The historical development, current status and future prospects of chlor-alkali electrolysis with oxygen depolarized cathodes (ODCs) are summarized. Over the last decades, membrane chlor-alkali technology has been optimized to such an extent that no substantial reduction of the energy demand can be expected from further process modifications. However, replacement of the hydrogen evolving cathodes in the classical membrane cells by ODCs allows for reduction of the cell voltage and correspondingly the energy consumption of up to 30%. This replacement requires the development of appropriate cathode materials and novel electrolysis cell designs. Due to their superior long-term stability, ODCs based on silver catalysts are very promising for oxygen reduction in concentrated NaOH solutions. Finite-gap falling film cells appear to be the technically most mature design among the several ODC electrolysis cells that have been investigated.

Alkaline water electrolysis is a key technology for large-scale hydrogen production powered by renewable energy. As conventional electrolyzers are designed for operation at fixed process conditions, the implementation of fluctuating and highly intermittent renewable energy is challenging. This contribution shows the recent state of system descriptions for alkaline water electrolysis and renewable energies, such as solar and wind power. Each component of a hydrogen energy system needs to be optimized to increase the operation time and system efficiency. Only in this way can hydrogen produced by electrolysis processes be competitive with the conventional path based on fossil energy sources. Conventional alkaline water electrolyzers show a limited part-load range due to an increased gas impurity at low power availability. As explosive mixtures of hydrogen and oxygen must be prevented, a safety shutdown is performed when reaching specific gas contamination. Furthermore, the cell voltage should be optimized to maintain a high efficiency. While photovoltaic panels can be directly coupled to alkaline water electrolyzers, wind turbines require suitable converters with additional losses. By combining alkaline water electrolysis with hydrogen storage tanks and fuel cells, power grid stabilization can be performed. As a consequence, the conventional spinning reserve can be reduced, which additionally lowers the carbon dioxide emissions.

This study provides a direct comparison of hydrogen crossover in PEM (Nafion 117) and alkaline water electrolysis (Zirfon) at a temperature of 60 • C applying state-of-the-art separating unit materials. To this end, occurring crossover mechanisms are described first, before experimental data of the anodic hydrogen content are shown in dependence of current density, system pressure and process management strategy. The results suggest that permeation in PEM electrolyzers is mainly governed by diffusion due to a supersaturated concentration of dissolved hydrogen within the catalyst layer, showing a share of 98% of the total permeation flux at 1 A cm −2 and atmospheric pressure. Permeation in alkaline electrolyzers also exhibits a significant influence of supersaturation, but the overall crossover is mainly influenced by mixing the electrolyte cycles, which makes up a share of 90% at 0.7 A cm −2 and 1 bar. Generally it becomes evident that hydrogen permeation across the separating unit is more than one order of magnitude smaller in alkaline electrolysis, which is mainly a consequence of the significantly lower hydrogen solubility in concentrated KOH electrolyte. Finally, this study concludes with an assessment of the impact of separating unit thickness and provides mitigation strategies to reduce hydrogen crossover.

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