Highly Proton-Conducting Membranes Based on Poly(arylene ether)s with Densely Sulfonated and Partially Fluorinated Multiphenyl for Fuel Cell Applications

Series of partially fluorinated sulfonated poly(arylene ether)s were synthesized through nucleophilic substitution polycondensation from three types of diols and superhydrophobic tetra-trifluoromethyl-substituted difluoro monomers with postsulfonation to obtain densely sulfonated ionomers. The membranes had similar ion exchange capacities of 2.92 ± 0.20 mmol g−1 and favorable mechanical properties (Young’s moduli of 1.60–1.83 GPa). The membranes exhibited considerable dimensional stability (43.1–122.3% change in area and 42.1–61.5% change in thickness at 80 °C) and oxidative stability (~55.5%). The proton conductivity of the membranes, higher (174.3–301.8 mS cm−1) than that of Nafion 211 (123.8 mS cm−1), was the percent conducting volume corresponding to the water uptake. The membranes were observed to comprise isolated to tailed ionic clusters of size 15–45 nm and 3–8 nm, respectively, in transmission electron microscopy images. A fuel cell containing one such material exhibited high single-cell performance—a maximum power density of 1.32 W cm2 and current density of >1600 mA cm−2 at 0.6 V. The results indicate that the material is a candidate for proton exchange membranes in fuel cell applications.