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Synthesis and properties of spirobifluorene-modified quaternized poly(biphenyl pyridine) high-temperature proton exchange membranes

Authors： ZHANG Qi, ZHANG Zhenguo, LIU Wen, LI Wen, WANG Lele, LU Shanfu, XIANG Yan

Units： Beijing Key Laboratory of Bio-inspired Energy Materials and Devices, School of Energy and Power Engineering, Beihang University, Beijing 102206, China

KeyWords： high-temperature proton exchange membrane fuel cell; ion-pair membrane; free volume; swelling; proton conductivity

ClassificationCode：TQ028; TM911.4

year,volume(issue):pagination： 2026,46(2):24-37

Abstract：

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.

Funds：

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）

AuthorIntro：

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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