Factors influencing electrochemical properties and performance of hydrocarbon based ionomer PEMFC catalyst layers

This work investigated the properties of catalyst layers for proton exchange membrane fuel cells (PEMFC) that contained sulfonated poly(ether ether ketone) (SPEEK). A series of SPEEK polymers were prepared with varying ion exchange capacity (IEC) to test their oxygen mass transport properties, electrochemical kinetic parameters, proton conductivity, and water sorption characteristics. A simple method to fabricate catalyst layers containing SPEEK and polytetrafluoroethylene (PTFE) was developed. Catalyst layers were analyzed using scanning electron microscopy (SEM), mercury porosimetry and contact angle determination. Electrochemical characterization in an operating fuel cell was performed using current-potential polarization, cyclic voltammetry, and electrochemical impedance spectroscopy. Electrochemical oxygen reduction in SPEEK membranes was examined in a solid-state electrochemical cell, which allowed determination of oxygen mass transport properties and kinetic parameters. The oxygen diffusion coefficient and permeability was found to increase with increasing ion exchange capacity (IEC), while the solubility of oxygen correspondingly decreased, these trends are due to an increase in water content with increasing IEC. In comparison to perfluorinated electrolytes, such as Nafion®, SPEEK exhibited a lower permeability of oxygen due to a considerably lower solubility of oxygen.A decrease in fuel cell performance was observed when SPEEK was employed in the cathode catalyst layer as the proton conducting medium. The fuel cell current density showed a strong dependence on the method of fabrication of the catalyst layer and the content of SPEEK. Compared to Nafion®-based catalyst layers, SPEEK catalyst layers were found to suffer from low electrochemically active surface area (ESA) and low ionic conductivity. The weight content of SPEEK electrolyte was found to strongly influence the mass transport limited current density.