Modeling the local potential at Pt nanoparticles in polymer electrolyte membranes

Abstract

We present a physical–analytical model for the potential distribution at Pt nanodeposits in a polymer electrolyte membrane (PEM). Experimental studies have shown that solid deposits of Pt in PEM play a dual role in radical-initiated membrane degradation. Surface reactions at Pt particles could facilitate the formation as well as the scavenging of ionomer-attacking radical species. The net radical balance depends on local equilibrium conditions at Pt nanodeposits in the PEM, specifically, their equivalent local electrode potential. Our approach utilizes a continuum description of crossover fluxes of reactant gases, coupled with the kinetics of electrochemical surface reactions at Pt nanodeposits to calculate the potential distribution. The local potential is a function of the PEM structure and composition, which is determined by PEM thickness, concentrations of H₂ and O₂, as well as the size and density distribution of Pt particles. Model results compare well with experimental data for the potential distribution in PEMs.