The relationship between chemical structure of perfluorinated sulfonic acid ionomers and their membrane properties for PEMEC application

Polymer electrolyte membrane electrolyzer cells (PEMECs) has been confirmed as a prototype electrochemical system that is effective in converting water into hydrogen and oxygen under the application of electricity. Among the core components of PEMEC, the polymer electrolyte membrane (PEM) determines critically an overall electrochemical performance of the PEMEC. Ideally a PEM system should exhibit a complex transport behavior of small molecules (e.g., gases and ions) while mediating flows of ions in the cell; it should exhibit high proton selectivity while serving as a gas barrier to hydrogen and oxygen to increase current efficiency, which are in turn vital factors in determining an effectiveness when the electric energy is used for water electrolysis. Until now, perfluorinated sulfonic acid (PFSA) ionomers have been extensively used as PEM materials in water electrolysis while in generating hydrogen and oxygen gases simultaneously in high purity. In this study we have examined the chemical structure of PEM membranes derived from various types of PFSA ionomers by employing solid-state 19F MAS NMR. Subsequently, a structure-property-performance correlation was sought in accordance with the chemical structure, the dispersion characteristics, and membrane properties of PFSA ionomers. Furthermore, the effects of the membrane morphology as well as the ionomer packing characteristics on proton conduction and hydrogen transportation were investigated. Lastly, the membrane properties exerted by varying the chemical architectures and equivalent weight (EW) values of PFSA ionomers in PEMEC were confirmed. 3 M 725 membrane, which has the highest concentration of sulfonic acid groups in the hydrated state, has the highest proton conductivity. In addition, it showed the best water electrolytic cell performance via the synergistic effect with low gas permeability obtained as a result from the short side chain structure.