Patent Publication Number: US-7906251-B2

Title: Oxygen-reducing catalyst layer

Description:
This invention was made with U.S. Government support under Cooperative Agreement DE-FC36-03GO13106 awarded by the Department of Energy. The U.S. Government has certain rights in this invention. 
    
    
     CROSS-REFERENCE TO RELATED APPLICATION(S) 
     Reference is hereby made to co-pending patent application Ser. No. 11/379,518 filed on even date, entitled “METHOD FOR MAKING OXYGEN-REDUCING CATALYST LAYERS”. 
     FIELD OF THE INVENTION 
     The present invention relates to membrane electrode assemblies for use in electrochemical devices, such as fuel cells. In particular, the present invention relates to catalyst layers for use in membrane electrode assemblies. 
     BACKGROUND OF THE INVENTION 
     Fuel cells are electrochemical devices that produce usable electricity by the catalyzed combination of a fuel such as hydrogen and an oxidant such as oxygen. In contrast to conventional power plants, such as internal combustion generators, fuel cells do not utilize combustion. As such, fuel cells produce little hazardous effluent. Fuel cells convert hydrogen fuel and oxygen directly into electricity, and can be operated at higher efficiencies compared to internal combustion generators. 
     A fuel cell such as a proton exchange membrane (PEM) fuel cell typically contains a membrane electrode assembly (MEA), formed by an electrolyte membrane disposed between a pair of catalyst layers, which are correspondingly disposed between a pair of gas diffusion layers. The respective sides of the electrolyte membrane are referred to as an anode portion and a cathode portion. In a typical PEM fuel cell, hydrogen fuel is introduced into the anode portion, where the hydrogen reacts and separates into protons and electrons. The electrolyte membrane transports the protons to the cathode portion, while allowing a current of electrons to flow through an external circuit to the cathode portion to provide power. Oxygen is introduced into the cathode portion and reacts with the protons and electrons to form water and heat. 
     A common obstacle in the commercial application of PEM fuel cells is the performance of the catalyst layers. Despite its cost, platinum is currently the material of choice for catalyst layers. However, to achieve desirable operation voltages, large amounts of platinum are required for the catalyst layers, which increases material costs. Additionally, at high voltages, platinum may react with water and/or oxygen, thereby producing an oxide layer that inhibits its catalytic activity in the oxygen reduction reaction. As such, there is a need for alternative catalyst materials that provide advantages in terms of cost, performance, and durability. 
     BRIEF SUMMARY OF THE INVENTION 
     The present invention relates to an oxygen-reducing catalyst layer that includes a thermally stable substrate and a catalytic material film disposed on the thermally stable substrate. The catalytic material film includes carbon, nitrogen, and a transition metal selected from the group consisting of iron, cobalt, and combinations thereof. The oxygen-reducing catalyst layer exhibits good catalytic activity and is corrosion resistant. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a sectional view of an oxygen-reducing catalyst layer of the present invention. 
         FIG. 2  is a flow diagram of a method for making an oxygen-reducing catalyst layer of the present invention. 
         FIG. 3A  is a schematic illustration of a physical vapor deposition system that is suitable for use with the method for making an oxygen-reducing catalyst layer of the present invention. 
         FIG. 3B  is a schematic illustration of an alternative physical vapor deposition system that is suitable for use with the method for making an oxygen-reducing catalyst layer of the present invention. 
         FIG. 4  is a flow diagram of an alternative method for making an oxygen-reducing catalyst layer of the present invention. 
         FIG. 5  is a schematic illustration of an MEA in use with an external electrical circuit, where the MEA includes an oxygen-reducing catalyst layer of the present invention. 
         FIG. 6  is a graph of polarization curves for MEAs containing oxygen-reducing catalyst layers of the present invention, and comparative MEAs. 
         FIG. 7  is a graph of AC impedances for MEAs containing oxygen-reducing catalyst layers of the present invention and comparative MEAs. 
         FIG. 8  is a graph of polarization curves for MEAs containing oxygen-reducing catalyst layers of the present invention and a comparative MEA, where the oxygen-reducing catalyst layers were formed with physical vapor depositions and thermal treatments performed in a substantially simultaneous manner. 
         FIG. 9  is a graph showing a rotating disk electrode measurements of an oxygen-reducing catalyst layer of the present invention. 
         FIGS. 10A-10C  are graphs showing rotating disk electrode measurements of additional oxygen-reducing catalyst layer of the present inventions. 
         FIG. 11  is a graph of polarization curves for MEAs containing additional oxygen-reducing catalyst layers of the present invention. 
     
    
    
     While the above-identified drawing figures set forth several embodiments of the invention, other embodiments are also contemplated, as noted in the discussion. In all cases, this disclosure presents the invention by way of representation and not limitation. It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art, which fall within the scope and spirit of the principles of the invention. The figures may not be drawn to scale. Like reference numbers have been used throughout the figures to denote like parts. 
     DETAILED DESCRIPTION 
       FIG. 1  is a sectional view of catalyst layer  10  of the present invention. Catalyst layer  10  includes substrate  12  and film  14 , and is suitable for use in a PEM fuel cell (e.g., a cathode catalyst layer in an MEA). Substrate  12  includes surface  16 , where film  14  is disposed on surface  16 . Film  14  compositionally includes catalyst material that is substantially free of platinum, and as discussed below, is formed by a combination of physical vapor deposition (PVD) processing and thermal treatment. As a result, catalyst layer  10  exhibits good catalytic activity for reducing oxygen while also being substantially free of platinum, which is defined herein to mean about 5 micrograms/centimeter 2  or less of platinum in catalyst layer  10 . 
       FIG. 2  is a flow diagram of method  18  for making catalyst layer  10 , and includes steps  20 - 28 . Method  18  initially involves generating a “first processing environment” in a physical vapor deposition (PVD) system (step  20 ), where the PVD system includes a carbon target and a transition metal target that is substantially free of platinum. The first processing environment is generated by evacuating the PVD system to a reduced pressure (e.g., about 1×10 −5  Torr or less), and then introducing a gas until an operating pressure is reached. Examples of suitable operating pressures for the first processing environment range from about 0.5 milliTorr to about 5 milliTorr. 
     Examples of suitable gases for the first processing environment include nitrogen-containing gases, oxygen, water vapor, hydrogen, argon, and combinations thereof. Examples of particularly suitable gases for the first processing environment include nitrogen-containing gases, such as nitrogen, ammonia, nitrogen-containing volatile organic compounds (e.g., pyridine, acetonitrile, pyrrole, pyrrolidine, and quinoline) and combinations thereof. 
     Substrate  12  is then passed through the PVD system (step  22 ), thereby exposing substrate  12  to the first processing environment. Examples of suitable materials for substrate  12  include nanostructured thin film substrates (e.g., substrates disclosed in Parsonage et al., U.S. Pat. No. 5,338,430, and in Debe, U.S. Pat. Nos. 4,812,352 and 5,039,561), microstructured thin film substrates (e.g., substrates disclosed in Spiewak et al., U.S. Pat. No. 6,136,412), carbon-containing substrates, carbon-containing woven fabrics, carbon-containing non-woven fabrics, titanium suboxide ceramics (e.g., ceramics commercially available under the trade designation “EBONEX” from Ebonex Corp., Melvindale, Mich.), nano-tin oxide films, nano-titanium oxide films, non-film-based carbon-containing particles and powders, carbon-containing fibers, and combinations thereof. 
     Such materials are thermally stable to withstand the high temperatures of the subsequent thermal treatment. As used herein, the term “thermally stable” refers to the ability of a material to withstand a temperature of at least about 350° C., and more desirably of at least about 500° C., for a duration of up to two hours with substantially no degradation. 
     The PVD system then deposits a catalytic material onto substrate  12  via generating atoms in the vapor phase by a physical process (e.g., sputtering and cathodic arc) in the first processing environment (step  24 ). For example, during a sputtering process, a field is applied to gas of the first processing environment, which creates a self-sustaining plasma of ionized atoms. The ionized atoms collide with the carbon target and the transition metal target, thereby dislodging carbon atoms and transition metal atoms. The dislodged atoms then travel toward substrate  12 , where they condense along with gas atoms. This provides film  14  of catalytic material on surface  16  of substrate  12 . In an alternative embodiment, the carbon and transition metal depositions may be carried out sequentially in two separate systems. 
     In embodiments where substrate  12  is derived from powders or particles, the powders or particles may be moved by agitation during the PVD process. An example of a suitable agitation process is described in Brey et al., U.S. Publication No. 2005/0095189. The resulting catalytic material-coated powders or particles are further activated as described herein for planar substrates and films. 
     As discussed above, the transition metal target is substantially free of platinum. Moreover, in one embodiment, the transition metal target is also substantially free of all precious metals, such as ruthenium, rhodium, palladium, osmium, iridium, platinum, gold, and silver. Precious materials have high material costs, and are required in large amounts to achieve desirable operation voltages and currents. In comparison, examples of suitable transition metals for the transition metal target include iron, cobalt, and combinations thereof. These suitable transition materials are less expensive than precious metals, thereby reducing material costs during manufacturing. 
     Because film  14  is formed by the condensation of the carbon atoms, the ionized atoms, and the transition metal atoms on substrate  12 , the catalytic material compositionally includes carbon, the transition metal, and the gas atoms deposited (e.g., nitrogen). Accordingly, the catalytic material of film  14  is also substantially free of platinum (and in one embodiment, is also free of all precious metals). An example of a particularly suitable composition of the catalytic material of film  14  may be represented by the formula C 1-x-y —N x -M y  (x+y&lt;1) where M y  is a non-platinum transition metal, such as iron, cobalt, and combinations thereof. 
     Examples of suitable atomic percentages of carbon in the catalytic material of film  14  range from about 50.0% to about 99.8%, with particularly suitable atomic percentages of carbon ranging from about 80.0% to about 95.0%. Examples of suitable atomic percentages of nitrogen in the catalytic material of film  14  range from about 0.1% to about 45.0%, with particularly suitable atomic percentages of carbon ranging from about 4.0% to about 20.0%. Examples of suitable atomic percentages of the transition metal in the catalytic material of film  14  range from about 0.01% to about 15.0%, with particularly suitable atomic percentages of carbon ranging from about 2.0% to about 10.0%. 
     PVD processing typically deposits thin layers of materials during a single pass. With respect to the current invention, the thickness of deposited film  14  may vary based on the PVD parameters, such as power settings, the composition and concentration of the gas in the first processing environment, and the line speed of substrate  12 . Therefore, to increase the thickness of deposited film  14 , substrate  12  may pass through the PVD system in multiple cycles (as represented by phantom arrow  25 ) until a suitable thickness of film  14  is obtained. Accordingly, examples of suitable thicknesses for film  14  range from about 10 nanometers to about 5,000 nanometers, with particularly suitable thicknesses ranging from about 100 nanometers to about 500 nanometers planar equivalent. 
     Once film  14  is deposited onto substrate  12 , the resulting coated substrate (referred to herein as  12 ′) is then placed in a thermal treatment system, and a second processing environment is generated in the thermal treatment system (step  26 ). The thermal treatment system may be any type of suitable heating system, such as a convection oven or a quartz-tube furnace. As discussed below, in one embodiment, the thermal treatment system is a heating element disposed in the PVD system. This allows the PVD processing (step  24 ) and the thermal treatment (step  28 , discussed below) to be performed substantially simultaneously in a single apparatus (as shown below in  FIG. 4 ). 
     The second processing environment is generated by introducing a treatment gas into the thermal treatment system to substantially purge the residual gases. Examples of suitable and particularly suitable treatment gases for the second processing environment include the suitable and particularly suitable gases discussed above for the first processing environment. It is believed that nitrogen atoms in the catalytic material increases the catalytic activity of catalyst layer  10 . Therefore, at least one of the first processing environment and the second processing environment includes a nitrogen-containing gas. Accordingly, processing environments including nitrogen-containing gases may be generated during either the PVD process or the thermal treatment. In one embodiment, processing environments including nitrogen-containing gases are generated during both the PVD process and the thermal treatment. 
     Once the second processing environment is generated, the catalytic material of film  14  is then thermally treated while in the second processing environment (step  28 ). The thermal treatment may be performed with a variety of thermal profiles and/or in multiple steps. For example, the temperature may be ramped up at a given rate (e.g., 6° C./minute) until a processing temperature is reached, and then held at the processing temperature for a desired duration (e.g., 15 minutes). Examples of suitable processing temperatures include temperatures of at least about 350° C., with even more suitable processing temperatures including temperatures of at least about 600° C., and with yet even more suitable processing temperatures including temperatures of at least about 900° C. 
     The composition of the gas employed for the second processing environment may also be changed during the thermal treatment process, providing two or more steps. For example, a processing environment including a first gas composition of ammonia and hydrogen can be used for an initial thermal treatment step (e.g., heating to temperatures of about 350° C. to about 600° C.), and a second gas composition of ammonia and nitrogen can be used for a second thermal treatment step (e.g., heating to about 600° C.). 
     Once the thermal treatment is complete, the resulting catalyst layer  10  may then be removed from the thermal treatment system for use in PEM fuel cells. The combination of the PVD processing and the thermal treatment allows catalyst layer  10  to exhibit good catalytic activity in reducing oxygen. Examples of suitable oxygen-reduction catalytic activities for catalyst layer  10  include at least about 0.02 milliamps/centimeter 2  (mA/cm 2 ) at 0.6 volts versus a reversible hydrogen electrode (RHE), with particularly suitable oxygen-reduction catalytic activities for catalyst layer  10  including at least about 0.05 mA/cm 2 . 
     Additionally, the above-discussed suitable atomic percentages for the catalytic material of film  14  allow catalyst layer  10  to be corrosion resistant for use in acidic environments (e.g., fuel cells). As used herein, the term “corrosion resistant” refers to the ability of catalyst layer  10  to retain at least the above-discussed suitable atomic percentages of carbon, nitrogen, and the transition metal after exposure to a 0.5-molar solution of sulfuric acid (H 2 SO 4 ) for at least one week. Moreover, because the catalytic material is substantially free of platinum, and in one embodiment, is substantially free of precious metals, the material costs of catalyst layer  10  are reduced. 
       FIGS. 3A and 3B  are schematic views of PVD systems  30   a  and  30   b , respectively, which are alternative systems for physical vapor depositing the catalytic material onto substrate  12 , pursuant to step  24  of method  18  (shown above in  FIG. 2 ). As shown in  FIG. 3A , PVD system  30   a  includes chamber  32 , supply rollers  34  and  36 , support wheel  38 , retrieval rollers  40  and  42 , carbon target  44 , and transition metal target  46 . Examples of suitable systems for PVD system  30   a  include DC magnetron sputtering system and pulsed-cathodic arc devices disclosed in Selifanov et al., U.S. Pat. Nos. 5,643,343 and 5,711,773, which are modified to include carbon target  44  and transition metal target  46 . 
     Chamber  32  is a PVD chamber in which the first processing environment is generated, pursuant to step  20  of method  18  (shown above in  FIG. 2 ). Supply rollers  34  and  36 , support wheel  38 , and retrieval rollers  40  and  42  are rollers than provide a web path for substrate  12  during the PVD processing. Carbon target  44  and transition metal target  46  are disposed adjacent support wheel  38  for respectively physical vapor depositing carbon atoms and transition metal atoms onto substrate  12  as substrate  12  rotates around support wheel  38  (in a clock-wise direction in  FIG. 3A ). 
     As further shown in  FIG. 3A , carbon target  44  is located upstream from transition metal target  46 . As a result, carbon target  44  deposits carbon atoms onto substrate  12  before transition metal target  46  deposits transition metal atoms. As substrate  12  passes under carbon target  44 , the dislodged carbon atoms travel toward substrate  12 , where they condense along with ionized atoms. Subsequently, as substrate  12  then passes under transition metal target  46 , the dislodged transition metal atoms travel toward substrate  12 , where they condense along with ionized nitrogen atoms, on top of the previously condensed carbon/nitrogen atoms. 
     This two-step deposition process generally provides two layers for film  14 , where the bottom layer disposed on surface  16  of substrate  12  generally includes carbon and gas atoms (e.g., nitrogen), and the top layer generally includes the transition metal and gas atoms (e.g., nitrogen). It is noted, however, that a substantial amount of intermixing occurs between the top layer and the bottom layer of film  14 . Additionally, as discussed above, the two-step deposition process may be performed multiple times to increase the amount of catalytic material deposited onto substrate  12 . After the PVD processing, the resulting coated substrate  12 ′ is then received at retrieval roller  42  for transport to the thermal treatment system (not shown). 
     In an alternative embodiment in which substrate  12  is provided as carbon particles, powders, or fibers, substrate  12  may function as a carbon target, thereby precluding the need for carbon target  44 . In this embodiment, the ionized gas atoms dislodge carbon atoms from substrate  12 , which condense on surface  16  with the transition metal atoms and ionized gas atoms, thereby forming film  14 . 
     As shown in  FIG. 3B , PVD system  30   b  includes the same components as PVD system  30   a , and generally operates in the same manner, except that carbon target  44  and transition metal target  46  are replaced with composite cathode  48 . Composite cathode  48  is a single component that includes the carbon target and the transition metal target, thereby depositing the carbon atoms and the transition metal atoms onto substrate  12  in a substantially simultaneous manner. In this embodiment, during the PVD process, the dislodged carbon atoms and transition metal atoms travel toward substrate  12  substantially simultaneously, where they condense along with ionized nitrogen atoms. As a result, film  14  is a single layer that includes a substantially homogenous mixture of carbon, nitrogen, and the transition metal. 
     An example of a suitable arrangement for composite cathode  48  includes a graphite-carbon target that contains drilled holes for the insertion of transition metal wires. In this embodiment, the transition metal target is actually made up of a plurality sub-targets of the transition metal wires. The relative surface areas of the graphite-carbon target and the transition metal wires will generally dictate the ratios of carbon-to-transition metal that are deposited. For example, composite cathode  48  may formed from a carbon/graphite cylinder. Holes are then drilled into the cross-sectional surface of the cylinder and wires of the transition metal are then secured in the drilled holes. 
     Examples of suitable carbon/graphite cylinders include graphite cathodes commercially available under the trade designation “FRAGE SFG2” from Poco Graphite, Decatur, Tex. Examples of suitable wires of the transition metal include iron wires commercially available from Alpha-Aesar, Ward Hill, Mass. Suitable dimensions for composite cathode  48  include a 33-millimeter diameter carbon/graphite cylinder, which is interpenetrated with a number of wires of the transition metal (e.g., 25-50 wires), each of which are 1-centimeter in length, and 1-2 millimeter diameters. 
     An example of another suitable arrangement for composite cathode  48  includes a mixed target, in which a carbon target is doped with the transition metal. For example carbon particles and transition metal particles may be hot pressed together to create a mixed target. This allows the carbon atoms and transition metal atoms to travel toward substrate  12  substantially simultaneously. 
       FIG. 4  is a flow diagram of method  50 , which is an alternative to method  18 , shown above in  FIG. 2 . As shown in  FIG. 4 , method  50  includes steps  52 - 56 , and initially involves generating a processing environment in the PVD system (e.g., PVD system  30   a  or  30   b ) (step  52 ). The processing environment is generated in the same manner as discussed above in step  22  of method  18  for the first processing environment (shown above in  FIG. 2 ). 
     In the embodiment shown in  FIG. 4 , the PVD system also includes a heating element (not shown in  FIG. 3A  or  3 B) to thermally treat the catalytic material during the PVD process. An example of a suitable heating element includes a heating plate that substrate  12  passes over (or is placed on for a non-continuous process). The heating plate conductively heats substrate  12 , thereby thermally treating the catalytic material as it is deposited. Examples of suitable processing temperatures for the heating element include temperatures of at least about 350° C., with even more suitable processing temperatures including temperatures of at least about 600° C. 
     Once the processing environment is generated, substrate  12  is passed through the PVD system (step  54 ), thereby exposing substrate  12  to the processing environment and the heating element. Substrate  12  is desirably exposed to the heating element for a sufficient duration to heat substrate  12  to the processing temperature. The PVD system then deposits catalytic material onto substrate  12  via a PVD process. This occurs while substrate  12  is disposed in the processing environment, and while the heating element thermally treats the deposited catalytic material (step  56 ). As a result, the PVD process and the thermal treatment are performed in a substantially simultaneous manner, which reduces the time required to manufacture catalyst layer  10 . 
     After the combined PVD processing/thermal treatment, catalyst layer  10  may be removed from the PVD system for subsequent use in PEM fuel cells. The resulting catalyst layer  10  formed pursuant to method  50  also exhibits good catalytic activity for reducing oxygen, is corrosion resistant, and is substantially free of platinum and/or precious metals, as discussed above. 
     In the embodiment of the present invention wherein particles or powders are used as the substrate for PVD deposition of the catalyst material, the thermally processed, PVD-treated particles or powders can be fashioned into a catalyst layer for use in a fuel cell through means known in the art. For example, the particles of powder can be mixed with an electrolytic material, such as a aqueous Nafion dispersion, to form an ink. This ink is thereafter deposited onto a membrane or a gas diffusion layer (GDL). If the material is deposited onto the GDL, the GDL is placed in contact with the membrane.) 
       FIG. 5  is a schematic illustration of MEA  58  in use with external electrical circuit  60 , where MEA  58  includes catalyst layer  10  formed pursuant to a method of the present invention (e.g., methods  20  and  50 ). MEA  58  is suitable for use in electrochemical cells, such as PEM fuel cells, and further includes anode portion  62 , cathode portion  64 , electrolyte membrane  66 , anode catalyst layer  68 , and gas diffusion layers  70  and  72 . Anode portion  62  and cathode portion  64  generally refer to the anode and cathode sides of MEA  58 . 
     Electrolyte membrane  66  may be any suitable ion-conductive membrane, such as a PEM. Examples of suitable materials for electrolyte membrane  66  include acid-functional fluoropolymers, such as copolymers of tetrafluoroethylene and one or more fluorinated, acid-functional comonomers. Examples of suitable commercially available materials include fluoropolymers under the trade designations “NAFION” from DuPont Chemicals, Wilmington, Del. 
     Catalyst layer  10  is a cathode catalyst layer disposed between electrolyte membrane  66  and gas diffusion layer  72 , where substrate  12  is in contact with gas diffusion layer  72 , and film  14  is in contact with electrolyte membrane  66 . In one embodiment, substrate  12  serves as gas diffusion layer  72 . During the assembly of MEA  50 , film  14  of catalyst layer  10  is positioned in contact with electrolyte membrane  66  such that substrate  12  contacts gas diffusion layer  72 . This provides conductive contact between electrolyte membrane  66  and gas diffusion layer  72 . In one embodiment, the catalytic activity of catalyst layer  10  is increased by acid washing prior to assembly in MEA  50 , which removes excess metal. 
     Anode catalyst layer  68  is disposed between electrolyte membrane  66  and gas diffusion layer  70 , where gas diffusion layer  70  is located at anode portion  62  of MEA  58 . Gas diffusion layers  70  and  72  may each be any suitable electrically conductive porous substrate, such as carbon fiber constructions (e.g., woven and non-woven carbon fiber constructions). Gas diffusion layers  70  and  72  may also be treated to increase or impart hydrophobic properties. 
     During operation of MEA  58 , hydrogen fuel (H 2 ) is introduced into gas diffusion layer  70  at anode portion  62 . MEA  58  may alternatively use other fuel sources, such as methanol, ethanol, formic acid, and reformed gases. The fuel passes through gas diffusion layer  70  and over anode catalyst layer  68 . At anode catalyst layer  68 , the fuel is separated into hydrogen ions (H + ) and electrons (e − ). Electrolyte membrane  66  only permits the hydrogen ions to pass through to reach catalyst layer  10  and gas diffusion layer  72 . The electrons generally cannot pass through electrolyte membrane  66 . As such, the electrons flow through external electrical circuit  60  in the form of electric current. This current can power an electric load, such as an electric motor, or be directed to an energy storage device, such as a rechargeable battery. 
     Oxygen (O 2 ) is introduced into gas diffusion layer  72  at cathode portion  64 . The oxygen passes through gas diffusion layer  72  and over catalyst layer  10 . At catalyst layer  10 , oxygen, hydrogen ions, and electrons combine to produce water and heat. As discussed above, catalyst layer  10  exhibits good catalytic activity for reducing oxygen which increases the efficiency of MEA  58 . Additionally, because catalyst layer  10  is corrosion resistant, catalyst layer  10  may perform in MEA  58  for extended periods of time. 
     EXAMPLES 
     The present invention is more particularly described in the following examples that are intended as illustrations only, since numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art. Unless otherwise noted, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples were obtained, or are available, from the chemical suppliers described below, or may be synthesized by conventional techniques. 
     Example 1 and Comparative Example A 
     An MEA of Example 1 was prepared pursuant to the following procedure. A catalyst layer was prepared by physical vapor depositing a catalyst material onto a carbon non-woven fabric substrate (commercially available under the product no. FC-H2315 from Freudenberg Non-Wovens Technical Division, Lowell, Mass.). The physical vapor deposition was performed in a processing environment containing nitrogen gas, with a pulsed cathodic arc plasma generating system described in Selifanov et al., U.S. Pat. Nos. 5,643,343 and 5,711,773. The use of the system for depositing carbon and nitrogen is described by Andrei Stanishevsky, “Quasiamorphous Carbon and Carbon Nitride Films Deposited from the Plasma of Pulsed Cathodic Arc Discharge” in Chaos, Solitons and Fractals, Vol. 10 pp 2045-2066 (1999). 
     The system was modified to include a composite cathode that contained a carbon target and a transition metal (i.e., iron) target. The composite cathode included a 33-millimeter-diameter graphite-carbon target (commercially available under the trade designation “GRADE SFG2” from Poco Graphite, Decatur, Tex.), having 56 drilled holes in the cross-section surface for retaining iron-wire targets. Each iron-wire target had a 2.0-millimeter diameter, and a 1-centimeter length (commercially available from Alpha-Aesar, Ward Hill, Mass.). 
     The system was evacuated to less than about 1×10 −5  Torr, and then nitrogen gas was introduced to provide any operating pressure of about 2-3 milliTorr. The system was operated with main, auxiliary and ignition capacitances of 2,200, 185, and 10 microfarads, respectively; main, auxiliary and ignition voltages of 250, 300, and 700 volts; and a discharge frequency of about 4 hertz. A web of the carbon non-woven fabric substrate was passed through the system 18 times with line speeds of 61 centimeters/minute (24 inches/minute). The multiple passes were used to increase the amount of catalyst material deposited per unit area of the substrate. After the PVD process was completed, the system was then filled with nitrogen gas to atmospheric pressure and the coated substrate was removed. 
     The coated substrate was then thermally treated in a quartz tube furnace (commercially available under the trade designation “RTP600S” from Modular Process Technology, San Jose, Calif.). Nitrogen gas was introduced into the furnace to purge residual gases. Once the residual gases were substantially purged, a second processing environment was prepared by continuously introducing ammonia gas into the furnace prior to, and during, the thermal treatment. The coated catalyst was placed in the furnace, and the temperature was ramped up at a rate of 6° C./minute until a processing temperature of 900° C. was reached. The temperature was then held at 900° C. for 15 minutes. The resulting catalyst layer remained in the furnace until it cooled to about room temperature prior to removal. 
     A pair of PEMs (commercially available under the trade designation “NAFION 112” from DuPont Chemical Co., Wilmington, Del. were then placed between the prepared catalyst layer (which functioned as a cathode catalyst layer) and a anode catalyst layer. The anode catalyst layer included a platinum/carbon-dispersed ink coated on a carbon-paper gas diffusion layer. The carbon-paper gas diffusion layer was fabricated by coating a gas diffusion micro-layer on one side of a carbon fiber paper (commercially available under the trade designation “AVCARB P50 Carbon Fiber Paper” from Ballard Material Products, Lowell, Mass.) that had been treated for hydrophobicity. The anode catalyst platinum loading ranged from about 0.3 milligrams Pt/centimeter 2  to about 0.4 milligrams Pt/centimeter 2 . The resulting MEA of Example 1 was assembled in a 50-centimeter 2  test cell fixture (available from Fuel Cell Technologies, Albuquerque, N. Mex.) having quad-serpentine flow fields, at about 25% to about 30% compression. 
     The MEA of Comparative Example A was prepared in the same manner as discussed above for the MEA of Example 1, except that the coated substrate was not thermally treated. Therefore, after the PVD process, the coated substrate was directly assembled with the pair of PEMs and the anode catalyst layer to provide the MEA of Comparative Example A. 
     The catalytic activity of each of the MEAs of Example 1 and Comparative Example A was measured pursuant to the following “polarization measurement method”. The measurement involved recording the polarization curves under oxygen using a potentiostat (commercially available under the trade designation “SOLARTRON CELLTEST 1470” from Solartron Analytical, Oak Ridge, Tenn.) and a software package (commercially available under the trade designation “CORWARE” from Scribner Associates, Inc., Southern Pines, N.C.). 
     Cyclic voltammograms were performed at 50, 20, 10 and 5 millivolts/second between 0.01 volts and 1.1 volts. In order to compare the catalytic activity, the comparisons were made at the same voltage using a scan rate of 5 millivolts/second. Hydrogen and oxygen streams introduced to the anode and cathode sides of the cell each had a flow rate of 500 standard cubic centimeters/minute (SCCM) at ambient pressure. The measurements were taken at 75° C. with approximately 150% relative humidity. 
       FIG. 6  is a graph of the polarization curves measured pursuant to the polarization measurement method for the MEAs of Example 1 and Comparative Example A. As shown, the MEA of Example 1 exhibited higher catalytic activity compared to the MEA of Comparative Example A. This is believed to be due to the thermal treatment of the catalyst layer. Accordingly, the catalyst layers of the present invention, which are made with the use of a PVD process and thermal treatment, exhibit good catalytic activity for use in electrochemical devices, such as fuel cells. 
     The alternating current (AC) impedances was measured for each of the MEAs of Example 1 and Comparative Example A pursuant to the following “AC impedance measurement” to determine resistance of the catalyst layer, as well as the interference resistance between the catalyst layer and the PEM. The AC impedance was measured using a potentiostat (commercially available under the trade designation “SOLARTRON CELLTEST 1470” from Solartron Analytical, Oak Ridge, Tenn.), with a frequency response analyzer (commercially available under the trade designation “SOLARTRON SI 1250” from Solartron Analytical), and a software package (commercially available under the trade designation “ZPLOT” from Scribner Associates, Inc., Southern Pines, N.C.). Measurements were taken at open circuit voltage under hydrogen in the frequency range of 1 hertz-10 kilohertz. The hydrogen streams introduced to the anode and cathode sides of the cell each had a flow rate of 500 standard cubic centimeters/minute (SCCM). The measurements were taken at 75° C. with approximately 150% relative humidity. 
       FIG. 7  is a graph of the AC impedances measured pursuant to the AC impedance measurement method for the MEAs of Example 1 and Comparative Example A. As shown, the MEA of Example 1 exhibits lower impedances compared to the MEA of Comparative Example A. Similar to catalytic activity, this is believed to be due to the thermal treatment of the catalyst layer. 
     Examples 2-7 and Comparative Example B 
     MEAs of Examples 2-7 were each prepared pursuant to the same procedure discussed above for the MEA of Example 1, except that the composite cathode included 45 iron-wire targets, where each iron-wire target had a 1.2-millimeter diameter, and a 1-centimeter length (also commercially available from Alpha-Aesar, Ward Hill, Mass.). Additionally, the system was operated with main, auxiliary and ignition capacitances of 2,200, 185, and 20 microfarads, respectively, and the web of the carbon non-woven fabric substrate was passed through the system 10 times with line speeds of 30.5 centimeters/minute (12 inches/minute). Furthermore, the conditions for thermally treating the coated substrates of Examples 2-7 were varied, as shown below in Table 1. After the thermal treatment the resulting catalyst layer was then assembled in an MEA in the same manner as discussed above for the MEA of Example 1. 
     The MEA of Comparative Example B was prepared in the same manner as discussed above for the MEAs of Examples 2-7, except that the coated substrate was not thermally treated. The catalytic activities of the MEAs of Examples 2-7 and Comparative Example B were then measured pursuant to the “polarization measurement method”, discussed above. Table 1 lists the processing temperature and processing environment gas used during the thermal treatment, and the catalytic activity results at 0.6 volts, for the MEAs of Examples 2-7 and Comparative Example B. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                   
                 Processing 
                 Processing 
                 Catalytic Activity at 
               
               
                 Example 
                 temperature (° C.) 
                 Environment Gas 
                 0.6 volts (mA/cm 2 ) 
               
               
                   
               
             
            
               
                 Comparative 
                 None 
                 None 
                 0.014 
               
               
                 Example B 
               
               
                 Example 2 
                 400 
                 Nitrogen 
                 0.031 
               
               
                 Example 3 
                 600 
                 Nitrogen 
                 0.069 
               
               
                 Example 4 
                 800 
                 Nitrogen 
                 0.088 
               
               
                 Example 5 
                 400 
                 Ammonia 
                 0.029 
               
               
                 Example 6 
                 600 
                 Ammonia 
                 0.108 
               
               
                 Example 7 
                 800 
                 Ammonia 
                 0.134 
               
               
                   
               
            
           
         
       
     
     As shown in Table 1, the thermal treatment increases the catalytic activity of the MEAs. Thus, the catalyst layers of the present invention exhibit good catalytic activity for use in electrochemical devices, such as fuel cells. In addition, as discussed above, the catalyst layers are substantially free of platinum (and precious metals in one embodiment), thereby reducing materials costs. 
     As further shown in Table 1, the thermal treatment in ammonia (i.e., Examples 5-7) provided MEAs having higher catalytic activities compared to the thermal treatment in nitrogen (i.e., Examples 2-4). This is believed to be due to the higher reactivity of ammonia during the thermal treatment relative to nitrogen. 
     Examples 8 and 9 
     MEAs of Examples 8 and 9 were each prepared pursuant to the following procedure, which involved performing the thermal treatment in a substantially simultaneous manner with the PVD process. The PVD system used was the same as discussed above for Example 1, except that the composite cathode included 42 iron-wire targets. Additionally, instead of a web drive, the substrate was mounted to a surface of a molybdenum plate, which included a heating element (commercially available under the trade designation “BORALECTRIC” Boron Nitride from Tectra GmbH, Germany) disposed on the reverse surface. The heater temperature was controlled via a proportional-integral-derivative (PID) controller (model REX-P300 from RKC Instrument Inc., South Bend, Ind.). 
     A processing environment was prepared by introducing a gas (90% nitrogen and 10% ammonia, by volume) at a flow rate of 250 SCCM, which provided an operating pressure of about 1 milliTorr. The system was operated with main, auxiliary and ignition capacitances of 2,200, 185, and 20 microfarads, respectively; main, auxiliary and ignition voltages of 250, 350, and 600 volts; and a discharge frequency of 8.0 hertz. For Example 8, the catalytic material was deposited with 2,500 pulses and a substrate temperature of 550° C. For Example 9, the catalytic material was deposited with 4,000 pulses and a substrate temperature of 625° C. After the PVD/thermal treatment, the resulting catalyst layers of Examples 8 and 9 were then assembled in an MEA in the same manner as discussed above for the MEA of Example 1. 
     The catalytic activities of the MEAs of Examples 8 and 9, and Comparative Example B, were then measured pursuant to the “polarization measurement method”, discussed above.  FIG. 9  is a graph of the polarization curves for the MEAs of Examples 8 and 9, and Comparative Example B. As shown, at 0.5 millivolts, the MEA of Example 8 exhibited a catalytic activity of 0.130 mA/cm 2 , and the MEA of Example 9 exhibited a catalytic activity of 0.234 mA/cm 2 . Moreover, as shown in  FIG. 9 , the thermal treatment increases the catalytic activity of the catalyst layer, and is generally proportional to the processing temperature used. 
     Example 10 
     A catalytic C 1-x-y N x Fe y  material film was prepared using a DC Magnetron sputtering system to deposit catalytic material onto a disk (e.g., a glassy carbon disk, silicon wafer, glass slide, or quartz slide). The sputtering system is outlined in J. R. Dahn, S. Trussler, T. D. Hatchard, A. Bonakdarpour, J. N. Meuller-Neuhaus, K. C. Hewitt and M. Fleischauer, “Economical sputtering system to produce large-size composition-spread libraries having linear and orthogonal stoichiometry variations”, Chemistry of Materials, 14 (8), 3519-3523(2002). The processing environment included an argon/nitrogen mixture as outlined in E. Bradley Easton, Th. Buhrmester and J. R. Dahn, “Preparation and Characterization of Sputtered Fe 1-x N x  Films”, Thin Solid Films 493, 60-66 (2005). The film was prepared using a constant mask over a graphite target and a linear mask over the transition metal target (i.e., iron or cobalt). 
     Once the sputtering process was complete for a given film, the film was thermally treated using a Modular Pro Rapid Thermal Processing station, and a processing environment of argon gas. A processing temperature of 1000° C. was used. However, for each film, the temperature was ramped up at a rate of 5° C./second until the processing temperature was reached. The processing temperature was then maintained for one minute. The resulting annealed film was then cooled to room temperature in an argon atmosphere. 
     A “composition analysis” of the film was made using a microanalyzer commercially available under the trade designation “JXA-8200 SUPERPROBE” Electron Probe Microanalyzer from JEOL USA, Inc., Peabody, Mass. The microanalyzer was equipped with one energy dispersive spectrometer, five wavelength dispersive (WDS) spectrometers, and an automated motion stage. Silicon nitride was used as the nitrogen standard while magnetite was used as the iron standard. The elemental composition was determined using the WDS detector and had an estimated uncertainty of ±0.3%. The composition was measured on a disk library, point by point, with point sizes of 5 micrometers. The disk library was 200-nanometers thick and both EDS and WDS measured the average composition throughout that thickness. 
     The film was then each measured using a “rotating-ring disk electrode measurement” method, which was performed in a one-compartment cell with 0.1-molar HClO 4  as the electrolyte. A mercury/mercury sulfate reference electrode was used. Data was collected at 65° C. Cyclic voltammograms (CVs) at 5 millivolts/second were performed in an oxygen saturated solution.  FIG. 9  is a graph showing a rotating disk electrode measurements at 65° C. under oxygen for the film of Example 10 at 900 RPM. 
     Examples 11 and 12 and Comparative Example C 
     Catalytic C 1-x-y N x Fe y  material films were each prepared on glass or quartz slides in the same manner as discussed above for the films of Example 10, except that the film of Comparative Example C was not thermally treated, the thermal treatment for film of Example 11 had a processing temperature of 600° C., and the thermal treatment for film of Example 12 had a processing temperature of 800° C. The films were otherwise compositionally the same. 
     The films of Examples 11 and 12, and Comparative Example C were then subjected to a “corrosion resistance test”, which involved placing each film in a 0.5-Molar sulfuric acid (H 2 SO 4 ) solution for 7 days. The films were then visually examined to determined how much of each film was dissolved. After the corrosion resistance test, the catalytic materials of the films of Example 11 and Comparative Example C were completely dissolved. In contrast, however, the catalytic material of the film of Example 12 remained with an atomic percentage of carbon, nitrogen, and iron within the above-discussed suitable atomic percentages. Accordingly, the thermal treatment at 800° C. increased the corrosion resistance of the film of Example 12. 
     The results of the rotating-ring disk electrode measurements of the film of Example 10, and the corrosion resistance results of the film of Example 12, illustrate the catalytic C 1-x-y N x Fe y  material films that exhibited good catalytic activity and which were corrosion resistant to acidic environments. Accordingly, such films are suitable for use in the acidic environments of electrochemical devices, such as fuel cells. 
     Examples 13a-13c 
     Catalytic C 1-x-y N x Co y  material films of Examples 13a-13c were each prepared in the same manner as discussed above for the films of Example 10, except that the iron target was replaced with a cobalt target. The atomic percentages of the films of Example 13a-12c were respectively C 0.90 N 0.04 Co 0.06 , C 0.86 N 0.06 Co 0.08 , and C 0.82 N 0.10 Co 0.08 . The films were each measured using the rotating-ring disk electrode measurement method, which was performed as discussed above in Example 10, except that the measurements were performed at room temperature (i.e., 25° C.).  FIGS. 10A-10C  are graphs showing rotating disk electrode measurements at room temperature under oxygen for the films of Example 13a-13c, respectively. 
     The results of the rotating-ring disk electrode measurements for the films of Example 13a-13c illustrate the catalytic C 1-x-y N x Co y  material films that exhibited measurable catalytic activity. The results also show that the behaviors of the catalyst films may be varied by the atomic percentages of the catalytic materials and by thermal processing. 
     Examples 14 and 15 
     An MEA of Example 14 involved a catalyst formed by PVD of iron on finely-divided carbon particles. The film was prepared by DC magnetron sputtering as described in Brey et al., U.S. Publication No. US 2005/0095189, with an iron target. A 30 grams sample of Acetylene Black (commercially available under the trade designation “Y50A” Acetylene Black, from SN2A, France) was dried for 12 hours at 130° C. in a box oven. The sputtering chamber was charged with 16.76 grams of the dry Acetylene Black. The chamber was then evacuated to 5×10 −5  Torr and argon gas was introduced into the chamber at a pressure of about 10 milliTorr. The iron deposition process was initiated by applying a cathodic power of 0.1 kW using a 99.9% iron target (3-inches round and 0.063-inches thick, from Kurt J. Lesker Company, Clairton, Pa.). Argon was introduced as the sputter gas at 34 SCCM. The carbon powder was agitated during the sputtering by turning the particle agitator shaft at 10 RPM. After a total of 0.23 kWH was expended, the reaction was stopped and the chamber was backfilled with air and the sample was removed from the reactor. The target weight loss after this treatment was 0.95 grams. 
     The iron-treated film was placed in a fused silica boat and placed in a tube furnace for the thermal treatment. The tube was flushed with nitrogen to remove traces of air and the heat treatment employed was as follows: room temperature to 400° C. at 6° C./minute under nitrogen, hold at 400° C. for 4 hours under nitrogen/30% ammonia (NH 3 ), heat to 900° C. at 8° C./minute, and hold at 900° C. for 1 hour under nitrogen/30% ammonia. The furnace was then allowed to cool while maintaining the nitrogen/ammonia atmosphere. 
     After cooling, the film was washed with 0.54 M sulfuric acid by soaking 4 grams of the film in 300 grams of the acid overnight. The sample was removed by filtration, washed extensively with deionized water, and dried at 130° C. in an oven. 2.0 grams of this dried catalyst material was then dispersed in 150 grams of water and the resulting dispersion was sonicated for 10 minutes using an ultrasonic horn (commercially available under the trade designation “Sonics VCX VIBRACELL” from Sonics and Materials Inc., Newton, Mass.). The dispersion was then dried at 130° C. and the dried particles were used to prepare the coating dispersion. 
     A dispersion of the catalyst particles was prepared by mixing 1.5 grams of the acid-washed, ultrasonically-treated catalyst particles with 10 grams of an 11.3% (by weight) aqueous dispersion (commercially available under the trade designation “NAFION” from E.I. Du Pont De Nemours Inc., Wilmington, Del.) and 10 grams of water in a beaker. The mixture was heated to about 100° C. on a hot plate for 30 minutes. After cooling, the sample was stirred. A coating of 88 milligrams of the catalyst ink dispersion was hand brushed onto a 50-centimeter 2  carbon paper support (commercially available under the trade designation “AVCARB P50” Carbon Fiber Paper from Ballard Material Products, Lowell, Mass.), which was previously treated for hydrophobicity and coated with a gas diffusion microlayer. The coated sample was dried at 110° C. under vacuum (˜25 in Hg) for approximately 20 minutes. This catalyst coated backing (CCB) was used as the cathode catalyst and GDL layer of an MEA. 
     The anode catalyst was a dispersed Pt/C catalyst layer as described in Example 1. Gaskets were selected for 25-30% compression on both the anode and the cathode. Using a static press, the anode and cathode catalysts were bonded to a pair of cast “NAFION” membranes (each approximately 30 micrometers thick, 1000 EW) at 132° C.-138° C. (270° F.-280° F.) and 1,361-1,814 kilograms (3,000-4,000 pounds) for 10 minutes. The resulting MEA was placed into a standard 50-centimeter 2  fuel cell test fixture with quad serpentine flow fields (Fuel Cell Technologies). 
     An MEA of Example 15 involved a catalyst formed by PVD of cobalt on finely-divided carbon particles, and was prepared in the same manner as discussed above for Example 14, except for the following: Cobalt nanoparticles were sputtered onto carbon powder as described in Example 10 with the exception that a 3-inch round and 0.25-inch thick cobalt target was employed rather than an iron target, and 0.3 kWh was used to sputter the cobalt. The target weight loss was 1.35 grams. The cobalt-treated sample heated strongly after exposure to air during the removal of the sample from the sputtering apparatus. The sample was blanketed with nitrogen to moderate the heating due to exposure to air. The resulting cobalt-carbon catalyst particles were then thermally treated in ammonia, dispersed and supported on a carbon paper as described in Example 10 with the exception that 87 milligrams of the sample dispersion was used to prepare the coated fabric. 
     The catalytic activity of each of the MEAs of Example 14 and 15 were measured by recording the polarization curves under oxygen in a similar manner to described in “polarization measurement method” discussed above with the following differences: The cell temperature was 80° C.; and hydrogen and oxygen gas streams introduced to the anode and cathode sides of the cell had flow rates of 180 sccm and 335 sccm, respectively. The outlet gas pressures were 30 psig (˜3 bar absolute) on the anode and 50 psig (˜4.5 bar absolute) on the cathode. Humidity on the gas streams was held at approximately 100% RH.  FIG. 11  is a graph of the polarization curves for the MEAs of Examples 14 and 15. The results show that the catalytic layers having carbon-particle substrates also exhibited measurable catalytic activity. 
     Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.