H+-Conducting Aromatic Multiblock Copolymer and Blend Membranes and Their Application in PEM Electrolysis.

As an alternative to common perfluorosulfonic acid-based polyelectrolytes, we present the synthesis and characterization of proton exchange membranes based on two different concepts: (i) Covalently bound multiblock-co-ionomers with a nanophase-separated structure exhibit tunable properties depending on hydrophilic and hydrophobic components' ratios. Here, the blocks were synthesized individually via step-growth polycondensation from either partially fluorinated or sulfonated aromatic monomers. (ii) Ionically crosslinked blend membranes of partially fluorinated polybenzimidazole and pyridine side-chain-modified polysulfones combine the hydrophilic component's high proton conductivities with high mechanical stability established by the hydrophobic components. In addition to the polymer synthesis, membrane preparation, and thorough characterization of the obtained materials, hydrogen permeability is determined using linear sweep voltammetry. Furthermore, initial in situ tests in a PEM electrolysis cell show promising cell performance, which can be increased by optimizing electrodes with regard to binders for the respective membrane material.

Model-Based Analysis of Low Stoichiometry Operation in Proton Exchange Membrane Water Electrolysis.

Proton exchange membrane water electrolysis cells are typically operated with high water flow rates in order to guarantee the feed supply for the reaction, the hydration of the ionomer phase and to homogenize the temperature distribution. However, the influence of low flow rates on the cell behavior and the cell performance cannot be fully explained. In this work, we developed a simple 1+1-dimensional mathematical model to analyze the cell polarization, current density distribution and the water flow paths inside a cell under low stoichiometry condition. The model analysis is in strong context to previous experimental findings on low water stoichiometry operations. The presented analysis shows that the low water stoichiometry can lead to dry-out at the outlet region of the anode channel, while a water splitting reaction is also present there. The simulation results show that the supply with water in this region is achieved by a net water transport from the cathode to the anode catalyst layer resulting in higher local proton resistances in the membrane and the anode catalyst layer.