Electrode Ionomer Accelerated Stress Test Applied to High Oxygen Permeability Ionomer in Fuel Cells

Abstract

Perfluorosulfonic acid (PFSA) polymer electrolytes are widely used in proton exchange membrane (PEM) fuel cell fabrication for the membrane separator and the electrode binder. The PEM serves to electrically insulate the cathode catalyst layer (CCL) from anode catalyst layer (ACL), provide proton conduction between both CCL and ACL, as well as prevent gas crossover. PFSA ionomers are also used in the CCL and ACL to mechanically bind the catalyst particles into thin-films, provide proton conduction between the PEM and catalyst surface, and produce a high proton reactant concentration at the oxygen reduction reaction catalyst. Despite their versatility to be used as a membrane and catalyst binder, the typical PFSA ionomers pose challenges due to the high oxygen transport resistance that is introduced by the thin ionomer films over the catalyst. In recent years, novel high oxygen permeability ionomers (HOPIs) have been developed as the successor to the traditional Nafion™ PFSA ionomers. Despite their remarkable results as a catalyst binder due to their increased oxygen transport rates, less is known regarding their degradation and functional lifetime. Although accelerated stress tests (ASTs) for platinum (Pt)/Pt-alloy catalysts, carbon supports, and membranes are well-established and commonly applied, there is no standard and easily implemented AST for electrode ionomers. One challenge is that membrane ASTs usually quantify the fluoride emission rate (FER) to assess chemical degradation, which is difficult to apply for electrode PFSA ionomer when also using a PFSA membrane because the FER is overwhelmed by membrane signal. In addition, changes in OCV and H2 crossover are not directly indicative of electrode ionomer degradation. Furthermore, concomitant degradation of the catalyst and support can interfere with interpreting electrode ionomer degradation. Here we present an effective and easily applied electrode ionomer chemical AST protocol that can be used to evaluate degradation in the functionality of the electrode ionomer. The approach borrows the chemical AST conditions of the chemical membrane AST’s open circuit voltage (OCV) hold and avoids excessive potential cycling to minimize catalyst and support degradation that will elicit changes in electrode properties separate from ionomer degradation. During the AST, we measure the cathode’s proton conduction resistance, oxygen permeability, and electrochemically surface area (ECSA) to evaluate the degradation of the ionomer’s functionality. Thus, this protocol can be used to assess if more complex and time consuming analyses of ionomer durability are needed as new chemistries emerge. Here we present results of this AST to both conventional PFSA ionomers and HOPIs.