WO2020235322A1 - Cathode de pile à combustible, son procédé de production et pile à combustible à polymère solide équipée d'une cathode de pile à combustible - Google Patents

Cathode de pile à combustible, son procédé de production et pile à combustible à polymère solide équipée d'une cathode de pile à combustible Download PDF

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WO2020235322A1
WO2020235322A1 PCT/JP2020/018212 JP2020018212W WO2020235322A1 WO 2020235322 A1 WO2020235322 A1 WO 2020235322A1 JP 2020018212 W JP2020018212 W JP 2020018212W WO 2020235322 A1 WO2020235322 A1 WO 2020235322A1
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catalyst
fuel cell
cathode electrode
metal oxide
composite metal
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Japanese (ja)
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北村　武昭
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株式会社 Ａｃｒ
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Priority to CN202080028626.7A priority Critical patent/CN113795332B/zh
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    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • 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
    • B01J37/16—Reducing
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a cathode electrode for a fuel cell, a method for manufacturing the same, and a polymer electrolyte fuel cell provided with a cathode electrode for a fuel cell.
  • ionomer fluorine ion exchange resin
  • a perfluorocarbon polymer having a strongly acidic sulfonic acid group in the side chain is used in order to enhance proton conductivity.
  • Patent Documents 1, 2 and 3 a polymer electrolyte fuel cell and an electrode layer treated with a fluororesin or a fluorine-based silane coupling agent for coating a catalyst are proposed.
  • the coating treatment with a fluororesin and a fluorosilane was not sufficient from the viewpoint of durability because the fluororesin was peeled off and the siloxane bond was hydrolyzed due to the fluctuation of the traveling load of the automobile and the start / stop.
  • a catalyst called a three-phase interface, ionomer and oxygen (in other words, hydrogen ions, oxygen, and electrons are associated with each other on the surface of the catalyst metal particles) are associated with each other during catalysis.
  • the purpose is to have more catalytic metal particles to have a reaction site to improve the effective utilization rate of platinum. Furthermore, it is to enable the continuous retention of the reaction site at the three-phase interface even in the presence of overvoltages in the traveling load fluctuation cycle and the start / stop cycle of the automobile.
  • Patent Document 4 when the oxygen absorber composed of the pyrochlor type Ce 2 Zr 2 O 7 is separately present on the surface of the catalyst-supporting conductor without being in direct contact with the catalyst metal particles, Oxygen is easily dissolved in the generated water, and the supply to the reaction site at the three-phase interface on the surface of the catalyst metal particles is reduced. Further, since the oxygen absorber made of the pyrochloro type Ce 2 Zr 2 O 7 has low electron conductivity, the internal resistance of the cathode electrode increases, and the overvoltage of the traveling load fluctuation cycle and the start / stop cycle of the automobile becomes high. , Oxidation and elution of platinum, decomposition of sulfonic acid groups of ionomer and corrosion of catalyst-bearing conductors (conductive carbon).
  • the metal oxide having protrusions is a catalyst metal so that the conduction of hydrogen ions, the conduction of electrons and oxygen can be associated with the surface of the catalyst metal particles to continuously form the site of the three-phase interface.
  • the cathode electrode for a fuel cell of the present invention has a catalyst layer composed of a catalyst-supporting conductor and a polymer electrolyte, and the surface of the catalyst-supporting conductor has protrusions. It is covered with a composite metal oxide, and catalyst metal particles are supported on the conductive composite metal oxide.
  • the height of the protrusions of the conductive composite metal oxide may be 5 nm to 15 nm.
  • the conductive composite metal oxide may have a water repellency of 140 degrees or more at a contact angle with water.
  • the catalyst-supported conductor may have a specific resistance of 0.2 ⁇ ⁇ cm or less.
  • the conductive composite metal oxide may be an oxygen absorber.
  • the conductive composite metal oxide may be a p-type semiconductor.
  • the conductive composite metal oxide may contain Ta-doped SnO 2 (0.01% by mass ⁇ Ta ⁇ 1.0% by mass).
  • the catalyst metal particles may have a core-shell structure composed of a Pt shell layer.
  • the core layer of the core-shell structure may be made of Pd and an alloy selected from at least one of Pt, Ru and Co.
  • the catalyst-supporting conductor may consist of at least one selected from conductive carbon, graphite, graphene and carbon alloy.
  • the method for manufacturing a cathode electrode for a fuel cell of the present invention is the above-mentioned method for manufacturing a cathode electrode for a fuel cell of the present invention, and the suspension of the catalyst-supporting conductor , Tin chloride (II) and tantalum chloride (V) are added, and the pH is controlled to 1.5 to 2.0 to obtain the conductive composite metal oxide.
  • the core layer of the catalyst metal particles may be formed on the surface of the protruding conductive composite metal oxide that covers the surface of the catalyst-supporting conductor by the first reduction step.
  • the Pt shell layer of the catalyst metal particles may be formed by the second reduction step.
  • the polymer electrolyte fuel cell of the present invention has a polymer arranged between the anode electrode, the cathode electrode of the present invention, and the anode electrode and the cathode electrode. It has an electrolyte membrane.
  • the conductive composite metal oxide may contain Ta-doped SnO 2 (0.01% by mass ⁇ Ta ⁇ 1.0% by mass).
  • a composite metal oxide composed of a pyrochloro-type Sn 2 Ta 2 O 7 having a protrusion and / or a crystal of Sn 2 Nb 2 O 7 has a long-lasting water repellency.
  • FIG. 1 shows a conceptual diagram of the catalyst carrier conductor, the composite oxide, the catalyst metal particles, and the ionomer in the cathode electrode of the present invention.
  • FIG. 2 shows a conceptual diagram of a reaction site at a three-phase interface due to the movement of hydrogen ions, electrons, and oxygen molecules onto the surface of the catalyst metal particles.
  • FIG. 3 shows a conceptual diagram of deterioration behavior during power generation in a conventional cathode electrode.
  • FIG. 4 shows a conceptual diagram of the core-shell type catalyst of the present invention.
  • the present invention by forming a composite metal oxide having protrusions of 5 nm to 15 nm on the surface of the catalyst-supported conductor, the wettability with ionomer is good, the platinum effectiveness rate is high, and water can be discharged. In addition, the catalyst and the ionomer can be brought into close contact with each other when the catalyst is operated, and the continuous water repellency can be maintained.
  • the composite metal oxide has a crystal structure of pyrochlore type Sn 2 Ta 2 O 7 and / or Sn 2 Nb 2 O 7 . The catalyst metal particles are in contact with the surface of the metal oxide and are not dissolved in the water generated by oxygen, so that the catalyst metal particles can be efficiently supplied. is there.
  • the composite metal oxide having an oxygen absorbing / releasing property having a crystal structure of pyrochlorotype Sn 2 Ta 2 O 7 and / or Sn 2 Nb 2 O 7 is a catalyst-supporting conductor and a catalyst metal. It is provided in contact with the particles and has electron conductivity, so that electrons can be supplied to the reaction site at the three-phase interface on the surface of the catalyst metal particles. At the same time, the metal oxide can prevent corrosion of the catalyst-supported conductor.
  • the present invention is an invention of a cathode electrode for a fuel cell having a catalyst layer composed of a catalyst-supporting conductor and an ionomer, and is a pyrochloro-type Sn 2 having a protrusion on the surface of the catalyst-supporting conductor.
  • Ta 2 O 7, Sn 2 Nb 2 O 7 and / or conductive composite metal oxide of the crystal structure of Ta-doped SnO 2 are formed, the catalyst metal particles are supported on the surface of the further conductive complex metal oxides Is preferable.
  • the cathode electrode of the present invention the conductive composite metal comprising a crystal structure of the catalyst carrier conductive pyrochlore type surface fine protruding Sn 2 Ta 2 O 7, Sn 2 Nb 2 O 7 and / or Ta-doped SnO 2
  • the oxide is further supported, it has long-lasting water repellency due to the formation of protrusions, and since the catalyst metal particles are supported on the surface of the conductive composite metal oxide, it is conductive to the catalyst metal particles.
  • the oxygen defect of the sex composite metal oxide conducts electrons, and the oxygen carrier of the crystal structure of the pyrochloro type Sn 2 Ta 2 O 7 , Sn 2 Nb 2 O 7 and / or Ta-doped Sn O 2 causes oxygen carriers.
  • a diffusion path for oxygen molecules is secured directly to the catalytic metal particles.
  • the electron conductivity and oxygen carrier properties of the crystal structure of pyrochloro-type Sn 2 Ta 2 O 7 , Sn 2 Nb 2 O 7 and / or Ta-doped Sn O 2 electrons And oxygen molecules can be associated with the surface of the catalytic metal particles to increase the exchange current density in the electrode reaction and reduce overvoltage. That is, high electrode characteristics can be obtained.
  • the overvoltage of the oxygen reduction reaction of the cathode electrode can be effectively reduced, so that the electrode characteristics of the cathode electrode can be improved.
  • the shortage of oxygen gas occurs especially during operation of the fuel cell, but according to the present invention, high electrode characteristics can be maintained even during long-term operation.
  • protrusions made of a conductive composite metal oxide having a height and an interval of 5 nm to 15 nm are formed on the surface of a catalyst carrier conductor having a particle size of 20 nm to 50 nm, and are resistant to corrosion by overvoltage and hydrogen peroxide. It made it possible to maintain durable water repellency that can be tolerated.
  • the conductive composite metal oxide of the present invention has a pyrochlore-type Sn 2 Ta 2 O 7 and / or Sn 2 Nb 2 O 7 crystal structure, holes are generated by oxygen defects and a P-type semiconductor is generated. It has characteristics and enables electron conductivity.
  • the pyrochlore-type Sn 2 Ta 2 O 7 and / or Sn 2 Nb 2 O 7 crystals that can be used in the present invention absorb and release oxygen due to oxygen defects in the crystals due to fluctuations in oxygen concentration in the vicinity.
  • the oxygen carrier materials having a function of being able to reversibly repeat. That is, oxygen can be absorbed when the O 2 concentration is relatively high, and oxygen can be released in an atmosphere where the O 2 concentration is low.
  • the catalyst-supported conductor in which the pyrochlore-type Sn 2 Ta 2 O 7 and / or Sn 2 Nb 2 O 7 is supported on the surface is preferably porous carbon powder, graphite powder or graphene powder. ..
  • the cathode electrode has a catalyst layer composed of a catalyst-supporting conductor and an ionomer, and the surface of the catalyst-supporting conductor has a pyrochlor-type Sn. It is preferable that an oxygen absorber composed of 2 Ta 2 O 7 and / or Sn 2 Nb 2 O 7 , or Ta-doped SnO 2 which is not an oxygen absorber, and catalyst metal particles are further supported on the surface thereof. ..
  • the cathode electrode of the present invention having excellent electrode characteristics for the oxygen reduction reaction described above, it is possible to construct a polymer electrolyte fuel cell having a high battery output. Further, as described above, in the cathode electrode of the present invention, the overvoltage of the traveling load fluctuation cycle and the start / stop cycle of the automobile becomes high, platinum oxidation and elution, decomposition of the sulfonic acid group of the ionomer, and catalyst-supported conductivity. Since the body (conductive carbon) can be prevented from corroding and has excellent durability, the polymer electrolyte fuel cell of the present invention provided with this can stably obtain a high battery output for a long period of time. It becomes.
  • the surface of the catalyst carrier conductor is coated with a composite metal oxide having fine protrusions.
  • Catalytic metal particles are supported on the surface of the composite metal oxide.
  • the protrusions act as spacers, and the ionomer covers the tops of the protrusions with a uniform thickness.
  • a pyrochlore-type Sn 2 Ta 2 O 7 and / or a Sn 2 Nb 2 O 7 conductive composite metal oxide having protrusions is supported on the surface of the catalyst-supporting conductor. Since the fine protrusions have continuous water repellency, the catalyst and the ionomer can maintain close contact even at high output, and many hydrogen ions can reach the catalyst metal particles.
  • oxygen when the fuel cell has a low output, the amount of oxygen consumed by the catalyst is small, and the oxygen concentration near the oxygen absorber is high, so excess oxygen is stored in the oxygen absorber. On the other hand, since the amount of oxygen consumed by the catalyst is large and the oxygen concentration in the vicinity of the oxygen absorber is low, oxygen is directly transferred from the composite metal oxide to the catalyst metal particles, so that the influence of gas diffusion in the catalyst layer The performance of the fuel cell is further improved by reducing oxygen on the catalyst without receiving oxygen in the generated water and consuming oxygen.
  • the electrode reaction proceeds at the site where the reaction gas, catalyst, and electrolyte meet, which is called the three-phase interface.
  • the supply of oxygen to the three-phase interface is one important topic.
  • the output of the battery is increased, a large amount of oxygen is required for the reaction, and if there is no oxygen in the vicinity of the catalyst, the power generation characteristics deteriorate sharply.
  • a high concentration of oxygen is supplied, but as shown in FIG. 1, the actual reaction is carried out at the three-phase interface (near the catalyst), so if oxygen is not supplied here, it will be the same. I can't fully demonstrate my abilities.
  • the output is increased, the oxygen consumption on the catalyst surface increases, but the diffusion rate of oxygen from the outside to the catalyst surface hardly changes.
  • the cathode electrode of the polymer electrolyte fuel cell of the present invention includes a catalyst layer, and is preferably composed of a catalyst layer and a gas diffusion layer arranged adjacent to the catalyst layer.
  • a constituent material of the gas diffusion layer for example, a porous body having electron conductivity (for example, carbon cloth or carbon paper) is used.
  • a pyrochlor type Sn 2 Ta 2 O 7 and / or Sn 2 Nb 2 O 7 having water repellency due to protrusions and conductivity and oxygen absorption / release property are present, and the cathode electrode
  • the electrode reaction rate of the cathode electrode is improved by reducing the overvoltage with respect to the oxygen reduction reaction in the above.
  • the electrode reaction rate of the cathode electrode can be improved by reducing the overvoltage with respect to the oxygen reduction reaction in the cathode electrode.
  • the content of the pyrochlore-type Sn 2 Ta 2 O 7 and / or Sn 2 Nb 2 O 7 composite metal oxide contained in the catalyst layer is the combination of the catalyst-supported conductor, the polymer electrolyte, and the catalyst metal particles.
  • the amount is preferably 0.01 to 30% by mass, more preferably 0.01 to 20% by mass, based on the amount.
  • the content of the pyrochlor type Sn 2 Ta 2 O 7 and / or Sn 2 Nb 2 O 7 is less than 0.01% by mass, the water repellency, the electron conductivity and the oxygen absorption / release property are lowered.
  • the content of the Ta-doped SnO 2 composite metal oxide contained in the catalyst layer is 0.01 to 30% by mass with respect to the total amount of the catalyst-supporting conductor, the polymer electrolyte, and the catalyst metal particles. It is preferably 0.01 to 20% by mass, and more preferably 0.01 to 20% by mass.
  • the content of Ta-doped SnO 2 is less than 0.01% by mass, the water repellency, electron conductivity and oxygen absorption / release property are lowered, the ionomer and the catalyst metal particles are separated, oxygen is dissolved in the produced water, and the catalyst metal is dissolved.
  • the Ta-doped SnO 2 preferably has a Ta content of 0.1 to 10% by mass, more preferably 0.5 to 5.0% by mass in SnO 2 .
  • the Ta content is less than 0.1% by mass, the association of electrons with the catalyst metal at the three-phase interface is reduced, resulting in a decrease in power generation.
  • the catalyst contained in the catalyst-supporting conductor of the cathode electrode of the present invention is not particularly limited, but platinum, platinum alloy or core-shell type (for example, the shell layer 6 surrounding the core layer 5 shown in FIG. 4 is platinum, core.
  • Layer 5 is preferably an alloy selected from Pd, Pt, Ru and / or Co).
  • the catalyst-supported conductor is not particularly limited, but a carbon material having a specific surface area of 200 m 2 / g or more is preferable. For example, carbon black, graphite or graphene is preferably used.
  • a fluorine-containing ion exchange resin is preferable, and a sulfonic acid type perfluorocarbon polymer is particularly preferable.
  • the sulfonic acid type perfluorocarbon polymer enables long-term chemically stable and rapid hydrogen ion conduction in the cathode electrode.
  • the thickness of the catalyst layer of the cathode electrode of the present invention may be the same as that of the polymer solid electrolyte sandwiched between the ordinary anode electrode and the cathode electrode, and is preferably 1 to 50 ⁇ m, preferably 5 to 20 ⁇ m. Is more preferable.
  • the overvoltage of the oxygen reduction reaction of the cathode electrode is usually very large compared to the overvoltage of the hydrogen oxidation reaction of the anode electrode, so that the generated hydrogen peroxide decomposes the sulfonic acid group of the ionomer.
  • Oxidation and elution of catalyst metal and corrosion of catalyst carrier conductor are likely to occur, and as described above, the catalyst carrier conductor is coated with a composite metal oxide having water repellency, electron conductivity and oxygen absorption / release property due to the protrusion shape. It can be prevented by doing.
  • the water-repellent effect of mosquito prevents the dissolution of oxygen in the generated water, and the oxygen absorption / release effect increases the oxygen concentration at the reaction site in the catalyst layer to suppress overvoltage, which is a continuous cathode. Improving the electrode characteristics of the electrodes is effective in stabilizing the output characteristics of the battery.
  • the configuration of the anode electrode is not particularly limited, and for example, it may have a known configuration of a gas diffusion electrode.
  • the polymer electrolyte membrane sandwiched between the anode electrode and the cathode electrode used in the polymer electrolyte fuel cell of the present invention is not particularly limited as long as it is an ion exchange membrane exhibiting good ionic conductivity under a wet state.
  • the solid polymer material constituting the polymer electrolyte membrane for example, a perfluorocarbon polymer having a sulfonic acid group, a polysulfone resin, a perfluorocarbon polymer having a phosphonic acid group or a carboxylic acid group and the like can be used. Of these, a sulfonic acid type perfluorocarbon polymer is preferable.
  • the polymer electrolyte membrane may be made of the same resin as the ionomer contained in the catalyst layer, or may be made of a different resin.
  • the surface of the catalyst carrier conductor is covered with a composite metal oxide having protrusions in advance, and the catalyst metal particles are supported on the surface and the ionomer is dispersed in a solvent or dispersion.
  • a solvent or dispersion medium for example, alcohol, fluorine-containing alcohol, fluorine-containing ether and the like can be used.
  • the catalyst layer is formed by applying the coating liquid to an ion exchange membrane, a carbon cloth serving as a gas diffusion layer, or the like.
  • the catalyst layer can also be formed on the polymer solid electrolyte membrane by applying the coating liquid to a separately prepared base material to form a coating layer and transferring the coating layer onto the polymer solid electrolyte membrane. ..
  • the catalyst layer when the catalyst layer is formed on the gas diffusion layer, it is preferable to bond the catalyst layer and the polymer solid electrolyte membrane by an adhesion method, a hot press method, or the like. Further, when the catalyst layer is formed on the polymer solid electrolyte membrane, the cathode electrode may be formed only by the catalyst layer, but a gas diffusion layer may be further arranged adjacent to the catalyst layer to serve as the cathode electrode. Good.
  • a separator having a normal gas flow path is arranged outside the cathode electrode, and a gas containing hydrogen is supplied to the anode electrode and a gas containing oxygen is supplied to the cathode electrode to the flow path to form a solid polymer type.
  • a fuel cell is configured.
  • the particle size distribution of the catalyst metal was measured by measuring 100 points using a transmission electron microscope (Titan Cubed G2 60-300, manufactured by FEI Company), and the average particle size was calculated by arithmetic mean.
  • the shape (height, spacing) of the convex composite metal oxide of the present invention is the same as that of the particle size distribution of the catalyst metal, and a transmission electron microscope (Titan Cubed G2 60-300, manufactured by FEI) is used. Using, 100 points were measured, and the height and interval were calculated by arithmetic mean.
  • Example 1 Prepare a mixture of Pt (5% by mass) / pyrochlore type Sn 2 Ta 2 O 7 (20%) / carbon black (75% by mass) according to the following procedure, prepare MEA, assemble MEA into the cell, and evaluate the performance. did.
  • Tin (II) chloride and tantalum (V) chloride were dissolved in pure water in a predetermined amount and stirred for 2 hours.
  • Carbon black (Ketjen Black EC300J, BET specific surface area 800 g / m2, manufactured by Lion Specialty Chemicals Co., Ltd.) was prepared into powder, and a predetermined amount was added to pure water and stirred to prepare a suspension. ..
  • the solution of (1) was slowly added to the suspension with stirring to adjust the pH to 1.5 with dilute hydrochloric acid, and the state was maintained for 3 hours. Then, filtration and washing with water were repeated three times to obtain a carbon black powder in which the carbon black particles were coated with Sn 2 Ta 2 O 7 .
  • a catalyst ink of 0.0% by mass, Pt (5% by mass) / pyrochloro type Sn 2 Ta 2 O 7 (20%) / carbon black (75% by mass) was prepared.
  • the above catalyst ink was cast on a Teflon (registered trademark) resin film (thickness 6 mil), dried, and cut into 25 (cm 2 ). It was used as an electrode film.
  • Example 2 the core-shell type catalyst metal is the same as in Example 1 except that the catalyst metal is changed from the Pt single metal to the core-shell type catalyst metal (shell layer Pt / core layer Pd / Ru / Co alloy).
  • An MEA was prepared using (5% by mass) / pyrochlore type Sn 2 Ta 2 O 7 (20%) / carbon black (75% by mass), and its performance was evaluated in a single cell.
  • the core-shell catalyst metal was produced by the following procedure. (1) The carbon black powder coated with Sn 2 Ta 2 O 7 obtained in (3) of Example 1 was dispersed in pure water with stirring, and combined with a palladium chloride solution (1% by mass as Pd). A predetermined amount of a ruthenium chloride solution (1% by mass as Ru) and a cobalt chloride solution (1% by mass as Co) were added. (2) A small amount of ethanol was slowly added thereto, and the mixture was heated to 40 ° C. and kept for 3 hours. Pd, Ru and Co were reduced to the surface of the composite metal oxide of Sn 2 Ta 2 O 7 . Then, filtration and washing with water were repeated 3 times, dried at 80 ° C.
  • the catalyst ink was cast on a Teflon (registered trademark) resin film (thickness 6 mil), dried, and cut into 25 (cm 2 ) to obtain an electrode film.
  • Example 3 is the same as in Example 2 except that the pyrochlore-type Sn 2 Ta 2 O 7 is replaced with Ta-doped SnO 2 , and the core-shell type catalyst metal (5% by mass) / Ta-doped SnO 2 (20%). ) / MEA using carbon black (75% by mass) was prepared, and the performance was evaluated with a single cell.
  • the composite metal oxide of Ta-doped SnO 2 was prepared by the following procedure. (1) A predetermined amount of tin (II) chloride was dissolved in pure water and stirred for 2 hours. (2) Carbon black (Ketjen Black EC300J, BET specific surface area 800 g / m 2 , manufactured by Lion Specialty Chemicals Co., Ltd.) is prepared into powder, and a predetermined amount is added to pure water and stirred to prepare a suspension. did. (3) The solution of (1) was slowly added to the suspension with stirring to adjust the pH to 1.5 with dilute hydrochloric acid, and the state was maintained for 3 hours. (4) A predetermined amount of tantalum chloride (V) was dissolved in pure water and stirred for 2 hours.
  • V tantalum chloride
  • the tantalum (V) chloride solution was slowly added in a predetermined amount, heated to 30 ° C., and held for 3 hours.
  • filtration and washing with water were repeated three times to obtain a carbon black powder coated with Ta-doped SnO 2 .
  • a small amount of the carbon black powder coated with the Ta-doped SnO 2 was collected, dried at 80 ° C. for 12 hours, pulverized in a mortar, and then calcined in an atmospheric baking oven at 500 ° C. for 2 hours.
  • the obtained powder was prepared into pellets having a diameter of 20 mm and a thickness of 5 mm using a press machine, and the water repellency was measured by the contact angle with water by the sessile drop method. This contact angle was 145 degrees. Moreover, when the specific resistance was measured using the pellet, it was 0.2 ⁇ ⁇ cm. (10) Next, the core-shell type catalyst (Pt / Pd / Ru / Co alloy) / Ta-doped SnO 2 / carbon black is mixed with ion-exchanged water, an ionomer electrolyte solution (Nafion D520), ethanol, and polyethylene glycol in a predetermined amount.
  • an ionomer electrolyte solution Nafion D520
  • Catalyst ink was prepared. (11) The catalyst ink was cast on a Teflon (registered trademark) resin film (thickness 6 mil), dried, and cut into 25 (cm 2 ) to obtain an electrode film. (12) When the electrode membrane was completely dissolved and ICP analyzed, Pt was 0.05 mg / cm 2 , Pd was 0.03 mg / cm 2 , Ru was 0.10 mg / cm 2 , and Co was 0.11 mg / cm.
  • the core-shell catalyst (Pt / Pd / Ru / Co alloy) / carbon black powder was observed with a transmission electron microscope, the core-shell catalyst (Pt / Pd / Ru / Co alloy) particles were observed. The average particle size of was 3 nm.
  • the obtained powder was prepared into pellets having a diameter of 20 mm and a thickness of 5 mm using a press machine, and the water repellency was measured by the contact angle with water by the sessile drop method. This contact angle was 90 degrees.
  • the specific resistance was measured using the pellet, it was 0.5 ⁇ ⁇ cm.
  • the core-shell type catalyst (Pt / Pd / Ru / Co alloy) / carbon black is mixed with ion-exchanged water, an ionomer electrolyte solution (Nafion D520), ethanol, and polyethylene glycol in a predetermined amount (Nafion /).
  • a catalyst ink having Carbon 1.0% by mass and a core-shell type catalyst (Pt / Pd / Ru / Co alloy) (5% by mass) / carbon black (95% by mass) was prepared.
  • the catalyst ink is cast on a Teflon (registered trademark) resin film (thickness 6 mil), dried, and cut into 25 (cm 2 ). It was used as an electrode film.
  • Comparative Example 1 MEA was prepared using TEC10E50E (50% by mass as Pt, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) in which platinum was supported on commercially available carbon black, and the MEA was assembled into a cell to evaluate its performance.
  • TEC10E50E 50% by mass as Pt, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.
  • the average particle size of the platinum catalyst metal particles was 4 nm.
  • the obtained powder was prepared into pellets having a diameter of 20 mm and a thickness of 5 mm using a press machine, and the water repellency was measured by the contact angle with water by the sessile drop method. This contact angle was 90 degrees.
  • the specific resistance was measured using the pellet, it was 0.01 ⁇ ⁇ cm.
  • MEA was assembled in the cell and the performance was evaluated.
  • Comparative Example 2 In Comparative Example 2, instead of the pyrochlore type Sn 2 Ta 2 O 7 , the pyrochlore type Ce 2 Zr 2 O 7 was used as the composite metal oxide, and the pyrochlore type Ce 2 Zr 2 O 7 was not supported with the catalyst metal particles. , The composite metal oxide and the catalyst metal particles were individually supported on carbon black, but MEA was prepared in the same manner as in Example 1, and the MEA was assembled into the cell to evaluate the performance.
  • a catalyst ink of 0.0% by mass, Pt (5% by mass) / pyrochroma type Ce 2 Zr 2 O (20% by mass) / carbon black (95% by mass) was prepared.
  • the above catalyst ink was cast on a Teflon (registered trademark) resin film (thickness 6 mil), dried, and cut into 25 (cm 2 ). It was used as an electrode film.
  • Comparative Example 3 MEA was prepared in the same manner as in Comparative Example 1 except that it was treated with fluorine silane (0.1% by mass) / Pt (5% by mass) / carbon black (94.9% by mass). Was assembled into the cell and the performance was evaluated.
  • the obtained powder was prepared into pellets having a diameter of 20 mm and a thickness of 5 mm using a press machine, and the water repellency was measured by the contact angle with water by the sessile drop method. This contact angle was 150 degrees. Moreover, when the specific resistance was measured using the pellet, it was 0.8 ⁇ ⁇ cm.
  • a fluorosilane-treated (0.1% by mass) / Pt (5% by mass) / carbon black (94.9% by mass) catalyst ink was prepared.
  • the catalyst ink was cast on a Teflon (registered trademark) resin film (thickness 6 mil), dried, and cut into 25 (cm 2 ). It was used as an electrode film.
  • thermocompression bonding (150) to a polymer solid electrolyte membrane (NafionNR211, t 25 ⁇ m). °C) to prepare MEA.
  • MEA was assembled in the cell and the performance was evaluated.
  • ECA test "Gas flow rate” Anode: H 2 200 NmL / min Cathode: N 2 200 ⁇ 0 NmL / min (N 2 nitrogen is blocked before measurement) "Humidification temperature” Anode dew point (relative humidity): 80 ° C (RH100%) Cathode dew point (relative humidity): 80 ° C (RH100%) "Set pressure” Normal pressure "Cell temperature” 80 ° C "Measurement conditions” After nitrogen blocking, scanning is performed 5 times at 50 mV / sec between 0.05 V and 0.9 V.
  • the fuel cell using the electrode in which the conductive composite metal oxide having a protrusion shape is supported on the surface of the catalyst-supporting conductor of the present invention is conductive, water-repellent, and / or absorbs and releases oxygen. It can be seen that the body is superior in power generation performance and durability performance as compared with Comparative Example 2 and Comparative Example 3 using an electrode made of a normal oxygen absorber or fluorine-based treatment. Furthermore, it can be seen that the amount of platinum used can be reduced if the core-shell type of the present invention is also used.
  • Catalyst metal carrier 2 Conductive composite metal oxide having protrusions 3: Catalyst metal particles 4: Ionomer (polymer solid electrolyte) 5: Core layer 6: Shell layer

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Abstract

L'invention concerne une cathode pour une pile à combustible à électrolyte solide polymère, dans laquelle le taux d'utilisation efficace de platine est amélioré en conséquence d'un plus grand nombre de particules métalliques catalytiques ayant des sites de réaction au niveau desquels un catalyseur, un ionomère et de l'oxygène se rencontrent pendant la catalyse, qui sont connus sous la forme d'interfaces à trois phases. En outre, même lorsqu'une surtension se produit en conséquence du cycle de démarrage/arrêt et du cycle de fluctuation de charge de déplacement d'un véhicule, il est possible de maintenir de manière durable les sites de réaction d'interface en trois phases.　Cette cathode pour pile à combustible comprend une couche de catalyseur comprenant un conducteur de support de catalyseur et un électrolyte polymère, la surface du conducteur de support de catalyseur est recouverte par un oxyde métallique complexe conducteur ayant des saillies, et l'oxyde métallique complexe conducteur supporte les particules métalliques catalytiques.
PCT/JP2020/018212 2019-05-20 2020-04-30 Cathode de pile à combustible, son procédé de production et pile à combustible à polymère solide équipée d'une cathode de pile à combustible WO2020235322A1 (fr)

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JP2012043612A (ja) * 2010-08-18 2012-03-01 Toppan Printing Co Ltd 電極触媒層の製造方法、及び固体高分子形燃料電池
JP2012049075A (ja) * 2010-08-30 2012-03-08 Jx Nippon Oil & Energy Corp パイロクロア型酸化物の調製方法および燃料電池用電極触媒の製造方法
JP2017157353A (ja) * 2016-02-29 2017-09-07 国立大学法人山梨大学 合金電極触媒およびにそれを用いた燃料電池

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JP2006066255A (ja) * 2004-08-27 2006-03-09 Toyota Motor Corp 燃料電池用カソード及びこれを備えた固体高分子型燃料電池
JP4857570B2 (ja) * 2005-02-14 2012-01-18 株式会社日立製作所 触媒構造体とその製造方法
KR101363797B1 (ko) * 2007-11-09 2014-02-14 고쿠리쓰다이가쿠호진 규슈다이가쿠 연료전지용 전극재료의 제조방법, 연료전지용 전극재료 및 이 연료전지 전극재료를 이용한 연료전지

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Publication number Priority date Publication date Assignee Title
JP2008091264A (ja) * 2006-10-04 2008-04-17 Toyota Motor Corp 燃料電池用カソード及びこれを備えた固体高分子型燃料電池
JP2012043612A (ja) * 2010-08-18 2012-03-01 Toppan Printing Co Ltd 電極触媒層の製造方法、及び固体高分子形燃料電池
JP2012049075A (ja) * 2010-08-30 2012-03-08 Jx Nippon Oil & Energy Corp パイロクロア型酸化物の調製方法および燃料電池用電極触媒の製造方法
JP2017157353A (ja) * 2016-02-29 2017-09-07 国立大学法人山梨大学 合金電極触媒およびにそれを用いた燃料電池

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