The key role of water activity for the operating behavior and dynamics of oxygen depolarized cathodes

Advanced chlor‐alkali electrolysis with oxygen depolarized cathodes (ODC) requires 30 % less electrical energy than conventional hydrogen‐evolution‐based technology. Herein, we confirm that the activities of hydroxide and water govern the ODC performance and its dynamics. Experimental characterization of ODC under varying mass transfer conditions on the liquid side reveals large differences in the polarization curves as well as in potential step responses of the electrodes. Under convective transport in the liquid electrolyte, the ODC is not limited by mass transfer in its current density at j>3.9 kA m−2, whereas transport limitations are already reached at j≈1.3 kA m−2 with a stagnant electrolyte. Since gas phase conditions do not differ significantly between the measurements, these results are in contrast the common assumption that oxygen supply determines ODC performance. A dynamic model reveals the strong influence of the electrolyte mass transfer conditions on oxygen availability and thus performance. Dynamic responses of the current density to step‐wise potential changes are dominated by the mass transport of water and hydroxide ions, which is by orders of magnitude faster with convective electrolyte flow. Without convective liquid electrolyte transport, a high accumulation of hydroxide ions significantly lowers the oxygen solubility. Thus, a fast mass transport of water and hydroxide is essential for high ODC performance and needs to be ensured for technical applications. The predicted accumulation of ions is furthermore validated experimentally by means of scanning electrochemical microscopy. We also show how the outlined processes can explain the distinctively different potential step responses with and without electrolyte convection

Design of an in-operando cell for X-ray and neutron imaging of oxygen-depolarized cathodes in chlor-alkali electrolysis

Oxygen-depolarized cathodes are a novel concept to be used in chlor-alkali electrolysis in order to generate significant energy savings. In these porous gas diffusion electrodes, hydrophilic and catalytically active microsized silver grains and a hydrophobic polytetrafluoroethylene cobweb structure are combined to obtain the optimum amount of three-phase boundaries between the highly alkaline electrolyte and the oxygen gas phase to achieve high current densities. However, the direct correlation between specific electrode structure and electrochemical performance is difficult. In this work, we report on the successful design and adaptation of an in-operando cell for X-ray (micro-computed tomography, synchrotron) and neutron imaging of an operating oxygen-depolarized cathode under realistic operation conditions, enabling the investigation of the electrolyte invasion into, and distribution inside, the porous electrode for the first time

Design of an In-Operando Cell for X-Ray and Neutron Imaging of Oxygen-Depolarized Cathodes in Chlor-Alkali Electrolysis

Oxygen-depolarized cathodes are a novel concept to be used in chlor-alkali electrolysis in order to generate significant energy savings. In these porous gas diffusion electrodes, hydrophilic and catalytically active microsized silver grains and a hydrophobic polytetrafluoroethylene cobweb structure are combined to obtain the optimum amount of three-phase boundaries between the highly alkaline electrolyte and the oxygen gas phase to achieve high current densities. However, the direct correlation between specific electrode structure and electrochemical performance is difficult. In this work, we report on the successful design and adaptation of an in-operando cell for X-ray (micro-computed tomography, synchrotron) and neutron imaging of an operating oxygen-depolarized cathode under realistic operation conditions, enabling the investigation of the electrolyte invasion into, and distribution inside, the porous electrode for the first time

Electrowetting limits electrochemical CO2 reduction in carbon-free gas diffusion electrodes

CO2 electrolysis might be a key process to utilize intermittent renewable electricity for the sustainable production of hydrocarbon chemicals without relying on fossil fuels. Commonly used carbon-based gas diffusion electrodes (GDEs) enable high Faradaic efficiencies for the desired carbon products at high current densities, but have limited stability. In this study, we explore the adaption of a carbon-free GDE from a Chlor-alkali electrolysis process as a cathode for gas-fed CO2 electrolysis. We determine the impact of electrowetting on the electrochemical performance by analyzing the Faradaic efficiency for CO at industrially relevant current density. The characterization of used GDEs with X-ray photoelectron spectroscopy (XPS) and X-Ray diffraction (XRD) reveals a potential-dependent degradation, which can be explained through chemical polytetrafluorethylene (PTFE) degradation and/or physical erosion of PTFE through the restructuring of the silver surface. Our results further suggest that electrowetting-induced flooding lets the Faradaic efficiency for CO drop below 40% after only 30 min of electrolysis. We conclude that the effect of electrowetting has to be managed more carefully before the investigated carbon-free GDEs can compete with carbon-based GDEs as cathodes for CO2 electrolysis. Further, not only the conductive phase (such as carbon), but also the binder (such as PTFE), should be carefully selected for stable CO2 reduction.ChemE/Transport Phenomen