Understanding the Role of Cu Electocatalyst, Binder, and Membrane Interfaces in CO₂ Electrolyzer Durability

Carbon dioxide electrolyzers capable of maintaining stable performance for thousands of hours are necessary for commercial electrochemical reduction of CO 2 to two-carbon products such as ethanol and ethylene. Currently, most studies containing CO 2 reduction to two-carbon products have been for durations of under 20h. Only a few (<5) instances of CO 2 reduction to two-carbon products at durations over 100h have been reported. Common cell failure mechanisms, such as carbonate salt precipitation and cathode flooding, can be mitigated by tuning the operating conditions of the reactor. Beyond these modes of failure, there are practical limitations related to materials' durabilities and long-term stabilities, including ionomeric membranes' operating lifetimes, gas diffusion cathodes, anodes, and other MEA components. In this presentation, we explore the role of CO 2 , water, and ion transport on cell performance over extended periods of operation. The polymeric anion exchange membrane and conductive binder have been identified as crucial components in tuning the transport properties of electrolyzer systems and, thus, will be the focus of this study. We consider several types of anion exchange membranes (e.g., imidazolium, ammonium, piperindinium) and conductive binders (e.g., Nafion, PVDF, PTFE, PSMIM) for use in the direct reduction of CO 2 to two-carbon products at nanoscale Cu electrodes (150mA/cm 2 , 0.01M KHCO 3 anolyte). This work improves upon previous analysis of membrane and binder transport properties by testing a wider variety of materials for >100h durations and reporting specific cell failure times and causes. We will discuss the balances between carbonate precipitation, flooding, and other membrane or electrode failures as a function of materials, MEA preparation, and operating conditions. A comprehensive set of failure standards based on electrolyzer performance (pressure, outlet mass flow, two-carbon product Faradaic efficiencies, energy efficiency, carbon efficiency) is introduced, and electrolyzer configurations are tested in triplicate to produce statistically significant failure data. Overall, this provides insight into CO 2 , ion, and water transport's role in electrolyzer cell performance and failure mechanisms. Figure 1