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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/18—Carbon
  • B01J21/185—Carbon nanotubes
• • 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
  • B01J35/393—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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • 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
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/96—Carbon-based 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
  • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
• • 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
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
• • 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
• • 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
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
  • B01J35/58—Fabrics or filaments
• • 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
  • B01J35/612—Surface area less than 10 m2/g
• • 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
• • 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
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to a catalyst carrier. More specifically, a catalyst carrier comprising a catalyst metal supported on carbon fibers, which can be used as an electrode catalyst for a fuel cell,
• the present invention relates to a manufacturing method thereof and a fuel cell using the catalyst carrier.
• Polymer electrolyte fuel cells are more compact than phosphoric acid fuel cells and molten carbonate fuel cells, and can operate at room temperature and have a high current density. It is attracting attention as a power source for use. In this field, many proposals have been made regarding components, system configuration, and the like.
• the conventional stack structure of a solid polymer fuel cell has, for example, a sandwich structure of a separation electrode (oxygen electrode) / a pyrolysis membrane / electrode (hydrogen electrode) / separation. The required characteristics of this fuel cell electrode are to prevent poisoning of the electrode with carbon monoxide and to increase the activity per unit of catalytic metal.
• the present invention provides a gas-phase carbon fiber suitable as a catalyst carrier or the like, which is capable of increasing the activity per unit amount of catalytic metal, reducing the reaction resistance, and improving the output density, and supporting a metal catalyst.
• An object of the present invention is to provide a catalyst carrier, a production method thereof, and a use for a fuel cell.
• the present invention relates to a catalyst carrier described below, a method for producing the same, and uses thereof.
• a catalyst carrier characterized in that a catalyst metal for promoting an oxidation-reduction reaction is supported on a phase-processed carbon fiber.
• a fuel cell assembly comprising electrodes comprising a catalyst layer and a gas diffusion layer on both surfaces of an electrolyte membrane, wherein the catalyst layer comprises the electrode material described in 13 above. Joints for batteries.
• a fuel cell unit comprising the fuel cell assembly according to the above item 14 sandwiched between separators.
• the present invention also relates to a vapor grown carbon fiber described below.
• FIG. 1 is a schematic longitudinal sectional view showing a structure near one end of a conventional fine carbon fiber.
• FIG. 2 is a schematic longitudinal sectional view showing a structure near one end of another conventional fine carbon fiber.
• FIG. 3 is a schematic longitudinal sectional view for explaining a structure near one end of the fine carbon fiber used in the present invention.
• FIG. 4 is a schematic longitudinal sectional view for explaining a structure near one end of the fine carbon fiber used in the present invention.
• FIG. 5 is a schematic side view of the fiber of FIG. 4 viewed from the end.
• FIG. 6 is a schematic longitudinal sectional view for explaining the structure near one end of the fine carbon fiber used in the present invention.
• FIG. 7 is a schematic longitudinal sectional view for explaining the structure near one end of the fine carbon fiber used in the present invention.
• FIG. 8 is a schematic longitudinal sectional view for explaining the structure near one end of the fine carbon fiber used in the present invention.
• FIG. 9 is a schematic longitudinal sectional view for explaining a structure near both ends of the fine carbon fiber used in the present invention.
• FIG. 10 is a schematic longitudinal sectional view for explaining the structure near both ends of the fine carbon fiber used in the present invention.
• FIG. 11 is a transmission electron micrograph of the catalyst carrier of Example 1.
• FIG. 12 is a transmission electron micrograph of the catalyst carrier of Example 2.
• FIG. 13 is a transmission electron micrograph of the catalyst carrier of Example 3.
• FIG. 14 is a transmission electron micrograph of the catalyst carrier of the example.
• FIG. 15 is a transmission electron micrograph of the catalyst carrier of Comparative Example 1.
• FIG. 16 is a transmission electron micrograph of the catalyst carrier of Comparative Example 2.
• FIG. 17 is a transmission electron micrograph of the catalyst carrier of Comparative Example 3.
• FIG. 18 is a Tafel plot of a fuel cell using the catalyst carriers of Examples 1 to 4 and Comparative Examples 1 to 3. Detailed description of the invention
• the vapor-grown carbon fiber used as the carrier of the catalyst carrier of the present invention has an average outer diameter of 2 to 500 nm and a BET specific surface area of 4 to 500 m 2 Zg. It has been pulverized so as to have a ratio of 1 to 200.
• the preferred average outer diameter is 15 to 20 O nm
• the preferred BET specific surface area is 10 to 20 O m 2 / g
• the preferred aspect ratio is 2 to 150.
• the average fiber length is preferably 2 to 10 Ozm.
• the pulverization is preferably performed such that the average fiber length after the pulverization treatment is 0.8 or less, when the average fiber length before the pulverization treatment is 1.
• the BET specific surface area after the pulverization treatment is 1.1 or more, more preferably 1.4 or more, when the BET specific surface area before the pulverization treatment is set to 1.
• the vapor grown carbon fibers used in the present invention may contain branched carbon fibers.
• a conductive path of carbon fibers is thereby formed, and the conductivity of the carrier is improved.
• the vapor grown carbon fiber used in the present invention is obtained by pulverizing fine carbon fiber produced by a vapor phase method.
• the discontinuous surface of the graphene sheet having a fracture surface at the fiber end and the end of at least one graphent sheet are bonded to the end of the adjacent graphene sheet.
• a multi-layered fine carbon fiber having a hollow structure in the center axis thereby reducing the electrical resistance of the carbon fiber and improving the conductivity as a carrier.
• FIGS. a graph ensheet (a layer of graphite or a crystal close to graphite) is schematically indicated by a solid line.
• the fine carbon fiber has a discontinuous surface (1) of a graphite sheet having a cut surface at the fiber end or a closed surface having a continuous surface of graphene sheet. It has a curved surface (2) and a hollow structure (3).
• FIG. 1 a preferred form as the fine carbon fiber used in the present invention is shown in FIG. 1
• the discontinuous surface (1) of the graph ensheet having a fractured surface at the fiber end and the graphene sheet in which the end of at least one graphene sheet is close It has a hollow structure (3) produced by a gas phase method and has a continuous surface (2) connected to the end of the hollow.
• the fracture surface shows a plane generated by crushing or the like.
• the continuity of the graphene sheet is broken at the fracture surface, and edge carbon atoms at the defect in the basal plane and edge carbon atoms at the crystallite boundary appear.
• the fracture surface is an end face that is, for example, substantially perpendicular to the central axis of the carbon fiber. Even in a fiber with a low aspect ratio (1 to 200), the hollow structure of the vapor-grown carbon fiber or the multilayer structure (annual ring) Structure) is maintained.
• the carbon fiber of Fig. 3 has a closed surface (2) with a continuous surface of two graphene sheets, and in one part (a), two adjacent graphene sheets Are joined at the ends. In the other part (b), four adjacent graphite sheets are joined at the ends of the outermost graphene sheets and at the ends of the inner graphene sheets.
• the discontinuous surface (1) of the graph ensheet is on the side of the hollow part (3) adjacent to the part (a).
• the carbon fiber in Fig. 4 is a carbon fiber consisting of four layers of graph ensheet (4, 6, 8, 10), and the outer two layers of graphene sheet (4, 6) have their ends all around. To form a continuous surface (2 (a)), and in the inner two layers of the graphite sheets (8, 10), the closed part (2 (b) )) And a part (1 (a)) where their ends have discontinuous surfaces coexist.
• FIG. 5 is a schematic side view of the carbon fiber having the structure of FIG. 4 as viewed from the end.
• the white part is a continuous plane (2 (a), 2 (b)), the black part is a discontinuous plane (1 (a)), the center is a hollow part, and the gray part is a graph sheet ( 6) and (8) show the space between the eyebrows.
• the continuous surface of the graphene sheet at one end of the fine carbon fiber is continuous in the circumferential direction, but the circumferential direction is affected by defects due to pulverization, heat treatment temperature, and impurity components other than carbon. It is considered that the discontinuity also occurs in
• 6 to 8 show carbon fibers composed of eight layers of graphene sheet.
• the outer two layers of the graph ensheet (12, 14) form a continuous surface whose ends are joined around the entire circumference, while the other six layers of the graph ensheet are discontinuous surfaces. Is formed.
• a continuous surface is formed around the entire circumference, and the other four layers of the graphite sheet form a discontinuous surface.
• the adjacent graph sheets (28, 30) on the third and fourth layers from the outermost layer form a continuous surface that is connected around the entire circumference at each end, and the other two The graph ensheets of the layers all form discontinuous surfaces.
• FIG. 9 and FIG. 10 are the whole images of the fine carbon fibers, respectively.
• FIG. 9 shows a configuration in which one end of the fiber forms only the same continuous surface as the conventional one, and the other end has both a continuous surface and a discontinuous surface.
• FIG. 10 shows a form in which both ends of the fiber have both continuous and discontinuous surfaces.
• a continuous surface that exists in the same plane as the fractured surface is one in which the Daraphen sheet laminated by thermal CVD (Chemical Vapor Deposition) has a defect, loses its regularity, and combines with the adjacent graphene sheet, or This shows that the edge of the graphene sheet that has been broken by a high temperature treatment of 2000 ° C or more is rejoined with the edge of another graph ensheet.
• the number of laminated graph ensheets in the curved portion is preferably 3 or more, more preferably 5 or more, and particularly preferably 5 to 10 sheets.
• the vapor-grown carbon fiber used in the present invention is a vapor-grown carbon fiber produced by a vapor-phase method, preferably a branched carbon fiber (a method disclosed in, for example, JP-A-2002-266170 (WO02 / 49412)). Can be produced by pulverizing carbon fibers containing
• the vapor grown carbon fiber used in the production can be generally obtained by thermally decomposing an organic compound using an organic transition metal compound as a catalyst.
• Organic compounds used as raw materials for carbon fiber include toluene, benzene, naphthylene, ethylene, Gases such as acetylene, ethane, natural gas, carbon monoxide and mixtures thereof are also possible. Among them, aromatic hydrocarbons such as toluene and benzene are preferred.
• the organic transition metal compound is a transition metal serving as a catalyst, specifically, an organic compound containing a metal of Group 4 to L0 of the periodic table. Of these, compounds such as fluorocene and nickelocene are preferred.
• the carbon fiber has a hexagonal mesh plane (0 2) plane spacing (cU 02 ) of 0.345 nm or more as measured by X-ray diffraction, and a peak height of the band of 1341 to 1349 cm- 1 of the Raman scattering spectrum. It is (I d) and ⁇ ⁇ ⁇ ⁇ band peak height ⁇ 1 (I g) the ratio of (I d / I g) carbon fiber is preferably 1 or more.
• I d is the broad band corresponding to the increased disorder of the carbon structure
• I g is the relatively sharp band associated with the complete graphite structure.
• heat treatment can be performed at 600 to 1300 ° C in order to remove organic substances such as coal adhering to the surface of the carbon fiber obtained by pyrolysis.
• a pulverizing method a rotary pulverizer, a high-speed rotary mill, a ball mill, a medium stirring mill, a jet mill, or the like can be used.
• a vibrating ball mill such as a circular vibrating mill, a driven vibrating mill, a centrifugal mill or the like by a method of crushing fibers using an impact force is used.
• the grinding media ceramic balls such as alumina, zirconia, and silicon nitride, or metal balls such as stainless steel can be used.
• stainless steel balls that can be removed by high-temperature heat treatment are used.
• the pulverization is preferably performed in an atmosphere having an oxygen concentration of 5% by volume or more.
• oxygen is present in an amount of 5% or more, the surface of the pulverized carbon fiber is modified, and the catalyst metal is easily supported.
• it can be performed in air.
• a graphitization treatment can be performed for the purpose of improving the conductivity of the vapor grown carbon fiber.
• Graphitization can be performed by heat treatment at a temperature of 2000 to 3000 ° C in an inert gas atmosphere.
• the catalyst carrier of the present invention comprises a crushed vapor grown carbon fiber carrying a catalyst metal that promotes a redox reaction.
• the catalytic metal that promotes the oxidation-reduction reaction is at least one selected from the group consisting of platinum and transition metals of the fourth and fifth cycles containing other white metal elements, or an alloy thereof.
• An element nickel, palladium, platinum or an alloy containing that element.
• the method of supporting the catalyst metal on the pulverized vapor-grown carbon fiber is not particularly limited, but may be, for example, a liquid phase reduction method.
• a liquid phase reduction method for example, an example in which fine platinum particles are supported on the pulverized vapor grown carbon fiber by a liquid phase reduction method will be described.
• the pulverized vapor grown carbon fiber is dispersed in distilled water, and the pH is adjusted by adding sodium carbonate or the like. Dispersion can be performed by ultrasonic treatment or the like while visually confirming the dispersion state. Since the vapor grown carbon fiber has high hydrophobicity, it is preferable to increase the hydrophilicity by performing a surface treatment (hydrophilic treatment) in advance, and thereby the specific surface area of the catalyst metal to be supported can be improved.
• the surface treatment can be performed by, for example, treating in an acid solution (for example, an aqueous solution of nitric acid) at 60 to 90 ° C. for 1 to 10 hours.
• the catalyst support of the present invention is a catalyst support in which fine catalytic metal particles are supported on vapor-grown carbon fiber as a support, and has a smaller size than a case where a powdery support such as a carbon black is used.
• the catalytic activity per unit of catalytic metal is improved.
• the particle size of the catalytic metal particles to be supported is significantly smaller than that in the case where the pulverized carbon fiber is not pulverized (the specific surface area of the catalytic metal is increased).
• the average particle diameter of the catalyst metal to be supported can be made 15 nm or less, and further, 1 O nm or less.
• the catalyst carrier of the present invention can be applied to an electrode material, a fuel cell assembly, a fuel cell, and a fuel cell, and they can be manufactured by a conventionally known method.
• the electrode material of the present invention can be produced by forming a catalyst layer containing the above-mentioned catalyst carrier on a conductive substrate such as carbon paper, carbon fiber woven fabric, and carbon nonwoven fabric.
• the formation of the catalyst layer can be performed, for example, by applying a slurry containing a catalyst carrier to a conductive substrate and then drying the slurry.
• the fuel cell assembly of the present invention can be manufactured by, for example, thermocompression bonding the electrode material comprising the gas diffusion layer and the catalyst layer to both surfaces of the electrolyte membrane.
• the electrolyte membrane is made of a polymer material, for example, a perfluorosulfonic acid-based polymer can be used.
• This assembly is sandwiched between electrically conductive separators to form a cell for a fuel cell.
• electrically conductive separators By stacking two or more cell units, a high-output fuel cell stack can be obtained.
• a gasket can be provided between the electrode material and the separator.
• the average fiber length ratio was determined by measuring the average fiber length before and after pulverizing the carbon fiber in a cross-sectional photograph of the carbon fiber with a transmission electron microscope (TEM).
• the specific surface area was measured by a BET method, which is a general method for measuring a specific surface area, using a specific surface area measuring device NOVA-1200 (manufactured by Urasa Ionics Co., Ltd.).
• BET method which is a general method for measuring a specific surface area, using a specific surface area measuring device NOVA-1200 (manufactured by Urasa Ionics Co., Ltd.).
• Example 2 the diameter of the platinum catalyst was measured by observing the TEM photograph, and the diameter distribution was determined. As a result, the average diameter of the platinum catalyst particles was 8 nm.
• Example 2 the diameter of the platinum catalyst was measured by observing the TEM photograph, and the diameter distribution was determined. As a result, the average diameter of the platinum catalyst particles was 8 nm.
• the diameter of the platinum catalyst was measured by observing a TEM photograph, and the diameter distribution was determined. As a result, the average diameter of the platinum catalyst particles was 5 nm.
• the diameter of the platinum catalyst was measured by observing a TEM photograph, and the diameter distribution was determined. As a result, the average diameter of the platinum catalyst particles was 6 nm.
• Example 2 The same operation as in Example 1 was performed except that the pulverization was not performed, to obtain a catalyst carrier in which platinum particles were supported on carbon fibers.
• Figure 15 shows the TEM photograph. Also, the diameter of the platinum catalyst was measured by observing a TEM photograph, and the diameter distribution was determined. As a result, the average diameter of the platinum catalyst particles was 19 nm. Comparative Example 2
• Example 3 The same operation as in Example 3 was performed except that the pulverization was not performed, to obtain a catalyst carrier in which platinum particles were supported on carbon fibers.
• Figure 16 shows the TEM photograph. Also, the diameter of the platinum catalyst was measured by observing the TEM photograph, and the diameter distribution was determined. It was. As a result, the average diameter of the platinum catalyst particles was 23 nm. Comparative Example 3
• the diameter of the platinum catalyst was measured by observing a TEM photograph, and the diameter distribution was determined. As a result, the average diameter of the platinum catalyst particles was 2 nm.
• the absolute value of the current density at a certain voltage, the logarithm of the current density, and the potential were obtained from the measurement of the slow scan voltammogram (SSV).
• SSV slow scan voltammogram
• the current value was measured when the potential was changed from 1.2 V to 0.4 V at a scan speed of 1 mV / sec.
• the surface area of the electrode was determined by cyclic voltammetry. The method for measuring the surface area of the electrode was determined by referring to Gihodo Shuppan Co., Ltd. ⁇ Electrochemical Measurement Method (1) P88.
• Table 2 shows the results.
• the absolute value of the current density at a potential of 0.5 V was Example 2>
• Fig. 18 shows an evening plot obtained from the logarithm of the current density and the potential at 0.82V to 0.94V.
• a higher current density was obtained than when the catalyst of the comparative example was used. It can be seen that is improved.
• Example 1 0.7V 0.6V 0.5V Example 1 -0.2 -0.3-0.4 Example 2 -0.3 -0.4 -0.5 Example 3 -0.2 -0.2 -0.2 -0.3 Example 4 -0.2 -0.2 -0.3 Comparative Example 1 -0.15- 0.2 -0.2 Comparative Example 2 -0.15 -0.2 -0.2 Comparative Example 3 -0.05 -0.06 -0.06

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