Anhydrous proton conducting polymer membrane materials have raised much attention in the application of high-temperature proton-exchange membranes (HT-PEMs) fuel cells, which convert chemical energy into electrical energy. Polybenzimidazole-based polymers, as typically materials for HT-PEMs, its compact structure results in a small larger fractional free volume (FFV), which is not conducive to the adsorption and retention of proton carriers. Herein, a series of polybenzimidazole-based polymers of intrinsic microporosity (PIM-PBIs) were synthesized. PIM-PBIs possess the benzimidazole units and porous structures, and have good thermal stability and large specific surface area (100 ∼ 400 m²/g). PIM-PBIs are further embedded in polyvinylidene fluoride (PVDF) to form mixed matrix membranes for high-temperature proton conduction. The resulting membrane exhibits high proton conductivity of 90.11 mS cm⁻¹ at 140 ℃ and high phosphoric acid (PA) retention rate of 90.0 %. This work provides a facile method for the precise design and preparation of proton-conducting porous materials.

无水质子导电聚合物膜材料在将化学能转化为电能的高温质子交换膜（HT-PEM）燃料电池中的应用引起了广泛关注。聚苯并咪唑基聚合物作为HT-PEMs的典型材料，其结构紧凑导致自由体积分数（FFV）较小，不利于质子载流子的吸附和保留。在此，合成了一系列基于聚苯并咪唑的固有微孔聚合物（PIM-PBI）。PIM-PBIs具有苯并咪唑单元和多孔结构，具有良好的热稳定性和较大的比表面积(100 ∼ 400 m ² /g)。PIM-PBI进一步嵌入聚偏二氟乙烯（PVDF）中，形成用于高温质子传导的混合基质膜。所得膜在140℃下表现出90.11 mS cm ^-1的高质子电导率和90.0%的高磷酸（PA）保留率。这项工作为质子传导多孔材料的精确设计和制备提供了一种简便的方法。