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WO2010050964A1 - Quaternary alloy catalyst for fuel cell - Google Patents

Quaternary alloy catalyst for fuel cell Download PDF

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Publication number
WO2010050964A1
WO2010050964A1 PCT/US2008/081919 US2008081919W WO2010050964A1 WO 2010050964 A1 WO2010050964 A1 WO 2010050964A1 US 2008081919 W US2008081919 W US 2008081919W WO 2010050964 A1 WO2010050964 A1 WO 2010050964A1
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WO
WIPO (PCT)
Prior art keywords
mol
recited
transition metal
catalytic alloy
quaternary catalytic
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.)
Ceased
Application number
PCT/US2008/081919
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French (fr)
Inventor
Tetsuo Kawamura
Minhua Shao
Susanne M. Opalka
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.)
Toyota Motor Corp
UTC Power Corp
Original Assignee
Toyota Motor Corp
UTC Power Corp
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Priority to PCT/US2008/081919 priority Critical patent/WO2010050964A1/en
Publication of WO2010050964A1 publication Critical patent/WO2010050964A1/en
Anticipated expiration legal-status Critical
Ceased 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
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/648—Vanadium, niobium or tantalum or polonium
    • B01J23/6482—Vanadium
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • B01J35/33—Electric or magnetic properties
    • 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

  • This disclosure relates to catalytic alloys and, more particularly, to a stable, high activity quaternary alloy catalyst for use in fuel cells.
  • Fuel cells are commonly known and used for generating electric current.
  • a single fuel cell typically includes an anode catalyst layer, a cathode catalyst layer, and an electrolyte between the anode catalyst layer and the cathode catalyst layer for generating an electric current in a known electrochemical reaction between a fuel and an oxidant.
  • One problem associated with fuel cells is the operational efficiency of the catalysts.
  • chemical activity at the cathode catalyst is one parameter that controls the efficiency.
  • An indication of the chemical activity is the rate of electrochemical reduction of the oxidant at the cathode catalyst.
  • Platinum has been used for the cathode catalyst.
  • platinum is expensive and has a high over-potential for the cathodic oxygen reduction reaction.
  • platinum is not stable in the harsh environment of the fuel cell. For instance, the elevated temperature and potential cycling may cause degradation of the chemical activity of platinum over time due to particle migration and dissolution.
  • An exemplary quaternary catalytic alloy composition for use in a fuel cell includes platinum, vanadium, a transition metal M, and iridium in a molar ratio of Pt w V x M y Ir z , where 30 ⁇ w ⁇ 75 mol%, 5 ⁇ x ⁇ 50 mol%, 5 ⁇ y ⁇ 50 mol%, and 5 ⁇ z ⁇ 30 mol%, and the transition metal M is selected from cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.
  • An exemplary fuel cell includes a quaternary catalytic alloy comprising platinum, vanadium, a transition metal M, and iridium in a molar ratio of Pt w V x M y Ir z , where 30 ⁇ w ⁇ 75 mol%, 5 ⁇ x ⁇ 50 mol%, 5 ⁇ y ⁇ 50 mol%, and 5 ⁇ z ⁇ 30 mol%, and the transition metal M is selected from cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.
  • Figure 1 illustrates an example fuel cell.
  • Figure 2 illustrates an example of a supported cathode catalyst.
  • FIG. 1 illustrates selected portions of an example fuel cell 10.
  • a single fuel cell unit 12 is shown; however, it is to be understood that multiple fuel cell units 12 may be stacked in a known manner in the fuel cell 10 to generate a desired amount of electric current. It is also to be understood that this disclosure is not limited to the arrangement of the example fuel cell 10, and the concepts disclosed herein may be applied to other fuel cell arrangements.
  • the fuel cell 10 includes an electrode assembly 14 located between an anode interconnect 16 and a cathode interconnect 18.
  • the anode interconnect 16 may deliver fuel, such as hydrogen gas, to the electrode assembly 14.
  • the cathode interconnect 18 may deliver an oxidant, such as oxygen gas, to the electrode assembly 14.
  • the anode interconnect 16 and the cathode interconnect 18 are not limited to any particular structure, but may include channels or the like for delivering the reactant gases to the electrode assembly 14.
  • the electrode assembly 14 includes an anode catalyst layer 20, a cathode catalyst layer 22, and an electrolyte 24 located between the anode catalyst layer 20 and the cathode catalyst layer 22.
  • the electrolyte 24 may be any suitable type of electrolyte for conducting ions between the anode catalyst layer 20 and the cathode catalyst layer 22 in the electrochemical reaction, to generate the electric current.
  • the electrolyte 24 may be a polymer electrolyte membrane, phosphoric acid, a solid oxide electrolyte, or other type of electrolyte.
  • the hydrogen at the anode catalyst 20 disassociates into protons that are conducted through the electrolyte 24 to the cathode catalyst 22 and electrons that flow through an external circuit 26 to power a load 28, for example.
  • the electrons from the external circuit 26 combine with the protons and oxygen at the cathode catalyst 22 to form water as a product.
  • the cathode catalyst 22, and optionally also the anode catalyst 20, is a supported catalyst 40.
  • the example supported catalyst 40 is not necessarily shown to scale.
  • the supported catalyst 40 includes a quaternary catalytic alloy 42 in the form of particles 44 disposed on a carbon support material 46.
  • the particles 44 may have an average particle size of about 2-20 nanometers.
  • the support material may be carbon black or other type of conductive material, and the quaternary catalytic alloy 42 may be about 10-70 wt% of the total weight of the supported catalyst 40.
  • the quaternary catalytic alloy 42 includes a composition of platinum, vanadium, a transition metal M, and iridium in a molar ratio of Pt w V x M y Ir z .
  • the transition metal M is selected from cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.
  • the sum of w, x, y, and z equals 100 mol%.
  • the quaternary catalytic alloy 42 is highly active and stable under typical fuel cell operating conditions. For instance, vanadium and the transition metal M enhance the activity of the quaternary catalytic alloy 42 and the iridium enhances the durability of the quaternary catalytic alloy 42 under elevated temperatures and potential cycling. Thus, the quaternary catalytic alloy 42 provides a desirable balance of activity and durability while also reducing costs by reducing the amount of platinum. In a further example, a composition where 30 ⁇ w ⁇ 60 mol%, 5 ⁇ x ⁇ 20 mol%, 20 ⁇ y ⁇ 40 mol%, and 5 ⁇ z ⁇ 15 mol% provides a desirable balance of activity and durability.
  • a composition where w equals about 40 mol%, x equals about 20 mol%, y equals about 30 mol%, and z equals about 10 mol% may provide an even more desirable balance of activity and durability.
  • the term "about” as used in this description relative to compositions or other values refers to possible variation in the given value, such as normally accepted variations or tolerances.
  • the quaternary catalytic alloy compositions may include impurity elements. Additionally, the quaternary catalytic alloy compositions may include only the given elements, or the given elements and any impurities. Any elements other than the listed elements are considered to be impurities.
  • the transition metal M may be cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.
  • One composition that may be particularly useful includes cobalt as the transition metal M such that the composition is Pt w V x Co y Ir z .
  • the combination of cobalt and vanadium enhances the activity of the quaternary catalytic alloy 42.
  • the composition consists only of platinum, vanadium, cobalt, and iridium in a composition where 30 ⁇ w ⁇ 60 mol%, 5 ⁇ x ⁇ 20 mol%, 20 ⁇ y ⁇ 40 mol%, and 5 ⁇ z ⁇ 15 mol%.
  • w equals about 40 mol%
  • x equals about 20 mol%
  • y equals about 30 mol%
  • z equals about 10 mol%.
  • the supported catalyst 40 may be formed according to known methods. The following examples are based on the composition Pt w V x Co y Ir z ; however, it is to be understood that, given this description, one of ordinary skill in the art will recognize that the methods may be modified for other transition metals to meet their particular needs.
  • the supported catalyst 40 may be formed by preparing a solution from 5 grams of Ketjen Black, 7.3 mmol of IrCl 4 and 29.3 mmol chloroplatanic acid in 600 ml water by ultrasonically blending for 30 minutes. The solution is then boiled and 40 ml of 37% HCHO is added into the solution to reduce the Pt and Ir. The Pt-Ir/C products are then filtered and rinsed with distilled water.
  • the Pt-Ir/KB is dispersed in 200 ml water and ultrasonically blended for 20 minutes, and 22 mmol Co(NOs) 2 -OH 2 O and 14.6 mmol NH 4 VO 3 are dissolved into the Pt-Ir/C slurry and stirred for 10 min.
  • the slurry is then dried in a vacuum oven at 80 0 C and heat treated at 900 0 C for 60 minutes.
  • the supported catalyst 40 may be formed by preparing a solution from 1.45 mmol of Ir(CO)s and 2.9 mmol of Pt (acetylacetonate, acac) 2 , 1.45 mmol of V (acac) 2 and 1.45 mmol of Co (CO)s in 100 ml ethyl glycol with 8 mmol of oleylamine and 8 mmol of oleic acid. The mixture is then be heated to boiling for 30 min with flux. 10 ml of 10 mmol NaBH 4 solution is added into the mixture to reduce all the metals. The mixture is then precipitated using centrifugation.
  • the solid is re-dispersed in 100 ml hexane with 500 mg Ketjen Black. The slurry is then stirred overnight and allowed to dry. The solid is collected and heated in N 2 at 260 0 C for 30 minutes and then annealed at 900 0 C for 60 min.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

A quaternary catalytic alloy composition for use in a fuel cell includes platinum vanadium, a transition metal M, and iridium in a molar ratio of PtwVxMyIrz, where 30 ≤ w ≤ 75 mol%, 5 ≤ x ≤ 50 mol%, 5 ≤y ≤ 50 mol%, and 5 ≤ z ≤ 30 mol%, and the transition metal M is cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.

Description

QUATERNARY ALLOY CATALYST FOR FUEL CELL
BACKGROUND OF THE DISCLOSURE
[0001] This disclosure relates to catalytic alloys and, more particularly, to a stable, high activity quaternary alloy catalyst for use in fuel cells.
[0002] Fuel cells are commonly known and used for generating electric current. For example, a single fuel cell typically includes an anode catalyst layer, a cathode catalyst layer, and an electrolyte between the anode catalyst layer and the cathode catalyst layer for generating an electric current in a known electrochemical reaction between a fuel and an oxidant.
[0003] One problem associated with fuel cells is the operational efficiency of the catalysts. For example, chemical activity at the cathode catalyst is one parameter that controls the efficiency. An indication of the chemical activity is the rate of electrochemical reduction of the oxidant at the cathode catalyst. Platinum has been used for the cathode catalyst. However, platinum is expensive and has a high over-potential for the cathodic oxygen reduction reaction. Also, platinum is not stable in the harsh environment of the fuel cell. For instance, the elevated temperature and potential cycling may cause degradation of the chemical activity of platinum over time due to particle migration and dissolution.
[0004] One solution has been alloying the platinum with certain noble metals to increase the catalytic activity. For instance, platinum has been included in ternary alloys with iridium and another metal. Although effective, such alloys still exhibit limited stability in the elevated temperature environment of the fuel cell.
SUMMARY OF THE DISCLOSURE
[0005] An exemplary quaternary catalytic alloy composition for use in a fuel cell includes platinum, vanadium, a transition metal M, and iridium in a molar ratio of PtwVxMyIrz, where 30 < w < 75 mol%, 5 < x < 50 mol%, 5 < y < 50 mol%, and 5 < z < 30 mol%, and the transition metal M is selected from cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.
[0006] An exemplary fuel cell includes a quaternary catalytic alloy comprising platinum, vanadium, a transition metal M, and iridium in a molar ratio of PtwVxMyIrz, where 30 < w < 75 mol%, 5 < x < 50 mol%, 5 < y < 50 mol%, and 5 < z < 30 mol%, and the transition metal M is selected from cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The various features and advantages of the disclosed examples will become apparent to those skilled in the art from the following detailed description. The drawings that accompany the detailed description can be briefly described as follows.
[0008] Figure 1 illustrates an example fuel cell.
[0009] Figure 2 illustrates an example of a supported cathode catalyst.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0010] Figure 1 illustrates selected portions of an example fuel cell 10. In this example, a single fuel cell unit 12 is shown; however, it is to be understood that multiple fuel cell units 12 may be stacked in a known manner in the fuel cell 10 to generate a desired amount of electric current. It is also to be understood that this disclosure is not limited to the arrangement of the example fuel cell 10, and the concepts disclosed herein may be applied to other fuel cell arrangements.
[0011] In the illustrated example, the fuel cell 10 includes an electrode assembly 14 located between an anode interconnect 16 and a cathode interconnect 18. For instance, the anode interconnect 16 may deliver fuel, such as hydrogen gas, to the electrode assembly 14. Likewise, the cathode interconnect 18 may deliver an oxidant, such as oxygen gas, to the electrode assembly 14. In this regard, the anode interconnect 16 and the cathode interconnect 18 are not limited to any particular structure, but may include channels or the like for delivering the reactant gases to the electrode assembly 14.
[0012] The electrode assembly 14 includes an anode catalyst layer 20, a cathode catalyst layer 22, and an electrolyte 24 located between the anode catalyst layer 20 and the cathode catalyst layer 22. For example, the electrolyte 24 may be any suitable type of electrolyte for conducting ions between the anode catalyst layer 20 and the cathode catalyst layer 22 in the electrochemical reaction, to generate the electric current. In a few non-limiting examples, the electrolyte 24 may be a polymer electrolyte membrane, phosphoric acid, a solid oxide electrolyte, or other type of electrolyte.
[0013] As is generally known, the hydrogen at the anode catalyst 20 disassociates into protons that are conducted through the electrolyte 24 to the cathode catalyst 22 and electrons that flow through an external circuit 26 to power a load 28, for example. The electrons from the external circuit 26 combine with the protons and oxygen at the cathode catalyst 22 to form water as a product.
[0014] Referring to Figure 2, at least the cathode catalyst 22, and optionally also the anode catalyst 20, is a supported catalyst 40. The example supported catalyst 40 is not necessarily shown to scale. The supported catalyst 40 includes a quaternary catalytic alloy 42 in the form of particles 44 disposed on a carbon support material 46. The particles 44 may have an average particle size of about 2-20 nanometers. The support material may be carbon black or other type of conductive material, and the quaternary catalytic alloy 42 may be about 10-70 wt% of the total weight of the supported catalyst 40.
[0015] The quaternary catalytic alloy 42 includes a composition of platinum, vanadium, a transition metal M, and iridium in a molar ratio of PtwVxMyIrz. In one example, 30 < w < 75 mol%, 5 < x < 50 mol%, 5 < y < 50 mol%, and 5 < z < 30 mol%, and the transition metal M is selected from cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof. The sum of w, x, y, and z equals 100 mol%.
[0016] The quaternary catalytic alloy 42 is highly active and stable under typical fuel cell operating conditions. For instance, vanadium and the transition metal M enhance the activity of the quaternary catalytic alloy 42 and the iridium enhances the durability of the quaternary catalytic alloy 42 under elevated temperatures and potential cycling. Thus, the quaternary catalytic alloy 42 provides a desirable balance of activity and durability while also reducing costs by reducing the amount of platinum. In a further example, a composition where 30 < w < 60 mol%, 5 < x < 20 mol%, 20 < y < 40 mol%, and 5 < z < 15 mol% provides a desirable balance of activity and durability. In a further example, a composition where w equals about 40 mol%, x equals about 20 mol%, y equals about 30 mol%, and z equals about 10 mol% may provide an even more desirable balance of activity and durability. The term "about" as used in this description relative to compositions or other values refers to possible variation in the given value, such as normally accepted variations or tolerances.
[0017] In the above examples, the quaternary catalytic alloy compositions may include impurity elements. Additionally, the quaternary catalytic alloy compositions may include only the given elements, or the given elements and any impurities. Any elements other than the listed elements are considered to be impurities.
[0018] In the example compositions, the transition metal M may be cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, or combinations thereof. One composition that may be particularly useful includes cobalt as the transition metal M such that the composition is PtwVxCoyIrz. The combination of cobalt and vanadium enhances the activity of the quaternary catalytic alloy 42. In a further example, the composition consists only of platinum, vanadium, cobalt, and iridium in a composition where 30 < w < 60 mol%, 5 < x < 20 mol%, 20 < y < 40 mol%, and 5 < z < 15 mol%. In a further example, w equals about 40 mol%, x equals about 20 mol%, y equals about 30 mol%, and z equals about 10 mol%.
[0019] The supported catalyst 40 may be formed according to known methods. The following examples are based on the composition PtwVxCoyIrz; however, it is to be understood that, given this description, one of ordinary skill in the art will recognize that the methods may be modified for other transition metals to meet their particular needs.
[0020] In one example, the supported catalyst 40 may be formed by preparing a solution from 5 grams of Ketjen Black, 7.3 mmol of IrCl4 and 29.3 mmol chloroplatanic acid in 600 ml water by ultrasonically blending for 30 minutes. The solution is then boiled and 40 ml of 37% HCHO is added into the solution to reduce the Pt and Ir. The Pt-Ir/C products are then filtered and rinsed with distilled water. After drying in an oven, the Pt-Ir/KB is dispersed in 200 ml water and ultrasonically blended for 20 minutes, and 22 mmol Co(NOs)2-OH2O and 14.6 mmol NH4VO3 are dissolved into the Pt-Ir/C slurry and stirred for 10 min. The slurry is then dried in a vacuum oven at 80 0C and heat treated at 900 0C for 60 minutes.
[0021] In another example, the supported catalyst 40 may be formed by preparing a solution from 1.45 mmol of Ir(CO)s and 2.9 mmol of Pt (acetylacetonate, acac)2, 1.45 mmol of V (acac)2 and 1.45 mmol of Co (CO)s in 100 ml ethyl glycol with 8 mmol of oleylamine and 8 mmol of oleic acid. The mixture is then be heated to boiling for 30 min with flux. 10 ml of 10 mmol NaBH4 solution is added into the mixture to reduce all the metals. The mixture is then precipitated using centrifugation. The solid is re-dispersed in 100 ml hexane with 500 mg Ketjen Black. The slurry is then stirred overnight and allowed to dry. The solid is collected and heated in N2 at 260 0C for 30 minutes and then annealed at 900 0C for 60 min.
[0022] Although a combination of features is shown in the illustrated examples, not all of them need to be combined to realize the benefits of various embodiments of this disclosure. In other words, a system designed according to an embodiment of this disclosure will not necessarily include all of the features shown in any one of the Figures or all of the portions schematically shown in the Figures. Moreover, selected features of one example embodiment may be combined with selected features of other example embodiments.
[0023] The preceding description is exemplary rather than limiting in nature. Variations and modifications to the disclosed examples may become apparent to those skilled in the art that do not necessarily depart from the essence of this disclosure. The scope of legal protection given to this disclosure can be determined by studying the following claims.

Claims

CLAIMSWhat is claimed is:
1. A quaternary catalytic alloy composition for use in a fuel cell, comprising: platinum (Pt), vanadium (V), a transition metal (M), and iridium (Ir) in a molar ratio of Ptw VxMyIrz, where 30 < w < 75 mol%, 5 < x < 50 mol%, 5 < y < 50 mol%, and 5 < z < 30 mol%, and the transition metal (M) is selected from a group consisting of cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, and combinations thereof.
2. The quaternary catalytic alloy composition as recited in claim 1, wherein the transition metal (M) is cobalt.
3. The quaternary catalytic alloy composition as recited in claim 1, where 30 < w < 60 mol%, 5 < x < 20 mol%, 20 < y < 40 mol%, and 5 < z < 15 mol%.
4. The quaternary catalytic alloy composition as recited in claim 1, wherein w equals about 40 mol%, x equals about 20 mol%, y equals about 30 mol%, and z equals about 10 mol%.
5. The quaternary catalytic alloy composition as recited in claim 1, wherein the transition metal (M) is titanium.
6. The quaternary catalytic alloy composition as recited in claim 1, wherein the transition metal (M) is chromium.
7. The quaternary catalytic alloy composition as recited in claim 1, wherein the transition metal (M) is manganese.
8. The quaternary catalytic alloy composition as recited in claim 1, wherein the transition metal (M) is iron.
9. The quaternary catalytic alloy composition as recited in claim 1, wherein the transition metal (M) is nickel.
10. The quaternary catalytic alloy composition as recited in claim 1, wherein the transition metal (M) is copper.
11. The quaternary catalytic alloy composition as recited in claim 1, wherein the transition metal (M) is zinc.
12. The quaternary catalytic alloy composition as recited in claim 1, wherein the transition metal (M) is molybdenum.
13. The quaternary catalytic alloy composition as recited in claim 1, wherein the transition metal (M) is tungsten.
14. A quaternary catalytic alloy composition for use in a fuel cell, consisting of: platinum (Pt), vanadium (V), cobalt (Co), and iridium (Ir) in a molar ratio of
PtwVxCoyIrz, where 30 < w < 60 mol%, 5 < x < 20 mol%, 20 < y < 40 mol%, and 5 < z < 15 mol%.
15. The quaternary catalytic alloy composition as recited in claim 14, wherein w equals about 40 mol%, x equals about 20 mol%, y equals about 30 mol%, and z equals about 10 mol%.
16. A fuel cell comprising: a quaternary catalytic alloy comprising platinum (Pt), vanadium (V), a transition metal (M), and iridium (Ir) in a molar ratio of PtwVxMyIrz, where 30 < w < 75 mol%, 5 < x < 50 mol%, 5 < y < 50 mol%, and 5 < z < 30 mol%, and the transition metal (M) is selected from a group consisting of cobalt, titanium, chromium, manganese, iron, nickel, copper, zinc, molybdenum, tungsten, and combinations thereof.
17. The fuel cell as recited in claim 16, wherein the quaternary catalytic alloy is disposed as particles on a carbon support material.
18. The fuel cell as recited in claim 17, wherein the quaternary catalytic alloy comprises about 10 - 70 wt% of a combined weight of the quaternary catalytic alloy and carbon support material.
19. The fuel cell as recited in claim 17, wherein the particles have an average particle size of about 2-20 nanometers.
20. The fuel cell as recited in claim 16, further comprising an electrolyte between a cathode catalyst and an anode catalyst, and the cathode catalyst includes the quaternary catalytic alloy.
21. The fuel cell as recited in claim 16, wherein the transition metal (M) is cobalt.
PCT/US2008/081919 2008-10-31 2008-10-31 Quaternary alloy catalyst for fuel cell Ceased WO2010050964A1 (en)

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