WO2009075036A1 - Procédé de préparation d'un catalyseur d'électrodes pour des piles à combustible et pile à combustible à électrolyte polymère - Google Patents

Procédé de préparation d'un catalyseur d'électrodes pour des piles à combustible et pile à combustible à électrolyte polymère Download PDF

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Publication number
WO2009075036A1
WO2009075036A1 PCT/JP2007/074351 JP2007074351W WO2009075036A1 WO 2009075036 A1 WO2009075036 A1 WO 2009075036A1 JP 2007074351 W JP2007074351 W JP 2007074351W WO 2009075036 A1 WO2009075036 A1 WO 2009075036A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
nitrogen
mnx
derivatives
fuel cells
Prior art date
Application number
PCT/JP2007/074351
Other languages
English (en)
Inventor
Naoko Iwata
Hiroaki Takahashi
Iris Herrmann
Christa Barkschat
Sebastian Fiechter
Peter Bogdanoff
Ulrike Koslowski
Original Assignee
Toyota Jidosha Kabushiki Kaisha
Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Toyota Jidosha Kabushiki Kaisha, Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh filed Critical Toyota Jidosha Kabushiki Kaisha
Priority to PCT/JP2007/074351 priority Critical patent/WO2009075036A1/fr
Publication of WO2009075036A1 publication Critical patent/WO2009075036A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/923—Compounds thereof with non-metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method of preparing an electrode catalyst for fuel cells having an excellent oxygen reduction activity.
  • the invention also relates to a polymer electrolyte fuel cell having such electrode catalyst in a catalyst layer of its electrode.
  • Polymer electrolyte fuel cells which comprise a polymer electrolyte membrane, are easy to reduce in size and weight For this reason, they are expected to provide power supplies for mobile vehicles such as electric vehicles, and small-sized cogeneration systems, for example.
  • the hydrogen ion produced at the anode by the reaction of equation (1) passes (diffuses) through the solid polymer electrolyte membrane in a hydrated state of H + (XH 2 O).
  • the hydrogen ion that has passed through the membrane is fed to the cathode for the reaction of equation (2).
  • These electrode reactions at the anode and cathode proceed at the interface between a catalyst in an electrode catalyst layer, which is closely attached to the solid polymer electrolyte membrane as a reaction site, and the solid polymer electrolyte membrane.
  • the electrode reaction in each of the catalyst layers for the anode and cathode of the polymer electrolyte fuel cell proceeds at a three-phase interface (reaction site) where the individual reaction gas, the catalyst, and a fluorine-containing ion exchange resin (electrolyte) simultaneously exist.
  • a catalyst comprising a metal-supported carbon, such as a carbon black support with a large specific surface area supporting a metal catalyst, such as platinum, is coated with the same or different kind of fluorine-containing ion exchange resin as or from the polymer electrolyte membrane and then used as the material of the catalyst layer.
  • the production of water from proton and electron at the cathode takes place in the presence of the three phases of catalyst, carbon particle, and electrolyte.
  • the electrolyte, which conducts proton, and the carbon particle, which conducts electron coexist, with which further the catalyst coexists, whereby the oxygen gas is reduced. Therefore, the greater the amount of catalyst supported by the carbon particle, the higher the generation efficiency.
  • the catalyst used in fuel cells comprises a noble metal, such as platinum, an increase in the amount of catalyst supported by the carbon particle results in an increase in fuel cell manufacturing cost
  • the catalyst is indispensable for promoting reactions. While as the catalyst material, platinum or platinum alloys have been the major candidates for both the hydrogen electrode and the oxygen electrode, there is a large overpotential, particularly at the oxygen electrode (cathode). The overpotential could be reduced by increasing the supported amount of platinum or platinum alloy in the catalyst However, increasing the amount of catalyst does not lead to much reduction in overpotential, while creating the bigger problem of an increase in cost Thus, there is the major question of how cost and catalyst performance can be balanced.
  • the disclosed catalyst comprises a catalyst material derived from a noble metal-containing macrocyclic compound precursor.
  • the catalyst material which is supported by a high-surface-area carbon, comprises a noble metal in a zero-oxidation state.
  • a disclosed preparation method involves dissolving a noble metal macrocyclic compound in water or an organic solvent, adding electrically conductive carbon to the resultant solution, causing the macrocyclic material to be adsorbed on the carbon support, and separating the macrocyclic material supported by the carbon.
  • a practical application may involve an electrode comprising, as a catalyst, a nitrogen-containing platinum-group complex having a PtN4 chelate structure in which platinum (Pt) is coordinated to the four nitrogen atoms.
  • JP Patent Publication (Kokai) No. 2004-532734 A indicated below discloses a non-platinum-containing chelate catalyst in which metal porphyrin is used.
  • JP Patent Publication (Kokai) No. 2006-035186 A indicated below discloses an electrode catalyst in which a macrocyclic metal complex is highly dispersed in the support surface.
  • JP Patent Publication (Kokai) No. 2003-168442 A indicated below discloses a fuel electrode for polymer electrolyte fuel cells comprising an ion-conductive substance, an electron conductive substance, and a catalyst substance, in which a metal complex, such as metallotetra porphyrin, is added.
  • JP Patent Publication (Kokai) No. 03-030838 A (1991) indicated below discloses a reducing catalyst comprising a tetraphenylporphyrin derivative and the compound.
  • a part of a macrocyclic metal complex will be decomposed into an electrical conductive carbon matrix by a heat treatment.
  • an active structure MNx (2 ⁇ x ⁇ 4) will be re-activated and a part of MNx (2 ⁇ x ⁇ 4) will be re-structured as a new active site.
  • the MN4 structure i.e., the active site
  • falls off during the preparation of the catalyst heat treatment thereby preventing the obtaining of sufficient current density, particularly in high-potential region.
  • the present inventors achieved the aforementioned object by repairing the fall-off of the MNx (2 ⁇ x ⁇ 4) structure and formation of the further or more additional active site during the heat treatment process of carbon-based MNx (2 ⁇ x ⁇ 4) centre catalyst material in which a transition metal (M) is coordinated to the two ⁇ four nitrogen atoms.
  • M transition metal
  • the present invention provides a method of preparing an electrode catalyst for fiiel cells comprising a carbon-based MNx (2 ⁇ x ⁇ 4) catalyst material in which a metal element (M) is coordinated to the two ⁇ four nitrogen atoms.
  • the method comprises subjecting the carbon-based MNx (2 ⁇ x ⁇ 4) catalyst material to nitrogen-compensating treatment.
  • the nitrogen-compensating treatment repairs the MNx (2 ⁇ x ⁇ 4) structure, i.e., the active site, that fell off during the preparation of the catalyst and more form further or more additional active sites(MNx structure), whereby catalyst activity can be improved.
  • the nitrogen-compensating treatment according to the present invention maintains the original MNx (2 ⁇ x ⁇ 4) structure by repairing the breakpoint of a carbon-carbon bond of a carbonaceous substance derived from a nitrogen-containing compound.
  • such nitrogen-compensating treatment involves heat treatment of the nitrogen-containing metal complex in an NH 3 or N 2 atmosphere after first heat treatment and subsequent etching step.
  • the nitrogen-containing transition metal complex which serves as a precursor for the catalysyt preparation by heat treatment, having the aforementioned MN4 chelate structure is not particularly limited.
  • a preferable example is a nitrogen-containing transition metal complex comprising one or more kinds of macrocyclic compound selected from porphyrin (PP) or its derivatives, phthalocyanine (Pc) or its derivatives, and tetraazaannulene (TAA) or its derivatives, wherein one or more kinds selected from iron (Fe), nickel (Ni), cobalt (Co), zinc (Zn), copper (Cu), manganese (Mn), and palladium (Pd) are coordinated as the transition metal.
  • PP porphyrin
  • Pc phthalocyanine
  • TAA tetraazaannulene
  • Another preferable example is a nitrogen-containing platinum group metal complex comprising one or more kinds of macrocyclic compounds selected from porphyrin (PP) or its derivatives, phthalocyanine (Pc) or its derivatives, and tetraazaannulene (TAA) or its derivatives, wherein one or more kinds of platinum group element selected from platinum, ruthenium, rhodium, palladium, osmium, and iridium, or such platinum-group element and one or more kinds selected from other elements are coordinated as the metal.
  • PP porphyrin
  • Pc phthalocyanine
  • TAA tetraazaannulene
  • the present invention provides a polymer electrolyte fuel cell comprising an electrode catalyst for fuel cells prepared by the above method.
  • Fig. 1 schematically shows how the basis for new catalytic centre are formed by performing nitrogen-compensating treatment on the carbon-based MNx (2 ⁇ x ⁇ 4) catalyst material by way of chemical formulate.
  • Fig. 2 shows the results of RDE evaluation of the generating performance of a CoTMPP/FeOx/S catalyst (Comparative Example) which has been pyrolysed in N 2 atmosphere but prior to nitrogen-compensating treatment, a CoTMPP/FeOx/S catalyst (Example 1) "comparative example” but with additional nitrogen-compensating treatment involving heat treatment process in an NH 3 atmosphere, and a CoTMPP/FeOx/S catalyst (Example 2) "comparative example” but with additional nitrogen-compensating treatment involving heat treatment process in an N 2 atmosphere.
  • Fig. 3 shows the results (NIs) of XPS measurement of the CoTMPP/FeOx/S catalyst (Comparative Example) prior to nitrogen-compensating treatment, the CoTMPP/FeOx/S catalyst (Example 1) after nitrogen-compensating treatment involving heat treatment process in an NH 3 atmosphere, and the CoTMPP/FeOx/S catalyst (Example 2) after nitrogen-compensating treatment involving heat treatment process in an N 2 atmosphere.
  • Fig. 1 shows by way of chemical formula how nitorogen van incorporate in the defect structure of the carbon matrix, which had been formed from the precursor by heat treatment.
  • defect structure are formed by the desorbtion of oxygen surface group and/or by fall of MNx (2 ⁇ x ⁇ 4) structure. So on these defect structures NH3 can react.
  • the incorporated nitorogen can be used for the repair of destructed MNx (2 ⁇ x ⁇ 4) centre and/or to the formation of new MNx (2 ⁇ x ⁇ 4) centres.
  • a schematic diagram shown below is that of a nitrogen-containing transition metal complex having an MN4 chelate structure in which a transition metal is coordinated to the four nitrogen atoms, and a nitrogen-containing platinum group metal complex having an MNx (2 ⁇ x ⁇ 4) chelate structure in which a platinum group element or a platinum-group element and another element are coordinated to the four nitrogen atoms and more the surrounding of the MNx (2 ⁇ x ⁇ 4) centre is a carbon matrix/grapheme structure.
  • a transition metal (M), a platinum-group element, or a platinum-group element and another element (M) is coordinated to the four nitrogen atoms in a macrocyclic compound, thus carbon-based MNx (2 ⁇ x ⁇ 4) catalyst material.
  • nitrogen-containing compound that forms the metal complex used in the present invention include N4-chelate structures such as porphyrin and its derivatives, phthalocyanine and its derivatives, azaporphyrin and its derivatives, tetraazaannulene and its derivatives, and a Schiffbase.
  • R 1 to R 12 are hydrogen or substituent groups.
  • R 13 to R 22 are hydrogen or substituent groups.
  • R 23 to R 36 are hydrogen or substituent groups.
  • the nitrogen-containing metal complex having the MNx (2 ⁇ x ⁇ 4) chelate structure in which a transition metal element, a platinum-group metal element, or a platinum-group element and another element (M) are coordinated to the four nitrogen atoms, may be either supported by a support or not; even without a support, catalyst performance can be obtained.
  • the nitrogen-containing compound used in the present invention is carbonized by pyrolysis so as to provide a support by itself, so that the advantage can be obtained that there is no need to use a separate support.
  • the electrically conductive support is not particularly limited. Examples are carbon black, carbon nanotube, and carbon nanofiber.
  • Example 1 [Preparation of a CoTMPP/FeOx/S catalyst]
  • a tetramethylpo ⁇ hyrin-cobalt complex/iron oxalate/sulfur catalyst (CoTMPP/FeOx/S catalyst) was prepared as follows in accordance with the German Patent publication 1013249 Al.
  • Tetramethylporphyrin, ⁇ iron oxalate (FeC 2 O 4 ), and (sulfur) (molar ratio 1/22/8) were mixed in a mortar.
  • Fig. 2 demonstrates the electricity generating performance of the CoTMPP/FeOx/S catalyst prior to nitrogen-compensating treatment (Comparative Example), the CoTMPP/FeOx/S catalyst (Example 1) after nitrogen-compensating treatment involving the heat treatment in an NH 3 atmosphere, and the CoTMPP/FeOx/S catalyst (Example 2) after nitrogen-compensating treatment involving heat treatment in an N 2 atmosphere, based on RDE evaluation.
  • Fig. 3 shows the results of XPS measurement (NIs) of the CoTMPP/FeOx/S catalyst (Comparative Example) prior to nitrogen-compensating treatment, the CoTMPP/FeOx/S catalyst (Example 1) after nitrogen-compensating treatment involving the heat treatment in an NH 3 atmosphere, and the CoTMPP/FeOx/S catalyst (Example 2) after nitrogen-compensating treatment involving heat treatment in an N 2 atmosphere.
  • NIs XPS measurement
  • the MNx (2 ⁇ x ⁇ 4) structure i.e., the active site, that fell off during the preparation of the catalyst can be repaired, whereby improved catalyst activity can be obtained.
  • an electrode catalyst for fuel cells having excellent characteristics can be obtained.
  • current density in high-potential region can be improved, hi this way, the invention contributes to the improvement in the electricity generating characteristics of a fuel cell.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

Selon l'invention, les performances catalytiques sont améliorées pour un catalyseur contenu dans des piles à combustibles, ledit catalyseur étant composé d'un matériau catalytique central à base de carbone MNx (2 ≤ x ≤ 4), dans lequel un métal de transition (M) est associé à un nombre d'atomes d'azote compris entre 2 et 4. Lesdites performances sont améliorées grâce à la réalisation d'un traitement de compensation d'azote sur le complexe métallique contenant de l'azote.
PCT/JP2007/074351 2007-12-12 2007-12-12 Procédé de préparation d'un catalyseur d'électrodes pour des piles à combustible et pile à combustible à électrolyte polymère WO2009075036A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014020541A1 (fr) * 2012-07-30 2014-02-06 Uniwersytet Warszawski Catalyseur sélectif, en particulier pour l'électroréduction de l'oxygène, système électrochimique le contenant, alliage palladium-gaz inerte et son utilisation, et cellule, en particulier cellule photovoltaïque le contenant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2019239A (en) * 1977-12-30 1979-10-31 Shell Int Research Process for activating a catalyst for fuel cell electrodes
EP0176831A2 (fr) * 1984-09-27 1986-04-09 Eltech Systems Corporation Electrode à diffusion gazeuse à réponse rapide destinée à une forte intensité et procédé pour sa fabrication
EP0512713A1 (fr) * 1991-05-04 1992-11-11 Johnson Matthey Public Limited Company Matière catalytique
US6245707B1 (en) * 1999-10-28 2001-06-12 The United States Of America As Represented By The Secretary Of The Army Methanol tolerant catalyst material
EP1854539A1 (fr) * 2005-02-03 2007-11-14 Toyota Jidosha Kabushiki Kaisha Materiau catalytique et procede pour sa preparation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2019239A (en) * 1977-12-30 1979-10-31 Shell Int Research Process for activating a catalyst for fuel cell electrodes
EP0176831A2 (fr) * 1984-09-27 1986-04-09 Eltech Systems Corporation Electrode à diffusion gazeuse à réponse rapide destinée à une forte intensité et procédé pour sa fabrication
EP0512713A1 (fr) * 1991-05-04 1992-11-11 Johnson Matthey Public Limited Company Matière catalytique
US6245707B1 (en) * 1999-10-28 2001-06-12 The United States Of America As Represented By The Secretary Of The Army Methanol tolerant catalyst material
EP1854539A1 (fr) * 2005-02-03 2007-11-14 Toyota Jidosha Kabushiki Kaisha Materiau catalytique et procede pour sa preparation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
G. FAUBERT, R. COTE, J.P. DODELET, M.LEFEVRE, P.BERTRAND: "Oxygen reduction catalyst for polymer electrolyte fuel cells from the pyrolysis of Fe II acetate adsorved on 3,4,9,10-perylenetetracarboxylic dianhydride", ELECTROCHEMICA ACTA, vol. 44, 1999, pages 2589 - 2603, XP002469619 *
LALANDE G ET AL: "Catalytic activity and stability of heat-treated iron phthalocyanines for the electroreduction of oxygen in polymer electrolyte fuel cells", JOURNAL OF POWER SOURCES, ELSEVIER, AMSTERDAM, NL, vol. 61, no. 1-2, 8 July 1996 (1996-07-08), pages 227 - 237, XP004071515, ISSN: 0378-7753 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014020541A1 (fr) * 2012-07-30 2014-02-06 Uniwersytet Warszawski Catalyseur sélectif, en particulier pour l'électroréduction de l'oxygène, système électrochimique le contenant, alliage palladium-gaz inerte et son utilisation, et cellule, en particulier cellule photovoltaïque le contenant
US10170771B2 (en) 2012-07-30 2019-01-01 Uniwersytet Warszawski Selective catalyst, particularly for electroreduction of oxygen, an electrochemical system containing thereof, an palladium-inert gas alloy and use thereof, and a cell, particularly a photovoltaic cell containing thereof

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