Effect of crosslinking on the durability and electrochemical performance of sulfonated aromatic polymer membranes at elevated temperatures

End-group crosslinked sulfonated poly(arylene sulfide nitrile) (XESPSN) membranes are prepared to investigate the effect of crosslinking on the properties of sulfonated aromatic polymer membranes at elevated temperatures (>100 °C). The morphological transformation during annealing and crosslinking is confirmed by atomic force microscopy. The XESPSN membranes show outstanding thermal and mechanical properties compared to pristine and non-crosslinked ESPSN and Nafion® up to 200 °C. In addition, the XESPSN membranes exhibit higher proton conductivities (0.011–0.023 S cm−1) than the as-prepared pristine ESPSN (0.004 S cm−1), particularly at elevated temperature (120 °C) and low relative humidity (35%) conditions due to its well-ordered hydrophilic morphology after crosslinking. Therefore, the XESPSN membranes demonstrate significantly improved maximum power densities (415–485 mW cm−2) compared to the ESPSN (281 mW cm−2) and Nafion® (314 mW cm−2) membranes in single cell performance tests conducted at 120 °C and 35% relative humidity. Furthermore, the XESPSN membrane exhibits a much longer duration than the ESPSN membrane during fuel cell operation under a constant current load as a result of its improved mechanical and thermal stabilities. [Display omitted] Crosslinked membrane with high degree of sulfonation showed enhanced durability and electrochemical performances particularly at elevated temperature and low relative humidity (120 °C, 35% RH). •Crosslinked membranes show enhanced thermal and mechanical stability.•Crosslinked membranes outperform non-crosslinked membrane at 120 °C and 35% relative humidity.•Crosslinking improves durability during fuel cell operation at 120 °C and 35% relative humidity.