Membrane electrode assembly with improved electrode

Abstract

A membrane electrode assembly comprises a polymer electrolyte interposed between an anode electrode and a cathode electrode, the anode electrode comprising an anode catalyst layer adjacent at least a portion of a first major surface of the polymer electrolyte, the cathode electrode comprising a cathode catalyst layer adjacent at least a portion of a second major surface of the polymer electrolyte; at least one of the anode and cathode catalyst layers comprising: a first catalyst composition comprising a noble metal; and a second composition comprising a metal oxide; wherein the second composition has been treated with a fluoro-phosphonic acid compound.

Claims

1. A method of making a membrane electrode assembly, the membrane electrode assembly comprising a polymer electrolyte interposed between an anode electrode and a cathode electrode, the anode electrode comprising an anode catalyst layer adjacent at least a portion of a first surface of the polymer electrolyte, the cathode electrode comprising a cathode catalyst layer adjacent at least a portion of a second surface of the polymer electrolyte, at least one of the anode and cathode catalyst layers comprising a first catalyst composition comprising a noble metal, other than ruthenium, and a second composition comprising a metal oxide, wherein the second composition has been treated with a fluoro-phosphonic acid compound, the method including: forming a fluoro-phosphonic acid compound dispersion by dissolving the fluoro-phosphonic acid compound in a solvent; dispersing the fluoro-phosphonic acid compound dispersion with a metal oxide; forming the treated second composition by removing the solvent after dispersing the fluoro-phosphonic acid compound dispersion with the metal oxide; and applying the treated second composition to at least one of the anode catalyst layer and the cathode catalyst layer.

2. The method of claim 1, further comprising heating the treated second composition at a temperature above room temperature prior to applying the treated second composition to at least one of the anode catalyst layer and the cathode catalyst layer.

3. The method of claim 1, wherein the fluoro-phosphonic acid compound is a fluoroalkyl-phosphonic acid compound.

4. The method of claim 1, wherein the fluoro-phosphonic acid compound is 2-perfluorohexyl ethyl phosphonic acid.

5. The method of claim 1, wherein the fluoro-phosphonic acid compound is (1H,1H,2H,2H-heptadecafluorodec-1-yl) phosphonic acid.

6. The method of claim 1, wherein the fluoro-phosphonic acid compound has a molecular weight of at least 300.

7. The method of claim 1, wherein the fluoro-phosphonic acid compound has a chain length of six to twelve carbons.

8. The method of claim 1, wherein the noble metal of the first catalyst composition comprises platinum or a platinum alloy.

9. The method of claim 1, wherein the metal oxide of the second composition is a single-phase solid solution comprising ruthenium.

10. The method of claim 1, wherein the metal oxide of the second composition is a single-phase solid solution comprising iridium.

11. The method of claim 1, wherein the metal oxide of the second composition is selected from the group consisting of ruthenium oxide, iridium oxide, titanium oxide, cerium oxide, and their mixtures, solid solutions and composites thereof.

12. The method of claim 1, wherein: the anode catalyst layer includes a first catalyst composition comprising a noble metal, other than ruthenium, and a second composition comprising a metal oxide, wherein the second composition has been treated with a fluoro-phosphonic acid compound; and the cathode catalyst layer does not include a first catalyst composition comprising a noble metal, other than ruthenium, and a second composition comprising a metal oxide, wherein the second composition has been treated with a fluoro-phosphonic acid compound.

13. The method of claim 1, wherein the first catalyst composition has not been treated with a fluoro-phosphonic acid compound.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1a shows the dispersion properties of the untreated RuIrOx powder in water.

(2) FIG. 1b shows the dispersion properties of the treated RuIrOx powder in water.

(3) FIG. 2 shows the cell reversal tolerance test results of the fuel cells with the treated and untreated catalyst compositions on the anode.

DETAILED DESCRIPTION

(4) In the following description, certain specific details are set forth in order to provide a thorough understanding of the various embodiments of the invention. However, one skilled in the art will understand that the invention may be practiced without these details. In other instances, well-known structures associated with fuel cells, fuel cell stacks, batteries and fuel cell systems have not been shown or described in detail to avoid unnecessarily obscuring descriptions of the embodiments of the invention.

(5) Unless the context requires otherwise, throughout the specification and claims which follow, the word “comprise” and variations thereof, such as, “comprises” and “comprising” are to be construed in an open, inclusive sense, that is as “including, but not limited to.”

(6) A “corrosion resistant support material” is at least as resistant to oxidative corrosion as Shawinigan acetylene black (Chevron Chemical Company, TX, USA).

(7) An electrochemical fuel cell includes a polymer electrolyte interposed between an anode electrode and a cathode electrode, a cathode catalyst layer between the polymer electrolyte and the cathode electrode, and an anode catalyst layer between the polymer electrolyte and the anode electrode. In one embodiment, the anode catalyst layer includes a first catalyst composition comprising a noble metal; and a second catalyst composition comprising a metal oxide; wherein the second catalyst composition has been treated with a fluoro-phosphonic acid compound. In specific embodiments, the metal oxide may be a ruthenium-containing metal oxide and/or an iridium-containing metal oxide.

(8) The inventors surprisingly discovered that by treating the ruthenium-containing metal oxide with a fluoro-phosphonic acid compound, performance degradation due to ruthenium dissolution under voltage cycling conditions (i.e., start-up/shutdown) was reduced, thus indicating the ruthenium dissolution was reduced.

(9) Without being bound by theory, the inventors suspect that covalent bonding of fluoroalkyl phosphonic acid with metal oxides through a self-assembly condensation process, which increased its hydrophobicity and reduced degradation.

(10) However, the inventors expected that by treating the ruthenium-containing metal oxide with a fluoro-phosphonic acid compound, cell reversal tolerance would be reduced because water would be pushed away from the ruthenium-containing metal oxide (due to the hydrophobic fluorinated alkyl groups), which would reduce the capability of the metal oxide to electrolyze water. It was surprisingly discovered that cell reversal tolerance was generally unaffected with the treatment. Furthermore, the inventors discovered that cell reversal tolerance was also improved for iridium-containing metal oxides. Without being bound by theory, it is suspected that the treatment forms a thin layer of fluoro-phosphonic acid at the surface of the ruthenium-containing metal oxide that renders it hydrophobic through the self-assembled surface via covalent bonding, without significantly affecting the reaction sites (or surface area) for water electrolysis. In other words, it is suspected that the treatment renders a change in the local relative humidity of the catalyst layer without negatively affecting cell reversal tolerance.

(11) In some embodiments, the average molecular weight of the fluoro-phosphonic acid compound ranges from about 200 to 1200. In specific embodiments, the average molecular weight of the fluoro-phosphonic acid compound ranges from about 300 to 1000.

(12) In some embodiments, the fluoro-phosphonic acid compound has a chain length of six to twelve carbons in its backbone.

(13) In one embodiment, the fluoro-phosphonic acid compound is a fluoroalkyl-phosphonic acid compound.

(14) In specific embodiments, the fluoroalkyl-phosphonic acid compound is a perfluoro-phosphonic acid compound, such as 2-perfluorohexyl ethyl phosphonic acid and 1H, 1H, 2h, 2H-heptadecaflurorodec-1-yl phosphoric acid (C10-PFPA).

(15) The first catalyst composition comprises at least one noble metal. The noble metal may comprise Pt or an alloy of Pt. In embodiments where a Pt alloy catalyst is employed, the alloy may include another noble metal, such as gold, ruthenium, iridium, osmium, palladium, silver; and compounds, alloys, solid solutions, and mixtures thereof. In some embodiments, the first catalyst composition comprises a mixture of a noble metal and non-noble metal, such as cobalt, iron, molybdenum, nickel, tantalum, tin, tungsten; and compounds, alloys, solid solutions, and mixtures thereof. While noble metals are described for the first catalyst composition, it is expected that non-noble metals, such as those described above, can also be used as the first catalyst composition in some applications.

(16) The first catalyst composition may either be unsupported or supported in dispersed form on a suitable electrically conducting particulate support. In some embodiments, the support used is itself tolerant to voltage reversal. Thus, it is desirable to consider using supports that are more corrosion resistant.

(17) The corrosion resistant support material may comprise carbon, if desired. High surface area carbons, such as acetylene or furnace blacks, are commonly used as supports for such catalysts. Generally, the corrosion resistance of a carbon support material is related to its graphitic nature: the more graphitic the carbon support, the more corrosion resistant it is. Graphitized carbon BA (TKK, Tokyo, JP) has a similar BET surface area to Shawinigan acetylene carbon and is a suitable carbon support material in some embodiments. In other embodiments suitable carbon support materials may include nitrogen-, boron-, sulfur-, and/or phosphorous-doped carbons, carbon nanofibres, carbon nanotubes, carbon nanohorns, graphenes, and aerogels.

(18) Instead of carbon, carbides or electrically conductive metal oxides may be considered as a suitable high surface area support for the corrosion resistant support material. For instance, tantalum, titanium and niobium oxides may serve as a corrosion resistant support material in some embodiments. In this regard, other valve metal oxides might be considered as well if they have acceptable electronic conductivity when acting as catalyst supports.

(19) In embodiments where the first catalyst composition is supported, the loading of the first catalyst composition on the support material is from about 20 to about 80% by weight, typically about 20 to about 50% by weight. For a noble metal catalyst, a lower catalyst loading on the support is typically preferred in terms of electrochemical surface area per gram of platinum (ECA), but a higher catalyst loading and coverage of the support appears preferable in terms of reducing corrosion of the support and in reducing catalyst loss during fuel cell operation.

(20) In some embodiments, the amount of the first catalyst composition that is desirably incorporated will depend on such factors as the fuel cell stack construction and operating conditions (for example, current that may be expected in reversal), cost, desired lifetime, and so on. For example, the catalyst loading of the first catalyst composition may range from about 0.05 mg Pt/cm.sup.2 on the low end for the anode electrode to about 0.8 mg Pt/cm.sup.2 on the high end for the cathode electrode.

(21) The second composition comprises a metal oxide, wherein the metal oxide may be, such as, but not limited to, ruthenium oxide, iridium oxide, titanium oxide, cerium oxide, and their mixtures, solid solutions and composites thereof. In addition, the metal oxide loading of the second composition may range from about 0.001 mg/cm.sup.2 to about 0.10 mg/cm.sup.2. It is expected that some empirical trials will determine an optimum amount for a given application. In some embodiments, the metal oxide may be supported on another metal oxide support.

(22) In one embodiment, the metal oxide of the second composition comprises ruthenium. In specific embodiments, the metal oxide is a single-phase solid solution comprising ruthenium. In further embodiments, the second composition comprises a single-phase solid solution of ruthenium oxide (90:10 mole ratio of Ru:Ir). For example, the metal oxide of the second composition is, but not limited to, RuO.sub.2 and RuIrO.sub.2. As mentioned, the metal oxide may be supported on a catalyst support, such as RuO.sub.2 supported on tantalum oxide, titanium oxide or niobium oxide.

(23) In other embodiments, the second catalyst composition comprises a metal oxide comprising iridium, such as a single-phase solid solution of iridium oxide. As mentioned, the metal oxide may be supported on a catalyst support, such as IrO.sub.2 supported on tantalum oxide, titanium oxide or niobium oxide.

(24) In further embodiments, a mixture of treated metal oxides may be used, depending on the application.

(25) In other embodiments, the first catalyst composition and the second composition may be in separate, discrete layers in the anode catalyst layer and/or cathode catalyst layer. For example, the first discrete layer with the first catalyst composition is adjacent the membrane and the second discrete layer with the second composition is adjacent the gas diffusion layer.

(26) In one general method to treat the metal oxide of the second composition, a fluoro-phosphonic acid compound is dissolved in a first solvent, a metal oxide is dispersed in another solvent that may be the same or different from the first solvent, and then the dispersions are dispersed together via conventional methods. The solvents are then removed from the dispersion, such as by evaporating the solvent or centrifuging the dispersion or other methods known in the art, and then further heat-treated at an elevated temperature for an adequate amount of time to form a powder of the fluoro-phosphonic acid-treated metal oxide. The fluoro-phosphonic acid-treated metal oxide may contain about 1.0 wt % to about 20.0 wt % of the fluoro-phosphonic acid compound. Without being bound by theory, the phosphonic acid covalently bonds to the surface oxygen at the surface of the metal oxide with this treatment.

(27) The second composition may be incorporated in the catalyst layer in various ways known in the art. In some embodiments, the first catalyst and second compositions may be mixed together and the mixture applied in a uniformly distributed common layer or layers on a suitable gas diffusion layer (GDL), polymer electrolyte membrane, or decal transfer sheet. With decal transfer, the catalyst layer may be decal transferred from the decal transfer sheet to a GDL to form a gas diffusion electrode, or may be decal transferred to a polymer electrolyte membrane to form a catalyst-coated membrane. As mentioned previously, the second composition may be supported on the same support material as the first catalyst composition, and thus both compositions are already “mixed” for application in one or more layers on an anode substrate, cathode substrate and membrane.

(28) In further embodiments, the first catalyst composition and the second composition may instead be applied in discrete, separate layers on a GDL, polymer electrolyte membrane, or decal transfer sheet, thereby making a bilayer or multilayer structure. By applying the first catalyst composition in one discrete layer and a second composition in a second discrete layer, one may use different ionomers, solvents and processing steps for each of the first and second compositions.

(29) In another embodiment, the second composition may be non-uniformly distributed, for example, located where degradation is expected to occur. Persons of ordinary skill in the art can readily select an appropriate manner of incorporation for a given application.

(30) The anode and cathode catalyst layers typically further include a binder, such as an ionomer and/or hydrophobic agent.

(31) In some embodiments, the through-plane concentration of ionomer in the present catalyst layer decreases as a function of distance from the polymer electrolyte interface. The presence of ionomer in the catalyst layer effectively increases the electrochemically active surface area of the catalyst, which requires an ionically conductive pathway to the cathode catalyst to generate electric current.

(32) As previously mentioned, the anode and cathode catalyst layers may be applied to a GDL to form anode and cathode electrodes, or to a decal transfer sheet which is then decal transferred to a surface of the GDL or polymer electrolyte, or applied directly to the surface of the polymer electrolyte to form a catalyst-coated membrane (CCM). The electrodes or CCM can then be bonded under heat and/or pressure with other components to form an MEA. Alternatively, the application of the catalyst layer on the desired substrate may occur at the same time the remaining MEA components are bonded together.

(33) The present catalyst layers may be applied according to known methods. For example, the catalyst may be applied as a catalyst ink or slurry, or as a dry mixture. Catalyst inks may be applied using a variety of suitable techniques (e.g., hand and machine methods, including hand brushing, notch bar coating, fluid bearing die coating, wire-wound rod coating, fluid bearing coating, slot-fed knife coating, three-roll coating, screen-printing and decal transfer) to the surface of the polymer electrolyte or GDL. Examples of dry deposition methods include spraying, vacuum deposition and electrostatic powder deposition techniques.

(34) Catalyst inks typically incorporate the catalysts and binder in a solvent/dispersant to form a solution, dispersion or colloidal mixture. Suitable solvents/dispersants include water, organic solvents such as alcohols and polar aprotic solvents (e.g., N-methylpyrrolidinone, dimethylsulfoxide, and N,N-dimethylacetamide), and mixtures thereof. Depending on the amount of water, one can distinguish water-based inks, wherein water forms the major part of the solvents used, from inks wherein organic solvents form the major part. Catalyst inks may further include surfactants and/or pore forming agents, if desired. Suitable pore formers include methyl cellulose; sublimating pore-forming agents such as durene, camphene, camphor and naphthalene; and pore-forming solvents that are immiscible with the catalyst ink solvent/dispersant, such as n-butyl acetate in polar aprotic solvent/dispersant systems.

(35) The selection of additional components for the catalyst mixture and the choice of application method and GDL to which it is applied are not essential to the present invention, and will depend on the physical characteristics of the mixture and the substrate to which it will be applied, the application method and desired structure of the catalyst layer. Persons of ordinary skill in the art can readily select suitable catalyst mixtures and application methods for a given application.

EXAMPLES

Example 1

(36) Five grams of ruthenium iridium oxide (RuIrO.sub.2) powder purchased from Johnson Matthey (Reading, UK) was dispersed in 60 mL of ethanol. 0.56 g of 2-perfluorohexyl ethyl phosphonic acid precursor (Unimatech, Japan) was separately dissolved in 5 mL of ethanol. Subsequently, the dispersion containing the RuIrO.sub.2 was probe ultasonicated. The solution containing the dissolved precursor was added to the sonicated dispersion in a dropwise manner (at about a flow rate of 1 mL/min) while stirring at room temperature for about 60 minutes. The dispersion was then transferred to a petri dish and evaporated at about 60 degrees Celsius overnight. The free flowing powder was transferred to an oven and heated to 150 degrees Celsius for 30 minutes, resulting in the final treated RuIrO.sub.2 powder with about 10 wt % of perfluorohexyl ethyl phosphonic acid.

(37) FIG. 1 shows the picture of treated RuIrO.sub.2 powder (right) in comparison to non-treated RuIrO.sub.2 (left) dispersed in water. As it can be seen, the treated RuIrO.sub.2 powder is completely hydrophobic and water could not wet the surface and, hence, it floats on water, even though the density of RuIrO.sub.2 is higher than water. On the other hand, non-treated RuIrO.sub.2 powder disperses well in water as it is highly hydrophilic.

Example 2

(38) Four grams of ruthenium iridium oxide (RuIrO.sub.2) powder purchased from Johnson Matthey (Reading, UK) was dispersed in 50 mL of isopropanol. 0.4 g of (1H,1H,2H,2H-heptadecafluorodec-1-YL) phosphonic acid (C10-PFPA) precursor (Advanced Technology and Industrial CO., LTD, Hong Kong) was separately dissolved in 50 mL of isopropanol. Subsequently, the dispersion containing the RuIrO.sub.2 was probe ultrasonicated. The solution containing the dissolved precursor was added to the sonicated dispersion in a dropwise manner (at about a flow rate of 1 mL/min) while stirring at room temperature overnight. The dispersion was then centrifuged to separate the catalyst from the solution. The powder at the bottom of the centrifuge tube was dried in a vacuum oven at 80 degrees Celsius for overnight, resulting in the final treated RuIrO.sub.2 powder with about 2 wt % of C10-PFPA.

Example 3

(39) Five grams of iridium oxide (IrO.sub.2) powder purchased from Tanaka Kikinzoku International, Inc. (USA) was dispersed in 50 mL of 1-propanol. 0.35 g of (1H,1H,2H,2H-heptadecafluorodec-1-YL) phosphonic acid (C10-PFPA) precursor was separately dissolved in 30 mL of 1-propanol. Subsequently, the dispersion containing the IrO.sub.2 was probe ultrasonicated. The solution containing the dissolved precursor was added to the sonicated dispersion in a dropwise manner (at about a flow rate of 1 mL/min) while stirring at room temperature. The dispersion was then heated up to 100 degrees Celsius for approximately 3 hours to evaporate all the solvent, resulting in the final treated IrO.sub.2 powder with about 7 wt % of C10-PFPA.

(40) The treated RuIrO.sub.2 powder of Examples 1 and 2, as well as the IrO.sub.2 powder of Example 3, were then dispersed in a Nafion®/alcohol mixture with a platinum-based catalyst, then applied to a decal transfer film and subsequently decal transferred via heat and pressure to a half CCM (Nafion® 211 membrane with cathode catalyst on one side) to form a full CCM. Untreated RuIrO.sub.2 powder and untreated IrO.sub.2 powder were also incorporated in a similar fashion to form full CCMs.

(41) The MEAs were made with the following electrode structures as listed in Table 1, with the CCM sandwiched between two AvCarb® GDLs (AvCarb Materials Solutions, Lowell, Mass.). The GDLs were bonded to the CCM via heat and pressure. The active area of each of the MEAs was 45 cm.sup.2.

(42) TABLE-US-00001 TABLE 1 Anode and cathode catalyst structures for MEAs MEA Example Anode Cathode Comparative 50% Pt supported on graphitized carbon black 50% Pt supported on MEA 1 at a catalyst loading of ~0.1 mg Pt/cm.sup.2; graphitized carbon ~0.06 mg/cm.sup.2 untreated RuIrO.sub.2 (single-phase black at ~0.4 mg Pt/cm.sup.2 solid solution (90:10 mole ratio Ru/Ir); Ionomer (23%): Nafion ® Johnson Matthey Plc, Reading, UK); Ionomer (23%): Nafion ® MEA 2 50% Pt supported on graphitized carbon black 50% Pt supported on (RuIrO.sub.2 of at a catalyst loading of ~0.1 mg Pt/cm.sup.2; graphitized carbon Example 1) ~0.06 mg/cm.sup.2 RuIrO.sub.2 (single-phase solid black at ~0.4 mg Pt/cm.sup.2 solution (90:10 mole ratio Ru/Ir); Johnson Ionomer (23%): Nafion ® Matthey Plc, Reading, UK) treated with 2- perfluorohexyl ethyl phosphonic acid; Ionomer (23%): Nafion ® MEA 3 50% Pt supported on graphitized carbon black 50% Pt supported on (RuIrO.sub.2 of at a catalyst loading of ~0.1 mg Pt/cm.sup.2; graphitized carbon Example 2) ~0.06 mg/cm.sup.2 RuIrO.sub.2 (single-phase solid black at ~0.4 mg Pt/cm.sup.2 solution (90:10 mole ratio Ru/Ir); Johnson Ionomer (23%): Nafion ® Matthey Plc, Reading, UK) treated with C10 PFPA; Ionomer (23%): Nafion ® Comparative 50% Pt supported on graphitized carbon black 50% Pt supported on MEA 4 at a catalyst loading of ~0.05 mg Pt/cm.sup.2; graphitized carbon ~0.026 mg/cm.sup.2 IrO.sub.2 (TKK); black at ~0.4 mg Pt/cm.sup.2 Ionomer (20%): Nafion ® Ionomer (23%): Nafion ® MEA 5 50% Pt supported on graphitized carbon black 50% Pt supported on (IrO.sub.2 of at a catalyst loading of ~0.05 mg Pt/cm.sup.2; graphitized carbon Example 3) ~0.026 mg/cm.sup.2 IrO.sub.2 (TKK); treated with C10 black at ~0.4 mg Pt/cm.sup.2 PFPA; Ionomer (23%): Nafion ® Ionomer (20%): Nafion ®

(43) The MEAs were then tested in a Ballard Standard Test Cell (STC) test fixture with graphite plates. The fuel cells were first conditioned overnight under the following conditions at 1.3 A/cm.sup.2:

(44) TABLE-US-00002 TABLE 2 Conditioning parameters Temperature 75° C. (coolant) Inlet Dew Point 75° C. (fuel and oxidant) Fuel 100% hydrogen Oxidant air Reactant inlet pressure 5 psig (fuel and oxidant) Reactant flow 4.5 (fuel), 9.0 (oxidant) slpm
Cell Reversal Testing

(45) The fuel cells were conditioned overnight at 1.3 A/cm.sup.2 at the conditions listed in Table 2. The fuel supply was then switched to humidified nitrogen and the cell was supplied with 200 mA/cm.sup.2 of current through an external power supply under current control mode. The cell reversal tolerance time was monitored until the cell voltage reached −2.0 V FIG. 2 shows that the first three fuel cells exhibited almost exactly the same behavior with almost the same cell reversal times (85 minutes for MEA 1 and MEA 1, and 89 minutes for MEA 3). Therefore, the treatment of RuIrO.sub.2 with either perfluorohexyl ethyl phosphonic acid or C10-PFPA did not significantly impact cell reversal tolerance, which, as discussed above, is a surprising and unexpected result due to the expected lower surface area of the RuIrO.sub.2 after treatment.

(46) For iridium oxide, it was shown that MEA 5 with a C10-PFPA-treated iridium oxide had a significantly improved cell reversal time in comparison to Comparative MEA 4, which did not have the C10-PFPA treatment. Comparative MEA 4 had a cell reversal time of less than 300 minutes while MEA 5 had a cell reversal time of greater than 450 minutes. Thus, the treatment of IrO.sub.2 with C10-PFPA had a positive effect on cell reversal tolerance.

(47) Anode Accelerated Stress Test

(48) Anode accelerated stress tests (ASTs) were used to simulate potential spikes that occur during fuel cell start-ups and shutdowns to induce ruthenium dissolution and crossover.

(49) The fuel cells were operated at 75° C., 5 psig (136 kPa) pressure, and 100% inlet RHs, 70% H.sub.2/30% N.sub.2 for the fuel, and a beginning of life (BOL) polarization was obtained. During the AST, the anode potential cycled between ˜0 and 0.9 V by switching the fuel between 70% H.sub.2/30% N.sub.2 for 1 minute and 100% N.sub.2 for 30 seconds, while the cathode potential was kept below 1.0 V to minimize cathode degradation. Unless otherwise stated, all half-cell potentials reported here are relative to the dynamic hydrogen reference electrode (DHE). After the AST, the fuel cells were again operated at the same conditions as the BOL polarization, and an end of life (EOL) polarization was obtained.

(50) At 1 A/cm.sup.2, it was shown that MEA 2 had a performance loss of 38 mV less than the baseline MEA 1, and MEA 3 had a performance loss of 67 mV less than the baseline MEA 1. Therefore, by treating the RuIrO.sub.2 catalyst with either perfluorohexyl ethyl phosphonic acid or C10-PFPA, the MEAs with the treated RuIrO.sub.2 catalyst exhibited significantly less performance loss at 1 A/cm.sup.2 than the untreated MEA.

(51) While the treated metal oxides have been described for the anode electrode in the preceding description, it is contemplated that such treated metal oxides may, additionally or alternatively, be used on the cathode electrode. Without being bound by theory, such treated metal oxides are beneficial for improved durability by mitigating carbon corrosion at high cathode potentials by acting as a water electrolysis catalyst.

(52) While the present electrodes have been described for use in PEM fuel cells, it is anticipated that they may be useful in other fuel cells having an operating temperature below about 250° C. They are particularly suited for acid electrolyte fuel cells, including phosphoric acid, PEM and liquid feed fuel cells. It is also contemplated that this treatment may also be useful for other metal oxides comprising ruthenium.

(53) All of the above U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification and/or listed in the Application Data Sheet, are incorporated herein by reference in their entirety.

(54) While particular elements, embodiments and applications of the present invention have been shown and described, it will be understood, of course, that the invention is not limited thereto since modifications may be made by those skilled in the art, particularly in light of the foregoing teachings. It is therefore contemplated by the appended claims to cover such modifications that incorporate those features coming within the scope of the invention.

(55) This application also claims the benefit of U.S. Provisional Patent Application No. 62/370,144, filed Aug. 2, 2016, and is incorporated herein by reference in its entirety.