Investigation of Electrolyte-Dependent Carbonate Formation on Gas Diffusion Electrodes for CO₂ Electrolysis

The electrochemical reduction of CO₂ (ECO₂R) is a promising method for reducing CO₂ emissions and producing carbon-neutral fuels if long-term durability of electrodes can be achieved by identifying and addressing electrode degradation mechanisms. This work investigates the degradation of gas diffusion electrodes (GDEs) in a flowing, alkaline CO₂ electrolyzer via the formation of carbonate deposits on the GDE surface. These carbonate deposits were found to impede electrode performance after only 6 h of operation at current densities ranging from -50 to -200 mA cm^-2. The rate of carbonate deposit formation on the GDE surface was determined to increase with increasing electrolyte molarity and became more prevalent in K⁺-containing as opposed to Cs⁺-containing electrolytes. Electrolyte composition and concentration also had significant effects on the morphology, distribution, and surface coverage of the carbonate deposits. For example, carbonates formed in K⁺-containing electrolytes formed concentrated deposit regions of varying morphology on the GDE surface, while those formed in Cs⁺-containing electrolytes appeared as small crystals, well dispersed across the electrode surface. Both deposits occluding the catalyst layer surface and those found within the microporous layer and carbon fiber substrate of the electrode were found to diminish performance in ECO₂R, leading to rapid loss of CO production after ∼50% of the catalyst layer surface was occluded. Additionally, carbonate deposits reduced GDE hydrophobicity, leading to increased flooding and internal deposits within the GDE substrate. Electrolyte engineering-based solutions are suggested for improved GDE durability in future work.