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表面选择性溶胀法制备PVDF离子筛膜

作者：甄翊含，郑卓凡，庞茂斌，林董澄，刘京，王保国

单位：清华大学化学工程系，北京 100084

关键词：聚偏氟乙烯; 离子筛膜; 选择性溶胀; 全钒液流电池

DOI号： 10.16159/j.cnki.issn1007-8924.2026.02.006

分类号： TQ152

出版年,卷(期):页码： 2026,46(2):59-68

摘要：

全钒液流电池（VFBs）储能技术发展，亟需解决现有质子传导膜成本高、选择性差，以及复合膜界面缺陷问题。本研究利用表面选择性溶胀方法，通过在聚偏氟乙烯（PVDF）多孔膜表面喷涂有机溶剂，诱导近表层聚合物链段重排，制备具有同源致密选择层的PVDF离子筛膜。利用同源PVDF结构有效避免了界面缺陷，提高离子选择性，优化的DMAc6.4离子筛膜的VO2+离子渗透系数降低至5.31×10-7 cm2/min。基于该膜组装的钒电池性能显著提升：在150 mA/cm2电流密度下，能量效率（EE）为81.0%；在超过500次充放电循环中，钒电池效率稳定；在200圈循环后，容量保持率仍达85.5%，远高于原始PVDF多孔膜。本研究提出的表面选择性溶胀制膜过程，操作简便，具有普适性，为制备高性能、低成本的质子传导膜提供了一种新策略。

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.

基金项目：

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

作者简介：

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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