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螺二芴结构单元调控的季铵化聚二联苯吡啶基高温质子交换膜的合成与性能研究

作者：张奇，张振国，刘雯，李文，王乐乐，卢善富，相艳

单位：北京航空航天大学能源与动力工程学院，北京仿生能源材料与器件重点实验室，北京 102206

关键词：高温质子交换膜燃料电池；离子对膜；自由体积；溶胀；质子传导率

DOI号： 10.16159/j.cnki.issn1007-8924.2026.02.003

分类号： TQ028; TM911.4

出版年,卷(期):页码： 2026,46(2):24-37

摘要：

高温质子交换膜燃料电池作为一种极具发展前景的能量转换器件，其性能关键取决于膜材料的综合表现。季铵化离子对膜虽具备高磷酸吸收率和良好质子传导性，但过量磷酸掺杂常导致膜过度溶胀，进而影响其尺寸稳定性和力学性能。为应对这一挑战，本研究设计了一种含有刚性螺二芴结构单元的聚二联苯吡啶基季铵化离子对聚合物（QBPSp）膜。该结构通过扭曲空间构型在膜内构建丰富的微孔与更大自由体积，从而有效抑制磷酸掺杂引起的溶胀，提升膜的尺寸稳定性与力学强度。实验结果表明，螺二芴单元的引入可在膜中形成0.5~0.8 nm的微孔，且随着该单元比例增加，QBPSp膜的摩尔自由体积逐步提升。磷酸掺杂测试显示，随着自由体积增大，膜的体积溶胀率逐渐降低，单位体积内磷酸浓度相应提高，且在压应力下磷酸流失减少。电导率测试进一步证实，在40~180 ℃无水条件下，质子传导率随自由体积增大而升高。其中，QBPSp17%膜在180 ℃无水条件下的质子传导率达到98.6 mS/cm，基于该膜组装的燃料电池在相同温度下的峰值功率密度高达1 059 mW/cm2。在0.2 A/cm2的电流密度下，72 h的测试时间内无明显电压衰减。本研究表明，通过引入刚性螺二芴结构调控膜的自由体积，能够协同增强高温质子交换膜的尺寸稳定性与质子传导性能。

High-temperature proton exchange membrane fuel cells are highly promising energy conversion devices, whose performance critically depends on membrane material properties. Quaternized ion-pair membranes exhibit high phosphoric acid (PA) uptake and good proton conductivity, but excessive doping typically induces over-swelling, compromising dimensional stability and mechanical performance. To address this issue, this study designed a quaternized ion-pair polymer (QBPSp) membrane based on poly(diphenyl pyridine) containing rigid spirobifluorene units. Experimental results demonstrated that spirobifluorene incorporation created 0.5~0.8 nm micropores, with molar free volume increasing proportionally with spirofluorene content. Phosphoric acid doping tests revealed that enhanced free volume reduced volumetric swelling ratio, elevated acid concentration per unit volume, and minimized acid loss under compressive stress. Conductivity measurements confirmed that proton conductivity under anhydrous conditions from 40 to 180 ℃ improved with expanding free volume. Notably, the QBPSp-17% membrane achieved a proton conductivity of 98.6 mS/cm at 180 ℃ under anhydrous conditions, enabling a fuel cell peak power density of 1 059 mW/cm2 at the same temperature. Under the current density of 0.2 A/cm2, no significant voltage decay was observed during the 72-hour test. This work demonstrates that regulating membrane free volume through rigid spirobifluorene incorporation provides an effective strategy for simultaneously enhancing dimensional stability and proton conductivity in high-temperature proton exchange membranes.

基金项目：

国家重点研发计划战略性科技创新合作项目（2024YFE0207700）；国家自然科学基金项目（U22A20419）；河北省省级科技计划资助项目（B2024209047）

作者简介：

张奇(1995-)，男，博士研究生，黑龙江大庆人，研究方向为高温质子交换膜燃料电池

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