A.c.-impedance spectroscopy study of oxygen reduction at Nafion® coated gas-diffusion electrodes in sulphuric acid: Teflon loading and methanol cross-over effects

The kinetics of oxygen reduction have been studied at Nafion®-coated dual layer gas-diffusion electrodes at 60 °C in 2.5 M H₂SO₄. A.c. impedance and steady state galvanostatic measurements have been carried out on electrodes containing various PTFE loadings. A.c. impedance spectroscopy supplied information on charge transfer resistance, series resistance and double layer capacitance of electrodes during the oxygen reduction process. These parameters, together with those derived by d.c. measurements (i.e. Tafel slopes, charge transfer coefficient, etc.), allowed a better identification of the features governing the electrode efficiency and the reduction mechanism. The best electrode was found to be one containing 30% PTFE; this showed both the lowest charge transfer resistance and the lowest overpotential for oxygen reduction. This electrode also showed lower overpotential than the same uncoated electrode at low current densities. The poisoning effect by methanol has been also investigated. Upon addition of methanol to the solution, no change was observed in the reaction mechanism at low overpotentials. In contrast, a significant variation of the Tafel slope was observed at high overpotentials. This behaviour is interpreted in terms of the variation of Pt-O bond strength as a function of electrode potential.