Irreducible IrO2 Anode Co-Catalysts for PEM Fuel Cell Voltage Reversal Mitigation and Their Stability Under Start-Up/Shut-Down Conditions

IrO2 has been widely used as the anode co-catalyst for mitigating cell voltage reversal damages in proton exchange membrane fuel cells (PEMFCs). However, under the PEMFC anode operation conditions, conventionally prepared IrO2 catalysts are reduced by H2, forming metallic Ir on their surface, which is prone to dissolution during start-up/shut-down (SUSD) cycles. The dissolved Irn+ ions can permeate through the membrane to the cathode electrode, poisoning the oxygen reduction reaction (ORR) activity of the Pt/C cathode catalyst. In this study, we introduce an unprecedented approach to synthesize IrO2 catalysts (irr-IrO2) which are not reduced in the PEMFC anode environment at 80°C over extended time. Their preparation is based on an industrially scalable procedure, consisting of a high-temperature (650-1000°C) heat treatment step, a subsequent ball milling step, and a final post-annealing step, thereby attaining catalysts with specific surface areas of ~ 25 m2 g-1. The high reduction resistance of the irr-IrO2 catalysts, attributed to their highly ordered crystalline structure compared to that of typically synthesized IrO2 catalysts, is reflected by the observation that SUSD cycling of MEAs with the irr-IrO2 as anode co-catalysts does not result in iridium dissolution and the associated iridium poisoning of the Pt/C cathode catalyst.