Carbonation in Low-Temperature CO₂ Electrolyzers: Causes, Consequences, and Solutions

<p>Electrochemical reduction of carbon dioxide (CO<sub>2</sub>) to useful products is an emerging power-to-X concept, which aims to produce chemicals and fuels with renewable electricity instead of fossil fuels. Depending on the catalyst, a range of chemicals can be produced from CO<sub>2</sub> electrolysis at industrial-scale current densities, high Faraday efficiencies, and relatively low cell voltages. One of the main challenges for up-scaling the process is related to (bi)carbonate formation (carbonation), which is a consequence of performing the reaction in alkaline media to suppress the competing hydrogen evolution reaction. The parasitic reactions of CO<sub>2</sub> with the alkaline electrolytes result in (bi)carbonate precipitation and flooding in gas diffusion electrodes, CO<sub>2</sub> crossover to the anode, low carbon utilization efficiencies, electrolyte carbonation, pH-drift in time, and additional cost for CO<sub>2</sub> and electrolyte recycling. We present a critical review of the causes, consequences, and possible solutions for the carbonation effect in CO<sub>2</sub> electrolyzers. The mechanism of (bi)carbonate crossover in different cell configurations, its effect on the overall process design, and the economics of CO<sub>2</sub> and electrolyte recovery are presented. The aim is to provide a better understanding of the (bi)carbonate problem and guide research directions to overcome the challenges related to low-temperature CO<sub>2</sub> electrolysis in alkaline media.</p>