Investigations of the O 2 Reduction Reaction at the Platinum/Nafion® Interface Using a Solid‐State Electrochemical Cell

Research in solid polymer electrolyte fuel cells is gaining momentum because of the prospects of attaining high energy efficiencies and power densities essential for transportation and space applications. The most advanced solid polymer electrolytes for these fuel cells are the perfluorosulfonate ionomers (PFSIs), such as Du Pont's Nafion and the Dow PFSIs. The high oxygen solubility, chemical stability, proton conductivity and permselectivity exhibited by Nafion and the Dow PFSIs make them ideal candidates as electrolytes for fuel cells. Furthermore, the minimal anion adsorption on electrodes from fluorinated acids enhances oxygen reduction kinetics. The objectives of this work were to determine the concentration and diffusion coefficient of oxygen in Nafion, and the electrode kinetic parameters for the reduction of oxygen at the Pt/Nafion interface under totally solid‐state conditions ( i.e. , no contacting liquid electrolyte phase). Cyclic voltammetric and potentiostatic transient measurements were made at the Pt/Nafion interface. From cyclic voltammetric measurements, the purity of Nafion was ascertained and the roughness factor of the electrode was calculated. The slow sweep experiments yielded the Tafel parameters for oxygen reduction. From the two‐section Tafel plot, the calculated exchange current densities were found to be higher than those obtained at any other Pt/acid interface. From an analysis of the potentiostatic transients, the calculated values of oxygen solubility and diffusion coefficient in Nafion were higher than previously reported. These differences in mass‐transfer data were attributed to differences in water content of the Nafion membrane.