The influences of the polytetrafluoroethylene (PTFE) content in silver-based gas diffusion electrodes on the resulting physical properties and the electrochemical performance during oxygen reduction in concentrated sodium hydroxide electrolyte were investigated through half-cell measurements. A systematic variation of the pore system was achieved by application of different silver/PTFE ratios during the production of the gas diffusion electrodes (GDE). In all electrodes, a silver skeleton structure with relatively constant properties was formed, while the PTFE fills up part of the open pore space. The resulting structures were characterized with a variety of methods for the physical properties supported by focused ion beam milling and scanning electron microscope (FIB/SEM) tomography. It could be shown that variations in the obtained pore system strongly influence the electrochemical performance of the electrodes. Determination of the Tafel slopes revealed that this is not due to changes in the electrocatalytic activity but rather caused by variations in the electrolyte uptake. While too small amounts of PTFE (1 wt%) lead to decreased performance through electrolyte flooding, higher PTFE contents above about 5 wt% also deteriorate the electrode performance because the extent of the three-phase boundary diminishes. The decisive role of the electrolyte intrusion was confirmed by measurements at higher electrolyte pressure. While the best electrochemical performance was achieved with an electrode containing 98 wt% silver, a slightly higher PTFE content is advisable to prevent breakthrough of the electrolyte.

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.