GB2485005A - Fuel cell catalyst - Google Patents

Fuel cell catalyst Download PDF

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Publication number
GB2485005A
GB2485005A GB1106634.7A GB201106634A GB2485005A GB 2485005 A GB2485005 A GB 2485005A GB 201106634 A GB201106634 A GB 201106634A GB 2485005 A GB2485005 A GB 2485005A
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GB
United Kingdom
Prior art keywords
oxide
core
catalyst
support
shell
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
GB1106634.7A
Other versions
GB201106634D0 (en
Inventor
Stephen A Campbell
Darija Susac
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mercedes Benz Group AG
Ford Motor Co
Original Assignee
Daimler AG
Ford Motor Co
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 Daimler AG, Ford Motor Co filed Critical Daimler AG
Priority to GB1106634.7A priority Critical patent/GB2485005A/en
Publication of GB201106634D0 publication Critical patent/GB201106634D0/en
Publication of GB2485005A publication Critical patent/GB2485005A/en
Withdrawn legal-status Critical Current

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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
    • H01M4/925—Metals of platinum group 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
    • 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
    • B01J23/42—Platinum
    • 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
    • B01J23/44—Palladium
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • 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
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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

Abstract

A fuel cell catalyst comprises a support of an oxide or a doped oxide of a metal M, a PdxM core catalyst deposited directly upon the support where x is greater than 1, and a Pt shell catalyst deposited directly upon the PdxM core catalyst. The metal M may be Nb, Ta, or Zr. The support may comprise NbO2 or NbMyOz, where y is less than 1 and z is greater than or equal to 2.

Description

A coreIsheU catalyst for a fuel cdl with enhanced oxygen reduction activity
Field of the invention
The present invention relates to catalysts for solid polymer electrolyte fuel cells and particularly to fuel cells intended for automotive applications.
Background
The current state of the ai for cathode catalysts in solid polymer electrolyte fuel cells includes platinum, or an alloy containing platinum supported on a conductive support (usually carbon) to maintain a high dispc:rsion and activity for oxygen reduction. To promote commercial viability it has become necessary to enhance the activity and durability of these catalysts. Degradation of the catalyst during normal operation involves dissolution of the metals involved and irreversible oxidation of the support material.
There are reports in the literature of the addition of oxides to catalysts (Sasaki et al; Phys. Chem. Chem. Phys. 10 (2008) 159-167) and the formation of core-shell metal particle structures to enhance activity (Sasaki et al; Eicctrochim. Acta 55 (2010) 2645-2652). In the former, the addition of the oxide is reported to enhance performance by interaction of the Pt with the oxide so that the adsorption of OH on the Pt surface is diminished and leads to enhanced oxygen reduction kinetics, TIre interaction of the Pt wrth the oxide also stabilizes the Pt so that the catalyst is more durable. in the latter, the lattice mismatch between the core and the monolayer shell compresses the Pt monolayer, modifying the d-hand electronic structure of that monolayer which reduces the adsorption of 011 and enhances the oxygen reduction kinetics. The issue of metal dissolution, especially in the case of monolayer Pt shells on other metal cores, still remains and despite improvements for carbon stability by graphitization, the catalytic oxidation of the carbon may he slowed hut not stopped. The requirement for a high activity, durable cathode catalyst remains as an obstacle to the comiriereialization of fuel cells, especially for automotive applications.
Summary
A fuel cell catalyst is described which comprises a support of an oxide or a dopcd ox ide of a metal M, a PdXM core catalyst deposited directly upon the support, and a Pt shell catalyst deposited directly upon the Pd,JvI core catalyst. The oxide may comprise a metal M where M is Nb, Ta, or Zr. This catalyst combines the high oxygen reduction activity of a core/shell catalyst with the stabilny and cnhanccd activity of a strong metal support interaction between the core catalyst and the oxide support.
Brief description of t:hc drawings
Fig. I shows the current ifiate of the art for a PdIPt core/shell nanoparticic catalyst dispersed upon a carbon support.
Fig. 2 shows two embodiments of the invention herein dtscioscd. (a) A ikt3t\b core Pt shell particle interacting with a conductive NbC)2 support, and (h) the same nanoparnclc mteracting with a doped.
conductive niobium oxide support.
Detailed description
The aim of this invention is to derive the benents of strong mctaisupport in1eraeflon between the metal catalyst and an oxide (for enhanced performance and durability) with the benefits of a core / shell catalyst structure (for enhanced performance). The interaction of the core with the oxide substrate provides a stabilization of the core whilst furthe:r enhancing the oxygen reduction kinetics of the Pt shell. To this end this invention discloses a core/shell catalytic particle interacting with the surfirce of an oxide. The oxide may be of niobium, tantal urn or zrcomurn.
in a first embodiment of the invention, a palladium nanoparticle is deposited upon a conductive NbC')2 oxide and heat treated in a reducing atmosphere such that it interacts strongly with the surface of the oxide. forming a Pd3Nb intermetailic, Subsequently, a platinum shell comprising between one and twenty ruonolayers, preferably between one a five ruonolayers, i.s deposited upon the palladium alloy core so that the core is completely encapsulated in platinum. The resulting catalytic particle is nOt soherical or eubo'.
octahedral bu.t interacts strongly with the oxide surface. The interaction with the oxide and the formation of a niobium alloy core imparts greater stability to the core/shell particle and enhanced activity for oxygen reduction, especially in the presence of poisons such as small organic molecules and carbon monoxide It is desirable that the core/shell particle size he <lOrun, preferably <5nni to ensure a high activity and the surface area of the oxide should be >20m2g', preib.rably >3OnCg'. The oxide may be crystalline or nanocrystalline or amorphous and may, additionally, he dispersed upon an inert, electronically conductive, high surface area material such as a carbon black for example Kctjen black, Cabot BP2OtJ or similar, or graphene sheets, in a second embodiment of the invention, the Nb02 oxide may he replaced wrth a doped niobium oxi Ic with electronic conductivity due to the dopant n�^etal which may he one or more selected from Pd, Pt, Os, Ru, Ni, Co, Ir, V. Mn, Co. The alloy core is formed on the oxide support in the same way and may incorporate elements from the dopant as well as niobium in to the Pd. The lb shell is added subsequently as described in the previous embodiment. The oxide may be crystalline or nanocrystalline or amorphous uDd: inv be dspe edupo3 ii: ;tefl. etec en.ieaU.v eoiduee.c b!.H *ee. ai:i nhon hhLk I L\flWk lS.t14fl %Ftj e ilk I 1 Uk UC'nt s.tl)bdbfl.flt' nid j3'R ililliN cit tik pi i..\. fl fiP LPUci1 13"\ c h... i.h'il fl iid ckseflhd. h ivi1 he tntdcrstood 1 earse. that the 3nvenuotI i net tUPLtCd theretO *WX nlodi..UcaHun flU b mal t 1hc.. 4ii1 in tb... irt Skill U U U K N3t nct.4N ç till de'.ilr rci{k ii Ut' 1a h3Iu it U JOIk°UHU h.dU1 ih\ \UIJI nck it P. 1 L tc 1K ad WUIUU..The purview and tieope oFth elahnsapptnnkd hereto.. IC)
GB1106634.7A 2011-04-20 2011-04-20 Fuel cell catalyst Withdrawn GB2485005A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB1106634.7A GB2485005A (en) 2011-04-20 2011-04-20 Fuel cell catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB1106634.7A GB2485005A (en) 2011-04-20 2011-04-20 Fuel cell catalyst

Publications (2)

Publication Number Publication Date
GB201106634D0 GB201106634D0 (en) 2011-06-01
GB2485005A true GB2485005A (en) 2012-05-02

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Family Applications (1)

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GB1106634.7A Withdrawn GB2485005A (en) 2011-04-20 2011-04-20 Fuel cell catalyst

Country Status (1)

Country Link
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060134505A1 (en) * 2004-12-22 2006-06-22 Wang Jia X Hydrogen absorption induced metal deposition on palladium and palladium-alloy particles

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060134505A1 (en) * 2004-12-22 2006-06-22 Wang Jia X Hydrogen absorption induced metal deposition on palladium and palladium-alloy particles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Sasaki et al., Phys. Chem. Chem. Phys., (2008), 10, 159-167 *

Also Published As

Publication number Publication date
GB201106634D0 (en) 2011-06-01

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