Heating dictates the scalability of CO₂ electrolyzer types

Electrochemical CO₂ reduction offers a promising method of converting renewable electrical energy into valuable hydrocarbon compounds vital to hard-to-abate sectors. Significant progress has been made on the lab scale, but scale-up demonstrations remain limited. Because of the low energy efficiency of CO₂ reduction, we suspect that significant thermal gradients may develop in industrially relevant dimensions. We describe here a model prediction for non-isothermal behavior beyond the typical 1D models to illustrate the severity of heating at larger scales. We develop a 2D model for two membrane electrode assembly (MEA) CO₂ electrolyzers; a liquid anolyte fed MEA (exchange MEA) and a fully gas fed configuration (full MEA). Our results indicate that full MEA configurations exhibit very poor electrochemical performance at moderately larger scales due to non-isothermal effects. Heating results in severe membrane dehydration, which induces large Ohmic losses in the membrane, resulting in a sharp decline in the current density along the flow direction. In contrast, the anolyte employed in the exchange MEA configuration is effective in preventing large thermal gradients. Membrane dehydration is not a problem for the exchange MEA configuration, leading to a nearly constant current density over the entire length of the modeled domain, and indicating that exchange MEA configurations are well suited for scale-up. Our results additionally indicate that a balance between faster kinetics, higher ionic conductivity, smaller pH gradients and lower CO₂ solubility causes an optimum operating temperature between 60 and 70 °C.