Polybenzimidazoles (PBIs) are the most promising binders for the catalyst layer (CL) in high‐temperature proton exchange membrane fuel cells (HT‐PEMFC). However, traditional commercial PBIs are not applied in binders because they do not enhance the electrochemical performance and because the related solvents are not environmentally friendly. In addition, proton transfer channels in PBIs are not investigated at the microscopic and atomic scales to date. In this study, a nitrogen‐rich rigid PBI binder containing pyridine, diazofluorene, and partially grafted nitrile (PBPBI‐3CN) is prepared with a functionalized structure, good thermal stability, and good solubility in an environmentally friendly solvent. A membrane electrode assembly (MEA) is fabricated with the PBPBI‐3CN binder, providing a high peak power density, low resistance, and good stability. The protonation, hydrogen bond networks, and platform for proton transfer are confirmed in the CLs. The protonation of PBPBI‐3CN occurs in two steps. First, some phosphoric acid (PA) molecules bind to nitrogen‐containing acidophilic groups via preliminary protonation; second, multiple PA molecules then interact with nitrogen‐containing acidophilic groups via further protonation. With protonation as the foundation, a sufficient amount of PA molecules form a hydrogen bond network, and proton transfer channels are established.

The introduction of basic groups in the polybenzimidazole (PBI) main chain or side chain with low phosphoric acid doping is an effective way to avoid the trade-off between proton conductivity and mechanical strength for high temperature proton exchange membrane (HT-PEM). In this study, the ethyl imidazole is grafted on the side chain of the PBI containing bipyridine in the main chain and blended with poly(2,2′-[p-oxydiphenylene]-5,5′-benzimidazole) (OPBI) to obtain a series of PBI composite membranes for HT-PEMs. The effects of the introduction of bipyridine in the main chain and the ethyl imidazole in the side chain on proton transport are investigated. The result suggests that the introduction of the imidazole and bipyridine group can effectively improve the comprehensive properties as HT-PEM. The highest of proton conductivity of the obtained membranes under saturated phosphoric acid (PA) doping can be up to 0.105 S cm−1 at 160 °C and the maximum output power density is 836 mW cm−2 at 160 °C, which is 2.3 times that of the OPBI membrane. Importantly, even at low acid doping content (~178%), the tensile strength of the membrane is 22.2 MPa, which is nearly 2 times that of the OPBI membrane, the proton conductivity of the membrane achieves 0.054 S cm−1 at 160 °C, which is 2.3 times that of the OPBI membrane, and the maximum output power density of a single cell is 540 mW cm−2 at 160 °C, which is 1.5 times that of the OPBI membrane. The results suggest that the introduction of a large number of nitrogen-containing sites in the main chain and side chain is an efficient way to improve the proton conductivity, even at a low PA doping level.

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