The trade-off between the mechanical properties and proton conductivity of phosphoric acid (PA)-doped polybenzimidazole (PBI) membranes presents a significant challenge to their development and practical application as high-temperature proton exchange membranes (HT-PEMs). In this study, we prepared hyper-crosslinked poly[2,2′-(p-oxydiphenylene)-5,5′-benzimidazole] (OPBI) membranes with porphyrins (TBPP) containing a substantial amount of halogen. The combination of the protonation effect of porphyrin and the support of the hyper-crosslinked structure results in TBPP-OPBI crosslinked membranes exhibiting excellent mechanical strength and proton conductivity at high PA doping levels (ADLs). In particular, the TBPP-15-OPBI crosslinked membrane exhibits high proton conductivity of 244 mS cm−1 at 180 °C, which is 3.64 times greater than that observed in the OPBI membrane. The H2/air fuel cells based on the TBPP-15-OPBI crosslinked membranes exhibit a peak power density of 521.1 mW cm−2 at 160 °C without humidification and back pressure, as well as excellent durability (over 100 h). Thus, this work provides a straightforward and feasible structural design approach to comprehensively enhance the performance of PA-PBI proton exchange membranes.
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