Effect of Elevated Temperature and Reduced Relative Humidity on ORR Kinetics for PEM Fuel Cells

As a measure of catalytic activity, i η = 0 . 3 v ,the current density at 0.3 V overpotential, was chosen to evaluate the oxygen reduction reaction (ORR) at elevated temperatures (> 100°C) and various relative humidities(RH) for polymer exchange membrane (PEM) fuel cells. The purely kinetic reaction order of the ORR with respect to oxygen partial pressure is less than 1.0 and changes with the RH. The activation energy is 49 kJ/mol at 100% RH and 55 kJ/mol at 50% RH. The active electrochemical surface area of platinum changes little with RH. RH has a strong effect on the catalytic activity under dry conditions (0-60% RH), but under wet conditions (>60% RH) its influence is unclear. The Tafel slope obtained in the 1-100 mA/cm 2 current density range changes significantly with RH: wet conditions produce low Tafel slopes ( 100 mV/dec). Dependence of the RH on the oxygen reduction reaction (ORR) may be explained by the changes of the rate-determining reaction, proton activity, and adsorbed -OH on the platinum surface. The ORR kinetic parameters obtained here are instructive for high-temperature fuel cell data analysis and performance improvement.

[1]  James Larminie,et al.  Fuel Cell Systems Explained , 2000 .

[2]  Sanjeev Mukerjee,et al.  Effect of sputtered film of platinum on low platinum loading electrodes on electrode kinetics of oxygen reduction in proton exchange membrane fuel cells , 1993 .

[3]  C. R. Martin,et al.  Investigations of the O sub 2 reduction reaction at the platinum/Nafion interface using a solid-state electrochemical cell. Technical report , 1991 .

[4]  T. Gierke,et al.  Elastic theory for ionic clustering in perfluorinated ionomers , 1982 .

[5]  A. Weber,et al.  Transport in Polymer-Electrolyte Membranes II. Mathematical Model , 2004 .

[6]  T. Mussini,et al.  Cathodic reduction of oxygen on smooth platinum in acid solutions , 1965 .

[7]  A. Riddiford Mechanisms for the evolution and ionization of oxygen at platinum electrodes , 1961 .

[8]  D. S. Gnanamuthu,et al.  A Generalized Expression for the Tafel Slope and the Kinetics of Oxygen Reduction on Noble Metals and Alloys , 1967 .

[9]  Francisco A. Uribe,et al.  A study of polymer electrolyte fuel cell performance at high voltages. Dependence on cathode catalyst layer composition and on voltage conditioning , 2002 .

[10]  P. Ross,et al.  Surface science studies of model fuel cell electrocatalysts , 2002 .

[11]  T. R. Ralph,et al.  Catalysis for low temperature fuel cells. Part I: The cathode challenges , 2002 .

[12]  S. Srinivasan,et al.  Kinetics of Fuel Cell Reactions at the Platinum/Solid Polymer Electrolyte Interface , 1989 .

[13]  Ronghuan He,et al.  The CO Poisoning Effect in PEMFCs Operational at Temperatures up to 200°C , 2003 .

[14]  M. Ciureanu,et al.  Electrochemical Impedance Study of Electrode‐Membrane Assemblies in PEM Fuel Cells: I. Electro‐oxidation of H 2 and H 2 / CO Mixtures on Pt‐Based Gas‐Diffusion Electrodes , 1999 .

[15]  Yann Bultel,et al.  Oxygen reduction reaction kinetics and mechanism on platinum nanoparticles inside Nafion , 2001 .

[16]  Allen J. Bard,et al.  Electrochemical Methods: Fundamentals and Applications , 1980 .

[17]  H. Wroblowa,et al.  Electroreduction of oxygen , 1976 .

[18]  W. M. Vogel,et al.  The reduction of oxygen on platium black in acid electrolytes , 1977 .

[19]  H. R. Kunz,et al.  CO Tolerance of Carbon-Supported Platinum-Ruthenium Catalyst at Elevated Temperature and Atmospheric Pressure in a PEM Fuel Cell , 2004 .

[20]  A. Appleby Oxygen Reduction on Oxide‐Free Platinum in 85%Orthophosphoric Acid: Temperature and Impurity Dependence , 1970 .

[21]  H. R. Kunz,et al.  Development of New CO Tolerant Ternary Anode Catalysts for Proton Exchange Membrane Fuel Cells , 2003 .

[22]  T. Abe,et al.  Study of PEFCs by AC Impedance, Current Interrupt, and Dew Point Measurements I. Effect of Humidity in Oxygen Gas , 2004 .

[23]  P. Pickup,et al.  CHARACTERIZATION OF IONIC CONDUCTIVITY PROFILES WITHIN PROTON EXCHANGE MEMBRANE FUEL CELL GAS DIFFUSION ELECTRODES BY IMPEDANCE SPECTROSCOPY , 1999 .

[24]  S. Srinivasan,et al.  Effect of Preparation Conditions of Pt Alloys on Their Electronic, Structural, and Electrocatalytic Activities for Oxygen Reduction-XRD, XAS, and Electrochemical Studies , 1995 .

[25]  A. Appleby Evolution and reduction of oxygen on oxidized platinum in 85% orthophosphoric acid , 1970 .

[26]  Adam Z. Weber,et al.  Transport in Polymer-Electrolyte Membranes I. Physical Model , 2004 .

[27]  Hubert A. Gasteiger,et al.  Effect of Relative Humidity on Oxygen Reduction Kinetics in a PEMFC , 2005 .

[28]  Shimshon Gottesfeld,et al.  Determination of water diffusion coefficients in perfluorosulfonate ionomeric membranes , 1991 .

[29]  Charles R. Martin,et al.  Electrode kinetics of oxygen reduction at carbon-supported and unsupported platinum microcrystallite/Nafion® interfaces , 1992 .