、
前記カーボン担体の単位表面積当たりの前記触媒金属粒子の個数が、4.3個/100nm2以上16.0個/100nm2以下である、燃料電池電極触媒。
《態様2》
前記カーボン担体の単位表面積当たりの前記触媒金属粒子の個数が、6.0個/100nm2以上10.0個/100nm2以下である、態様1に記載の燃料電池電極触媒。
《態様3》
前記触媒金属粒子の平均粒径が、5.0nm以下である、態様1又は2に記載の燃料電池電極触媒。
《態様4》
前記触媒金属粒子の平均粒径が、2.0nm以上3.5nm以下である、態様1~3のいずれか一項に記載の燃料電池電極触媒。
《態様5》
前記カーボン担体の単位表面積当たりの前記触媒金属粒子の担持量が、6.0mg/m2以上である、態様1~4のいずれか一項に記載の燃料電池電極触媒。
《態様6》
前記カーボン担体の単位表面積当たりの前記触媒金属粒子の担持量が、6.5mg/m2以上25.0mg/m2以下である、態様5に記載の燃料電池電極触媒。
《態様7》
前記カーボン担体が、黒鉛化カーボンの粒子である、態様1~6のいずれか一項に記載の燃料電池電極触媒。
《態様8》
前記カーボン担体の比表面積が、10m2/g以上100m2/g以下である、態様1~7のいずれか一項に記載の燃料電池電極触媒。
《態様9》
前記カーボン担体の比表面積が、20m2/g以上70m2/g以下である、態様8に記載の燃料電池電極触媒。
《態様10》
態様1~9のいずれか一項に記載の燃料電池電極触媒を含む触媒層を有する、燃料電池のアノード。
《態様11》
態様10に記載のアノードを含む、燃料電池電極接合体。
《態様12》
態様11に記載の燃料電池電極接合体を含む、燃料電池。
本発明の燃料電池電極触媒は、
カーボン担体に、Pt又はPt合金から成る触媒金属粒子が担持されている、燃料電池電極触媒であって、
カーボン担体の単位表面積当たりの触媒金属粒子の個数が、4.3個/100nm2以上16.0個/100nm2以下である、
燃料電池電極触媒である。
本発明の燃料電池電極触媒におけるカーボン担体は、例えば、カーボンブラック、黒鉛、炭素繊維、活性炭、アモルファス炭素、ナノカーボン材料等であってよい。ナノカーボン材料は、カーボンナノチューブ、グラフェン、フラーレン等を包含する。
触媒金属粒子は、Pt又はPt合金から成り、カーボン担体に担持されている。
Ptと、
Ti、Cr、Mn、Fe、Co、Ni、Cu、Ga、Zr、Hf、Ru、Ir、Pd、Os、及びRhから成る群から選択される1種又は2種以上の金属と
を含む合金であってよい。
本発明の燃料電池電極触媒は、カーボン担体及び触媒金属粒子以外に、これら以外の任意成分を含んでいてもよい。本発明の燃料電池電極触媒に、含まれてもよい任意成分は、例えば、カーボン担体以外の炭素材料、Ir粒子、Ir・Ru合金粒子、Ir酸化物等から選択される、1種又は2種以上の成分であってよい。カーボン担体以外の炭素材料は、触媒金属粒子を担持していない炭素材料であり、例えば、黒鉛、炭素繊維、黒鉛化カーボンブラック、カーボンナノチューブ等から選択されてよい。
本発明の燃料電池電極触媒は、例えば、カーボン担体と触媒金属前駆体とを接触させること(前駆体接触工程)、及び触媒金属前駆体を還元して、カーボン担体上に触媒金属粒子を担持すること(担持工程)を含む方法によって、製造されてよい。
(1)Ptと合金金属とを順次に還元担持する方法(方法1):
適当な溶媒中で、カーボン担体とPt前駆体とを接触させた後、Pt前駆体を還元し、カーボン担体上にPt粒子を担持して、Pt担持カーボンを得ること;
適当な溶媒中で、Pt担持カーボンと合金金属前駆体とを接触させた後、合金金属前駆体を還元し、Pt担持カーボン上に合金金属粒子が担持された、Pt-合金金属担持カーボンを得ること;及び
Pt-合金金属担持カーボンを加熱し、Ptと合金金属とを合金化することにより、カーボン担体上にPt合金粒子が担持された、燃料電池電極触媒を得ること。
適当な溶媒中で、カーボン担体と、Pt前駆体及び合金金属前駆体とを接触させた後、Pt前駆体及び合金金属前駆体を還元して、カーボン担体上にPt粒子及び合金金属粒子が担持された、Pt-合金金属担持カーボンを得ること;
Pt-合金金属担持カーボンを加熱して、Ptと合金金属とを合金化することにより、カーボン担体上にPt合金粒子が担持された、燃料電池電極触媒を得ること。
方法1では、先ず、適当な溶媒中で、カーボン担体とPt前駆体とを接触させた後、Pt前駆体を還元し、カーボン担体上にPt粒子を担持して、Pt担持カーボンを得る。この工程は、触媒金属粒子がPt粒子であるときの、燃料電池電極触媒の製造と同様に行われてよい。
本発明の別の観点では、本発明の燃料電池電極触媒を含む触媒層を有する、燃料電池のアノードが提供される。
本発明の更に別の観点では、上記のアノードを含む、燃料電池電極接合体が提供される。
本発明の更に別の観点では、上記の燃料電池電極接合体を含む、燃料電池が提供される。本発明の燃料電池は、固体高分子形燃料電池であってよい。
(1)触媒の調製
カーボン担体として、市販の黒鉛化カーボンブラック(東海カーボン(株)製、品名「トーカブラック#3845」)用いた。この黒鉛化カーボンブラックについて、窒素を吸着質としてBET法により測定した比表面積は、49m2/gであった。
得られた触媒粉末をエタノール中に分散させた後、アイオノマーとしてのナフィオンを含む水分散液を添加し、超音波分散して、アノード触媒層形成用塗工液を調製した。得られたアノード触媒層形成用塗工液を、テフロン(登録商標)製のシートの片面上に塗布した後、乾燥して、シート上にアノード触媒層を形成した。
セル温度40℃、加湿度128%の環境下で、カソード側に水素を供給し、アノード側に窒素を供給しつつ、ポテンショスタット(北斗電工(株)製、型名「HZ-5000」)を用いて、1.8Vの電圧を4,400秒間印加した。上記セル条件下のCV測定により、高電圧耐久試験前後のECSA(電気化学活性面積)を測定した。
カーボン担体の種類、及びジニトロジアンミン白金の使用量(金属Pt相当量)を、それぞれ、表1に記載のとおりとした他は、実施例1と同様にして、触媒粉末を調製し、これを用いて高電圧耐久試験用単セルを製造して、高電圧耐久試験を行った。
実施例3で得られた触媒粉末をアルゴン気流中で熱処理したものを用いた他は、実施例1と同様にして、高電圧耐久試験用単セルを製造して、高電圧耐久試験を行った。熱処理の条件は、実施例8では250℃、2時間とし、比較例5では300℃、2時間とした。
#3845:トーカブラック#3845、東海カーボン(株)製、比表面積49m2/g(BET法(N2))
FCX80:FCX80、CABOT社製、比表面積73m2/g
600JD:Ketjen600JD(ライオン・スペシャリティ・ケミカルズ(株)製、比表面積300m2/g)を黒鉛化したもの
Li435:
Claims (12)
- カーボン担体に、Pt又はPt合金から成る触媒金属粒子が担持されている、燃料電池電極触媒であって、
前記カーボン担体の単位表面積当たりの前記触媒金属粒子の個数が、4.3個/100nm2以上16.0個/100nm2以下である、燃料電池電極触媒。 - 前記カーボン担体の単位表面積当たりの前記触媒金属粒子の個数が、6.0個/100nm2以上10.0個/100nm2以下である、請求項1に記載の燃料電池電極触媒。
- 前記触媒金属粒子の平均粒径が、5.0nm以下である、請求項1又は2に記載の燃料電池電極触媒。
- 前記触媒金属粒子の平均粒径が、2.0nm以上3.5nm以下である、請求項1~3のいずれか一項に記載の燃料電池電極触媒。
- 前記カーボン担体の単位表面積当たりの前記触媒金属粒子の担持量が、6.0mg/m2以上である、請求項1~4のいずれか一項に記載の燃料電池電極触媒。
- 前記カーボン担体の単位表面積当たりの前記触媒金属粒子の担持量が、6.5mg/m2以上25.0mg/m2以下である、請求項5に記載の燃料電池電極触媒。
- 前記カーボン担体が、黒鉛化カーボンの粒子である、請求項1~6のいずれか一項に記載の燃料電池電極触媒。
- 前記カーボン担体の比表面積が、10m2/g以上100m2/g以下である、請求項1~7のいずれか一項に記載の燃料電池電極触媒。
- 前記カーボン担体の比表面積が、20m2/g以上70m2/g以下である、請求項8に記載の燃料電池電極触媒。
- 請求項1~9のいずれか一項に記載の燃料電池電極触媒を含む触媒層を有する、燃料電池のアノード。
- 請求項10に記載のアノードを含む、燃料電池電極接合体。
- 請求項11に記載の燃料電池電極接合体を含む、燃料電池。
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KR1020237016857A KR20230091951A (ko) | 2021-01-19 | 2022-01-14 | 연료 전지 전극 촉매 |
EP22742517.0A EP4282528A1 (en) | 2021-01-19 | 2022-01-14 | Fuel cell electrode catalyst |
CN202280010630.XA CN116745942A (zh) | 2021-01-19 | 2022-01-14 | 燃料电池电极催化剂 |
US18/272,675 US20240097146A1 (en) | 2021-01-19 | 2022-01-14 | Fuel cell electrode catalyst |
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JP2021006426A JP7093860B1 (ja) | 2021-01-19 | 2021-01-19 | 燃料電池電極触媒 |
JP2021-006426 | 2021-01-19 |
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JP (1) | JP7093860B1 (ja) |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0884930A (ja) | 1994-09-16 | 1996-04-02 | Tanaka Kikinzoku Kogyo Kk | 白金担持触媒の製造方法 |
JP2003142112A (ja) | 2001-10-31 | 2003-05-16 | Tanaka Kikinzoku Kogyo Kk | 高分子固体電解質形燃料電池の空気極用触媒及び該触媒の製造方法 |
JP2009009815A (ja) * | 2007-06-28 | 2009-01-15 | Toyota Central R&D Labs Inc | 電極触媒基板及びその製造方法、並びに、固体高分子型燃料電池 |
JP2009152143A (ja) | 2007-12-21 | 2009-07-09 | Asahi Glass Co Ltd | 固体高分子形燃料電池用膜電極接合体および固体高分子形燃料電池用膜電極接合体の製造方法 |
JP2010089032A (ja) * | 2008-10-09 | 2010-04-22 | Jgc Catalysts & Chemicals Ltd | 金属粒子担持触媒およびその製造方法 |
WO2017094648A1 (ja) * | 2015-11-30 | 2017-06-08 | 国立大学法人山梨大学 | カーボンブラック、それを用いた電極触媒及び燃料電池、並びにカーボンブラックの製造方法 |
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2022
- 2022-01-14 US US18/272,675 patent/US20240097146A1/en active Pending
- 2022-01-14 EP EP22742517.0A patent/EP4282528A1/en active Pending
- 2022-01-14 KR KR1020237016857A patent/KR20230091951A/ko unknown
- 2022-01-14 WO PCT/JP2022/001183 patent/WO2022158395A1/ja active Application Filing
- 2022-01-14 CN CN202280010630.XA patent/CN116745942A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0884930A (ja) | 1994-09-16 | 1996-04-02 | Tanaka Kikinzoku Kogyo Kk | 白金担持触媒の製造方法 |
JP2003142112A (ja) | 2001-10-31 | 2003-05-16 | Tanaka Kikinzoku Kogyo Kk | 高分子固体電解質形燃料電池の空気極用触媒及び該触媒の製造方法 |
JP2009009815A (ja) * | 2007-06-28 | 2009-01-15 | Toyota Central R&D Labs Inc | 電極触媒基板及びその製造方法、並びに、固体高分子型燃料電池 |
JP2009152143A (ja) | 2007-12-21 | 2009-07-09 | Asahi Glass Co Ltd | 固体高分子形燃料電池用膜電極接合体および固体高分子形燃料電池用膜電極接合体の製造方法 |
JP2010089032A (ja) * | 2008-10-09 | 2010-04-22 | Jgc Catalysts & Chemicals Ltd | 金属粒子担持触媒およびその製造方法 |
WO2017094648A1 (ja) * | 2015-11-30 | 2017-06-08 | 国立大学法人山梨大学 | カーボンブラック、それを用いた電極触媒及び燃料電池、並びにカーボンブラックの製造方法 |
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CN116745942A (zh) | 2023-09-12 |
JP2022110799A (ja) | 2022-07-29 |
EP4282528A1 (en) | 2023-11-29 |
JP7093860B1 (ja) | 2022-06-30 |
US20240097146A1 (en) | 2024-03-21 |
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