Synthesis and Properties of Phosphoric-Acid-Doped Polybenzimidazole with Hyperbranched Cross-Linkers Decorated with Imidazolium Groups as High-Temperature Proton Exchange Membranes

Highly phosphoric-acid (PA)-doped polybenzimidazole (PBI) membranes exhibit good proton conductivity at high temperatures; however, they suffer from reduced mechanical properties and loss of PA molecules due to the plasticity of PA and the weak interactions between PA and benzimidazoles, especially with the absorption of water. In this work, a series of PBIs with hyperbranched cross-linkers decorated with imidazolium groups (ImOPBI-x, where x is the weight ratio of the hyperbranched cross-linker) as high-temperature proton exchange membranes are designed and synthesized for the first time. We observe how the hyperbranched cross-linkers can endow the membranes with improved oxidative stability and acceptable mechanical performance, and imidazolium groups with strong basicity can stabilize the PA molecules by delocalization and hydrogen bond formation to endow the membranes with an enhanced proton conductivity and a decreased loss of PA molecules. We measured a high proton conductivity of the ImOPBI-x membranes, ranging from 0.058 to 0.089 S cm⁻¹ at 160 °C. In addition, all the ImOPBI-x membranes displayed good mechanical and oxidative properties. At 160 °C, a fuel cell based on the ImOPBI-5 membrane showed a power density of 638 mW cm⁻² and good durability under a hydrogen/oxygen atmosphere, indicating its promising use in anhydrous proton exchange membrane applications.