Nitrogen-Rich Covalent Organic Frameworks Composited High-Temperature Proton Exchange Membranes with Ultralow Volume Expansion and Reduced Phosphoric Acid Leakage

Phosphoric acid (PA) leakage and volume expansion are critical factors limiting long-term stable operation of PA-doped polybenzimidazole (PBI) for high-temperature proton exchange membrane fuel cells. Enhancing the interaction between the polymer matrix and PA provides an effective way to minimize PA loss and inhibit excessive membrane swelling. The covalent organic frameworks (COFs) are helpful in improving the performance of PA-PBI membranes due to the robust frameworks, adjustable structures, and good compatibility with polymers. Here, in this work, we synthesized porous COFs named TTA-DFP containing triazine rings and pyridine groups at room temperature for as short as 2 h without oxygen isolation. TTA-DFP was then blended with commercial poly[2,2'-(p-oxidiphenylene)-5,5'-benzimidazole] (OPBI) to prepare composite membranes. The abundant alkaline N sites in TTA-DFP exhibit strong interactions with PA and OPBI, which not only provide more proton transport pathways to promote proton conduction but also immobilize PA in acidophilic micropores to reduce PA leakage. The composite membranes exhibit a much lower volume swelling ratio than that of the OPBI membrane. The PA retention of the composite membrane after 120 h of treatment at 80 °C and 40% relative humidity can reach as high as 84.6%. Particularly, the proton conductivity of the composite membrane doped with 15 wt% TTA-DFP achieves 0.112 S cm^-1 at 180 °C without humidification with a swelling ratio of 24.1%. In addition, it has an optimal peak power density of 824.4 mW cm^-2 at 180 °C, which is 1.7 times that of the OPBI membrane. The stability of the composite membrane is much better than that of OPBI at a current density of 0.3 A cm^-2 at 140 °C for 120 h.