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

Owing to their notable power efficiency and zero greenhouse emissions, High Temperature Polymer Electrolyte Membrane Fuel Cells (HTPEMFCs) hold immense promise as a prospective candidate for generating clean energy. However, their commercialization is still impeded by the cathodic Oxygen Reduction Reaction (ORR) kinetics, which after almost half a century not only remain elusive, but constitute the most energy-intensive process, requiring large amounts of the expensive Pt catalyst to mitigate. In this work we provide solid experimental evidence, that the simple three elementary step Dissociative Adsorption Pathway (DAP) with two intermediate species (O ad and OH ad ), can accurately capture both the steady state (IV) and the Electrochemical Impedance Spectra (EIS) as well. Detailed EIS and IV experimental data were recorded at 180 °C under differential conditions, using a single serpentine HTPEMFC with a 4 cm 2 active area. The fuel cell operated at the activation regime, where ORR potential losses dominate but mass transport limitations are negligible. The experimental data were successfully fitted with the derived analytic IV and EIS microkinetic model. The use of the DAP in accordance with the Transitions State Theory (TST), allowed the extraction and analysis of ORR kinetics and energetics. The deconvoluted EIS outlined the important role of the intrinsic kinetic inertia , i.e. the outcome of the competitive nature of the elementary reaction steps on the adsorbed intermediate species. Kinetic inertia not only dominated EIS and the polarization resistance, but demonstrated that the commonly used Butler Volmer and apparent Tafel slope kinetic approach is incapable of describing the multistep ORR kinetics. With the help of the Degree of Rate Control (DRC) analysis, we successfully identified the O 2(g) dissociative adsorption as the rate limiting step. Finally, from an energetics perspective, by employing the TST kinetics formulation, we were able to calculate the free Gibbs’ transition states activation (kinetics) and reaction steps’ energies (thermodynamics). These results clarified that, the high ORR overpotential losses stem from the combined strength of both kinetically and thermodynamically imposed barriers, which originate from the high bonding strength of O ad on the Pt surface and the rather high activation energy of the O 2(g) adsorption step.