While the performance and durability of proton exchange membrane fuel cells (PEMFCs) have been considerably improved over the last decade, high-temperature operation (above 100 °C) is still an issue. We designed a sulfonated polyphenylene containing tetrafluorophenylene groups (SPP-QP-f) for high-temperature and low-humidity operation of PEMFCs. Compared to state-of-the-art perfluorinated PEMs and the previous polyphenylene ionomer membrane with no fluorine-containing groups, the SPP-QP-f membrane exhibited superior proton conductivity under all testing conditions (80−120 °C, 20−95% RH). Because of the improved interfacial compatibility with the catalyst layers, the SPP-QP-f membrane induced high cathode catalytic activity. These attractive properties of the SPP-QP-f membrane resulted in high fuel cell performance (390 mW cm −2 maximum power density) at 120 °C and 30% RH. The durability was confirmed under accelerated degradation conditions (100 °C, 30% RH) for 1000 h.

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