Investigating the electrowetting of silver-based gas-diffusion electrodes during oxygen reduction reaction with electrochemical and optical methods

Abstract

Porous gas-diffusion electrodes (GDEs) are widely used in electrochemical applications where a gaseous reactant is converted to a target product. Important applications for silver-based GDEs are the chlor-alkali and the CO₂ electrolysis processes in which silver catalyzes the oxygen- or carbon dioxide reduction reaction. The wetting of the porous GDEs is of utmost importance for the achieved performance of the electrode: a completely dry electrode will result in low current densities due to the reduced active surface area while on the other hand, a completely flooded electrode will deteriorate the access of the gaseous reactant. Therefore, we investigated silver-based GDEs for the oxygen reduction reaction with different amounts of the hydrophobic agent polytetrafluoroethylene (PTFE) and analyzed the potential-induced wetting behavior (electrowetting). The electrolyte breakthrough was recorded by a digital microscope and subsequently evaluated via imaging analysis of the observed breached electrolyte droplets. In order to characterize the wetting state during transition to the steady-state, we applied electrochemical impedance spectroscopy measurements and retrieved the double-layer capacitance. Our results indicate that a higher overvoltage facilitates the breakthrough of electrolytes through the gas-diffusion electrode. Surprisingly, a faster breakthrough of electrolyte was observed for electrodes with higher PTFE content. Porometry measurements revealed that the GDE with low PTFE content has a monomodal pore size distribution, whereas electrodes with higher PTFE amount exhibit a bimodal pore size distribution. In GDEs with monomodal pore size distribution the time in which the double layer capacitance is leveling off correlates with the breakthrough time of the electrolyte. In summary, we emphasize that the wetting of GDEs is a complex interplay of the applied potential, electrode composition, and resulting porous structure which requires further advanced measurements and analysis considering the parameters affecting the wetting behavior as a whole.