Amino-type polybenzimidazole is prepared, then ionic liquid with three nitrogen positive sites ([CTDTr]Br3) is polymerized into polymeric ionic liquids (PILs) by in-situ radical polymerization, and AmPBI-CTDTr-Px membranes were prepared by piperidinium (PPd) and [CTDTr]Br3 combination to cross-linked with AmPBI. Following treatment with KOH and phosphoric acid (PA), the ion pairs (N+ - H2PO4-) generated in the composite membrane system can enhance proton conductivity and facilitate proton transport. The AmPBI-CTDTr-Px membranes shown exceptional PA retention as a result of the alkaline properties of both [CTDTr]Br3 and PPd, which can engage in acid-base interactions with phosphoric acid. Specifically, the proton conductivity of AmPBI-CTDTr-P5 at 180 °C is 129.7 mS cm-1, which is 2.52 times that of pure membranes. Acid retention of AmPBI-CTDTr-P5 at 80 °C/40% RH and 160 °C are 64.4% and 84%.
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