Finely Adjusted Intrinsically Microporous Copolyimide Electrolyte Membranes for Fuel Cells Operating in a Wide Temperature Range

The development of proton exchange membrane fuel cells (PEMFCs) that operate over a wide temperature range without additional humidification systems remains challenging. In this work, wide-temperature-range proton exchange membranes (PEMs) were constructed from novel Tröger’s base (TB)-based intrinsically microporous copolyimides (co-PIs) finely adjusted by incorporating crown ether units into chain backbones. Owing to the strong siphoning effect of existing microporosity and hydrogen bonds or the acid–base interactions of crown ether and TB units with phosphoric acid (PA) and/or H2O, the PA-doped co-PI membrane electrode assemblies (MEAs) can easily operate stably from 30 to 160 °C under H2/air conditions even without any external humidifiers. Regarding its single-cell performance, PI-TB-N30C achieved maximum power densities of 250 and 361 mW cm–2 at 80 and 160 °C, respectively, under anhydrous conditions. In addition, PA-doped co-PI MEA can accomplish long-term stable operation under low or high temperatures for 120 h. The structural architectures for PEMs based on finely adjusted microporous co-PIs extend beyond the current capabilities of existing PEMFCs.