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Surface-selective swelling for preparing PVDF ion-sieving membranes

Authors： ZHEN Yihan, ZHENG Zhuofan, PANG Maobin, LIN Dongcheng, LIU Jing, WANG Baoguo

Units： Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

KeyWords： poly(vinylidene fluoride); ion-sieving membrane; selective swelling; all-vanadium redox flow battery

ClassificationCode：TQ152

year,volume(issue):pagination： 2026,46(2):59-68

Abstract：

The industrialization of all-vanadium redox flow batteries (VFBs) is critically hampered by challenges associated with traditional proton exchange membranes, including high cost, poor selectivity and insufficient interfacial compatibility in composite membranes. This paper introduced a novel approach, surface-selective swelling, to fabricate a poly(vinylidene fluoride) (PVDF) ion-sieving membrane featuring a homogeneous dense selective layer on a porous substrate. This method involved ultrasonically spraying a polar organic solvent onto the surface of a porous PVDF membrane, which induced the rearrangement of polymer chains in the near-surface region. This process successfully created a dense selective layer that was homogeneous with the porous PVDF support, effectively avoiding interfacial defects and enhancing ion selectivity. The optimized DMAc6.4 composite membrane demonstrated a significantly reduced on VO2+ ion permeability coefficient of 5.31×10-7 cm2/min. VFBs assembled with this membrane exhibited substantial performance improvements: an energy efficiency (EE) of 81.0% at a current density of 150 mA/cm2; stable coulombic efficiency (CE) and EE over 500 charge-discharge cycles; and a capacity retention rate of 85.5% after 200 cycles, far surpassing the original PVDF porous membrane. This surface-selective swelling method is characterized by its simplicity, ease of operation, and universality, offering an efficient and low-cost strategy for developing high-performance, high-stability proton exchange membranes.

Funds：

国家重点研发计划(2022YFB2404903); 国家自然科学基金项目(22278239，22509109)

AuthorIntro：

甄翊含（1993-）,女，甘肃庆阳人，博士，讲师，研究方向为离子传导膜

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