WO2018180676A1 - Catalyseur d'électrode, composition de formation d'électrode à diffusion gazeuse, électrode à diffusion gazeuse, ensemble film-électrode, et empilement de piles à combustible - Google Patents

Catalyseur d'électrode, composition de formation d'électrode à diffusion gazeuse, électrode à diffusion gazeuse, ensemble film-électrode, et empilement de piles à combustible Download PDF

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WO2018180676A1
WO2018180676A1 PCT/JP2018/010726 JP2018010726W WO2018180676A1 WO 2018180676 A1 WO2018180676 A1 WO 2018180676A1 JP 2018010726 W JP2018010726 W JP 2018010726W WO 2018180676 A1 WO2018180676 A1 WO 2018180676A1
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catalyst
electrode
core
electrode catalyst
particles
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PCT/JP2018/010726
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English (en)
Japanese (ja)
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聖崇 永森
智照 水崎
中村　葉子
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エヌ・イー ケムキャット株式会社
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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
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid 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 an electrode catalyst having a core-shell structure. More specifically, the present invention relates to an electrode catalyst suitably used for a gas diffusion electrode, and relates to an electrode catalyst suitably used for a gas diffusion electrode of a fuel cell. The present invention also relates to a composition for forming a gas diffusion electrode, a membrane / electrode assembly, and a fuel cell stack comprising the electrode catalyst particles.
  • PEFC polymer electrolyte fuel cell
  • a noble metal catalyst composed of noble metal particles of a platinum group element such as platinum (Pt) is used.
  • Pt platinum
  • Pt-supported carbon catalyst which is a powder of catalyst particles in which Pt fine particles are supported on conductive carbon powder
  • Pt / C catalyst a Pt / C catalyst having a Pt loading rate of 50 wt% manufactured by NE CHEMCAT, trade name: “NE-F50” is known.
  • Non-Patent Document 1 describes an outline of development so far.
  • Patent Document 1 discloses a particle composite material (a core-shell catalyst particle having a structure in which palladium (Pd) or a Pd alloy (corresponding to a core part) is covered with an atomic thin layer (corresponding to a shell part) of Pt atoms. Equivalent). Furthermore, this patent document 1 describes, as an example, core-shell catalyst particles having a layer structure in which the core portion is made of Pd particles and the shell portion is made of Pt.
  • the core-shell catalyst is an effective catalyst capable of reducing the amount of Pt used, but further improvement in catalytic activity is required.
  • a core-shell catalyst having a structure in which Pd (zero valence) is contained in the core portion and Pt (zero valence) is contained in the shell portion on a porous carrier containing a conductive carbon material as a constituent component (hereinafter referred to as necessary)
  • Pt / Pd / C catalyst still has room for improvement.
  • This invention is made
  • Another object of the present invention is to provide a gas diffusion electrode forming composition, a gas diffusion electrode, a membrane / electrode assembly (MEA), and a fuel cell stack, each including the electrode catalyst.
  • the inventors of the present invention have proposed a Pt / Pd / C catalyst (particularly, Pt / Pd / Cd having a structure in which the main component of the core is Pd (zero valent) and the main component of the shell is Pt (zero valent)).
  • a Pt / Pd / C catalyst having a structure in which the main component of the core is Pd (zero valent) and the main component of the shell is Pt (zero valent)
  • C catalyst an intensive study was made on a configuration for further improving the catalytic activity.
  • the present inventors have found that it is effective for improving the catalytic activity that the following two parameters satisfy the condition of the following formula (1), and have completed the present invention.
  • a composite particle composed of a carrier and particles that serve as a precursor of a core portion supported on the carrier (hereinafter referred to as “core particle” if necessary) Is the number of atoms (mol) of Pd exposed on the surface of the core particle.
  • core particle a composite particle
  • the core-shell catalyst obtained by forming a shell part on the surface of the core particle of the composite particle (core-shell catalyst precursor) described above contains Pt (0 This is the number of atoms (mol) of Pt (zero valence) atoms calculated on the assumption that the total amount of (valence) is coated on the surface of the core particle in a state of one atomic layer.
  • the present invention includes the following technical matters.
  • the present invention includes a support containing a conductive carbon material as a constituent component, and catalyst particles supported on the support,
  • the catalyst particles have a core part formed on the carrier, and a shell part formed so as to cover at least a part of the surface of the core part,
  • the core portion is made of Pd (zero valence)
  • the shell portion contains Pt (zero valence)
  • an electrode catalyst which satisfies the conditions of the following formulas (1), (2) and (3).
  • the SPd and the IPt are parameters calculated when the core particles are approximated to a sphere with respect to the electrode catalyst precursor composed of the support and the core particles formed on the support,
  • the SPd is the number of atoms (mol) of Pd (zero valent) exposed on the surface of the core particle.
  • the I Pt is an atom of Pt (zero valence) calculated on the assumption that the total amount of Pt (zero valence) contained in the shell part is coated on the surface of the core particle in a single atomic layer state.
  • the CR Pt represents the Pt loading (wt%) of Pt (zero valence) contained in the electrode catalyst measured by high frequency inductively coupled plasma (ICP) emission spectroscopy.
  • D represents the mass (g) of the electrode catalyst to be analyzed;
  • AW Pt represents the atomic weight of Pt,
  • the CR Pd indicates the Pd loading (wt%) of Pd (zero valence) contained in the electrode catalyst measured by high frequency inductively coupled plasma (ICP) emission spectroscopy.
  • the AW Pd is the atomic weight of Pd.
  • the XPd is calculated when the electrode catalyst precursor composed of the support and the core particles formed on the support is approximated to a spherical particle composed of Pd (zero valence). A ratio of Pd (zero-valent) atoms exposed on the surface of the core particle, The r is the average value (nm) of the crystallite size of the core particle obtained from the peak of the Pd (111) plane obtained by measuring the precursor powder of the electrode catalyst with powder X-ray diffraction (XRD). ).
  • the electrode catalyst of the present invention can exhibit excellent catalytic activity that can contribute to cost reduction of PEFC.
  • the detailed reason why the electrode catalyst of the present invention has excellent catalytic activity has not been fully elucidated.
  • the configuration of the electrode catalyst includes “a shell portion made of Pt, a core portion made of Pd, and a carrier made of conductive carbon”, it is expressed as “Pt / Pd / C”.
  • the value of [I Pt / S Pd ] in the formula (1) is more preferably 0.70 to 1.40.
  • the core portion is made of Pd (0 valence) and the shell portion is made of Pt (0 valence) from the viewpoint of more reliably obtaining excellent catalytic activity.
  • the core part may contain Pd oxide and the shell part may contain Pt oxide as long as the catalyst particles can exhibit excellent catalytic activity.
  • the average thickness of the shell portion can be changed within a range in which the effects of the present invention can be obtained, but in order to exhibit excellent catalytic activity, the average thickness of the shell portion is the so-called core portion. It is preferable to have a sufficiently thin thickness that can exhibit the ground effect (ligand effect). That is, the average thickness of the shell portion of the electrode catalyst of the present invention is preferably 0.2 to 1.0 nm. In the present invention, when the average thickness of the shell part is 0.2 nm or more, the surface of the core part tends to be sufficiently covered with the shell part. Thereby, sufficient catalytic activity as a core-shell catalyst can be easily obtained. Moreover, durability and reliability are also easily obtained, which is preferable.
  • the average thickness of the shell portion is 1.0 nm or less, it is possible to easily contribute to the cost reduction (low platinumization) of PEFC. Further, in this case, it is preferable to obtain a so-called base effect (ligand effect) of the core part, and it becomes easier to obtain a catalytic activity that exceeds the conventional Pt / C catalyst.
  • the average thickness of the shell portion of the electrode catalyst of the present invention is more preferably 0.2 to 0.9 nm, and more preferably 0.2 to 0.7 nm. Is more preferably 0.2 to 0.5 nm.
  • the shell layer is a layer made of Pt
  • the Pt atomic layer can have a thickness of 4 layers or less, preferably 3 layers or less, more preferably 2 layers or less, within the above average thickness range.
  • the metal bond radius of Pt is 0.139 nm
  • the average thickness of one Pt atom layer is about 0.21 nm to 0.23 nm.
  • the average particle size of the catalyst particles and the average particle size of the core portion are evaluated by an SEM image (Scanning Electron Microscopy image) or a TEM image (Transmission Electron Microscopy image), respectively. It can ask for. That is, it can be determined from the difference between the average particle diameter of the catalyst particles and the average particle diameter of the core portion.
  • the average thickness of the shell is, for example, TEM-EDX (Transmission Electron Microscopy-Energy Dispersive X-ray Spectroscopy) or TEM in the particle direction of the catalyst particles. -Obtained by determining the average particle size of the catalyst particles and the average particle size of the core by line analysis using EDX (Transmission Electron Microscopy-Energy Dispersive X-ray Spectroscopy). You can also.
  • the catalyst particles preferably have an average crystallite size of 2.5 to 16.0 nm as measured by powder X-ray diffraction (XRD). Furthermore, when the average value of the crystallite size is 2.5 nm or more, it becomes easier to form the particles serving as the core portion on the support, and on the support so as to satisfy the expression (1). It is preferable because it becomes easier to form catalyst particles. In addition, when the average value of the crystallite size is 16.0 nm or less, it becomes easier to form the core part particles on the carrier in a highly dispersed state, and the catalyst satisfies the condition of the formula (1). It is preferable because it becomes easier to form the particles on the carrier.
  • XRD powder X-ray diffraction
  • the catalyst particles of the electrode catalyst of the present invention have an average crystallite size of 3.0 to 6.0 nm as measured by powder X-ray diffraction (XRD). Is more preferable.
  • XRD powder X-ray diffraction
  • the surreal part made of Pt of the catalyst particles has one or two Pt atomic layers, the peak of the Pt (111) plane cannot be seen by XRD.
  • the average value calculated from the peak of the surface is the average value of the crystallite size of the catalyst particles.
  • the Pt loading of the catalyst particles is preferably 0.6 to 33.0 wt%.
  • the Pt loading is 0.6 wt% or more, sufficient catalytic activity can be obtained more easily.
  • the Pt loading is 33.0 wt% or less, it becomes easier to form catalyst particles having a core-shell structure on the carrier in a highly dispersed state.
  • the catalyst particles of the electrode catalyst of the present invention preferably have a Pt loading of 15.0 to 19.0 wt%.
  • the Pd support rate of the catalyst particles is preferably 4.7 to 47.0 wt%.
  • the Pd loading ratio is 4.7 wt% or more, it becomes easy to sufficiently increase the number of particles serving as the core portion formed on the support, and consequently the number of catalyst particles formed on the support is sufficiently increased. And sufficient catalytic activity can be obtained more easily.
  • the Pd loading rate is 47.0 wt% or less, it becomes easier to carry the particles serving as the core portion on the carrier in a highly dispersed state. As a result, it becomes easier to form catalyst particles having a core-shell structure on a carrier in a highly dispersed state. From the viewpoint of obtaining the above-described effect more reliably, the catalyst particles of the electrode catalyst of the present invention preferably have a Pd loading of 24.0 to 27.0 wt%.
  • the precious metal loading ratio of the catalyst particles including Pt and Pd is 5.6 to 66.5 Wt%.
  • the supporting ratio of the noble metal combined with Pt and Pd is 5.6 Wt% or more, sufficient catalytic activity can be obtained more easily.
  • the precious metal supporting ratio of Pt and Pd is 66.5 Wt% or less, catalyst particles having a core-shell structure can be more easily formed in a highly dispersed state on the support.
  • the catalyst particles of the electrode catalyst of the present invention preferably have a precious metal loading ratio of 39.0 to 46.0 Wt% in combination of Pt and Pd.
  • the value measured by ICP emission analysis using the electrode catalyst is adopted for the Pt loading rate and the Pd loading rate.
  • this invention provides the composition for gas diffusion electrode formation containing the catalyst for electrodes of the above-mentioned this invention. Since the composition for forming a gas diffusion electrode of the present invention contains the electrode catalyst of the present invention, a gas diffusion electrode having excellent catalytic activity (polarization characteristics) that can contribute to cost reduction of PEFC is easily produced. be able to.
  • the present invention also provides a gas diffusion electrode containing the electrode catalyst of the present invention described above.
  • the gas diffusion electrode of the present invention includes the electrode catalyst of the present invention.
  • the gas diffusion electrode of this invention is formed using the composition for gas diffusion electrode formation of this invention. Therefore, it becomes easy to set it as the structure which has the outstanding catalyst activity (polarization characteristic) which can contribute to the cost reduction of PEFC.
  • the present invention provides a membrane / electrode assembly (MEA) including the gas diffusion electrode of the present invention described above. Since the membrane-electrode assembly (MEA) of the present invention includes the gas diffusion electrode of the present invention, it is easy to have a configuration having battery characteristics that can contribute to cost reduction of PEFC.
  • MEA membrane / electrode assembly
  • the present invention also provides a fuel cell stack including the above-described membrane-electrode assembly (MEA) of the present invention. According to the fuel cell stack of the present invention, since the membrane-electrode assembly (MEA) of the present invention is included, it is easy to obtain a configuration having battery characteristics that can contribute to cost reduction of PEFC.
  • MEA membrane-electrode assembly
  • the catalyst for electrodes which has the outstanding catalytic activity which can contribute to the cost reduction of PEFC is provided.
  • the present invention also provides a gas diffusion electrode forming composition, a gas diffusion electrode, a membrane / electrode assembly (MEA), and a fuel cell stack comprising such an electrode catalyst.
  • FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the electrode catalyst (core-shell catalyst) of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing another preferred embodiment of the electrode catalyst (core-shell catalyst) of the present invention.
  • the electrode catalyst 10 of the present invention includes a carrier 2 and catalyst particles 3 having a so-called “core-shell structure” formed on the carrier 2. Further, the catalyst particle 3 has a so-called “core-shell structure” including a core part 4 formed on the carrier 2 and a shell part 6 formed on the core part 4.
  • the electrode catalyst 10 has a structure in which the core portion 4 is a nucleus (core) on the carrier 2 and the shell portion 6 covers the surface of the core portion 4. Further, the constituent elements (chemical composition) of the core portion and the constituent elements (chemical composition) of the shell portion 6 are different.
  • the electrode catalyst only needs to have a shell portion formed on at least a part of the surface of the core portion.
  • the electrode catalyst 10 is preferably in a state in which substantially the entire surface of the core portion 4 is covered by the shell portion 7. .
  • the electrode catalyst 10 ⁇ / b> A is covered with a part of the surface of the core part 4 and the surface of the core part 4 is partially exposed within the range in which the effect of the present invention can be obtained ( For example, a state in which a part 4s of the surface of the core portion 4 shown in FIG.
  • the shell portion 6a and the shell portion 6b may be partially formed on part of the surface of the core portion 4 as in the electrode catalyst 10A shown in FIG.
  • the electrode catalyst of the present invention may be in a state where the electrode catalyst 10 shown in FIG. 1 and the electrode catalyst 10A shown in FIG.
  • the shell portion 6a and the shell portion 6b may be mixed with respect to the same core portion 4 as shown in FIG. .
  • “shell part (shell parts 6, 6a, 6b ) May carry a state in which “particles of only the core portion 4 not covered” are supported (not shown).
  • the electrode catalyst 1 includes “shell part (shell parts 6, 6 a, 6 a) in addition to at least one of the above-described electrode catalyst 10 and electrode catalyst 10 A. 6b) includes particles in which only the core part 4 not covered “and” particles composed only of the constituent elements of the shell part (shell parts 6, 6a, 6b) "are independently supported. May be.
  • the average thickness of the shell portion 6 is preferably 0.2 to 1.0 nm as described above. Further, the average thickness of the shell portion 6 is preferably 0.2 to 0.9 nm, more preferably 0.2 to 0.7 nm, and still more preferably 0.2 to 0.5 nm.
  • the Pt atomic layer has a thickness of 4 layers or less, preferably 3 layers or less, more preferably 2 layers or less within the above average thickness range. Yes.
  • Pt atomic layer when it is intended to minimize the amount of Pt used as the constituent material of the shell portion 6, it is preferably a layer composed of Pt1 atoms (Pt atomic layer).
  • the carrier 2 is not particularly limited as long as it can support a composite composed of the core portion 4 and the shell portion 6 and has a relatively large surface area. Furthermore, it is preferable that the support
  • Carrier 2 is glassy carbon (GC), fine carbon, carbon black, graphite, carbon fiber, activated carbon, pulverized product of activated carbon, carbon nanofiber, carbon nanotube, etc., or glass or ceramics material such as oxide. It can be adopted as appropriate. Among these, a carbon-based material is preferable from the viewpoint of the adsorptivity with the core portion 4 and the BET specific surface area of the carrier 2.
  • conductive carbon is preferable, and as the conductive carbon, conductive carbon black is particularly preferable.
  • conductive carbon black include trade names “Ketjen Black EC300J”, “Ketjen Black EC600”, “Carbon EPC” and the like (manufactured by Lion Chemical Co., Ltd.).
  • the core part 4 includes Pd (zero valence). From the viewpoints of obtaining the effects of the present invention more reliably and manufacturing easiness, the core part 4 is preferably composed of Pd (0 valence) as a main component (50 wt% or more). ) Is more preferable.
  • the shell part 6 contains Pt (zero valence). From the viewpoints of obtaining the effects of the present invention more reliably and manufacturing easiness, the shell portion 6 is preferably composed of Pt (0 valence) as a main component (50 wt% or more). ) Is more preferable.
  • the electrode catalyst 10 and the electrode catalyst 10A satisfy the following conditions from the viewpoint of more reliably obtaining the effects of the present invention. That is, as described above, in the electrode catalyst 10 and the electrode catalyst 10A, the average value of the crystallite size measured by powder X-ray diffraction (XRD) is preferably 2.5 to 16.0 nm. Yes. Further, as described above, the electrode catalyst 10 and the electrode catalyst 10A have a Pt loading rate of preferably 0.6 to 33.0 wt%, and a Pd loading rate of preferably 4.7 to 47. 0.0 wt%.
  • S Pd and I Pt are the cores of the electrode catalyst precursor (not shown) composed of the carrier 2 and the core particles (not shown) formed on the carrier 2. This is a parameter calculated when a particle is approximated to a sphere.
  • the core particles of the electrode catalyst precursor are particles that become the precursor of the core portion 4.
  • S Pd is the number of atoms (mol) of Pd (zero valent) exposed on the surface of the core particle.
  • I Ptt is calculated when it is assumed that the entire amount of Pt (zero valence) contained in the shell portion 6 is coated on the surface of the core particle of the precursor in a single atomic layer state.
  • Atom number (mol) Atom number (mol).
  • CRPt represents a Pt loading (wt%) of Pt (zero valence) contained in the electrode catalyst measured by high frequency inductively coupled plasma (ICP) emission spectroscopy.
  • D represents the mass (g) of the electrode catalyst to be analyzed.
  • AW Pt indicates the atomic weight of Pt.
  • CRPd indicates the Pd loading (wt%) of Pd (zero valence) contained in the electrode catalyst measured by high frequency inductively coupled plasma (ICP) emission spectroscopy.
  • XPd is a parameter calculated when the core particle is approximated to a spherical particle made of Pd (zero valence) for the electrode catalyst precursor described above, and is exposed to the surface of the core particle.
  • the ratio of Pd (zero valent) atoms present (0 ⁇ X Pd ⁇ 1).
  • r is the average value (nm) of the crystallite size of the core particle obtained from the peak of the Pd (111) plane obtained by measuring the powder of the electrode catalyst precursor by powder X-ray diffraction (XRD). .
  • X Pd “number of Pd atoms exposed on the surface of the core particle (mol)” / “total number of Pd atoms constituting the core particle (mol)” (4)
  • occupied area per Pd atom ⁇ (8.26 ⁇ ) 2 is the occupied area (7.57 ⁇ ) 2 and (110) plane obtained for the (100) plane in the face-centered cubic lattice of Pd. Occupied area (10.70 ⁇ ) 2 obtained, average value of occupied area (6.55 ⁇ ) 2 obtained for the (111) plane [ ⁇ (7.57 ⁇ ) + (10.70 ⁇ ) 2 + (6.55 ⁇ ) 2 ⁇ / 3].
  • the electrode catalyst 10 is produced by a method of producing Pd / Pd / core particles (core particles) containing Pd (zero valence) supported on a carrier containing a conductive carbon material as a constituent component.
  • a “shell portion forming step” for forming the shell portion 6 (or 6a, 6b) containing Pt (zero valence) so as to cover a part.
  • the electrode catalyst 10 (or 10A) is manufactured by sequentially supporting the core part 4 and the shell part 6 (6a, 6b) constituting the catalyst particle 3 (3a) as the catalyst component of the electrode catalyst on the carrier 2. Is done.
  • the method for producing the electrode catalyst 10 (10A) is not particularly limited as long as the catalyst particles 3 (3a) as the catalyst component can be supported on the carrier 2.
  • an impregnation method in which a solution containing a catalyst component is brought into contact with the support 2 and the support component 2 is impregnated with the catalyst component
  • a liquid phase reduction method in which a reducing agent is added to the solution containing the catalyst component
  • underpotential deposition UPD
  • electrochemical deposition methods chemical reduction methods, reduction deposition methods using adsorbed hydrogen, alloy catalyst surface leaching methods, displacement plating methods, sputtering methods, vacuum deposition methods and the like can be exemplified.
  • the average value of the crystallite size measured by powder X-ray diffraction (XRD) of the core particles constituting the Pd / C particles obtained through the core portion forming step is preferably 2 to 15 nm. It is adjusting.
  • XRD powder X-ray diffraction
  • the chemical composition and structure of the product (catalyst) are analyzed using various known analysis methods, The analysis results obtained are fed back to the production process, and the raw materials to be selected, the blending ratio of the raw materials, the synthesis reaction to be selected, the reaction conditions for the synthesis reaction, and the like can be mentioned.
  • FIG. 3 shows a gas diffusion electrode forming composition containing the electrode catalyst of the present invention, a gas diffusion electrode produced using this gas diffusion electrode forming composition, and a membrane / electrode assembly comprising this gas diffusion electrode
  • FIG. 2 is a schematic diagram showing a preferred embodiment of a fuel cell stack including a MEMBRANE ELECTRODE ASSEMBLY (hereinafter abbreviated as “MEA” as necessary).
  • the fuel cell stack 40 shown in FIG. 3 has a configuration in which the MEA 42 is a unit cell and a plurality of the unit cells are stacked.
  • the fuel cell stack 40 includes an MEA 42 including an anode 43 that is a gas diffusion electrode, a cathode 44 that is a gas diffusion electrode, and an electrolyte membrane 45 disposed between these electrodes.
  • the fuel cell stack 40 has a configuration in which the MEA 42 is sandwiched between a separator 46 and a separator 48.
  • the gas diffusion electrode forming composition, the anode 43 and the cathode 44, and the MEA 42, which are members of the fuel cell stack 40 including the electrode catalyst of the present invention, will be described.
  • the electrode catalyst of the present invention can be used as a so-called catalyst ink component to form the gas diffusion electrode forming composition of the present invention.
  • the gas diffusion electrode forming composition of the present invention is characterized by containing the electrode catalyst of the present invention.
  • the composition for forming a gas diffusion electrode contains the electrode catalyst and an ionomer solution as main components.
  • the composition of the ionomer solution is not particularly limited.
  • the ionomer solution may contain a polymer electrolyte having hydrogen ion conductivity, water, and alcohol.
  • the polymer electrolyte contained in the ionomer solution is not particularly limited.
  • the polymer electrolyte can be exemplified by a perfluorocarbon resin having a known sulfonic acid group or carboxylic acid group.
  • a perfluorocarbon resin having a known sulfonic acid group or carboxylic acid group.
  • polymer electrolytes having hydrogen ion conductivity Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei Co., Ltd.), Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.) It can be illustrated.
  • the composition for forming a gas diffusion electrode can be prepared by mixing, crushing, and stirring an electrode catalyst and an ionomer solution.
  • the composition for forming a gas diffusion electrode can be prepared using a pulverizing mixer such as a ball mill or an ultrasonic disperser.
  • the pulverization conditions and the stirring conditions when operating the pulverization mixer can be appropriately set according to the mode of the gas diffusion electrode forming composition.
  • Each composition of the electrode catalyst, water, alcohol, and polymer electrolyte having hydrogen ion conductivity contained in the gas diffusion electrode forming composition has a good dispersion state of the electrode catalyst, and the electrode catalyst is gas diffused. It is appropriately set so that the entire catalyst layer of the electrode can be widely spread and the power generation performance of the fuel cell can be improved.
  • the anode 43 which is a gas diffusion electrode, has a configuration including a gas diffusion layer 43a and a catalyst layer 43b formed on the surface of the gas diffusion layer 43a on the electrolyte membrane 45 side.
  • the cathode 44 has a gas diffusion layer (not shown) and a catalyst layer (not shown) formed on the surface of the gas diffusion layer on the electrolyte membrane 45 side.
  • the electrode catalyst of the present invention may be contained in at least one of the anode 43 and the cathode 44.
  • the gas diffusion electrode of this invention can be used as an anode and can also be used as a cathode.
  • the catalyst layer 43b is a layer in which a reaction in which the hydrogen gas sent from the gas diffusion layer 43a is dissociated into hydrogen ions proceeds.
  • the catalyst layer (not shown) proceeds with a reaction between air (oxygen gas) coming from the gas diffusion layer (not shown) and hydrogen ions moving from the anode 43 through the electrolyte membrane 45. It is a layer to do.
  • At least one of the catalyst layer 43b of the anode 43 and the catalyst layer (not shown) of the cathode 44 is formed using the gas diffusion electrode forming composition described above.
  • the gas diffusion layer provided in the anode 43 serving as the gas diffusion electrode and the cathode 44 serving as the gas diffusion electrode is introduced into the gas flow path formed between the separator 46 and the anode 43 from the outside of the fuel cell stack 40.
  • This is a layer provided for diffusing the hydrogen gas and the air (oxygen gas) introduced into the gas flow path formed between the separator 48 and the cathode 44 into each catalyst layer.
  • the gas diffusion layer has a role of supporting the catalyst layer and immobilizing it on the surface of the gas diffusion electrode.
  • the gas diffusion layer has a function / structure that allows hydrogen gas or air (oxygen gas) to pass through well and reach the catalyst layer. For this reason, it is preferable that the gas diffusion layer has water repellency.
  • the gas diffusion layer has a water repellent component such as polyethylene terephthalate (PTFE).
  • the member that can be used for the gas diffusion layer is not particularly limited, and a known member used for the gas diffusion layer of the fuel cell electrode can be used.
  • a known member used for the gas diffusion layer of the fuel cell electrode can be used.
  • carbon paper, carbon paper as a main raw material, and carbon powder, ion-exchanged water as optional components, and a secondary material made of polyethylene terephthalate dispersion as a binder are applied to carbon paper.
  • the anode 43 that is a gas diffusion electrode and the cathode 44 that is a gas diffusion electrode may include an intermediate layer (not shown) between the gas diffusion layer and the catalyst layer.
  • the gas diffusion electrode of this invention should just be manufactured so that the electrode catalyst of this invention may become a structural component of a catalyst layer, and a manufacturing method is not specifically limited, A well-known manufacturing method is employable.
  • the gas diffusion electrode is formed by applying a gas diffusion electrode forming composition containing an electrode catalyst, a polymer electrolyte having hydrogen ion conductivity, and an ionomer to the gas diffusion layer, and You may manufacture through the process of drying the gas diffusion layer with which the composition was apply
  • the MEA 42 shown in FIG. 4 has a configuration including an anode 43, a cathode 44, and an electrolyte membrane 45.
  • the MEA 42 has a configuration in which at least one of an anode and a cathode includes a gas diffusion electrode containing the electrode catalyst of the present invention.
  • the MEA 42 can be manufactured by laminating the anode 43, the electrolyte 300, and the cathode 44 in this order, and then press-bonding them.
  • the fuel cell stack 40 shown in FIG. 3 has a configuration in which a separator 46 is disposed outside the anode 43 of the MEA 42 and a separator 48 is disposed outside the cathode 44 as one unit cell (unit cell). A single cell) or a configuration in which two or more cells are integrated (not shown).
  • the fuel cell system is completed by attaching and assembling peripheral devices to the fuel cell stack 40.
  • Example 1 ⁇ Manufacture of electrode catalyst> [“Pt / Pd / C” powder in which a shell portion made of Pt is formed on Pd / C] “Pt / Pd / C” powder in which a shell portion made of Pt is formed on Pd of the following “Pd / C” powder particles ⁇ Pt loading 16.8 wt% (ICP analysis result), trade name “NE- H10217-BD "(manufactured by NE CHEMCAT) ⁇ was prepared as the electrode catalyst of Example 1.
  • Pt / Pd / C powder As this Pt / Pd / C powder, the following Pd / C powder is used, and a coating film made of Cu is formed on the surface of the core particles made of Pd / C Pd by a general Cu-UPD method. It is prepared by allowing galvanic substitution reaction of Cu and Pt to proceed using potassium platinate.
  • Pd / C powder Pd / C powder ⁇ Pd loading 30 wt%, trade name “NE-H00230-D”, manufactured by NE CHEMCAT) ⁇ in which core particles made of Pd were supported on carbon black powder was prepared.
  • Pd / C powder a mixture of commercially available carbon black powder (specific surface area 750 to 800 m 2 / g), sodium tetrachloropalladium (II) and water is prepared, and a reducing agent is added thereto. Prepared by reducing palladium ions in the liquid obtained.
  • the Pt loading rate (wt%) and the Pd loading rate (wt%) were measured by the following methods.
  • the electrode catalyst of Example 1 was immersed in aqua regia to dissolve the metal. Next, insoluble component carbon was removed from the aqua regia. Next, aqua regia without carbon was analyzed by ICP. The results of ICP analysis are shown in Table 1. Further, by using the analytical results of the ICP, and calculate the value of I Pt in the formula (1).
  • Example 2 The electrode catalyst and the Pd / C powder (core particles) as the raw material were subjected to the same raw materials as in the electrode catalyst of Example 1 and the same production procedure except that the analytical values shown in Table 1 were obtained.
  • the electrocatalyst of Example 2 was prepared.
  • the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 3 ⁇ Manufacture of electrode catalyst> ["Pt / Pd / C” powder]
  • the same “Pd / C” powder as used in Example 1 (Pd loading 30 wt%, trade name “NE-H00230-D”, manufactured by NE CHEMCAT) ⁇ is used, and the shell portion "Pt / Pd / C” powder ⁇ Pt loading 16.4 wt% (ICP analysis result), trade name "NE-H10216-BD”, manufactured by NE CHEMCAT) ⁇
  • ICP analysis result trade name "NE-H10216-BD" manufactured by NE CHEMCAT” ⁇
  • About the Pd / C powder (core particle) used as a raw material the same raw material as the electrode catalyst of Example 1 and the same production procedure except that the analytical values shown in Table 1 were obtained.
  • the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 4 Manufacture of electrode catalyst> ["Pt / Pd / C" powder]
  • a “Pd / C” powder different from that used in Example 1 (Pd loading 30 wt%, trade name “NE-H00230-F”, manufactured by NE CHEMCAT) ⁇ was used, and the shell portion was used.
  • the raw material Pd / C powder (core particles) was prepared using a commercially available carbon black powder (specific surface area of 750 to 800 m 2 / g) different from the carbon black used in Example 1. Further, for the Pd / C powder (core particles) as the raw material, the same raw materials as in the electrode catalyst of Example 1 and the same production procedure were used except that the analytical values shown in Table 1 were obtained. An electrode catalyst was prepared. For the electrode catalyst of Example 4, the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 5 ⁇ Manufacture of electrode catalyst> ["Pt / Pd / C" powder]
  • the same “Pd / C” powder as used in Example 4 (Pd loading 30 wt%, trade name “NE-H00230-F”, manufactured by NE CHEMCAT) ⁇ is used, and the shell portion [Pt / Pd / C] powder ⁇ Pt loading 17.9 wt% (ICP analysis result), trade name “NE-H10218-BF”, manufactured by NE CHEMCAT) ⁇
  • ICP analysis result trade name “NE-H10218-BF”, manufactured by NE CHEMCAT) ⁇
  • About the Pd / C powder (core particle) used as a raw material the same raw material as the electrode catalyst of Example 1 and the same production procedure except that the analytical values shown in Table 1 were obtained.
  • the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 6 ⁇ Manufacture of electrode catalyst> ["Pt / Pd / C” powder]
  • the same “Pd / C” powder as used in Example 4 (Pd loading 30 wt%, trade name “NE-H00230-F”, manufactured by NE CHEMCAT) ⁇ is used, and the shell portion "Pt / Pd / C” powder (Pt loading 18.1 wt% (ICP analysis result), trade name "NE-H10218-BF", manufactured by NE CHEMCAT) ⁇
  • Pd / C powder core particle
  • the same raw material as the electrode catalyst of Example 1 and the same production procedure except that the analytical values shown in Table 1 were obtained.
  • the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 7 ⁇ Manufacture of electrode catalyst> ["Pt / Pd / C" powder]
  • the same “Pd / C” powder as used in Example 4 Pd loading 30 wt%, trade name “NE-H00230-F”, manufactured by NE CHEMCAT) ⁇ is used, and the shell portion [Pt / Pd / C] powder ⁇ Pt loading 17.6 wt% (ICP analysis result), trade name “NE-H10218-BF”, manufactured by NE CHEMCAT) ⁇
  • the electrode catalyst of Example 7 was prepared in the same manner as in the electrode catalyst of Example 1, except that the analytical values shown in Table 1 were obtained. Was prepared.
  • the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 8 ⁇ Manufacture of electrode catalyst> ["Pt / Pd / C” powder]
  • the same “Pd / C” powder as used in Example 4 (Pd loading 30 wt%, trade name “NE-H00230-F”, manufactured by NE CHEMCAT) ⁇ is used, and the shell portion "Pt / Pd / C” powder ⁇ Pt loading 18.1 wt% (ICP analysis result), trade name "NE-H10218-BF", manufactured by NE CHEMCAT) ⁇
  • the electrode catalyst of Example 8 was prepared in the same manner as in the electrode catalyst of Example 1, except that the analytical values shown in Table 1 were obtained. Was prepared.
  • the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 9 Manufacture of electrode catalyst> ["Pt / Pd / C" powder]
  • the same “Pd / C” powder as used in Example 4 (Pd loading 30 wt%, trade name “NE-H00230-F”, manufactured by NE CHEMCAT) ⁇ is used, and the shell portion "Pt / Pd / C" powder (Pt loading 18.0 wt% (ICP analysis result), trade name "NE-H10218-BF", manufactured by NE CHEMCAT)) ⁇
  • the Pd / C powder (core particles) used as the raw material was the same as the electrode catalyst of Example 1 except that the analytical values shown in Table 1 were obtained.
  • Table 1 were obtained.
  • Example 10 ⁇ Manufacture of electrode catalyst> ["Pt / Pd / C" powder]
  • the same “Pd / C” powder as used in Example 4 (Pd loading 30 wt%, trade name “NE-H00230-F”, manufactured by NE CHEMCAT) ⁇ is used, and the shell portion [Pt / Pd / C] powder formed into a Pt support rate of 18.3 wt% (ICP analysis result, trade name “NE-H10218-BF”, manufactured by NE CHEMCAT) ⁇
  • the Pd / C powder (core particles) used as the raw material was the same as the electrode catalyst of Example 1 except that the analytical values shown in Table 1 were obtained.
  • Example 10 the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 11 ⁇ Manufacture of electrode catalyst> ["Pt / Pd / C" powder]
  • the same “Pd / C” powder as used in Example 4 (Pd loading 30 wt%, trade name “NE-H00230-F”, manufactured by NE CHEMCAT) ⁇ is used, and the shell portion "Pt / Pd / C” powder ⁇ Pt loading rate 18.4 wt% (ICP analysis result), trade name "NE-H10218-BF", manufactured by NE CHEMCAT) ⁇
  • ICP analysis result trade name "NE-H10218-BF", manufactured by NE CHEMCAT) ⁇
  • About the Pd / C powder (core particle) used as a raw material the same raw material as the electrode catalyst of Example 1 and the same production procedure except that the analytical values shown in Table 1 were obtained.
  • the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 12 ⁇ Manufacture of electrode catalyst> ["Pt / Pd / C" powder] Using a “Pd / C” powder different from that used in Example 1 and Example 4 (Pd loading ratio 30 wt%, trade name “NE-K00230-F”, manufactured by NE CHEMCAT) ⁇ Example of “Pt / Pd / C” powder ⁇ Pt loading 17.7 wt% (ICP analysis result), trade name “NE-K10218-BF”, manufactured by NE CHEMCAT) ⁇ having a shell portion 12 electrode catalysts were prepared.
  • the Pd / C powder (core particles) used as a raw material was a carbon black used in Example 1 and a commercially available carbon black powder (specific surface area 750 to 800 m 2 / g) different from the carbon black used in Example 4.
  • the electrode of Example 12 was prepared in the same manner as in the electrode catalyst of Example 1, except that the analytical values shown in Table 1 were obtained for the Pd / C powder (core particles) used as the raw material.
  • a catalyst was prepared.
  • the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 13 Manufacture of electrode catalyst> ["Pt / Pd / C" powder] Using a “Pd / C” powder different from that used in Example 1 and Example 4 (Pd loading ratio 30 wt%, trade name “NE-K00230-F”, manufactured by NE CHEMCAT) ⁇ Example of “Pt / Pd / C” powder ⁇ Pt loading 17.9 wt% (ICP analysis result), trade name “NE-K10218-BF”, manufactured by NE CHEMCAT Co., Ltd.) ⁇ 13 electrode catalysts were prepared.
  • the Pd / C powder (core particles) used as a raw material was a carbon black used in Example 1 and a commercially available carbon black powder (specific surface area 750 to 800 m 2 / g) different from the carbon black used in Example 4. Prepared. Further, the Pd / C powder (core particles) used as the raw material was the same as the electrode catalyst of Example 1 except that the analytical values shown in Table 1 were obtained. A catalyst was prepared. For the electrode catalyst of Example 13, the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 14 ⁇ Manufacture of electrode catalyst> ["Pt / Pd / C" powder] Using a “Pd / C” powder different from that used in Example 1 and Example 4 (Pd loading ratio 30 wt%, trade name “NE-K00230-F”, manufactured by NE CHEMCAT) ⁇ Example of “Pt / Pd / C” powder ⁇ Pt loading 17.6 wt% (ICP analysis result), trade name “NE-K10218-BF”, manufactured by NE CHEMCAT Co., Ltd.) ⁇ 14 electrode catalysts were prepared.
  • the Pd / C powder (core particles) used as a raw material was a carbon black used in Example 1 and a commercially available carbon black powder (specific surface area 750 to 800 m 2 / g) different from the carbon black used in Example 4. Prepared. Further, the Pd / C powder (core particles) used as the raw material was the same as the electrode catalyst of Example 1 except that the analytical values shown in Table 1 were obtained. A catalyst was prepared. For the electrode catalyst of Example 14, the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 15 ⁇ Manufacture of electrode catalyst> ["Pt / Pd / C” powder] Using a “Pd / C” powder different from that used in Example 1 and Example 4 (Pd loading ratio 30 wt%, trade name “NE-K00230-F”, manufactured by NE CHEMCAT) ⁇ Example of “Pt / Pd / C” powder ⁇ Pt loading 18.4 wt% (ICP analysis result), trade name “NE-K10218-BF”, manufactured by NE CHEMCAT) ⁇ having a shell portion Fifteen electrode catalysts were prepared.
  • the Pd / C powder (core particles) used as a raw material was a carbon black used in Example 1 and a commercially available carbon black powder (specific surface area 750 to 800 m 2 / g) different from the carbon black used in Example 4. Prepared. Further, the Pd / C powder (core particle) used as the raw material was the same as the electrode catalyst of Example 1 except that the analytical values shown in Table 1 were obtained. A catalyst was prepared. For the electrode catalyst of Example 15, the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Example 16 Manufacture of electrode catalyst> ["Pt / Pd / C" powder] “Pd / C” powder different from that used in Example 1, Example 4 and Example 12 (Pd loading 30 wt%, trade name “NE-E00230-F”, manufactured by NE CHEMCAT) ⁇ “Pt / Pd / C” powder used with a shell portion formed thereon (Pt loading 17.9 wt% (ICP analysis result), trade name “NE-E10218-BF”, manufactured by NE CHEMCAT) ⁇ Was prepared as an electrode catalyst of Example 16.
  • the Pd / C powder (core particles) used as a raw material was carbon black used in Example 1, carbon black used in Example 4, and commercially available carbon black powder different from carbon black used in Example 12 (specific surface area of 300 to 400 m 2 / g). Further, the Pd / C powder (core particles) used as the raw material was the same as the electrode catalyst of Example 1 except that the analytical values shown in Table 1 were obtained. A catalyst was prepared. For the electrode catalyst of Example 16, the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Pt / Pd / C powder As this Pt / Pd / C powder, the following Pd / C powder is used, and a coating film made of Cu is formed on the surface of the core particles made of Pd / C Pd by a general Cu-UPD method. It was prepared by allowing galvanic substitution reaction of Cu and Pt to proceed using potassium platinate.
  • Pd / C powder Pd / C powder ⁇ Pd loading rate 30 wt%, trade name “NE-H00230-C”, manufactured by NE CHEMCAT) ⁇ in which core particles composed of Pd were supported on carbon black powder was prepared.
  • This Pd / C powder was prepared so that the ratio R0 Pd of Pd (zero valence) in the analysis region near the surface measured by X-ray photoelectron spectroscopy (XPS) was less than 3.0 atom%.
  • XPS X-ray photoelectron spectroscopy
  • a mixture of commercially available carbon black powder (specific surface area 750 to 800 m 2 / g), sodium tetrachloropalladium (II) and water is prepared, and a reducing agent is added thereto.
  • the above R0 Pd is prepared so as to be less than 3.0 atom% by reducing palladium ions in the liquid obtained.
  • the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • Comparative Example 2 For the electrode catalyst and the Pd / C powder (core particles) used as the raw material, except that the analytical values shown in Table 1 were obtained, the same raw material as the electrode catalyst of Comparative Example 1 and the same production procedure were used for comparison. The electrocatalyst of Example 2 was prepared. For the electrode catalyst of Comparative Example 2, the same ICP analysis and XRD analysis as those of the electrode catalyst of Example 1 were performed. The results are shown in Table 1.
  • FIG. 4 is a schematic diagram showing a schematic configuration of a rotating disk electrode measuring apparatus 50 used in the rotating disk electrode method (RDE method).
  • the rotating disk electrode measuring device 50 mainly includes a measurement cell 51, a reference electrode RE, a counter electrode CE, and a rotating disk electrode WE. Furthermore, when evaluating a catalyst, electrolyte solution ES is put into the measurement cell 51.
  • the measurement cell 51 has a substantially cylindrical shape having an opening on the upper surface, and a fixing member 52 for the rotating disk electrode WE that also serves as a lid capable of gas sealing is disposed in the opening.
  • a gas sealable opening for fixing the electrode main body portion of the rotating disk electrode WE while being inserted into the measurement cell 51 is provided at the center of the fixing member 52.
  • a substantially L-shaped Lugin tube 53 is arranged. Further, one end portion of the Luggin tube 53 has a Luggin capillary structure, and is inserted into the measurement cell 51, so that the electrolyte ES of the measurement cell 51 also enters the Luggin tube 53. .
  • the other end of the Lugin tube 53 has an opening, and the reference electrode RE is inserted into the Lugin tube 53 through the opening.
  • “Model HSV110” manufactured by Hokuto Denko Co., Ltd. was used as the rotating disk electrode measuring device 50.
  • an Ag / AgCl saturated electrode was used as the reference electrode RE, a Pt mesh with Pt black was used as the counter electrode CE, and an electrode having a diameter of 5.0 mm ⁇ and an area of 19.6 mm 2 was used as the rotating disk electrode WE. . Furthermore, using the HCl0 4 of 0.1M as the electrolyte ES.
  • the rotational speed of the rotating disk electrode WE was set to 400 rpm, 625 rpm, 900 rpm, 1225 rpm, 2025 rpm, 2500 rpm, and 3025 rpm, respectively, and oxygen reduction (ORR) current measurement was performed for each cycle.
  • ORR oxygen reduction
  • the Pt mass activity (Mass Act) value shown in Table 1 represents each electrode when the Pt mass activity (Mass Act) value of the electrode catalyst of Comparative Example 3 (conventional Pt / C catalyst) is 1.00.
  • the relative values of the Pt mass activity values of the catalysts for catalysts are shown.
  • the ECSA values shown in Table 1 are the electrode catalysts (electrodes of Examples 1 to 16) when the ECSA value of the electrode catalyst of Comparative Example 3 (conventional Pt / C catalyst) is 1.00.
  • the relative values of ECSA values of the catalyst for use and Comparative Examples 1 and 2) are shown.
  • the electrode catalysts of Examples 1 to 16 have a Pt mass activity exceeding 4 times that of the electrode catalyst of Comparative Example 3 (conventional Pt / C catalyst). It became clear that Furthermore, the electrode catalysts of Examples 1 to 16 are approximately twice as much Pt mass activity as compared with the electrode catalysts of Comparative Examples 1 to 3 (conventional Pt / Pd / C core-shell catalyst). It became clear to have. From the above results, it was revealed that the electrode catalyst of this example has excellent catalytic activity and can contribute to the cost reduction of PEFC.
  • the electrode catalyst of the present invention has excellent catalytic activity and can contribute to the cost reduction of PEFC. Accordingly, the present invention is an electrode catalyst that can be applied not only to the electric equipment industry such as fuel cells, fuel cell vehicles, and portable mobiles, but also to energy farms, cogeneration systems, etc. Contribute to development.

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Abstract

L'invention concerne un catalyseur d'électrodes (catalyseur cœur-écorce) qui présente une excellente activité catalytique et qui peut contribuer à une réduction de coût de PEFC. Ledit catalyseur d'électrodes comprend des particules de catalyseur supportées par un support. Lesdites particules de catalyseur satisfont les conditions indiquées par : la formule (1) 0,70 ≤ [IPt/SPd] ≤ 2,00 ; la formule (2) [IPt/SPd] = (CRPt × D/AWPt)/{(CRPd × D/AWPd) × XPd} ; et la formule (3) XPd = 1,071/r. Selon l'invention, SPd et IPt sont des paramètres calculés lors d'une approximation sphérique de particules de cœur formées sur le support, pour un précurseur destiné à un catalyseur d'électrode comprenant le support et lesdites particules de cœur. SPd est le nombre (mole) d'atomes de Pd exposés sur la surface des particules de cœur et est calculé à l'aide de la valeur moyenne de la taille de cristallite de particules de cœur trouvées à partir du pic dans un plan de Pd (111) obtenu par une mesure XRD de particules de précurseur. IPt est le nombre (mole) d'atomes de Pt (valence 0), calculé en supposant que le volume total de Pt (valence 0) inclus dans l'écorce obtenue par une analyse ICP soit revêtu d'une seule couche atomique sur la surface des particules de cœur.
PCT/JP2018/010726 2017-03-28 2018-03-19 Catalyseur d'électrode, composition de formation d'électrode à diffusion gazeuse, électrode à diffusion gazeuse, ensemble film-électrode, et empilement de piles à combustible WO2018180676A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016031251A1 (fr) * 2014-08-28 2016-03-03 エヌ・イー ケムキャット株式会社 Catalyseur pour électrode, composition pour former une électrode à diffusion de gaz, électrode à diffusion de gaz, ensemble d'électrode à membrane, et empilement de piles à combustible
WO2016157897A1 (fr) * 2015-03-31 2016-10-06 エヌ・イー ケムキャット株式会社 Catalyseur d'électrode, composition pour former une électrode à diffusion gazeuse, électrode à diffusion gazeuse, ensemble membrane-électrodes, empilement de piles à combustible, procédé de fabrication de catalyseur d'électrode et particule composite
WO2016170775A1 (fr) * 2015-04-20 2016-10-27 エヌ・イー ケムキャット株式会社 Procédé de fabrication d'électrode à diffusion de gaz, et procédé de fabrication d'ensemble membrane-électrodes (mea)

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016031251A1 (fr) * 2014-08-28 2016-03-03 エヌ・イー ケムキャット株式会社 Catalyseur pour électrode, composition pour former une électrode à diffusion de gaz, électrode à diffusion de gaz, ensemble d'électrode à membrane, et empilement de piles à combustible
WO2016157897A1 (fr) * 2015-03-31 2016-10-06 エヌ・イー ケムキャット株式会社 Catalyseur d'électrode, composition pour former une électrode à diffusion gazeuse, électrode à diffusion gazeuse, ensemble membrane-électrodes, empilement de piles à combustible, procédé de fabrication de catalyseur d'électrode et particule composite
WO2016170775A1 (fr) * 2015-04-20 2016-10-27 エヌ・イー ケムキャット株式会社 Procédé de fabrication d'électrode à diffusion de gaz, et procédé de fabrication d'ensemble membrane-électrodes (mea)

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