On the Proton Conduction Pathways in Polyelectrolyte Membranes Based on Syndiotactic-Polystyrene.

When functionalized by the solid-state sulfonation process, the amorphous regions of the semi-crystalline syndiotactic-polystyrene (sPS) become hydrophilic, and thus can conduct protons upon membrane hydration, which increases the interest in this material as a potential candidate for applications with proton exchange membranes. The resistance of sulfonated sPS to oxidative decomposition can be improved by doping the membrane with fullerenes. In previous work, we have described the morphology in hydrated sulfonated sPS films doped with fullerenes on different length scales as determined by small-angle neutron scattering (SANS) and the structural changes in such membranes as a function of the degree of hydration and temperature. In the current work, we report on the relationship between the morphology of hydrated domains as obtained by SANS and the proton conductivity in sulfonated sPS-fullerene composite membranes at different temperature and relative humidity (RH) conditions. Based on this combined experimental approach, clear evidence for the formation and evolution of the hydrated domains in functionalized sPS membranes has been provided and a better understanding of the hydration and conductivity pathways in this material has been obtained.