WO2012004639A1 - Catalyseurs en alliage de palladium pour cathodes de piles à combustible et leur procédé de préparation - Google Patents

Catalyseurs en alliage de palladium pour cathodes de piles à combustible et leur procédé de préparation Download PDF

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Publication number
WO2012004639A1
WO2012004639A1 PCT/IB2010/055605 IB2010055605W WO2012004639A1 WO 2012004639 A1 WO2012004639 A1 WO 2012004639A1 IB 2010055605 W IB2010055605 W IB 2010055605W WO 2012004639 A1 WO2012004639 A1 WO 2012004639A1
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WIPO (PCT)
Prior art keywords
catalyst
support material
catalyst according
particles
solution
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PCT/IB2010/055605
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English (en)
Inventor
Rosa Maria MAGALHÃES REGO
Maria Cristina Fialho Oliveira
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Universidade De Trás-Os-Montes E Alto Douro
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Publication of WO2012004639A1 publication Critical patent/WO2012004639A1/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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8846—Impregnation
    • H01M4/885—Impregnation followed by reduction of the catalyst salt precursor
    • 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 object of the invention is to prepare a cathode catalyst for low and medium temperature fuel cells.
  • This catalyst exhibits a catalytic activity as good, or better, than commercial Pt for oxygen reduction reaction (ORR) in acid medium, a good tolerance to methanol and a low production cost.
  • ORR oxygen reduction reaction
  • This catalyst comprises an alloy containing a metal (Pd) and a non-metal (P or B) .
  • Pd metal
  • P or B non-metal
  • a fuel cell is a device that converts continuously the chemical energy of an external supplied fuel and oxidant into electrical energy.
  • the basic structure of a fuel cell includes:
  • an anode which is fed by a gaseous (H 2 ) or liquid fuel (e.g. MeOH, EtOH) ;
  • a gaseous (H 2 ) or liquid fuel e.g. MeOH, EtOH
  • an ion-conductor electrolyte e.g. conductive polymer
  • the anode and cathode are both gas diffusion materials containing a catalyst layer where the anodic (fuel oxidation) and cathodic (oxygen reduction) reactions occur, respectively.
  • the catalysts are needed to speed up the rates of the electrochemical ' reactions, which are particularly sluggish on the cathodic side of the fuel cell device.
  • the rate of the oxygen reduction reaction (ORR) is ca . 10 2 "10 3 times lower than for the anodic reaction.
  • platinum and platinum alloys are the most active catalysts for ORR. Conventionally these are prepared as nanoparticles on the surface of somewhat larger particles of finely divided carbon powder. However, these Pt-based catalysts are too expensive for making commercially viable fuel cells.
  • Pt catalysts are related to fuel cells that use methanol as fuel (direct methanol fuel cells - DMFC) and electrolyte membranes (acid electrolyte) that permeates methanol.
  • fuel cells direct methanol fuel cells - DMFC
  • electrolyte membranes acid electrolyte
  • Pt has a problem of low selectivity for reduction of oxygen in the presence of methanol, being inactivated.
  • Palladium alloys with Ni, Co, Cr [1], Fe [2], Sn [3], Mo [4], Cu [5] and Ti [6] have shown catalytic activity close to that of platinum and good tolerance to methanol. This is very important because each of the alloying elements is more available than Pd itself. However, non- precious metals are known to be unstable in acid medium and consequently do not display a long-term stability.
  • bimetallic palladium alloys comes from amorphous alloys composed of Pd and a nonmetal element (P or B) .
  • Pd96.4P3.6 alloy displays a high catalytic activity in the alkaline medium (XQ - 1.5 X 10 ⁇ 5 A cm -2 ) , however its activity in acid medium or its resistance to methanol oxidation were not evaluated [13] .
  • L. Cheng et al . disclosed another Pd-P alloy composition, PdgiPg, which exhibits an apparent catalytic activity close to Pt in acid medium, however the real catalytic activity (based on the real surface area of the catalyst) was not determined, neither its ability to the ORR in the presence of methanol [14] .
  • the method that is proposed in the present invention is also an alternative to the methods that are usually used on the preparation of catalytic material for fuel cells.
  • carbon black (XC-72CB) is impregnated by immersion into a solution containing the metal salt or complex, followed by chemical reduction, giving rise to a powder type catalyst, which is then dispersed in a Nafion solution.
  • This paste is then painted onto an electrode support, a porous and conductive material such as carbon cloth or carbon paper.
  • One of the main disadvantages of this method concerns the catalyst sintering phenomena because the catalyst particles are transported over the carbon support and coalesce.
  • Another disadvantage comes from the fact that the catalyst is usually uniformly distributed throughout the gas diffusion layer. Not all the catalyst particles are then utilized due to the lack of ionic and/or electronic contacts, resulting in a low catalyst efficiency.
  • the present invention aims to prepare a catalyst material, in the form of nanoparticles deposited on a substrate which is itself a gas diffusion layer (GDL) material, to work as cathode in low temperature fuel cells, i.e. at temperatures below 250 °C.
  • GDL gas diffusion layer
  • the catalyst particles are composed by an alloy of Pd-M, where M is a non metallic element, which can be phosphorus (P) or boron (B).
  • the alloy composition can be variable.
  • the non metal must be present in an amount ranging 10-35% at.
  • the quantification is determined on basis of EDS spectra.
  • Figure 1 is representative of an EDS spectrum of a Pd-P alloy .
  • the particles that are deposited are spherical-type particles with nanometric dimensions. Their diameter ranges from 5 to 70 ran in size, depending on the time deposition and plating solution composition. The particles size is determined by SEM and HRTEM, Figure 2 and 3, respectively.
  • the Pd-P alloys have a typical amorphous structure, as illustrated in Figure 4 by a broad peak centered at 40.1°. This peak contrasts with the well defined diffraction peaks on crystalline Pd, deposited on the carbon paper and using the electroless deposition methodology as well.
  • the amount of deposited Pd in the form of Pd-M, depends essentially on the time deposition; the lower the deposition time, the lower the amount of palladium deposited and consequently the lower is the production cost of the material. However, if the amount of palladium is too low, so is the rate of the ORR.
  • a balance between a low Pd loading and a high ORR rate (same order as Pt) is achieved with a Pd loading of approximately 0.2 mg cm -2 .
  • the Pd loading on the carbon paper is determined by atomic absorption spectroscopy (AAS) , after metal dissolution in HC1/HN0 3 (1:1) during 15-20 min. The obtained solution is then diluted with HC1 before being analyzed by AAS-
  • the catalytic material Is deposited by electroless deposition on a gas diffusion material, such as a commercial carbon paper or a commercial carbon cloth substrates.
  • a gas diffusion material such as a commercial carbon paper or a commercial carbon cloth substrates.
  • these materials are hydrophobic and not catalytic for the electroless deposition, it requires a pre-treatrnent before being immersed on the electroless solution.
  • composition of the electroless plating solution is: H 2 P0 2 " 5-50 mM, Pd 2+ 5-50 mM/ EDTA 0.3 M and 150-200 ml/L NH 3 .
  • Deposition is performed at a temperature raging 20-60 °C, with or without solution stirring. Time of deposition is variable and it determines the amount of Pd loading. Despite deposition rate is not very reproducible, a 0.2 rag cm -2 Fd loading requires more or less 10 min. After deposition the deposit is rinsed with distilled water and dried at 40 °C.
  • onset oxygen reduction potential E DnS et
  • ⁇ the current density at a constant potential
  • io the exchange current density
  • b the Tafel slope
  • the voltammetric experiments employ a three-electrode electrochemical cell and make use of the prepared catalyst material as the working electrode.
  • a Pt foil and a double-junction AgjAgCl electrode were used as the counter and reference electrodes, respectively.
  • a 0.1 M H 2 SO4 solution was used as the electrolytic solution. Prior to each electrochemical measurement the solution was saturated with 0 2 by bubbling the gas for 45 min.
  • the voltammetric conditions are:
  • the current density is expressed as i rea i and i ge0 m/ where I /EASA and I/geometric surface area.
  • I and EASA represent the current intensity and electrochemical active surface area, respectively.
  • the present invention concerns a catalytic material that comprises an alloy of palladium and a non-metal.
  • the non metal is phosphorous and boron with an atomic content ranging 10-35 %.
  • the catalytic material of this invention is preferentially in the form of spherical nanoparticles with dimensions ranging 5-70 nm, but other forms can be obtained, as for example, nanorods.
  • the present invention concerns also a process of preparation of the catalytic material that was previously described, comprising the following steps:
  • the catalyst material of this invention prepared by the process describe above exhibits a very high catalytic activity towards ORR and tolerance to methanol, so it can be used as fuel cell cathode on low and medium temperature fuel cells containing an acid electrolyte, including DMFC.
  • FIG. 2 SEM image (scanning ' electron microscopy) of a Pd-P sample (0.19 mg cm "2 of Pd; 15 % at.) deposited on carbon paper.
  • FIG. 3 HRTEM image (high resolution transmisson electron microscopy) of a Pd-P sample (0.19 mg cm -2 of Pd; 15 % at.) deposited on carbon paper.
  • Figure 4 Diffractogram of a Pd-P sample (0.73 mg cm -2 of Pd; 15 % at.) deposited on carbon paper.
  • the diffractograms of the carbon paper support and pure Pd (also deposited on this support) are included for comparison.
  • Figure 5 Linear sweep voltammogram of Pd-P sample (0.19 mg cm "2 of Pd; 15 % at.) in a 0.1 M H 2 S0 4 solution saturated with 0 2 .
  • the voltammogram of commercial Pt/C is included for comparison.
  • the density current has been normalized to the geometric surface area.
  • Figure 6 Linear sweep voltammogram of Pd-P sample (0.19 mg cm "2 of Pd; 15 % at.) in a 0.1 M H 2 S0 4 solution saturated with 0 2 .
  • the voltammog am of commercial Pt/C is included for comparison.
  • the density current is normalized to EASA.
  • Figure 7 Linear sweep voltammogram of Pd-P sample (0.19 mg cm "2 of Pd; 15 % at.) in a 0.1 M H 2 S0 4 solution saturated with 0 2 and containing or not 0.5 M MeOH. The density current has been normalized to the geometric surface area.

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

Abstract

L'invention a pour objet de préparer un catalyseur de cathode pour des piles à combustible basse et moyenne température. Ce catalyseur présente une activité catalytique aussi bonne, ou meilleure, que le Pt du commerce pour la réaction de réduction de l'oxygène (ORR) en milieu acide, une bonne tolérance au méthanol et un faible coût de production. Ce catalyseur comprend un alliage contenant un métal (Pd) et un non-métal (P ou B). Le procédé de production de l'alliage comprend le dépôt direct du catalyseur sur un substrat à couche de diffusion de gaz par un procédé chimique.
PCT/IB2010/055605 2010-07-09 2010-12-06 Catalyseurs en alliage de palladium pour cathodes de piles à combustible et leur procédé de préparation WO2012004639A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PT105193A PT105193A (pt) 2010-07-09 2010-07-09 Catalisadores de ligas de paládio para cátodos de pilhas de combustível e respectivo método de produção
PT105193 2010-07-09

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WO2012004639A1 true WO2012004639A1 (fr) 2012-01-12

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104538648A (zh) * 2014-12-10 2015-04-22 北京化工大学 一种石墨烯负载铂钴合金纳米粒子复合催化剂及其制备方法
CN110729491A (zh) * 2019-10-29 2020-01-24 福州大学 一种细化含钴阴极粉体的方法
CN113193206A (zh) * 2021-03-26 2021-07-30 南通大学 一种乙醇燃料电池阳极催化剂的制备方法
CN114284511A (zh) * 2021-12-24 2022-04-05 兰州大学 一种基于超声辅助合成直接醇类燃料电池阳极催化剂的方法

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WO2005067082A2 (fr) * 2004-01-06 2005-07-21 Ic Innovations Limited Catalyseur de palladium nanoporeux/mesoporeux
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104538648A (zh) * 2014-12-10 2015-04-22 北京化工大学 一种石墨烯负载铂钴合金纳米粒子复合催化剂及其制备方法
CN110729491A (zh) * 2019-10-29 2020-01-24 福州大学 一种细化含钴阴极粉体的方法
CN110729491B (zh) * 2019-10-29 2022-05-31 福州大学 一种细化含钴阴极粉体的方法
CN113193206A (zh) * 2021-03-26 2021-07-30 南通大学 一种乙醇燃料电池阳极催化剂的制备方法
CN114284511A (zh) * 2021-12-24 2022-04-05 兰州大学 一种基于超声辅助合成直接醇类燃料电池阳极催化剂的方法

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