Toward a Comprehensive Understanding of Cation Effects in Proton Exchange Membrane Fuel Cells

Metal alloy catalysts (e.g., Pt-Co) are widely used in fuel cells for improving the oxygen reduction reaction kinetics. Despite the promise, the leaching of the alloying element contaminates the ionomer/membrane, leading to poor durability. However, the underlying mechanisms by which cation contamination affects fuel cell performance remain poorly understood. Here, we provide a comprehensive understanding of cation contamination effects through the controlled doping of electrodes. We couple electrochemical testing results with membrane conductivity/water uptake measurements and impedance modeling to pinpoint where and how the losses in performance occur. We identify that (1) ∼44% of Co²⁺ exchange of the ionomer can be tolerated in the electrode, (2) loss in performance is predominantly induced by O₂ and proton transport losses, and (3) Co²⁺ preferentially resides in the electrode under wet operating conditions. Our results provide a first-of-its-kind mechanistic explanation for cation effects and inform strategies for mitigating these undesired effects when using alloy catalysts.