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氟功能化离子传导膜用于高性能全钒液流电池

作者：王鹤蓉¹，田力¹，刘禹芃¹，陈泽宇¹，逄博¹，姜晓滨¹，崔福军²，吴雪梅¹，贺高红¹

单位： 1. 大连理工大学精细化工国家重点实验室，膜科学与技术研究开发中心，大连 116024； 2. 大连理工大学盘锦产业技术研究院，盘锦 124221

关键词：质子交换膜；全钒液流电池；氟功能化侧链；氢钒离子选择性

DOI号： 10.16159/j.cnki.issn1007-8924.2026.02.004

分类号： TM912.1

出版年,卷(期):页码： 2026,46(2):38-46

摘要：

氢钒离子选择性是全钒液流电池离子传导膜性能的关键指标。现阶段商业化Nafion 212膜存在质子传导率低、选择性差的问题，严重制约全钒液流电池性能的进一步提升。本研究提出氟功能化离子传导膜（PBI8F），通过引入含氟功能化侧链，强化离子传导膜微相分离结构，离子传导膜内离子簇尺寸提升至约12 nm，形成高效氢质子传导通道，阻隔钒离子。分子动力学模拟发现PBI8F离子传导膜中微相分离能力源自于氟原子与磺酸基团的自聚现象。同时氟功能化憎水侧链的引入，限制了吸水率（9.8%）与溶胀率（3.2%），提升了离子传导膜的尺寸稳定性。PBI8F膜的面电阻为0.21 Ω·cm2，相较于PBI膜下降69.6%，钒离子渗透速率保持在2.35×10-10 cm2/s，相比Nafion 212（3.41×10-8 cm2/s）降低两个数量级，PBI8F膜展现出高氢钒离子选择性。在200 mA/cm2下拥有高库仑效率（99.6%）、电压效率（80.4%）和能量效率（80.1%）。循环前后离子传导膜特征峰没有任何变化，证明了PBI8F膜拥有优异的VRFB性能。

The selectivity between proton(H+) and vanadium ions(Vn+) is a key factor for the ion-conductive membranes in vanadium redox flow batteries (VRFBs). Currently, the commercially Nafion 212 membrane suffers from low proton conductivity and poor selectivity, which severely restricts further performance improvements for vanadium redox flow batteries. In this work, the construction of highly selective ion-conductive membranes (PBI-8F) by incorporating fluorinated functionalized side chains was proposed for VRFBs. By grafting fluorinated functionalized side chains, the microphase-separated structure of the ion-conductive membrane could be enhanced, forming both high proton conductivity and low vanadium ions permeability. After introducing fluorinated side chains, the ion cluster size of PBI-8F membrane increased to approximately 12 nm, indicating stronger microphase separation capability. Molecular dynamics simulations revealed that the enhanced microphase separation in the PBI-8F membrane originated from the self-aggregation of both fluorine atoms and sulfonic acid groups. Additionally, the incorporation of fluorinated hydrophobic side chains restricted the water uptake (9.8%) and swelling ratio (3.2%), improving the dimensional stability of the membrane. Moreover, the area resistance of the PBI-8F membrane was 0.21 Ω·cm2, which was 69.6% lower than that of the pristine PBI membrane, while the vanadium ion permeation rate remained low at 2.35×10-10 cm2/s, two orders of magnitude lower than that of Nafion 212(3.41×10-10 cm2/s), demonstrating high H+/Vn+ selectivity. The PBI-8F membrane exhibited high coulombic efficiency (99.6%), voltage efficiency (80.4%), and energy efficiency(80.1%) at 200 mA/cm2. No changes in the characteristic peaks of the ion-conducting membrane were observed before and after cycling, confirming the excellent VRFB performance of the PBI-8F membrane.

基金项目：

国家青年基金(C类)(22408039); 国家自然科学基金面上项目(22378042, 22021005); 国家资助博士后人员计划(GZC20240184)

作者简介：

王鹤蓉（2005-），女,陕西汉中人，研究方向为质子交换膜材料

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