Hydrogen produced in a polymer electrolyte membrane (PEM) electrolyzer must be stored under high pressure. It is discussed whether the gas should be compressed in subsequent gas compressors or by the electrolyzer. While gas compressor stages can be reduced in the case of electrochemical compression, safety problems arise for thin membranes due to the undesired permeation of hydrogen across the membrane to the oxygen side, forming an explosive gas. In this study, a PEM system is modeled to evaluate the membrane-specific total system efficiency. The optimum efficiency is given depending on the external heat requirement, permeation, cell pressure, current density, and membrane thickness. It shows that the heat requirement and hydrogen permeation dominate the maximum efficiency below 1.6 V, while, above, the cell polarization is decisive. In addition, a pressure-optimized cell operation is introduced by which the optimum cathode pressure is set as a function of current density and membrane thickness. This approach indicates that thin membranes do not provide increased safety issues compared to thick membranes. However, operating an N212-based system instead of an N117-based one can generate twice the amount of hydrogen at the same system efficiency while only one compressor stage must be added.

Hydrogen crossover poses a crucial issue for polymer electrolyte membrane (PEM) water electrolysers in terms of safe operation and efficiency losses, especially at increased hydrogen pressures. Besides the impact of external operating conditions, the structural properties of the materials also influence the mass transport within the cell. In this study, we provide an analysis of the effect of elevated cathode pressures (up to 15 bar) in addition to increased compression of the membrane electrode assembly on hydrogen crossover and the cell performance, using thin Nafion 212 membranes and current densities up to 3.6 A cm⁻². It is shown that a higher compression leads to increased mass transport overpotentials, although the overall cell performance is improved due to the decreased ohmic losses. The mass transport limitations also become visible in enhanced anodic hydrogen contents with increasing compression at high current densities. Moreover, increases in cathode pressure are amplifying the compression effect on hydrogen crossover and mass transport losses. The results indicate that the cell voltage should not be the only criterion for optimizing the system design, but that the material design has to be considered for the reduction of hydrogen crossover in PEM water electrolysis.

It has been well-established that effects such as cracking are observable when wet layers are dried. In particular, the layer thickness, as well as the surface tension of the liquid, is responsible for this behavior. The layer formation of polymer electrolyte fuel cells and electrolyzer electrodes, however, has not yet been analyzed in relation to these issues, even though the effect of cracks on cell performance and durability has been frequently discussed. In this paper, water propanol polymer-containing carbon-black dispersions are analyzed in situ with regard to their composition during drying. We demonstrate that crack behavior can be steered by slight variations in the initial dispersion when the solvent mixture is near the dynamic azeotropic point. This minor adjustment may strongly affect the drying behavior, leading to either propanol or water-enriched liquid phases at the end of the drying process. If the evaporation of the solvent results in propanol enrichment, the critical layer thickness at which cracks occur will be increased by about 30% due to a decrease in the capillary pressure. Microscopic images indicate that the crack area ratio and width depend on the wet layer thickness and initial liquid phase composition. These results are of much value for future electrode fabrication, as cracks affect electrode properties.