磺化聚醚醚酮基全钒液流电池隔膜研究进展
Research Progress on Sulfonated Poly(ether ether ketone)-based Membranes for All-vanadium Redox Flow Batteries
- 高分子通报 2026年39卷第4期 页码：574-584
- 作者机构：
武汉理工大学化学与生命科学学院 武汉 430070
华中科技大学电气与电子工程学院强电磁工程与新技术国家重点实验室 武汉 430074
- 作者简介：
zhendong@whut.edu.cn
zhaolong@hust.edu.cn
- 基金信息：
DOI：10.14028/j.cnki.1003-3726.2026.25.375
中图分类号：收稿：2025-10-10，
录用：2026-01-22，
网络首发：2026-03-06，
纸质出版：2026-04-20
- 稿件说明：
移动端阅览
范禹江, 郑霄, 董珍, 赵龙. 磺化聚醚醚酮基全钒液流电池隔膜研究进展. 高分子通报, 2026, 39(4), 574–584.
Fan, Y. J.; Zheng, X.; Dong, Z.; Zhao, L. Research progress on sulfonated poly(ether ether ketone)-based membranes for all-vanadium redox flow batteries. Polym. Bull. (in Chinese), 2026, 39(4), 574–584.
范禹江, 郑霄, 董珍, 赵龙. 磺化聚醚醚酮基全钒液流电池隔膜研究进展. 高分子通报, 2026, 39(4), 574–584. DOI： 10.14028/j.cnki.1003-3726.2026.25.375.
Fan, Y. J.; Zheng, X.; Dong, Z.; Zhao, L. Research progress on sulfonated poly(ether ether ketone)-based membranes for all-vanadium redox flow batteries. Polym. Bull. (in Chinese), 2026, 39(4), 574–584. DOI： 10.14028/j.cnki.1003-3726.2026.25.375.
摘要
全钒液流电池质子交换膜性能直接决定电池性能。磺化聚醚醚酮(SPEEK)膜凭借结构简单、可调控的磺化度及成本优势，展现出替代Nafion膜的潜力。本文以SPEEK基隔膜为综述对象，围绕“如何平衡质子传导率与阻钒性能”这一核心问题展开，系统梳理了有机−无机复合、交联结构构筑、表面功能化及多孔结构调控等主流改性策略，重点探讨了不同改性方法对膜材料选择性的提升机制。最后对SPEEK基隔膜的开发所面临的挑战以及可能的未来研究方向进行了探讨。
Abstract
The performance of proton exchange membranes in vanadium redox flow batteries directly determines battery efficiency. Sulfonated polyether ether ketone (SPEEK) membranes demonstrate great potential to replace Nafion membranes due to their simple structure
controllable sulfonation degree
and cost advantages. This review focuses on SPEEK-based membranes
centering on the core issue of “how to balance proton conductivity and vanadium ion permeation resistance”. It systematically summarizes mainstream modification strategies including organic-inorganic hybridization
cross-linked structure construction
surface functionalization
and porous structure regulation
with a focus on discussing the enhancement mechanisms of different modification methods on the selectivity of membrane materials. Finally
the challenges faced in the development of SPEEK-based membranes and potential future research directions are discussed.
关键词
Keywords
references
Chen, Y. Y. ; Xiong, P. ; Xiao, S. S. ; Zhu, Y. Z. ; Peng, S. S. ; He, G. H . Ion conductive mechanisms and redox flow battery applications of polybenzimidazole-based membranes . Energy Storage Mater. , 2022 , 45 , 595 – 617 .
Aluko, A. ; Knight, A . A review on vanadium redox flow battery storage systems for large-scale power systems application . IEEE Access , 2023 , 11 , 13773 – 13793 .
Yuan, Z. Z. ; Zhu, X. X. ; Li, M. R. ; Lu, W. J. ; Li, X. F. ; Zhang, H. M . A highly ion-selective zeolite flake layer on porous membranes for flow battery applications . Angew. Chem. Int. Ed. , 2016 , 55 ( 9 ), 3058 – 3062 .
鲁惠 , 姜春萍 , 杨鑫 , 顾佳林 , 胥诚成 , 陈金伟 , 刘效疆 , 王瑞林 . 磺化条件对SPEEK膜性能的影响 . 化学研究与应用 , 2011 , 23 ( 6 ), 689 – 695 .
Yuan, Z. Z. ; Liang, L. X. ; Dai, Q. ; Li, T. Y. ; Song, Q. L. ; Zhang, H. M. ; Hou, G. J. ; Li, X. F . Low-cost hydrocarbon membrane enables commercial-scale flow batteries for long-duration energy storage . Joule , 2022 , 6 ( 4 ), 884 – 905 .
Li, L. ; Wang, H. X. ; Wei, Q. Q. ; Cui, X. R. ; Shi, H. F . Homogeneous-strengthened SPEEK membrane with ultrahigh conductivity regulated by main/side-chain bisulfonated PEEK for vanadium flow battery . J. Membr. Sci. , 2024 , 701 , 122790 .
Li, Z. H. ; Dai, W. J. ; Yu, L. H. ; Xi, J. Y. ; Qiu, X. P. ; Chen, L. Q . Sulfonated poly(ether ether ketone)/mesoporous silica hybrid membrane for high performance vanadium redox flow battery . J. Power Sources , 2014 , 257 , 221 – 229 .
Yin, B. B. ; Yu, L. H. ; Jiang, B. ; Wang, L. ; Xi, J. Y . Nano oxides incorporated sulfonated poly(ether ether ketone) membranes with improved selectivity and stability for vanadium redox flow battery . J. Solid State Electrochem. , 2016 , 20 ( 5 ), 1271 – 1283 .
Ji, Y. ; Tay, Z. Y. ; Li, S. F. Y . Highly selective sulfonated poly(ether ether ketone)/titanium oxide composite membranes for vanadium redox flow batteries . J. Membr. Sci. , 2017 , 539 , 197 – 205 .
Zhang, L. ; Jiang, Y. H. ; Wang, H. X. ; Qian, P. H. ; Sheng, J. X. ; Shi, H. F . Sulfonated poly(ether ketone)/sulfonated titanium dioxide hybrid membrane with high selectivity and good stability for vanadium redox flow battery . J. Energy Storage , 2022 , 45 , 103705 .
Lou, X. C. ; Lu, B. ; He, M. R. ; Yu, Y. S. ; Zhu, X. B. ; Peng, F. ; Qin, C. P. ; Ding, M. ; Jia, C. K . Functionalized carbon black modified sulfonated polyether ether ketone membrane for highly stable vanadium redox flow battery . J. Membr. Sci. , 2022 , 643 , 120015 .
Wu, C. X. ; Lu, S. F. ; Zhang, J. ; Xiang, Y . Inducing microstructural changes in Nafion by incorporating graphitic carbon nitride to enhance the vanadium-blocking effect . Phys. Chem. Chem. Phys. , 2018 , 20 ( 11 ), 7694 – 7700 .
Liu, B. ; Jiang, Y. H. ; Wang, H. X. ; Ge, J. ; Shi, H. F . Sulfonated poly(ether ether ketone) hybrid membranes with amphoteric graphene oxide nanosheets as interfacial reinforcement for vanadium redox flow battery . Energy Fuels , 2020 , 34 ( 2 ), 2452 – 2461 .
Zhang, Y. X. ; Liu, H. J. ; Liu, M. H. ; Ma, X. F. ; Liang, D. ; Qian, P. H. ; Yan, J. F . Highly ion selective sulfonated poly(ether ether ketone)/polyzwitterion functionalized graphene oxides hybrid membrane for vanadium redox flow battery . Int. J. Hydrog. Energy , 2024 , 53 , 229 – 238 .
Zhang, Y. X. ; Liu, H. J. ; Liu, M. ; Li, X. Z. ; Zhang, Y. T. ; Sun, H. Z. ; Shi, H. F. ; Feng, Y. Y . Enhanced selectivity of SPEEK membrane incorporated covalent organic nanosheet crosslinked graphene oxide for vanadium redox flow battery . J. Membr. Sci. , 2025 , 714 , 123410 .
Zhang, Y. X. ; Wang, H. X. ; Liu, B. ; Shi, J. L. ; Zhang, J. ; Shi, H. F . An ultra-high ion selective hybrid proton exchange membrane incorporated with zwitterion-decorated graphene oxide for vanadium redox flow batteries . J. Mater. Chem. A , 2019 , 7 ( 20 ), 12669 – 12680 .
Wang, F. ; Wang, G. ; Zhang, J. C. ; Li, B. Q. ; Zhang, J. ; Deng, J. ; Chen, J. W. ; Wang, R. L . Novel sulfonated poly(ether ether ketone)/oxidized g-C 3 N 4 composite membrane for vanadium redox flow battery applications . J. Electroanal. Chem. , 2017 , 797 , 107 – 112 .
Qian, P. H. ; Chen, C. ; Chen, Y. ; Zhang, L. ; Song, M. ; Zhang, N . High-performance proton exchange membrane for vanadium redox flow battery reinforced by amphoteric graphitic carbon nitride nanosheets as proton conductor . Energy Fuels , 2025 , 39 ( 25 ), 12197 – 12208 .
Dai, W. J. ; Shen, Y. ; Li, Z. H. ; Yu, L. H. ; Xi, J. Y. ; Qiu, X. P . SPEEK/Graphene oxide nanocomposite membranes with superior cyclability for highly efficient vanadium redox flow battery . J. Mater. Chem. A , 2014 , 2 ( 31 ), 12423 – 12432 .
Niu, R. T. ; Kong, L. Q. ; Zheng, L. Y. ; Wang, H. X. ; Shi, H. F . Novel graphitic carbon nitride nanosheets/sulfonated poly(ether ether ketone) acid-base hybrid membrane for vanadium redox flow battery . J. Membr. Sci. , 2017 , 525 , 220 – 228 .
Zheng, L. Y. ; Wang, H. X. ; Niu, R. T. ; Zhang, Y. X. ; Shi, H. F . Sulfonated poly(ether ether ketone)/sulfonated graphene oxide hybrid membrane for vanadium redox flow battery . Electrochim. Acta , 2018 , 282 , 437 – 447 .
Kong, L. Q. ; Zheng, L. Y. ; Niu, R. T. ; Wang, H. X. ; Shi, H. F . A sulfonated poly(ether ether ketone)/amine-functionalized graphene oxide hybrid membrane for vanadium redox flow batteries . RSC Adv. , 2016 , 6 ( 102 ), 100262-100270 .
Liu, S. ; Li, D. ; Wang, L. H. ; Yang, H. J. ; Han, X. T. ; Liu, B. Q . Ethylenediamine-functionalized graphene oxide incorporated acid-base ion exchange membranes for vanadium redox flow battery . Electrochim. Acta , 2017 , 230 , 204 – 211 .
Michel Myures, X. ; Suresh, S. ; Arthanareeswaran, G . Construction of thermal, chemical and mechanically stable ion exchange membranes with improved ion selectivity for vanadium redox flow batteries applications . J. Power Sources , 2024 , 591 , 233818 .
Afzal, Chen, W. T. ; Pang, B. ; Yan, X. M. ; Jiang, X. B. ; Cui, F. J. ; Wu, X. M. ; He, G. H . Oxidized black phosphorus nanosheets/sulfonated poly(ether ether ketone) composite membrane for vanadium redox flow battery . J. Membr. Sci. , 2022 , 644 , 120084 .
Liu, S. ; Sang, X. X. ; Wang, L. H. ; Zhang, J. L. ; Song, J. L. ; Han, B. X . Incorporation of metal-organic framework in polymer membrane enhances vanadium flow battery performance . Electrochim. Acta , 2017 , 257 , 243 – 249 .
Zhang, D. H. ; Yu, W. J. ; Zhang, Y. ; Cheng, S. H. ; Zhu, M. Y. ; Zeng, S. ; Zhang, X. H. ; Zhang, Y. F. ; Luan, C. ; Yu, Z. S. ; Liu, L. S. ; Zhang, K. Y. ; Liu, J. G. ; Yan, C. W . Reconstructing proton channels via Zr-MOFs realizes highly ion-selective and proton- conductive SPEEK-based hybrid membrane for vanadium flow battery . J. Energy Chem. , 2022 , 75 , 448 – 456 .
Zhang, Y. X. ; Liu, M. ; Liu, H. J. ; Li, X. Z. ; Ding, C. J. ; Zhang, Y. T. ; Sun, H. Z. ; Yu, Y. ; Shi, H. F . High ion-selective SPEEK-based composite membrane containing zwitterionic polymer-modified MOFs for vanadium redox flow battery . Chem. Eng. J. , 2025 , 516 , 164246 .
Li, J. ; Xu, F. ; Chen, Y. B. ; Han, Y. Y. ; Lin, B. C . Sulfonated poly(ether ether ketone)/sulfonated covalent organic framework composite membranes with enhanced performance for application in vanadium redox flow batteries . ACS Appl. Energy Mater. , 2022 , 5 ( 12 ), 15856 – 15863 .
Zhao, L. ; Li, F. Z. ; Guo, Y. Q. ; Dong, Y. L. ; Liu, J. Y. ; Wang, Y. ; Kang, J. R. ; Zhou, G. ; Liu, Q. F . SPEEK/PVDF binary membrane as an alternative proton-exchange membrane in vanadium redox flow battery application . High Perform. Polym. , 2017 , 29 ( 2 ), 127 – 132 .
Liu, S. ; Wang, L. H. ; Ding, Y. ; Liu, B. Q. ; Han, X. T. ; Song, Y. L . Novel sulfonated poly(ether ether keton)/polyetherimide acid-base blend membranes for vanadium redox flow battery applications . Electrochim. Acta , 2014 , 130 , 90 – 96 .
Liu, S. ; Wang, L. H. ; Li, D. ; Liu, B. Q. ; Wang, J. J. ; Song, Y. L . Novel amphoteric ion exchange membranes by blending sulfonated poly(ether ether ketone)/quaternized poly(ether imide) for vanadium redox flow battery applications . J. Mater. Chem. A , 2015 , 3 ( 34 ), 17590 – 17597 .
Chu, F. Q. ; Chu, X. F. ; Lv, T. ; Chen, Z. Y. ; Ren, Y. R. ; Zhang, S. ; Yuan, N. Y. ; Lin, B. C. ; Ding, J. N . Amphoteric membranes based on sulfonated polyether ether ketone and imidazolium-functionalized polyphenylene oxide for vanadium redox flow battery applications . ChemElectroChem , 2019 , 6 ( 19 ), 5041 – 5050 .
Qian, P. H. ; Wang, H. X. ; Zhang, L. ; Zhou, Y. ; Shi, H. F . An enhanced stability and efficiency of SPEEK-based composite membrane influenced by amphoteric side-chain polymer for vanadium redox flow battery . J. Membr. Sci. , 2022 , 643 , 120011 .
Qian, P. H. ; Wang, H. X. ; Jiang, Y. H. ; Zhou, Y. ; Shi, H. F . High-performance composite membrane based on synergistic main-chain/side-chain proton conduction channels for the vanadium redox flow battery . J. Mater. Chem. A , 2021 , 9 ( 7 ), 4240 – 4252 .
Qian, P. H. ; Jiang, Y. H. ; Wang, H. X. ; Zhang, L. ; Shi, H. F . Improved proton conductivity and structure stability of an SPEEK/SPPS blend membrane for vanadium redox flow batteries . Mater. Chem. Front. , 2021 , 5 ( 23 ), 8171 – 8182 .
Maranesi, B. ; Hou, H. ; Polini, R. ; Sgreccia, E. ; Alberti, G. ; Narducci, R. ; Knauth, P. ; di Vona, M. L . Cross-linking of sulfonated poly(ether ether ketone) by thermal treatment: how does the reaction occur . Fuel Cells , 2013 , 13 ( 2 ), 107 – 117 .
Kim, J. ; Han, J. ; Kim, H. ; Kim, K. ; Lee, H. ; Kim, E. ; Choi, W. ; Lee, J. C . Thermally cross-linked sulfonated poly(ether ether ketone) membranes containing a basic polymer-grafted graphene oxide for vanadium redox flow battery application . J. Energy Storage , 2022 , 45 , 103784 .
Li, G. ; Wang, G. ; Wei, S. G. ; Yu, Y. ; Li, X. S. ; Zhang, J. ; Chen, J. W. ; Wang, R. L . Side-chain grafting-modified sulfonated poly(ether ether ketone) with significantly improved selectivity for a vanadium redox flow battery . Ind. Eng. Chem. Res. , 2023 , 62 ( 6 ), 2460 – 2468 .
Jia, C. K. ; Liu, J. G. ; Yan, C. W . A significantly improved membrane for vanadium redox flow battery . J. Power Sources , 2010 , 195 ( 13 ), 4380 – 4383 .
Zeng, P. J. ; Su, Y. ; Huang, B. ; Sun, F. ; Zhao, F. ; Guo, Y. H . Sulfonated poly(ether ether ketone) asymmetrical pore-filling PTFE composite membrane with highly selective for vanadium flow batteries . Int. J. Hydrog. Energy , 2025 , 120 , 365 – 373 .
Il Han, S. ; Hyok Jon, S. ; Hyang Kim, U. ; Hyok Kim, G. ; Mo Jon, S . High durable SPEEK/TiO 2 nanopaper composite membrane for vanadium redox flow battery . J. Saudi Chem. Soc. , 2024 , 28 ( 6 ), 101931 .
Qian, P. H. ; Wang, H. X. ; Sheng, J. X. ; Zhou, Y. ; Shi, H. F . Ultrahigh proton conductive nanofibrous composite membrane with an interpenetrating framework and enhanced acid-base interfacial layers for vanadium redox flow battery . J. Membr. Sci. , 2022 , 647 , 120327 .
Tang, Y. H. ; Lin, Y. K. ; Ford, D. M. ; Qian, X. H. ; Cervellere, M. R. ; Millett, P. C. ; Wang, X. L . A review on models and simulations of membrane formation via phase inversion processes . J. Membr. Sci. , 2021 , 640 , 119810 .
Lu, W. J. ; Yuan, Z. Z. ; Li, M. R. ; Li, X. F. ; Zhang, H. M. ; Vankelecom, I . Solvent-induced rearrangement of ion-transport channels: A way to create advanced porous membranes for vanadium flow batteries . Adv. Funct. Mater. , 2017 , 27 ( 4 ), 1604587 .
Chen, D. J. ; Li, D. D. ; Li, X. F . Hierarchical porous poly(ether sulfone) membranes with excellent capacity retention for vanadium flow battery application . J. Power Sources , 2017 , 353 , 11 – 18 .
Low, Z. X. ; Chua, Y. T. ; Ray, B. M. ; Mattia, D. ; Metcalfe, I. S. ; Patterson, D. A . Perspective on 3D printing of separation membranes and comparison to related unconventional fabrication techniques . J. Membr. Sci. , 2017 , 523 , 596 – 613 .
Thiam, B. G. ; El Magri, A. ; Vaudreuil, S . Optimization through response surface methodology of 3D printed membrane preparation conditions for use in vanadium redox flow battery: a vanadium/proton selectivity study . J.Appl. Polym. Sci. , 2023 , 140 ( 35 ), e54343 .
Thiam, B. G. ; El Magri, A. ; Vaudreuil, S . Sulfonated 3D printed poly(ether ether ketone) membrane coated with polydopamine for application in vanadium redox flow batteries . Solid State Ion. , 2024 , 410 , 116544 .
Pini Pereira, P. ; Pacola Gonçalves, I. ; Molina, L. C. A. ; Delcolle, R. ; Dzyazko, Y. S. ; Moser Paraiso, C. ; Batista Neto, G. L. ; Diório, A. ; Marquetotti Salcedo Vieira, A. ; Bergamasco, R . Membrane for pressure-driven separation prepared with a method of 3D printing: performance in concentrating orange peel extract . Membranes , 2025 , 15 ( 4 ), 105 .
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