Advances in the HCl gas-phase electrolysis employing an oxygen-depolarized cathode

The electrolysis of HCl to form Cl₂ is an integral part of the production of polycarbonates and polyurethanes. In recent years, the direct gas-phase electrolysis was shown to be significantly more efficient than the current state-of-the-art process based on the oxidation of hydrochloric acid. Still, three phenomena significantly limit the performance and industrial applicability of this process and have so far only been investigated theoretically. Firstly, a limiting behavior in the HCl oxidation reaction was observed, which seems to be of purely kinetic origin. Secondly, also in the full-cell employing an oxygen depolarized cathode, a limiting behavior was detected, which however appears to have a different origin. Lastly, the performance of the oxygen reduction is significantly reduced in comparison to classical H₂ PEM fuel cells. The present work utilizes a combined experimental and theoretical approach to confirm that the HCl oxidation is purely reaction limited while the limiting behavior in the full-cell system employing an oxygen depolarized cathode is caused by flooding at low reactor temperatures and, lastly, that the reduced performance of the oxygen reduction reaction is a consequence of significant HCl crossover that can be mitigated by means of increased cathode humidification. These insights are furthermore used to operate the HCl gas phase electrolyzer employing an oxygen depolarized cathode at current densities of more than 5000 A/m² for the first time, while also substituting the previously employed platinum based cathode catalyst with RhxSy, decreasing the impact of HCl crossover and allowing for the lowest so far measured cell potentials over a wide interval of current densities.