WO2009116157A1 - Procédé de fabrication de catalyseur pour pile à combustible, ensemble électrode, et pile à combustible - Google Patents

Procédé de fabrication de catalyseur pour pile à combustible, ensemble électrode, et pile à combustible Download PDF

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WO2009116157A1
WO2009116157A1 PCT/JP2008/055145 JP2008055145W WO2009116157A1 WO 2009116157 A1 WO2009116157 A1 WO 2009116157A1 JP 2008055145 W JP2008055145 W JP 2008055145W WO 2009116157 A1 WO2009116157 A1 WO 2009116157A1
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fuel cell
catalyst
producing
fibrous nanocarbon
metal catalyst
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PCT/JP2008/055145
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English (en)
Japanese (ja)
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勲 持田
聖昊 尹
聖和 洪
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住友商事株式会社
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Priority to PCT/JP2008/055145 priority Critical patent/WO2009116157A1/fr
Priority to JP2010503710A priority patent/JPWO2009116157A1/ja
Publication of WO2009116157A1 publication Critical patent/WO2009116157A1/fr

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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
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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 method for producing a fuel cell catalyst, an electrode assembly, and a fuel cell.
  • Non-Patent Document 1 a fuel cell catalyst having a structure in which noble metal catalyst particles are supported on fibrous nanocarbon having tunnel-type mesopores is known (for example, see Non-Patent Document 1).
  • FIG. 11 is a flowchart shown for explaining a conventional method of manufacturing a fuel cell catalyst described in Non-Patent Document 1.
  • FIG. 12 is a view for explaining a tunnel-type mesopore forming step S930 in the conventional method for producing a fuel cell catalyst.
  • FIG. 12A is a diagram showing a reaction surface in fibrous nanocarbon
  • FIG. 12B is a diagram showing a change in the bonding state of carbon.
  • the conventional method for producing a catalyst for a fuel cell includes a fibrous nanocarbon production step S910 for producing a fibrous nanocarbon having a herringbone structure or a fibrous nanocarbon having a platelet structure, A new catalyst particle attaching step S920 for attaching new catalyst particles to the surface of the fibrous nanocarbon, and contacting the fibrous nanocarbon with hydrogen gas in a temperature range of 600 ° C. to 1200 ° C.
  • a tunnel type mesopore forming step S930 for forming pores and a noble metal catalyst particle supporting step S940 for supporting noble metal catalyst particles such as PtRu in the tunnel type mesopores are included in this order.
  • the nanorod constituting the fibrous nanocarbon is selected partially and by using a novel catalytic gasification method using hydrogen gas.
  • tunnel type mesopores having an average pore diameter of about 3 nm to 10 nm are formed.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a fuel cell catalyst capable of obtaining higher fuel cell efficiency than conventional ones. Moreover, it aims at providing the electrode assembly manufactured using the catalyst for fuel cells manufactured by such a method, and a fuel cell.
  • the present inventors have formed tunnel-type mesopores in fibrous nanocarbons using an oxidizing gas. As a result, a large amount of oxygen functional groups are formed on the pore walls, so that a larger amount of noble metal catalyst particles can be supported in the tunnel-type mesopores, resulting in higher fuel cell efficiency than before.
  • the present invention has been completed.
  • the method for producing a fuel cell catalyst of the present invention comprises a fibrous nanocarbon by thermally decomposing a carbon-containing gas in the temperature range of 400 ° C. to 1200 ° C. in the presence of a metal catalyst or an alloy catalyst.
  • a tunnel-type mesopore forming step for forming a tunnel-type mesopore in the fibrous nanocarbon by contacting an oxidizing gas with the nanocarbon, and a noble-metal catalyst particle support for supporting a noble-metal catalyst particle in the tunnel-type mesopore The steps are included in this order.
  • the fibrous nanocarbon has a large average particle diameter of 2 nm. It becomes possible to disperse and carry fine noble metal catalyst particles of about ⁇ 5 nm, and as a result, high fuel cell efficiency can be obtained.
  • tunnel mesopores are formed in the fibrous nanocarbon using an oxidizing gas in the tunnel-type mesopore forming step.
  • a large amount of oxygen functional groups are formed on the pore walls of the type mesopores. For this reason, it becomes possible to carry
  • a fuel cell catalyst capable of obtaining higher fuel cell efficiency than before can be produced.
  • a catalyst for a fuel cell of the present invention it becomes possible to form tunnel-type mesopores in fibrous nanocarbon at a temperature lower than that in the past, so that fuel can be produced at a lower production cost than in the past.
  • a battery catalyst can be produced.
  • the fibrous nanocarbon produced in the fibrous nanocarbon production step is a fibrous nanocarbon having a herringbone structure or a fibrous nanocarbon having a platelet structure. Carbon is preferred.
  • the fibrous nanocarbon having a herringbone structure or the fibrous nanocarbon having a platelet structure has an axial width D (see FIG. 2C described later) of nanorods constituting these fibrous nanocarbons, for example, 2. It is about 5 nm. Therefore, by using the above-described method, a tunnel-type mesopore capable of supporting a large amount of fine noble metal catalyst particles having an average particle diameter of about 2 nm to 5 nm dispersed in fibrous nanocarbon can be formed. Is possible.
  • the noble metal catalyst particles have an average particle diameter in the range of 2 nm to 5 nm, and the tunnel-type mesopores have an average pore diameter of 2.5 nm to 100 nm. It is preferable that the average depth is in the range of 10 nm or more.
  • fine noble metal catalyst particles having an average particle diameter of about 2 nm to 5 nm can be reliably supported in the tunnel type mesopores.
  • the iron-based transition metal catalyst particles preferably have an average particle size in the range of 2.5 nm to 100 nm.
  • tunnel-type mesopores having an average pore diameter in the range of 2.5 nm to 100 nm, in other words, fine noble metal catalyst particles having an average particle diameter of about 2 to 5 nm. Possible tunnel-type mesopores can be formed.
  • the fibrous nanocarbon produced at the said fibrous nanocarbon preparation process has a BET specific surface area of 200 m ⁇ 2 > / g or more.
  • the oxidizing gas is preferably air, a mixed gas of inert gas and oxygen gas, or pure oxygen gas.
  • the fibrous nanocarbon after the completion of the tunnel-type mesopore formation step contains 0.5 wt% to 20 wt% oxygen. Is preferred.
  • the iron-based transition metal catalyst particles are preferably composed of fine particles of Fe, Ni, Co, or an alloy thereof.
  • the noble metal catalyst particles are preferably composed of fine particles of Pt, Ru or Pd or an alloy containing these noble metals.
  • the electrode assembly of the present invention is a fuel cell catalyst produced from a slurry obtained by mixing a carbon-containing paste with a fuel cell catalyst produced by the method for producing a fuel cell catalyst of the invention.
  • the ratio of the total weight of the noble metal catalyst particles to the sum of the total weight of the noble metal catalyst particles and the total weight of carbon in the slurry is 40% or less.
  • the electrode assembly of the present invention is an electrode assembly manufactured from a slurry obtained by mixing a carbon-containing paste with a fuel cell catalyst manufactured by the method for manufacturing a fuel cell catalyst of the present invention, In other words, the electrode assembly can obtain high fuel cell efficiency.
  • the electrode assembly of the present invention can make the amount of precious metal used about 80% or more, but by making the amount of precious metal used 40% or less, the amount of precious metal catalyst particles used is small and the production cost is low. It becomes a relatively inexpensive electrode assembly.
  • the fuel cell of the present invention is characterized in that it can produce electric power of 160 mW / cm 2 or more during operation at 90 ° C.
  • the fuel cell of the present invention is a fuel cell including the above-described electrode assembly, as is clear from the examples described later, the amount of noble metal catalyst particles used is small and the manufacturing cost is relatively low. However, the fuel cell can achieve a predetermined fuel cell efficiency.
  • the fuel cell of the present invention is characterized in that it can produce electric power of 185 mW / cm 2 or more during operation at 90 ° C.
  • the fuel cell of the present invention is a fuel cell including the above-described electrode assembly, as is clear from the examples described later, the amount of noble metal catalyst particles used is small and the manufacturing cost is relatively low. However, the fuel cell can achieve a predetermined fuel cell efficiency.
  • FIG. It is a flowchart shown in order to demonstrate the manufacturing method of the catalyst for fuel cells which concerns on embodiment. It is a figure shown in order to demonstrate the structure of fibrous nanocarbon 100.
  • FIG. It is a figure shown in order to demonstrate the manufacturing method of the catalyst for fuel cells which concerns on embodiment. It is a figure shown in order to demonstrate the manufacturing method of the catalyst for fuel cells which concerns on embodiment. It is a figure shown in order to demonstrate the catalyst 100b for fuel cells which concerns on embodiment. It is a figure shown in order to demonstrate the cell evaluation system 200.
  • FIG. It is a figure which shows the power density which the catalyst for fuel cells which concerns on the comparative example 1 produces. It is a figure which shows the power density which the catalyst for fuel cells which concerns on the comparative example 2 produces.
  • FIG. 1 is a flowchart showing a method for manufacturing a fuel cell catalyst according to an embodiment.
  • FIG. 2 is a diagram shown for explaining the structure of the fibrous nanocarbon 100 after completion of the fibrous nanocarbon production step S10.
  • 2 (a) is a diagram showing one fibrous nanocarbon 100 schematically
  • FIG. 2 (b) is an enlarged view of a portion indicated by reference sign A 1 in FIG. 2 (a)
  • 2 ( c) is an enlarged view of the nanorod 106.
  • FIG. 1 is a flowchart showing a method for manufacturing a fuel cell catalyst according to an embodiment.
  • FIG. 2 is a diagram shown for explaining the structure of the fibrous nanocarbon 100 after completion of the fibrous nanocarbon production step S10.
  • 2 (a) is a diagram showing one fibrous nanocarbon 100 schematically
  • FIG. 2 (b) is an enlarged view of a portion indicated by reference sign A 1 in FIG. 2 (a)
  • 2 ( c) is an enlarged view of the nanorod 106.
  • FIG. 3 and FIG. 4 are diagrams for explaining a method of manufacturing a fuel cell catalyst according to the embodiment.
  • FIG. 3A is a diagram showing the structure of the fibrous nanocarbon 100 after the completion of the fibrous nanocarbon production step S10
  • FIG. 3B is the fibrous nanocarbon after the completion of the iron-based transition metal catalyst particle attaching step S20.
  • FIG. 3 (c), FIG. 3 (d), and FIG. 4 (a) are diagrams showing the structure of fibrous nanocarbon 100 during tunnel-type mesopore formation step S30.
  • 4 (b) is a diagram showing the structure of the fibrous nanocarbon 100 after the iron-based transition metal catalyst particles 110 are removed after the tunnel-type mesopore forming step S30 is completed, and
  • FIG. 4 (c) is the noble metal catalyst particles. It is a figure which shows the structure of fibrous nanocarbon 100 after completion
  • FIG. 5 is a view for explaining the fuel cell catalyst 100b according to the embodiment.
  • FIG. 5A is a transmission electron microscope photograph of the fuel cell catalyst 100b
  • FIG. 5B is an enlarged photograph of FIG. 5A.
  • the method for producing a fuel cell catalyst includes a fibrous nanocarbon production step S10, an iron-based transition metal catalyst particle adhesion step S20, a tunnel-type mesopore formation step S30, and a noble metal.
  • the catalyst particle supporting step S40 is included in this order.
  • each process will be described in detail.
  • Fibrous nanocarbon production process S10 is a step of producing fibrous nanocarbon 100 by subjecting a carbon-containing gas to a thermal decomposition reaction in the temperature range of 400 ° C. to 1200 ° C. in the presence of a metal catalyst or an alloy catalyst. Yes (see FIG. 3A).
  • the metal catalyst or alloy catalyst a transition metal such as iron, nickel, cobalt, or a catalyst produced from an alloy thereof (for example, iron nitrate, nickel nitrate, etc.) is used.
  • the carbon-containing gas carbon monoxide (CO) or hydrocarbon (for example, methane (CH 3 ), ethylene (C 2 H 4 ), propane (C 3 H 8 ), etc.) is used.
  • Hydrogen hydrogen partial pressure of 0% to 90%
  • the thermal decomposition reaction is performed by bringing the above-mentioned carbon-containing gas into contact with the above-described metal catalyst or alloy catalyst in a temperature range of 400 ° C. to 1200 ° C.
  • the arrangement angle of the nanorod group is more than 20 degrees with respect to the axis perpendicular to the fiber axis in the nanorod stacking direction. It is a fibrous nanocarbon having a herringbone structure arranged at an angle of largely less than 80 degrees.
  • the nanorod group has a structure in which a large number of nanorods 106 are arranged in parallel to each other.
  • the nanorod 106 has a hexagonal column shape and a structure in which carbon hexagonal mesh surfaces are stacked concentrically.
  • reference numeral 102 indicates a metal catalyst or alloy catalyst
  • reference numeral 104 indicates a structure in which a number of nanorods 106 are arranged in parallel to each other.
  • the short diameter Wa of the metal catalyst or alloy catalyst 102 is, for example, 50 to 150 nm
  • the long diameter Wb of the metal catalyst or alloy catalyst 102 is, for example, 50 nm to 300 nm.
  • the axial width D of the nanorod 106 illustrated in FIG. 2C is, for example, 2.5 nm
  • the length L of the nanorod 106 is, for example, 20 nm.
  • the length of the fibrous nanocarbon 100 is, for example, 500 nm to 3000 nm.
  • Iron-based transition metal catalyst particle adhesion step S20 The iron-based transition metal catalyst particle attaching step S20 is a step of attaching the iron-based transition metal catalyst particles 110 to the surface of the fibrous nanocarbon 100 (see FIG. 3B).
  • the iron-based transition metal catalyst particle adhering step S20 is performed by immersing the fibrous nanocarbon 100 in a solution containing the iron-based transition metal catalyst particles 110, and then drying the fibrous nanocarbon 100.
  • the iron-based transition metal catalyst particles 110 those composed of fine particles of Fe, Ni, Co, or alloys thereof are used. Further, as the iron-based transition metal catalyst particles 110, those having an average particle diameter in the range of 2.5 nm to 100 nm are used.
  • tunnel type mesopore forming step S30 is a step of forming the tunnel-type mesopores 120 in the fibrous nanocarbon 100 by contacting the fibrous nanocarbon 100 with an oxidizing gas in a temperature range of 200 ° C. to 600 ° C. (See FIG. 3C, FIG. 3D, and FIG. 4A.)
  • the oxidizing gas for example, air, a mixed gas of inert gas and oxygen gas, or pure oxygen gas is used.
  • the tunnel-type mesopores grow gradually as the contact time elapses, so that the average pore diameter is in the range of 2.5 nm to 100 nm, and the axial direction B of the nanorod 106 (FIG. 4).
  • Tunnel type mesopores having an average length (average depth) of 10 nm or more along (b) and FIG. 2B) can be formed with good controllability.
  • the noble metal catalyst particle supporting step S40 is a step of supporting the noble metal catalyst particles 130 in the tunnel-type mesopores 120 (see FIGS. 4B to 4D).
  • the noble metal catalyst particle supporting step S40 is performed by removing the iron-based transition metal catalyst particles 110 from the fibrous nanocarbon 100 and then immersing the fibrous nanocarbon 100 in a solution containing the noble metal catalyst particles 130.
  • the noble metal catalyst particles 130 those made of fine particles of Pt, Ru, Pd, or an alloy containing these noble metals are used. Further, as the noble metal catalyst particles 130, those having an average particle diameter in the range of 2 nm to 5 nm are used.
  • a fuel cell catalyst 140 having a structure in which a large number of noble metal catalyst particles 130 are supported in the tunnel type mesopores 120 is obtained (FIGS. 4C and 4D) and FIG. (See FIG. 5A and FIG. 5B.)
  • the fuel cell catalyst 140 according to the embodiment can be manufactured as described above.
  • an electrode assembly can be manufactured using the slurry obtained by mixing a carbon containing paste with the catalyst 140 for fuel cells manufactured in this way.
  • a fuel cell can be manufactured using the electrode assembly manufactured in this way.
  • the tunnel-type mesopores in the fibrous nanocarbon 100 Since noble metal catalyst particles 130 are supported in 120, a large amount of fine noble metal catalyst particles 130 having an average particle diameter of about 2 nm to 5 nm can be dispersed and supported on the fibrous nanocarbon 100. As a result, high fuel cell efficiency can be obtained.
  • the tunnel-type mesopores 120 are formed in the fibrous nanocarbon 100 using the oxidizing gas in the tunnel-type mesopore formation step S30.
  • a large amount of oxygen functional groups are formed on the pore walls of the tunnel-type mesopores 120 to be formed. For this reason, it becomes possible to make the fibrous nanocarbon 100 carry a larger amount of the noble metal catalyst 130 than before.
  • a fuel cell catalyst according to the embodiment, it is possible to form the tunnel mesopores 120 in the fibrous nanocarbon 100 at a temperature lower than that of the conventional method, and therefore, the manufacturing cost is lower than that of the conventional method.
  • a fuel cell catalyst can be produced at low cost.
  • the fibrous nanocarbon 100 produced in the fibrous nanocarbon production step S10 is a fibrous nanocarbon having a herringbone structure, the fibrous nanocarbon. It is possible to form a tunnel-type mesopore 120 capable of dispersing and supporting a large amount of fine noble metal catalyst particles having an average particle diameter of about 2 nm to 5 nm.
  • the noble metal catalyst particles 130 have an average particle diameter in the range of 2 nm to 5 nm, and the tunnel-type mesopores 120 have an average pore diameter of 2.5 nm to Since it is in the range of 100 nm and the average depth is in the range of 10 nm or more, minute noble metal catalyst particles 130 having an average particle diameter of about 2 nm to 5 nm can be supported in the tunnel type mesopores 120.
  • the average pore diameter is 2.5 nm to 100 nm.
  • the tunnel-type mesopores 120 within the range that is, the tunnel-type mesopores capable of supporting a large amount of fine noble metal catalyst particles 130 having an average particle diameter of about 2 nm to 5 nm can be formed.
  • the fibrous nanocarbon 100 produced in the fibrous nanocarbon production step S10 has a BET specific surface area of 200 m 2 / g or more.
  • a large amount of noble metal catalyst particles 130 can be supported on the carbon 100.
  • the oxidizing gas is air, a mixed gas of inert gas and oxygen gas, or pure oxygen gas, so It is possible to introduce the oxygen functional group.
  • the fibrous nanocarbon 100 after the completion of the tunnel-type mesopore forming step S30 contains 0.5 wt% to 20 wt% of oxygen. Therefore, the noble metal catalyst particles 130 can be stably supported in the tunnel type mesopores 120.
  • the iron-based transition metal catalyst particles 110 are made of fine particles of Fe, Ni, Co, or an alloy thereof. It is possible to form the tunnel-type mesopores 120 as described above in carbon.
  • Example 1 Implementing a method for producing a catalyst for a fuel cell comprising the following fibrous nanocarbon production step, iron-based transition metal catalyst particle adhesion step, tunnel-type mesopore formation step, and noble metal catalyst particle support step in this order Thus, a fuel cell catalyst according to Example 1 was produced.
  • Fibrous nanocarbon was prepared.
  • Tunnel-type mesopore formation step Thereafter, fibrous nanocarbon is brought into contact with fibrous nanocarbon in a temperature range of 200 ° C. to 600 ° C. in a quartz glass tube having an inner diameter of 5 cm. Tunnel-type mesopores having an average pore diameter of 20 nm and an average depth of 20 nm were formed in carbon. After completion of the tunnel-type mesopore formation step, the residual carbon content, oxygen content, and BET specific surface area were measured. The residual carbon amount was calculated from the weight reduction rate, and the oxygen content was calculated from the CHN elemental analysis results.
  • Table 1 is a table showing the relationship between the air flow rate and the contact time with air during the tunnel-type mesopore formation process and the residual carbon amount, oxygen content, and BET specific surface area after the tunnel-type mesopore formation process. is there.
  • Example 1 As shown in Table 1, if the air flow rate in the tunnel mesopore formation process is increased or the contact time with the air is increased, the residual carbon amount decreases, the oxygen content increases, and the BET It can be seen that the specific surface area increases.
  • the flow rate of air is 150 sccm
  • the contact time with air is 2 hours
  • the residual carbon content is 72%
  • the oxygen content is 11.7%
  • the BET specific surface area is 222 m 2 / g.
  • the tunnel-type mesopore formation process was performed under the conditions (conditions on the fourth line from the top of Table 1).
  • Comparative Example 1 Implementing a method for producing a catalyst for a fuel cell comprising the following fibrous nanocarbon production step, iron-based transition metal catalyst particle adhesion step, tunnel-type mesopore formation step, and noble metal catalyst particle support step in this order
  • a fuel cell catalyst according to Comparative Example 1 was produced.
  • the fibrous nanocarbon production step, the iron-based transition metal catalyst particle adhesion step, and the noble metal catalyst particle supporting step are the same as in Example 1, and the tunnel-type mesopore forming step is different from that in Example 1.
  • the tunnel-type mesopore forming process is as follows.
  • Tunnel-type mesopore formation step Thereafter, a mixed gas (1: 1) of hydrogen gas / helium gas is brought into contact with fibrous nanocarbon at a temperature of 850 ° C. for 3 hours in a quartz glass tube having an inner diameter of 5 cm.
  • a mixed gas (1: 1) of hydrogen gas / helium gas is brought into contact with fibrous nanocarbon at a temperature of 850 ° C. for 3 hours in a quartz glass tube having an inner diameter of 5 cm.
  • Comparative Example 2 A fuel cell catalyst according to Comparative Example 2 was produced by carrying out a method for producing a fuel cell catalyst comprising the following fibrous nanocarbon production step and noble metal catalyst particle supporting step in this order. That is, in Comparative Example 2, noble metal catalyst particles were supported on the fibrous nanocarbon using the fibrous nanocarbon produced in the fibrous nanocarbon production step as it was. The fibrous nanocarbon production process and the noble metal catalyst particle supporting process are the same as those in Example 1.
  • Comparative Example 3 was a fuel cell catalyst sold by E-TEK in which noble metal catalyst particles were supported on carbon fine particles.
  • FIG. 6 is a diagram for explaining the single cell evaluation system 200.
  • Catalyst for fuel cell according to Example 1 and Comparative Examples 1 to 3 “Nafion 115 (manufactured by DuPont, Nafion is a trademark of DuPont Co., Ltd.) and Nafion dispersion 20% by weight” and “commercially available Pt-black (manufactured by Johnson Matthey, 6 mg / cm 2 ) ”was laminated, and an electrode assembly (MEA) 204 was produced by applying a pressure of 100 kg / cm 2 for 10 minutes at a temperature of 135 ° C. .
  • MEA electrode assembly
  • the fuel cell catalyst according to Example 1 and Comparative Examples 1 to 3 becomes the fuel electrode catalyst 212, “Nafion 115” and the Nafion dispersion become the electrolyte membrane 230, and the commercially available Pt-black becomes the air electrode catalyst 222.
  • the area of the electrode assembly 204 is 25 mm ⁇ 25 mm.
  • a fuel cell (direct methanol fuel cell) 202 is fabricated by attaching the fuel electrode current collector 214 and the air electrode current collector 224 to the electrode assembly 204, and FIG. A single cell evaluation system 200 as shown was produced.
  • FIG. 7 to 10 are diagrams showing the results of cell evaluation.
  • FIG. 7 is a diagram showing the produced power density in the unit cell using the fuel cell catalyst according to Example 1
  • FIG. 8 is the produced power density in the unit cell using the fuel cell catalyst according to Comparative Example 1.
  • FIG. 9 is a diagram showing a generated power density in a unit cell using the fuel cell catalyst according to Comparative Example 2
  • FIG. 10 is a graph using the fuel cell catalyst according to Comparative Example 3. It is a figure which shows the production electric power density in a cell.
  • Table 3 is a table showing the cell evaluation results. Table 3 shows the maximum production power density in Example 1 and Comparative Examples 1 to 3.
  • the unit cell using the fuel cell catalyst according to Example 1 is the largest compared to the unit cell using the fuel cell catalyst according to Comparative Examples 1 to 3. It was found that the produced power density is high and the fuel cell efficiency is high. *
  • fibrous nanocarbon which has a herringbone structure was used as fibrous nanocarbon
  • this invention is not limited to this.
  • fibrous nanocarbon having a platelet structure can be used.
  • the present invention is not limited to this.
  • the amount of noble metal used may be 40% by weight or more, or less than 40% by weight.
  • the fuel cell catalyst produced by the fuel cell catalyst of the present invention is used as the material for the fuel electrode catalyst, but the present invention is not limited to this.
  • it can be used as a material for an air electrode catalyst.

Abstract

Cette invention porte sur un procédé de fabrication d'un catalyseur pour une pile à combustible. Le procédé de fabrication comprend, dans l'ordre suivant, une étape de production de nanofibres de carbone (S10) consistant à décomposer thermiquement un gaz contenant du carbone en la présence d'un catalyseur métallique ou d'un catalyseur en alliage dans la plage de températures de 400 °C à 1 200 °C afin de produire des nanofibres de carbone, une étape de dépôt de particules de catalyseur métal de transition de type fer (S20) consistant à déposer des particules de catalyseur métal de transition de type fer sur la surface des nanofibres de carbone, une étape de formation de mésopores de type tunnel (S30) consistant à amener un gaz oxydant en contact avec les nanofibres de carbone dans la plage de températures de 200 °C à 600 °C afin de former des mésopores de type tunnel dans les nanofibres de carbone, et une étape de support de particules de catalyseur métal noble (S40) consistant à supporter des particules de catalyseur métal noble dans les mésopores de type tunnel. Selon la constitution précédente, le procédé de fabrication d'un catalyseur pour pile à combustible peut produire un catalyseur pour une pile à combustible qui peut réaliser un rendement de pile à combustible plus élevé que l'état de la technique.
PCT/JP2008/055145 2008-03-19 2008-03-19 Procédé de fabrication de catalyseur pour pile à combustible, ensemble électrode, et pile à combustible WO2009116157A1 (fr)

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JP2010503710A JPWO2009116157A1 (ja) 2008-03-19 2008-03-19 燃料電池用触媒の製造方法、電極接合体及び燃料電池

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JP2012009212A (ja) * 2010-06-23 2012-01-12 Toyota Motor Corp 燃料電池の製造方法
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JP2012164492A (ja) * 2011-02-04 2012-08-30 Tokyo Institute Of Technology 燃料電池用空気極触媒とその製造方法
JP2016538228A (ja) * 2013-08-28 2016-12-08 ナショナル・インスティチュート・オブ・エアロスペース・アソシエイツ 制御された触媒酸化による穴の多い炭素同素体の大量調製
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JPWO2014175099A1 (ja) * 2013-04-25 2017-02-23 日産自動車株式会社 触媒ならびに当該触媒を用いる電極触媒層、膜電極接合体および燃料電池
JP2018183743A (ja) * 2017-04-26 2018-11-22 シャープ株式会社 触媒の製造方法
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JP2011090911A (ja) * 2009-10-22 2011-05-06 Toyota Motor Corp 触媒担持方法および膜−電極接合体
JP2012009212A (ja) * 2010-06-23 2012-01-12 Toyota Motor Corp 燃料電池の製造方法
WO2012053303A1 (fr) * 2010-10-22 2012-04-26 日産自動車株式会社 Électrocatalyseur pour pile à combustible à polymère solide
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JPWO2019107241A1 (ja) * 2017-11-29 2020-10-01 東レ株式会社 マイクロポーラス層およびその製造方法、ガス拡散電極基材、燃料電池
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