WO2004073096A1 - Procede de synthese pour electrocatalyseur de pile a combustible - Google Patents

Procede de synthese pour electrocatalyseur de pile a combustible Download PDF

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Publication number
WO2004073096A1
WO2004073096A1 PCT/US2004/004545 US2004004545W WO2004073096A1 WO 2004073096 A1 WO2004073096 A1 WO 2004073096A1 US 2004004545 W US2004004545 W US 2004004545W WO 2004073096 A1 WO2004073096 A1 WO 2004073096A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
dispersion
solution
particulate support
alloy
Prior art date
Application number
PCT/US2004/004545
Other languages
English (en)
Inventor
Konstantinos Chondroudis
Martin Devenney
Alexander Gorer
Original Assignee
Symyx Technologies Inc.
Honda Giken Kogyo Kabushiki Kaisha
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
Publication date
Application filed by Symyx Technologies Inc., Honda Giken Kogyo Kabushiki Kaisha filed Critical Symyx Technologies Inc.
Publication of WO2004073096A1 publication Critical patent/WO2004073096A1/fr

Links

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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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

  • a fuel cell is an electrochemical device for directly converting the chemical energy generated from an oxidation-reduction reaction of a fuel such as hydrogen or hydrocarbon-based fuels and an oxidizer such as oxygen gas (e.g., in air) supplied thereto into a low-voltage direct current.
  • a fuel such as hydrogen or hydrocarbon-based fuels
  • an oxidizer such as oxygen gas (e.g., in air) supplied thereto into a low-voltage direct current.
  • oxygen gas e.g., in air
  • the present invention is also directed to a fuel cell electrode, the fuel cell electrode comprising a supported electrocatalyst powder and an electrode substrate upon which the supported electrocatalyst powder is deposited.
  • the fuel cell is characterized in that the supported electrocatalyst powder comprises: supports; deposits comprising a metal alloy on the supports, wherein the metal alloy comprises a non-noble metal; a loading of deposits on the supports of at least about 20 weight percent; an average deposit size that is no greater than about 10 nm; and a deposit size distribution wherein at least about 70 percent of the metal alloy deposits are between about 50 and about 150 percent of the average metal alloy deposit size.
  • each of the dispersions in the array is prepared by a method comprising dispersing the support particles in a solution comprising a solvent and a first, and/or second, dissolved metal (as the case may be).
  • FIG. 1 is a TEM image of a carbon support with platinum alloy nanoparticles deposited thereon in accordance with an embodiment of the present invention.
  • the solute portion comprises an inorganic metal-containing compound as a source of the metal species being deposited.
  • the inorganic-metal containing compound include indium (III) nitrate pentahydrate, manganese (II) nitrate, iron (III) nitrate nonahydrate, (NH 4 )Mo 7 O 24 *4H 2 0, ammonium paratungstate ((NH 4 ) 10 W 12 O 41 # 5H 2 O), rhodium (III) nitrate, chromium (III) nitrate, zinc (II) nitrate hexahydrate, copper (II) nitrate, nickel (II) nitrate hexahydrate, and vanadium (IV) sulfate oxide.
  • Adding the second source solution after the supports have been dispersed/suspended allows the particles of the insoluble species that form upon mixing the solutions to deposit (e.g., precipitate) uniformly on the supports. What remains is a dispersion/suspension comprising the supports with deposits of the insoluble species thereon in a solution comprising the solvent portion and any remaining soluble compound(s) of the solute portion.
  • the specifics of mixing a solution and the supports to form the suspension are set forth in detail below.
  • the incompatibility issue may be addressed by performing all or part of the method of the present of the invention more than once.
  • the method of the present invention may be performed to deposit on or more metals on the particulate support from a first solution.
  • the total concentration of inorganic metal-containing compounds in the solution is between about 0.1 and about 1 M. Concentrations below the solubility limit are used because it is desirable to maximize the loading of the supported metal alloy electrocatalysts without decreasing the surface area of the metal deposits.
  • the loading may typically be between about 5 and about 60 weight percent. Preferably, the loading is between about 10 and about 50 weight percent. More preferably, the loading is between about 20 and 40 weight percent. Still more preferably, the loading is about 40 weight percent.
  • the supports may have a pre-deposited material thereon, which may be, for example, a pre-deposited metal such as platinum, palladium, nickel, etc.
  • a pre-deposited metal such as platinum, palladium, nickel, etc.
  • the final composition of the deposits on the carbon supports is a platinum alloy
  • Such powders are commercially available from companies such as Johnson Matthey, Inc., of New Jersey and E- Tek Div. of De-Nora, N.A., Inc., of Sommerset, New Jersey an may be selected to have a particular loading of platinum.
  • the amount of platinum loading is selected in order to achieve the desired stoichiometry of the supported metal alloy.
  • the loading of platinum is between about 5 and about 60 weight percent.
  • the uniformity of the distribution of particles in the dispersion/suspension is maintained throughout the removal of heat from the dispersion/suspension. This uniformity may be maintained by continuing the mixing of the dispersion/suspension as it is being cooled. The uniformity may, however, be maintained without mixing by the viscosity of the dispersion/suspension.
  • the actual viscosity needed to uniformly suspend the particles depends in large part on the amount of supports in the dispersion/suspension and the size of the supports. To a lesser degree, the necessary viscosity depends on the density of the supports and the specific gravity of the solution.
  • the viscosity is typically sufficient to prevent substantial settling of the supports as the heat is being removed from the suspension to precipitate the deposits, and/or, if desired, until the dispersion/suspension is solidified by the freezing of the solution or solvent.
  • the degree of settling, if any, may be determined, for example, by examining portions of the solidified or frozen suspension. Typically, substantial settling would be considered to have occurred if the concentration of supports in any two portions vary by more than about ⁇ 10%.
  • the viscosity of the suspension/dispersion is typically sufficient to prevent substantial settling for at least about 4 minutes.
  • the rapid heat removal may comprise cooling the dispersion/suspension from a temperature of at least about 20 °C to a temperature below the freezing point of the solvent at a rate of, for example, at least about 20 °C/minute.
  • the heat removal comprises cooling the dispersion/suspension at a rate of at least about 50, 60, 70, 80, 90, or 100 °C/minute.
  • the dispersion/suspension may be cooled at a rate that is between about 50 and about 100 °C/minute or at a rate that is between about 60 and about 80 °C/minute.
  • a frozen or solidified suspension is freeze- dried to remove the solvent portion.
  • the freeze-drying may be carried out in any appropriate apparatus such as a LABCONCO FREEZE DRY SYSTEM (Model 79480).
  • LABCONCO FREEZE DRY SYSTEM Model 79480
  • one of skill in the art would typically maintain the temperature of the frozen suspension below the melting point of the solvent (i.e., the solvent is removed by sublimation) in order to prevent agglomeration of the supports.
  • the process of the present invention may be carried out under such conditions. Surprisingly, however, it is not critical that solvent portion be prevented from melting.
  • an interstitial solid solution is formed if a smaller atom occupies the interstices between the larger atoms. Combinations of the two types are also possible. Furthermore, in certain solid solutions, some level of regular arrangement may occur under the appropriate conditions resulting in a partial ordering that may be described as a superstructure. These solid solutions may have characteristics that may be distinguishable through characterization techniques such as XRD. Significant changes in XRD may be apparent due to changes in symmetry, if more complete ordering occurs such as that which occurs between Pt metal and Pt 3 Fe. Although the global arrangement of the atoms is extremely similar in both cases, the relationship between the locations of the Pt and Fe atoms is now ordered and not random resulting in different diffraction patterns.
  • a dispersion is a two-phase system in which one phase consists of particles distributed throughout a bulk substance, the particles being the disperse or internal phase and bulk substance the continuous or external phase.
  • the particles may be kept dispersed in the bulk substance by agitation.
  • the particles may be kept dispersed in the bulk substance by the molecular motion in the surrounding medium and/or buoyancy. If this is the case, the dispersion is often referred to as a suspension.
  • the actual compositions of the prepared supported electrocatalyst alloys were analyzed by EDS (Electron Dispersive Spectroscopy) elemental analysis by compressing samples of the powders into pellets having a diameter of 6 mm and a thickness of about 1 mm.
  • the target alloy composition Pt 38 Rh 7 Mo 19 Ni 36 had an actual composition of Pt 33 Rh 7 Mo 25 Ni 35 and the target alloy composition Pt 20 Rh 20 Mo 40 Fe 20 had an actual composition of Pt 1g Rh 18 Mo 46 Fe 17 .
  • the method of the present invention produced actual compositions that were quite close to the target compositions in a first attempt. The slight differences observed between the targeted and the measured compositions are due to limitations of the EDS analysis technique.

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

Abstract

Cette invention concerne un procédé de fabrication d'une poudre métallique sur support. Le procédé consiste à former une dispersion de support particulaire dans une solution comprenant un solvant et un métal dissous. On extrait la chaleur de la dispersion pour précipiter le métal dissous dans la solution sur le support particulaire. On extrait de préférence une quantité de chaleur suffisante pour congeler la solution. La chaleur est de préférence extraite de la dispersion par mise en contact d'un récipient contenant ladite dispersion avec un liquide cryogénique tel que de l'azote liquide. Par ailleurs, l'extraction de la chaleur de la dispersion se fait de préférence par contact du récipient contenant la dispersion avec un liquide cryogénique. Une fois le métal dissous précipité sur le support particulaire, on sépare ce dernier de la solution, de préférence par lyophilisation pour obtenir la poudre métallique sur support qui renferme le support particulaire et le métal précipité.
PCT/US2004/004545 2003-02-12 2004-02-12 Procede de synthese pour electrocatalyseur de pile a combustible WO2004073096A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US44708903P 2003-02-12 2003-02-12
US44670903P 2003-02-12 2003-02-12
US60/446,709 2003-02-12
US60/447,089 2003-02-12

Publications (1)

Publication Number Publication Date
WO2004073096A1 true WO2004073096A1 (fr) 2004-08-26

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Family Applications (1)

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PCT/US2004/004545 WO2004073096A1 (fr) 2003-02-12 2004-02-12 Procede de synthese pour electrocatalyseur de pile a combustible

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169731B2 (en) * 2003-02-12 2007-01-30 Symyx Technologies, Inc. Method for the synthesis of a fuel cell electrocatalyst
US7485390B2 (en) 2003-02-12 2009-02-03 Symyx Technologies, Inc. Combinatorial methods for preparing electrocatalysts
GB2436509B (en) * 2005-01-12 2009-05-27 Toyota Eng & Mfg North America Photocatalytic methods for preparation of electrocatalyst materials
RU2467798C1 (ru) * 2011-11-02 2012-11-27 Федеральное государственное бюджетное учреждение "Национальный исследовательский центр "Курчатовский институт" Способ получения катализатора на углеродном носителе
CN103272589A (zh) * 2013-06-13 2013-09-04 苏州诺信创新能源有限公司 空气电池电极催化剂的制备方法
US8549768B2 (en) * 2011-03-11 2013-10-08 Linde Aktiengesellschaft Methods for freeze drying
US10186711B2 (en) 2005-01-12 2019-01-22 Toyota Motor Engineering & Manufacturing North America, Inc. Photocatalytic methods for preparation of electrocatalyst materials

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2315318A1 (fr) * 1975-06-26 1977-01-21 Alsthom Cgee Procede de preparation d'un catalyseur electrochimique
EP0129399A1 (fr) * 1983-06-14 1984-12-27 Engelhard Corporation Electrocatalyseur au platine/fer et électrode pour cellule à combustible l'utilisant
US20010027160A1 (en) * 2000-04-04 2001-10-04 Lee Seol Ah Method of preparing platinum alloy electrode catalyst for direct methanol fuel cell using anhydrous metal chloride
US6348431B1 (en) * 1999-04-19 2002-02-19 Sandia National Laboratories Method for low temperature preparation of a noble metal alloy
EP1254712A1 (fr) * 2001-05-05 2002-11-06 OMG AG & Co. KG Catalyseur supporté à base de métal noble et son procédé de préparation
WO2003069706A2 (fr) * 2002-02-12 2003-08-21 Symyx Technologies, Inc. Electrocatalyseur de pile a combustible constitue de pt-rh-mo-ni/fe
WO2003077337A1 (fr) * 2002-03-06 2003-09-18 Symyx Technologies, Inc. Electrocatalyseur de pile a combustible contenant pt, zn et fe ou ni, ou fe et ni
WO2003081702A2 (fr) * 2002-03-21 2003-10-02 Symyx Technologies, Inc. Catalyseur au pt-rh-w/sn/cu/mo pour pile a combustible

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2315318A1 (fr) * 1975-06-26 1977-01-21 Alsthom Cgee Procede de preparation d'un catalyseur electrochimique
EP0129399A1 (fr) * 1983-06-14 1984-12-27 Engelhard Corporation Electrocatalyseur au platine/fer et électrode pour cellule à combustible l'utilisant
US6348431B1 (en) * 1999-04-19 2002-02-19 Sandia National Laboratories Method for low temperature preparation of a noble metal alloy
US20010027160A1 (en) * 2000-04-04 2001-10-04 Lee Seol Ah Method of preparing platinum alloy electrode catalyst for direct methanol fuel cell using anhydrous metal chloride
EP1254712A1 (fr) * 2001-05-05 2002-11-06 OMG AG & Co. KG Catalyseur supporté à base de métal noble et son procédé de préparation
WO2003069706A2 (fr) * 2002-02-12 2003-08-21 Symyx Technologies, Inc. Electrocatalyseur de pile a combustible constitue de pt-rh-mo-ni/fe
WO2003077337A1 (fr) * 2002-03-06 2003-09-18 Symyx Technologies, Inc. Electrocatalyseur de pile a combustible contenant pt, zn et fe ou ni, ou fe et ni
WO2003081702A2 (fr) * 2002-03-21 2003-10-02 Symyx Technologies, Inc. Catalyseur au pt-rh-w/sn/cu/mo pour pile a combustible

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169731B2 (en) * 2003-02-12 2007-01-30 Symyx Technologies, Inc. Method for the synthesis of a fuel cell electrocatalyst
US7485390B2 (en) 2003-02-12 2009-02-03 Symyx Technologies, Inc. Combinatorial methods for preparing electrocatalysts
GB2436509B (en) * 2005-01-12 2009-05-27 Toyota Eng & Mfg North America Photocatalytic methods for preparation of electrocatalyst materials
US8541146B2 (en) 2005-01-12 2013-09-24 Toyota Motor Engineering & Manufacturing North America, Inc. Photocatalytic methods for preparation of electrocatalyst materials
US10186711B2 (en) 2005-01-12 2019-01-22 Toyota Motor Engineering & Manufacturing North America, Inc. Photocatalytic methods for preparation of electrocatalyst materials
US8549768B2 (en) * 2011-03-11 2013-10-08 Linde Aktiengesellschaft Methods for freeze drying
RU2467798C1 (ru) * 2011-11-02 2012-11-27 Федеральное государственное бюджетное учреждение "Национальный исследовательский центр "Курчатовский институт" Способ получения катализатора на углеродном носителе
CN103272589A (zh) * 2013-06-13 2013-09-04 苏州诺信创新能源有限公司 空气电池电极催化剂的制备方法

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