Illuminating Oxygen Reduction Reaction Kinetics in High Temperature Polymer Electrolyte Membrane Fuel Cells Using EIS

High Temperature Polymer Electrolyte Membrane Fuel Cells (HTPEMFCs) commercialization, is impeded by the sluggish, power intensive and elusive cathodic Oxygen Reduction Reaction (ORR) kinetics. In this work we provide solid experimental evidence that the simple three elementary step Dissociative Adsorption (DA) pathway, with two intermediate species (O ad and OH ad ), can accurately describe the steady state (IV) and the Electrochemical Impedance Spectra (EIS) response of a HTPEMFC. Deconvoluted EIS outlined the important role of Intrinsic Kinetic Inertia , which dominated both EIS and polarization resistance. The Degree of Rate Control (DRC) analysis, identified the O 2(g) dissociative adsorption as the rate limiting step. Finally, Transition State Theory (TST) allowed the extraction and analysis of ORR energetics, demonstrating that the high ORR overpotential losses originate from the combined strength of both kinetically and thermodynamically imposed barriers, due to the high bonding strength of O ad on Pt and the high activation energy of O 2(g) adsorption.