Proceedings of MATSUS Spring 2025 Conference (MATSUSSpring25)
DOI: https://doi.org/10.29363/nanoge.matsusspring.2025.392
Publication date: 16th December 2024
Cs+ and Rb+ have previously been shown to enhance C2+ product selectivity during CO2 electrolysis on Cu catalysts. In a membrane electrode assembly (MEA) electrolyzer, these cations migrate to the cathode surface from the anolyte through an anion exchange membrane (AEM). The long-term durability of the electrolyzer depends significantly on the type of AEM used, as cation transport indirectly influences durability through its role in water transport. Various membrane properties, such as the nature of cationic head groups, ion exchange capacity, and water uptake, play critical roles in determining the diffusion and migration of cations across AEMs. Understanding these transport mechanisms is essential for designing membranes that prevent flooding of the gas diffusion electrode (GDE) while enabling optimal cation transport. In this work, we investigate the transport mechanisms of two specific cations Cs+ and Rb+, across five different ion exchange membranes. We use in-situ wide-angle X-ray scattering (WAXS) measurements to study the dynamic changes in the catalysts, flow field, membranes, and water transport during electrolysis. The transport of cations is understood from X-ray fluorescence (XRF) spectroscopic measurements performed simultaneously. Overall, we map the key components of the electrolyzer during electrolysis using high-energy X-rays including the electrodes, membrane, water, and cations, and how they change as a function of time. Our findings reveal significant changes when different membranes are used, as well as a strong dependence between the Donnan potential and cation transport. A comparative analysis indicates that structural and compositional differences among membranes influence Donnan potential, preferential cation transport, and solvation shell dynamics, thereby impacting the overall electrochemical durability. The insights from this study are expected to guide the design of ion-selective and durable AEMs for advanced electrolysis systems.
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