%0 Journal Article %A ChungHyuk Lee %A Xiaohua Wang %A Jui-Kun Peng %A Adlai Katzenberg %A Rajesh K Ahluwalia %A Ahmet Kusoglu %A Siddharth Komini Babu %A Jacob S Spendelow %A Rangachary Mukundan %A Rodney L Borup %B ACS Applied Materials & Interfaces %D 2022 %G eng %N 31 %P 35555 - 35568 %R 10.1021/acsami.2c07085 %T Toward a Comprehensive Understanding of Cation Effects in Proton Exchange Membrane Fuel Cells %U https://pubs.acs.org/doi/10.1021/acsami.2c07085 %V 14 %8 08/2022 %! ACS Appl. Mater. Interfaces %X

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.