WO2005008814A2

WO2005008814A2 - Electrodes and other fuel cell components having ultra low catalyst loadings coated thereon and processes for making and using the same

Info

Publication number: WO2005008814A2
Application number: PCT/US2004/022559
Authority: WO
Inventors: Juan C. Figueroa
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 2003-07-10
Filing date: 2004-07-09
Publication date: 2005-01-27
Anticipated expiration: 2006-01-10
Also published as: WO2005008814A3; TW200505093A

Abstract

The present invention relates to fuel cells and various fuel cell components comprising electrocatalysts comprising composite materials that deliver high mass specific current densities through the use of activated precursor electrocatalysts.

Description

TITLE ELECTRODES AND OTHER FUEL CELL COMPONENTS HAVING ULTRA LOW CATALYST LOADINGS COATED THEREON AND PROCESSES FOR MAKING AND USING THE SAME FIELD OF THE INVENTION The present invention relates to fluid diffusive electrodes, fuel cells and various fuel cell components comprising electrocatalysts comprising composite materials that deliver high mass specific current densities. In particular, the present invention relates to the use of activated precursor catalysts. The catalysts are useful in fuel cells and may be used as anode or cathode catalysts. BACKGROUND Electrochemical cells generally include an anode electrode and a cathode electrode separated by an electrolyte. A well-known use of electrochemical cells is in a stack for a fuel cell (a cell that converts fuel and oxidants to electrical energy) that uses a proton exchange membrane (hereafter "PEM") as the electrolyte. In such a cell, a reactant or reducing fluid such as hydrogen is supplied to the anode electrode, and an oxidant such as oxygen or air is supplied to the cathode electrode. The hydrogen electrochemically reacts at a surface of the anode electrode to produce hydrogen ions and electrons. The electrons are conducted to an external load circuit and then returned to the cathode electrode, while hydrogen ions transfer through the electrolyte to the cathode electrode, where they react with the oxidant and electrons to produce water and release thermal energy. Fuel cells utilize electrocatalysts in order to facilitate these reactions involving oxygen and hydrogen. Some electrocatalysts known in the art describe the use of aluminide precursor powders, milled in the form of a pellet, are not capable of delivering fuel cell components having ultra-low catalyst loadings due to the excessively large particle size of these powders. Other known electrocatalysts utilize nano-scale crystalline powder precursors, however this is problematic because such powders can not be synthesized on substrates such as ionomeric membrane films or carbon fiber sheets that are useful for manufacturing fuel cell electrodes. The present invention is advantageous, inter alia, because it relates to an electrocatalyst, which can exhibit both electron-conducting and proton-conducting properties and can utilize a platinum loading of less than 200 micrograms/cm². This significantly reduces the cost per kW for fuel cells, while not compromising fuel cell performance in that it delivers high mass specific current densities. SUMMARY OF THE INVENTION The present invention relates to membrane electrode assemblies, coated substrates, and fuel cells utilizing an electrocatalyst comprising an activated catalyst precursor comprising an electron-conductive porous nano-scale columnar structure penetratively coated with a proton- conductive material. The electron-conductive columnar precursor has the general formula (PtX_a)Yb, wherein X indicates an individual element or mixture of elements from at least one of columns IMA, IVA, VA, VIA, VIIA, VINA, IB, and IIB of the periodic table, Y indicates an individual element or mixture of elements from at least one of Al, Li, Be, Mg, Zn, Cd, Hg, Ga, In, Ge, Sn, Pb, As, Sb or Bi; a is at least 0.001 , and b is at least 0.85*»(1+a) ("•" denotes the multiplication of 0.85 and (1+a)). Several methods may be used for activating the electrocatalyst of the present invention, including, by way of example, subjecting it to caustic solutions containing 0 to 20% NaOH and further subjecting it to a nitric acid solution. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a catalyst utilization comparison between a Control MEA (Example 1) and an experimental MEA (Example 2), in terms of the relationship between cell power density and mass specific anode current. DETAILED DESCRIPTION Fuel cells are electrochemical devices that convert the chemical energy of a fuel, such as a hydrogen gas, and an oxidant into electrical energy. Typical fuel cells comprise an anode (a negatively charged electrode), a cathode (a positively charged electrode) separated by an electrolyte that are formed as stacks or assemblages of membrane electrode assemblies (MEA), and preferably include a coated substrate, an anode and cathode as well as other optional components. The present invention is intended for use in conjunction with electrodes or other substrates utilized in fuel cell applications, membrane electrode assemblies, coated membranes and fuel cells utilizing proton- exchange membranes (also known as "PEM"), for example direct methanol fuel cells, hydrogen fuel cells, reformed hydrogen fuel cells, as well as other liquid feed fuel cells (e.g. those utilizing feed fuels of ethanol, propanol, formic acid and the like). As used herein, "fluid" shall include any material in the liquid or gaseous state. As used herein, "composite material" shall mean an electrocatalyst exhibiting both electron-conducting and proton-conducting properties. As used herein, "activated" shall mean the attainment of practical catalytic activity for a given precursor formulation upon its exposure to a chemical treatment, wherein it is in a material state simultaneously displaying catalytic properties, electron-conductive properties, proton- conductive properties and fluid transport properties. As used herein, "precursor" means a material that does not have useful electrocatalytic activity, wherein upon activation, attains a useful electrocatalystic activity. As used herein, "ultra-low loading" means an areal loading of less than 200 μgpt/cm² (0.200 mgp_t/cm²), preferably less than 150 μgpt/cm², more preferably less than 100 μgp_t/cm². As used herein, "penetratively coated" shall mean a porous material having both its external and internal surfaces coated with a proton- conducting material. As used herein, "vapor depositing" or variations thereof, shall mean a physical phase transformation process by which a gas transforms into a solid layer deposited on the surface of a solid substrate. The electrocatalyst according to the present invention comprises an activated catalyst precursor comprising an electron-conductive porous nano-scale columnar structure that is penitratively coated with a proton- conductive material. Typically the electrocatalyst contains less than 200 μg_Pt/cm², preferably less than 150 μg_Pt/cm², more preferably less than 100 μgpt/cm². The precursor becomes activated upon being subjected to chemical treatments as set forth below. The electrocatalyst according to the present invention is a multifunctional composite material having catalyst capabilities and is conductive of both electrons and protons. Typically, the electrocatalyst comprises an electron-conducting Pt-based catalytic material, and a proton-conducting material (a.k.a. an ion exchange polymer). The electron-conductive columnar precursor has the formula

(PtX_a)Yb, wherein X indicates an individual element or mixture of elements from at least one of columns IIIA, IVA, VA, VIA, VI IA, VI 11 A, IB, and IIB of the periodic table, Y indicates an individual element or mixture of elements from at least one of Al, Li, Be, Mg, Zn, Cd, Hg, Ga, In, Ge, Sn, Pb, As, Sb or Bi; a is at least 0.001 , and b is at least 0.85* (1+a)Preferably, X is at least one of Ru, Rh, Mo, W, V, Hf, Zr, Nb and/or Co; Y at least one of Al, Mg, Zn, Ge, and/or Sn, most preferably Al; a is at least 0.01 , and b is at least 1.5« (1+a). The precursor may be crystalline or semi-crystalline, wherein if semi-crystalline the precursor is a solid comprising regions that do not have long range atomic order (amorphous regions) that coexist with others having long range atomic order (crystalline regions). The electron-conductive porous nano-scale columnar precursor structures of the present invention typically comprise skeletal laminar columns having a substantially elliptical cross-section configuration. The cross section of the ellipse has both a major and minor axis, such that the length of the minor axis is less than about 10 micrometers (μm) and the height of the column is generally determined by the desired areal loading of platinum. In general, the columns are configured in such a manner that when the electrocatalyst precursor is deposited onto a substrate, the columnar structures may be configured to be parallel, perpendicular or any angle there between with respect to the surface upon which the electrocatalyst is deposited. Preferably, the columnar structures are deposited in such a manner that they are perpendicular to the surface of the substrate. Additionally, the columns have a diameter generally ranging from about from about 10 μm to about 10 nm, preferably 1 μm to about 10 nm, more preferably about 500 nm to about 10 nm, most preferably about 100 nm to about 10 nm. In addition typical precursor electron-conductive structures have both an intra-columnar and inter-columnar porosity. The intra-columnar is provided by voids within the columns, while the inter-columnar porosity is provided by the voided spaces between the columns. Preferably, the inter- columnar porosity is greater than one hundred nanometers (100 nm) and the intra-columnar porosity is less than one hundred nanometers (100 nm). Measurements of volume per unit mass have indicated that the overall porosity for a caustic-activated precursor structure prior to being penetratively coated is at least 85 % in volume. Typically, the precursor electron-conducting nanoscale columnar structures according to the present invention may be made according to the processes known in the art such as vapor deposition, for example, using the process set forth below, or in U.S Patent 5,993,979; which is hereby incorporated by reference, and will produce a wide variety of applied layers of columns, the layer having essentially any thickness ranging from very thick, e.g., 20 μm or more to very thin, e.g., 1 μm or less. Generally, the precursor may be synthesized via vapor deposition using a water-cooled cylindrical stainless steel holder that rotates around its vertical axis. Other vapor deposition reactors include resistively heated vacuum evaporators, inductively heated vacuum evaporators, electron beam heated vacuum evaporators, secondary ion beam sputtering evaporators and chemical vapor deposition reactors. The substrate can be fastened onto a holder at a given elevation. Four magnetron sputter vaporization sources, each using several centimeters in diameter target, typically about 5 to about 20 cm in diameter target, and most typically about 5 cm diameter target, may be located around the holder at about 90 degrees from each other and radially face the cylindrical holder. The elevation "z" of the substrate is defined as z = 0. The elevation "z" of the centerline of each magnetron sputter vaporization source may be independently controlled and referred to that of the substrate. The position of a magnetron sputter vaporization source located above the substrate may be defined as z > 0; the position of a magnetron sputter vaporization source located below the substrate may be defined as z < 0. The precursor may also be vapor deposited onto a moving substrate, for example a sheet substrate such as carbon paper. The substrate should be properly masked to yield a set coatable surface region, and the elemental vapors, each emitted from a separate magnetron sputter vaporization source may be sequentially deposited by repeated exposure of the substrate to the vapors to form the precursor coating of the required size. Control of the precursor stoichiometry may be achieved via independent control of the ignition power fed to each magnetron sputter vaporization source and its elevation relative to that of the substrate. An external substrate heating step may also be exercised during the vapor deposition. For each synthesis, the vapor deposition system may be pumped down to a pre-synthesis base pressure below 5 • 10^"6 Torr, and it may be backfilled with flowing gas to a process pressure suitable to glow discharge treat the substrate prior to vapor deposition of the precursor. The vapor deposition system may be backfilled with flowing Ar to a process pressure of about 10 mTorr to vapor deposit the precursor. The vapor deposition process may occur over a time of about 0.05 hours to about 6 hours, but usually about 0J hours to about 0.5 hours. Electrocatalysts in accordance with the present invention typically take the form of platinum-containing electron-conducting clusters, proton- conducting clusters and other components. It is preferable to adjust the relative amounts of the Pt-containing electron-conductive clusters, the proton-conducting clusters and other components, if present, so that the electrocatalyst attains a balanced distribution of these clusters. Clusters are typically assemblies of particles in intimate contact, whereby a particle is a solid having a uniform composition and atomic arrangement. More preferably, the volume ratio of Pt-based electron-conductive clusters to proton-conducting clusters in the electrode is about 5:95 to about 15:1. Optionally, the precursor compositions utilized in the present invention may be supported on those conventional supports known in the art. Preferably, the support comprises at least one of polyaniline or polypyrrole, silica, zirconia, particulate carbon, conducting polymers, transition metal carbide, metal carbide composites, metal oxides, metal oxide bronze, alumina and zeolite as well as combinations thereof. Preferably, the support is particulate carbon. Preferred carbon supports are turbostratic or graphitic carbons of varying surface areas such as Cabot Corporation's Vulcan® XC72R, Akzo Noble Ketjen® 600 or 300, Vulcan® Black Pearls (Cabot Corporation), acetylene black (Denki Kagku Kogyo Kabushiki Kaisha), as well as other conducting carbon varieties. Other carbons include graphite powders, single or multiwalled carbon nanotubes, fibers or other carbon structures (fullerenes, nanohorns). Subsequent to their formation, the electron-conductive columnar precursor structures according to the present invention are penetratively coated with a proton-conducting material (i.e., an ion exchange polymer), wherein the volume fraction of the proton-conductive material is at least 1%, preferably at least 5% and more preferably at least 10% of the electrocatalyst. When the precursor has been deposited on a gas diffusion layer, care must be exercised upon penetrative coating of the precursor to minimize the extent of plugging of gas diffusion pores within the gas diffusion layer. Generally, the electron-conductive columnar precursor is determined to be adequately penetratively coated based upon its peak power performance subsequent to being subjected to the chemical treatment, wherein there is a correlation between cell peak power performance and the volume fraction of the proton-conducting material. However, if the precursor is over penetratively coated with the proton- conducting material, as noted above, plugging can occur. The dominant factor that facilitates the plugging of the pores is the ability of the solvent to wet or or spread into the gas diffusion layer. Therefore preferred solvents are those that are phobic to the constituents of the gas diffusion layer (i.e., carbon and PTFE) The proton-conducting material may be an organic material such as the ion exchange polymers described herein or an inorganic material such as a hydrated oxide, or a heteropolyacid hydrate, or a chalcogenide-based glass. Since the ion exchange polymer employed in the present invention assists in securing the electrode to the membrane and in reducing the protonic resistance of the interface between the electrocatalyst and the membrane, it is preferred that the ion exchange polymers in the electrocatalyst be compatible with the ion exchange polymer in the membrane. Most typically, ion exchange polymers in the electrocatalyst composition are the same type as the ion exchange polymer in the membrane. Ion exchange polymers suitable for use in the present invention includes, but is not limited to, highly fluorinated ion-exchange polymers. "Highly fluorinated" means that at least 90% of the total number of univalent atoms in the polymer are fluorine atoms. Most typically, the polymer is perfluorinated. It is typical for polymers used in fuel cells to have sulfonate ion exchange groups. The term "sulfonate ion exchange groups" as used herein means either sulfonic acid groups or salts of sulfonic acid groups, typically alkali metal or ammonium salts. For applications where the polymer is to be used for proton exchange such as in fuel cells, the sulfonic acid form of the polymer is typical. If the polymer in the electrocatalyst coating composition is not in sulfonic acid form when used, a post treatment acid exchange step can be used to convert the polymer to acid form prior to use. Typically, the ion exchange polymer employed comprises a polymer backbone with recurring side chains attached to the backbone with the side chains carrying the ion exchange groups. Homopolymers or copolymes can be used. Copolymers are typically formed from one monomer that is a nonfunctional monomer and that provides carbon atoms for the polymer backbone, and a second monomer that provides carbon atoms for the polymer backbone and also contributes a side chain carrying a cation exchange group or its precursor, e.g., a sulfonyl halide group such a sulfonyl fluoride (-S0₂F), which can be subsequently hydrolyzed to a sulfonate ion exchange group. For example, copolymers of a first fluorinated vinyl monomer together with a second fluorinated vinyl monomer having a sulfonyl fluoride group (-S0₂F) can be used. Exemplary first fluorinated vinyl monomers include tetrafluoroethylene (TFE), hexafluoropropylene, vinyl fluoride, vinylidine fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and mixtures of two or more thereof. Exemplary second monomers include fluorinated vinyl ethers with sulfonate ion exchange groups or precursor groups that can provide the desired side chain in the polymer. The first monomer can also have a side chain that does not interfere with the ion exchange function of the sulfonate ion exchange group. Additional monomers can also be incorporated into the polymers if desired. Typical polymers for use in making coated substrates include polymers having a highly fluorinated, most typically a perfluorinated, carbon backbone with a side chain represented by the formula

-(0-CF₂CFRf)_a-0 -CF₂CFR'fS0₃H, wherein Rf and R'f are independently selected from F, Cl and perfluorinated alkyl groups having 1 to 10 carbon atoms, wherein a = 0, 1 or 2. Specific examples of suitable polymers include those disclosed in U.S. Patents 3,282,875; 4,358,545; and 4,940,525. One exemplary polymer comprises a perfluorocarbon backbone and a side chain represented by the formula -0-CF₂CF(CF₃)-0-CF₂CF₂S0₃H. Such polymers are disclosed in U.S. Patent 3,282,875 and can be made by copolymerization of tetrafluoroethylene (TFE) and the perfluorinated vinyl ether CF₂=CF-0-CF₂CF(CF₃)-0-CF₂CF₂S0₂F, perfluoro(3,6-dioxa-

4-methyl-7-octene-sulfonyl fluoride) (PDMOF), followed by conversion to sulfonate groups by hydrolysis of the sulfonyl fluoride groups and ion exchanging to convert to the acid, also known as the proton form. An exemplary polymer of the type disclosed in U.S. Patents 4,358,545 and 4,940,525 has a side chain -0-CF₂CF₂S0₃H. The polymer can be made by copolymerization of tetrafluoroethylene (TFE) and the perfluorinated vinyl ether CF₂=CF-0-CF₂CF₂S0₂F, perfluoro(3-oxa-4-pentenesulfonyl fluoride) (POPF), followed by hydrolysis and acid exchange. For perfluorinated polymers of the type described herein above, the ion exchange capacity of a polymer can be expressed in terms of ion exchange ratio ("IXR"). Ion exchange ratio is the number of carbon atoms in the polymer backbone in relation to the ion exchange groups. A wide range of IXR values for the polymer are possible. Typically, however, the IXR range for perfluorinated sulfonate polymers is from about 7 to about 33. For perfluorinated polymers of the type described herein above, the cation exchange capacity of a polymer can be expressed in terms of equivalent weight (EW). Equivalent weight (EW), as used herein, is the weight of the polymer in acid form required to neutralize one equivalent of NaOH. For a sulfonate polymer having a perfluorocarbon backbone and a side chain -0-CF₂-CF(CF₃)-0-CF₂-CF₂-S0₃H (or a salt thereof), the equivalent weight range corresponding to an IXR of about 7 to about 33 is about 700 EW to about 2000 EW. A preferred range for IXR for such a polymer is from about 8 to about 23 (750 to 1500 EW), and a more preferred range is from about 9 to about 15 (800 to 1100 EW). Any liquid medium compatible with the process for creating a gas diffusion electrode or a catalyst-coated membrane, or for coating the catalyst onto a substrate can be used. It is advantageous for the medium to have a boiling point that facilitates optimum drying of electrode layers under the process conditions employed, provided however, that the composition does not dry so fast that the effective penetrative coating of the electrocatalyst composition is detrimentally affected, wherein the coating does not fully penetrate the columnar structures. When flammable constituents are to be employed, the medium can be selected to minimize process risks associated with such constituents, as the medium is in contact with the catalyst during use. The medium is also sufficiently stable in the presence of the ion exchange polymer that, in the acid form, has strong acidic activity. The liquid medium is typically polar for compatibility with the ion exchange polymer, and is preferably able to wet the porous precursor. While it is possible for water to be used as the liquid medium, the medium is preferably such that the ion exchange polymer coalesces upon drying and does not require post treatment steps such as heating to form a stable electrode layer. A wide variety of polar organic liquids or mixtures thereof can serve as suitable liquid media for the penetrative coating of the electrocatalyst composition, including amyl alcohol, water, 1-propanol and ethanol. Water can be present in the medium if it does not interfere with the coating process. In the utilization of decal transfer techniques; although some polar organic liquids can swell the membrane when present in sufficiently large quantity, the amount of liquid used in the process of transferring an electrocatalyst decal to a membrane is preferably small enough that the adverse effects from bulk membrane swelling during the process are minor or undetectable. It is believed that residual solvents able to swell the ion exchange membrane can provide better contact and more secure application of the electrode decal transferred to the membrane. A variety of alcohols are well suited for use as the liquid medium. Typical liquid media include suitable C₄ to C₈ alkyl alcohols such as n-, iso-, sec- and tert-butyl alcohols; the isomeric 5-carbon alcohols such as 1 , 2- and 3-pentanol, 2-methyl-l-butanol, 3-methyl-1-butanol, etc.; the isomeric 6-carbon alcohols, such as 1-, 2-, and 3-hexanol, 2-methyl-1- pentanol, 3-methyl-1-pentanol, 2-methyl-l-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, etc.; the isomeric C₇ alcohols and the isomeric C₈ alcohols. Cyclic alcohols are also suitable. Preferred alcohols are 3- methyl-1-butanol (isoamyl alcohol), n-butanol and n-hexanol, and 3- methyl-1-butanol (isoamyl alcohol) is more preferred. The amount of penetrative coating solution varies and is determined by the solvent employed, the desired volume fraction of proton-conducting material in the electrocatalyst, the type of coating equipment employed, electrode thickness, process speeds etc. The dispersion of the acid form of the perfluorinated sulfonic acid polymer, sold by E.I. du Pont de Nemours and Company under the trademark Nation®, in an isoamyl alcohol dispersion, is preferably used to penetratively coat the electron-conducting columnar structures of the present invention. The caustic-treated precursor according to the present invention generally has a Brunauer, Emmett & Teller (BET) surface area greater than 10 m²/gp_t, preferably greater than 30 m²/g_Pt, more preferably greater than 45 m²/g_Pt, most preferably greater than 60 m²/gp_t. This increase in BET surface area is effectuated by vapor depositing thinner columns, strengthening the caustic solution and lengthening the caustic treatment. Typically, an electrocatalyst of the present invention is applied to a substrate, wherein the columnar structures are preferably oriented perpendicularly to the surface upon which the electrocatalyst is deposited. A substrate in accordance with the present invention may be an ion exchange membrane (which acts as the electrolyte (ion-exchanger) as well a barrier film which separates the reactant gases in the anode and cathode compartments of fuel ceil) or a porous, conductive sheet material, typically known as a gas diffusion backing, each of which may have a catalyst coated thereon, thereby forming a catalyst-coated membrane (CCM), to form an anode or cathode thereon, and or a gas diffusion electrode (GDE) respectively. The gas diffusion backing substrate can be coated on one or both surfaces with a gas diffusion layer, typically comprising a film of carbon support particles and a binder, for example, fluoropolymers such as PTFE. The thin porous layer is usually referred to as the "gas diffusion layer". Preferably, the gas diffusion backing is a woven or non-woven carbon fiber substrate, more preferably, carbon-based papers or cloths, that can optionally be treated to exhibit hydrophilic or hydrophobic behavior. A variety of techniques are known for the manufacture of a catalyst coated membrane. Typical manufacturing techniques involve the application of a catalyst coating composition onto substrates such as the ion exchange polymer membrane. Methods for applying the catalyst onto the substrate include spraying, painting, patch coating, screen-printing and decal transfer. The ion exchange membrane for use in preparing a catalyst-coated membrane (CCM) can be a membrane of the same ion exchange polymers discussed above for use in the electrocatalyst coating compositions. The membranes can be made by known extrusion or casting techniques and have thicknesses that can vary depending upon the intended application. The membranes typically have a thickness of 350 μm or less, although recently membranes that are quite thin, i.e., 50 μm or less, are being employed. While the polymer can be in alkali metal or ammonium salt form, it is typical for the polymer in the membrane to be in acid form to avoid post treatment acid exchange steps. Suitable perfluorinated sulfonic acid polymer membranes in acid form are available under the trademark Nation® by E.I. du Pont de Nemours and Company. Reinforced perfluorinated ion exchange polymer membranes can also be utilized in CCM manufacture. Reinforced membranes can be made by impregnating porous, expanded PTFE (ePTFE) with ion exchange polymer. ePTFE is available under the tradename "Goretex" from W. L. Gore and Associates, Inc., Elkton, MD, and under the tradename "Tetratex" from Tetratec, Feasterville, PA. Impregnation of ePTFE with perfluorinated sulfonic acid polymer is disclosed in U.S. Patents 5,547,551 and 6,110,333. Alternately, the ion exchange membrane can be a porous support. A porous support may improve mechanical properties for some applications and/or decrease costs. The porous support can be made from a wide range of components, including hydrocarbons and polyolefins, e.g., polyethylene, polypropylene, polybutylene, copolymers of these matrials including polyolefins, and the like. Perhalogenated polymers such as polychlorotrifluoroethylene can also be used. The membrane can also be made from a polybenzimadazole polymer, for example, by casting a solution of polybenzimadazole in phosphoric acid (H₃P0 ) doped with trifluoroacetic acid (TFA) as described in U.S. Patent Nos. 5,525,436, 5,716,727, 6,025,085 and 6,099,988. Activation of the precursors allows the electrocatalyst to simultaneously display catalytic properties, electron-conductive properties, proton-conductive properties and fluid transport properties. Thus, the activation process transforms the precursor to a composite material having a useful electrocatalystic activity. The precursors according to the present invention may be made and activated according to various methods including, but not limited to: (a) penetratively coating a vapor deposited columnar precursor with a proton-conductive solution composed of a solvent and an ion exchange polymer dispersion;and removing the solvent from the penetratively coated proton-conductive solution by evaporation and coalescing thermally the proton-conductive coating, where the temperature is at or slightly above the glass transition point of the proton-conductive material (i.e., Nation has a glass transition temperature of approximately 120°C) for a period of time that is long enough to allow sufficient molecular diffusion but short enough to minimize polymer degradation; also a nitrogen atmosphere to eliminate oxidation is used; and (b) subjecting the proton-conductive-coated vapor deposited columnar precursor to a chemical treatment, wherein the chemical treatment comprises (b1) immersing the proton-conductive- coated vapor deposited columnar precursor in a first solution (aqueous) held at room temperature and having a volume at least 10.000X larger than the volume of the vapor deposited columnar precursor, whereby the composition of the solution is increased from 0 to 20 wt% NaOH in less than one hour, where the NaOH is added dropwise or a premixed 20% NaOH solution is prepared; or (b2) immersing the proton-conductive - coated vapor deposited columnar precursor in a solution held at room temperature and having a volume at least 10,000X larger than the volume of the vapor deposited columnar precursor, whereby the composition of the aqueous solution is; increased from 0 to 20 wt-% NaOH in less than two hours, where the NaOH is added dropwise; followed by continuous heating the 20 wt-% NaOH solution up to 80°C in less than one hour; and (c) extensively rinsing the caustic treated material from (b) with water; (d) immersing the water rinsed material from (c) in a 20 wt-% nitric acid solution (aqueous) held at 90°C for a period of up to 2 hours, followed by extensive water rinsing at room temperature. Alternatively, the process of producing an activated columnar electrocatalyst may comprise (a) subjecting the vapor deposited columnar precursor to a chemical treatment, wherein the chemical treatment comprises (a1) immersing the vapor deposited columnar precursor in an aqueous solution held at room temperature and having a volume at least 10,000X larger than the volume of the vapor deposited columnar precursor, whereby the composition of the solution is increased from 0 to 20 wt-% NaOH in less than two hours, where the NaOH is added dropwise followed by extensive water rinsing at room temperature; or (a2) immersing the vapor deposited columnar precursor in an aqueous solution held at room temperature and having a volume at least 10.000X larger than the volume of the vapor deposited columnar precursor, whereby the composition of the solution is increased from 0 to 20 wt-% NaOH in less than two hours, where the NaOH is added dropwise; followed by continuous heating the 20 wt-% NaOH up to 80°C in less than one hour; followed by extensive water rinsing at room temperature; and (b) penetratively coating the product of (a) with a proton-conductive solution; and removing the solvent from the penetratively coated proton-conductive solution by evaporation; and coalescing thermally the proton-conductive coating, where the temperature is at or slightly above the glass transition point of the proton-conductive material (i.e., Nation has a glass transition temperature of approximately 120°C) for a period of time that is long enough to allow sufficient molecular diffusion but short enough to minimize polymer degradation; also a nitrogen atmosphere to eliminate oxidation is used; and (c) immersing the product of (b) in a 20 wt-% nitric acid solution held at 90°C for a period of up to 2 hours, followed by extensive water rinsing at room temperature. Still another alternative provides for producing an activated electrocatalyst comprising an electron-conductive porous nano-scale columnar precursor penetratively coated with a proton-conductive material , wherein the complete penetrative coating occurs in steps, the process comprising: (a) subjecting the penetratively coated electron-conductive porous nano-scale columnar structure to a chemical treatment, wherein the chemical treatment comprises: (a1) immersing the penetratively coated electron-conductive porous nano-scale columnar structure in a solution held at room temperature and having a volume at least 10,000X larger than the volume of the columnar structure, whereby the composition of the solution is increased from 0 to 20 wt- % NaOH in less than two hours followed by extensive water rinsing at room temperature; or (a2) immersing the penetratively coated electron-conductive porous nano-scale columnar structure in a solution held at room temperature and having a volume at least 10,000X larger than the volume of the structure, whereby the composition of the solution is increased from 0 to 20 wt-% NaOH in less than two hours; followed by heating the 20 wt- % NaOH up to 80°C in less than one hour; followed by extensive water rinsing at room temperature, (b) penetratively coating the product of (a) with a proton- conductive solution, and removing the solvent from the penetratively coated proton-conductive solution; and coalescing thermally the proton-conductive coating; and (c) immersing the product of (b) in a 20 wt-% nitric acid solution held at 90°C for a period of up to 2 hours, followed by extensive water rinsing at room temperature. Other alternative chemical treatments include a cyclic electrochemical dealloying of the precursor, wherein the precursor is immersed in a sulfuric acid solution. The present invention also contemplates an assembly including the membrane, and gas diffusion backings with the electrocatalyst composition coated either on the membrane or the gas diffusion backings or on both, wherein this is sometimes referred to as a membrane electrode assembly ("MEA"). Bipolar separator plates, made of a conductive material and providing flow fields for the reactants, are placed between a number of adjacent MEAs. A number of MEAs and bipolar plates are assembled in this manner to provide a fuel cell stack. In accordance with the present invention, MEA's and fuel cells comprising these MEA's deliver high mass specific current densities. For the electrodes to function effectively in the fuel cells, effective anode and cathode electrocatalyst sites are provided. Effective anode and cathode electrocatalyst sites have several desirable characteristics: (1) the sites are accessible to the reactant, (2) the sites are electrically connected to the gas diffusion layer, and (3) the sites are ionically connected to the fuel cell electrolyte. It is desirable to seal reactant fluid stream passages in a fuel cell stack to prevent leaks or inter-mixing of the fuel and oxidant fluid streams. Fuel cell stacks typically employ fluid tight resilient seals, such as elastomeric gaskets between the separator plates and membranes. Such seals typically circumscribe the manifolds and the electrochemically active area. Sealing can be achieved by applying a compressive force to the resilient gasket seals. Compression enhances both sealing and electrical contact between the surfaces of the separator plates and the MEAs, and sealing between adjacent fuel cell stack components. In conventional fuel cell stacks, the fuel cell stacks are typically compressed and maintained in their assembled state between a pair of end plates by one or more metal tie rods or tension members. The tie rods typically extend through holes formed in the stack end plates, and have associated nuts or other fastening means to secure them in the stack assembly. The tie rods may be external, that is, not extending through the fuel cell plates and MEAs, however, external tie rods can add significantly to the stack weight and volume. It is generally preferable to use one or more internal tie rods that extend between the stack end plates through openings in the fuel cell plates and MEAs as described in U.S. Patent No. 5,484,666. Typically resilient members are utilized to cooperate with the tie rods and end plates to urge the two end plates towards each other to compress the fuel cell stack. The resilient members accommodate changes in stack length caused by, for example, thermal or pressure induced expansion and contraction, and/or deformation. That is, the resilient member expands to maintain a compressive load on the fuel cell assemblies if the thickness of the fuel cell assemblies shrinks. The resilient member may also compress to accommodate increases in the thickness of the fuel cell assemblies. Preferably, the resilient member is selected to provide a substantially uniform compressive force to the fuel cell assemblies, within anticipated expansion and contraction limits for an operating fuel cell. The resilient member can comprise mechanical springs, or a hydraulic or pneumatic piston, or spring plates, or pressure pads, or other resilient compressive devices or mechanisms. For example, one or more spring plates can be layered in the stack. The resilient member cooperates with the tension member to urge the end plates toward each other, thereby applying a compressive load to the fuel cell assemblies and a tensile load to the tension member. EXAMPLES Vapor Deposition Step: A carbon cloth single-sided coated with a carbon/PTFE microporous layer, manufactured and sold by ETEK (manufactured by DeNora North America, Somerset, NJ) as an ELAT SS V3 gas diffusion backer, and measuring 4.5 x 4.5 inches was placed on the rotary table of a Perkin Elmer 2400 sputter vapor deposition reactor. Following attainment of a base pressure below 5 • 10^"6 Torr, the chamber was backfilled with flowing Ar to a process pressure of 10 mTorr. The rotary table was grounded and placed in motion a 4 RPM, and a RF diode sputter vaporization sourced having a Pt target was ignited at 500 watts, and simultaneously a DC magnetron vaporization source having an Al target was ignited at 1500 watts. Under these co-ignition conditions, the GDB substrate was repeatedly transported under the vaporization sources to deposit the metal vapors onto the carbon/PTFE microporous layer. Co- ignition was terminated after a period of 2.5 minutes. Activation Treatment: An ink composed of 8wt.-% solids in an amyl alcohol solvent was used to spray a microporous Nation® 990EW/Carbon XC72 layer over the vapor deposited layer to penetratively coat it. The Nafion®:carbon weight ratio of such layer was 1 :4, and the ionomer was in proton form. Following spraying, the electrode was heat treated for 15 minutes at 125°C in a flowing N₂ atmosphere held at 15 inches of Hg of pressure. Caustic immersion -Vapor deposited fluid diffusive substrates prepared as above were immersed for 15 minutes in a 20wt-% NaOH solution held at RT, followed by immersion in a 20 wt-% NaOH solution held at 80°C for 15 minutes. Nitric acid treatment -Vapor deposited and caustic-treated fluid diffusive substrates prepared as above were subsequently immersed in a 20 wt-% HN0₃ solution held at 90°C for 120 minutes. Deionized water treatment -Vapor deposited and caustic and acid- treated fluid diffusive substrates prepared as above were subsequently immersed for 5 minutes in three sequential deionized water solutions held at RT. Cell Assembly Procedure: Fuel cell hardware was supplied by Fuel Cell Technologies, Inc., (located in Albuquerque, NM). Anode and cathode field flow plates were POCO graphite with a machined single serpentine flow field on both sides over a 25 cm² active area. Lay one gasket assembly on anode graphite block. Place gas diffusion anode (catalyst + microporous layer facing up) measuring 25 cm² into the gasket opening so that it does not overlap the gasket. Place the Nation® 112 membrane film (1100EW, 50 μm thick) onto the gas diffusion anode and the gasket. Lay one gasket assembly on the stack of materials. Place gas diffusion cathode (catalyst + microporous layer facing down) measuring 25 cm² into the cathode gasket opening so that it does not overlap the gasket. Place cathode graphite block on the stack and close hardware with end plates. Torque bolts in a diagonal pattern in increments of 10 in-lbs to a final torque of 36 in-lb. Cell Conditioning and Polarization Procedure: Started-up fuel cell at 65°C with fully humidified hydrogen and air at 0 psig (hydrogen flow = 0.563 SLPM; air flow = 1.786 SLPM), and held voltage at 0.2 V for 2.5 hours to hydrate the membrane. The IV polarization curve was determined under fixed hydrogen flow rate set by a stoichiometric ratio of 1.5 at 2 A/cm², and fixed air flow rate set by a stoichiometric ratio of 2.0 at 2.0 A/cm². Water flow for membrane humidification at 100%RH for both electrodes. Cell current was measured at the following sequence of controlled voltages: 0.9 V, 0.7 V, 0.5 V, 0.3 V, 0.2 V, 0.3 V, 0.5 V, 0.7 V and 0.9 V. Each voltage level was held for 15 minutes. Reported current was the average of the current readings taken during the last five minutes of each voltage level, for the voltage-increasing excursion. Catalyst Loadings: Inductively coupled plasma (ICP) and/or X-ray fluorescence (XRF) analysis were preferentially used to measure the loading of catalysts on the electrodes. Example 1 : A Control MEA comprised of commercially available ETEK gas diffusion electrodes, nominally loaded at 0.500 mg_Pt/cm², was assembled into a cell with 10-mil thick gasket assemblies and yielded a cell power density dependency on the mass specific anode current density as shown in Figure 1. Example 2: An experimental MEA comprised of an experimental gas diffusion anode loaded at 0.013 mgpt/cm²and an ETEK gas diffusion cathode nominally loaded at 0.500 mgpt/cm²was assembled into a cell with 10-mil thick gasket assemblies and yielded a cell power density dependency on the mass specific anode current density as shown in Figure 1. The results set forth according to Figure 1 , shows that the MEA comprising a skeletal gas diffusion anode according to the present invention was able to attain the same cell peak power density (maximun ordinate value of roughly 635+3 mW/cm²) as the commercially available MEA of Example 1 , but with a much better utilized anode electrocatalyst given that its mass specific current density at peak power density was roughly forty times (40X) higher than that of the Control.

Claims

CLAIMS What is claimed is: 1. An electrocatalyst comprising: an activated precursor comprising an electron-conductive porous nano-scale columnar structure penetratively coated with a proton- conductive material. 2. The electrocatalyst according to claim 1 , wherein the electron- conductive columnar precursor has the formula (PtX_a)Yt_>, wherein X indicates an individual element or mixture of elements from at least one of columns IMA, IVA, VA, VIA, VIIA, VIIIA, IB, and MB of the periodic table, Y is an individual element or mixture of elements from at least one of Al, Li, Be, Mg, Zn, Cd, Hg, Ga, In, Ge, Sn, Pb, As, Sb or Bi; and a is at least 0.001 , and b is at least 0.85*» (1+a). 3. The electrocatalyst according to claim 2, wherein X is Ru, Rh, Mo, W, V, Hf, Zr, Nb, Co and mixtures thereof, Y is at least one of Al, Mg, Zn,

Ge or Sn; a is at least 0.01 , and b is at least 1.5*»(1+a). 4. The electrocatalyst according to claim 3, wherein X is Ru, Rh, Mo, W, V, Hf, Zr, Nb, Co and mixtures thereof, Y is Al; a is at least 0.01 , and b is at least 1.5*(1+a). 5. The electrocatalyst according to claim 1 , wherein the electrocatalyst contains less than 200 μgp_t/cm². 6. The electrocatalyst according to claim 5, wherein the electrocatalyst contains less than 150 μg_Pt/cm² of the electrocatalyst. 7. The electrocatalyst according to claim 6, wherein the electrocatalyst contains less than 100 μgp_t/cm² of the electrocatalyst. 8. The electrocatalyst according to claim 1 , wherein the volume fraction of the proton-conductive material is at least 1 %. 9. The electrocatalyst according to claim 8, wherein the volume fraction of the proton-conductive material is at least 5 %. 10. The electrocatalyst according to claim 9, wherein the volume fraction of the proton-conductive material is at least 10 %. 11.The electrocatalyst according to claim 1 , wherein a caustic activated precursor has a BET surface area greater than 10 m²/gp_t. 12. The electrocatalyst according to claim 11 , wherein a caustic activated precursor has a BET surface area greater than 30 m²/gp_t. 13. The electrocatalyst according to claim 12, wherein a caustic activated precursor has a BET surface area greater than 60 m²/gp_t. 14. A coated substrate comprising: (a.) a substrate; and (b.) the electrocatalyst according to claim 1 coated thereon. 15. The coated substrate according to claim 14, wherein the coated substrate is a catalyst-coated membrane or a gas diffusion backing. 16. A membrane electrode assembly comprising the electrocatalyst of claim 1. 17. A fuel cell comprising the electrocatalyst of claim 1. 18. An electron-conductive columnar precursor comprising the general the formula: wherein X indicates an individual element or mixture of elements from at least one of columns MIA, IVA, VA, VIA, VIIA, VIIIA, IB, and MB of the periodic table, Y is an individual element or mixture of elements from at least one of Al, Li, Be, Mg, Zn, Cd, Hg, Ga, In, Ge, Sn, Pb, As, Sb or Bi; a is at least 0.001 , and b is at least 0.85* (1+a). 19. The electron-conductive columnar precursor according to claim 18, wherein X is at least one of Ru, Rh, Mo, W, V, Hf, Zr, Nb, Co, Y at least one of Al, Mg, Zn, Ge or Sn; a is at least 0.01 , and b is at least 1.5»(1+a). 20. The electrocatalyst according to claim 18, wherein X is Ru, Rh, Mo, W, V, Hf, Zr, Nb, Co and mixtures thereof, Y is Al; a is at least 0.01 , and b is at least 1.5*»(1+a). 21. A method for producing an electrocatalyst comprising an electron- conductive porous nano-scale columnar precursor penetratively coated with a proton-conductive material comprises: (a) subjecting the penetratively coated electron-conductive porous nano-scale columnar structure to a chemical treatment, wherein the chemical treatment comprises: (a1) immersing the penetratively coated electron-conductive porous nano-scale columnar structure in a solution held at room temperature and having a volume at least 10,000X larger than the volume of the structure, whereby the composition of the solution is increased from 0 to 20 wt-% NaOH in less than two hours followed by extensive water rinsing at room temperature; or (a2) immersing the penetratively coated electron-conductive porous nano-scale columnar structure in a solution held at room temperature and having a volume at least 10,000X larger than the volume of the structure, whereby the composition of the solution is increased from 0 to 20 wt-% NaOH in less than two hours; followed by heating the 20 wt-% NaOH up to 80°C in less than one hour; followed by extensive water rinsing at room temperature, (b) penetratively coating the product of (a) with a proton-conductive solution, and removing the solvent from the penetratively coated proton- conductive solution; and coalescing thermally the proton-conductive coating; and (c) immersing the product of (b) in a 20 wt-% nitric acid solution held at 90°C for a period of up to 2 hours, followed by extensive water rinsing at room temperature. 22. A method of producing a columnar electrocatalyst comprising: (a) penetratively coating a columnar precursor with a proton- conductive solution; and removing the solvent from the penetratively coated proton-conductive solution; and thermally coalescing the proton- conductive coating; and (b) subjecting the proton-conductive -coated columnar precursor to a chemical treatment, wherein the chemical treatment comprises: (b1) immersing the proton-conductive -coated columnar precursor in a first solution held at room temperature and having a volume at least 10,000X larger than the volume of the columnar precursor, whereby the composition of the solution is increased from 0 to 20 wt% NaOH in less than one hour; or (b2) immersing the proton-conductive coated columnar precursor in a solution held at room temperature and having a volume at least 10,000X larger than the volume of the vapor deposited columnar precursor, whereby the composition of the solution is increased from 0 to 20 wt-% NaOH in less than two hours; followed by heating the 20 wt-% NaOH solution up to 80°C in less than one hour; and (c) extensively rinsing the caustic treated material from (b) with water; (d) immersing the water rinsed material from (c) in a 20 wt-% nitric acid solution held at 90°C for a period of up to 2 hours, followed by extensive water rinsing at room temperature. 23. A method of producing an columnar electrocatalyst comprising: (a) subjecting the columnar precursor to a chemical treatment, wherein the chemical treatment comprises: (a1) immersing the columnar precursor in a solution held at room temperature and having a volume at least 10.000X larger than the volume of the columnar precursor, whereby the composition of the solution is increased from 0 to 20 wt-% NaOH in less than two hours followed by extensive water rinsing at room temperature; or (a2) immersing the columnar precursor in a solution held at room temperature and having a volume at least 10.000X larger than the volume of the columnar precursor, whereby the composition of the solution is increased from 0 to 20 wt-% NaOH in less than two hours; followed by heating the 20 wt-% NaOH up to 80°C in less than one hour; followed by extensive water rinsing at room temperature; and (b) penetratively coating the product of (a) with a proton- conductive solution; and removing the solvent from the penetratively coated proton-conductive solution; and coalescing thermally the proton- conductive coating; and (c) immersing the product of (b) in a 20 wt-% nitric acid solution held at 90°C for a period of up to 2 hours, followed by extensive water rinsing at room temperature.