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交联型含吡啶聚芳醚酮膜的制备及钒液流电池性能研究

作者：何靖俊，庞欣雨，张本贵

单位：沈阳化工大学化学工程学院，沈阳 110142

关键词：钒液流电池；交联；吡啶；聚芳醚酮；离子交换膜

DOI号： 10.16159/j.cnki.issn1007-8924.2026.02.005

分类号： TQ150

出版年,卷(期):页码： 2026,46(2):47-58

摘要：

钒液流电池（VRFB）作为一种大规模储能技术，在可再生能源利用领域具有广阔的应用前景。隔膜作为钒液流电池的核心部件，显著影响VRFB的电池效率和寿命。因此，开发面向钒液流电池的高性能、低成本的膜及膜材料至关重要。本工作制备了溴化聚苯醚（BPPO）交联的交联型含吡啶聚芳醚酮膜（POPEK），再通过磷酸选择性溶胀诱导微相分离增强膜传导性。研究发现，BPPO作为交联剂与PyPEK形成的交联结构能显著提高膜的耐溶胀性和机械强度，例如，POPEK3膜的极限拉伸强度为45.8 MPa，在3 mol/L硫酸中的溶胀率降低为6.56%，且呈现优秀的膜选择性。POPEK1膜在VRFB呈现的能量效率均优于相同电流密度下的Nafion 212膜，例如，在80 mA/cm2时的能量效率为90.99%，明显优于Nafion 212膜的能量效率（81.87%）。POPEK膜表现出良好的VRFB电池性能，为高性能VRFB膜的设计与优化提供了新思路。

Vanadium redox flow batteries (VRFBs), as a large-scale energy storage technology, have broad application prospects in the field of renewable energy utilization. The separator, as a core component of vanadium redox flow batteries, significantly affects the battery efficiency and lifespan. Therefore, developing high-performance, low-cost membranes and membrane materials for vanadium redox flow batteries is crucial. In this work, a cross-linked pyridine-containing poly(aryl ether ketone) (POPEK) membrane cross-linked with brominated poly(phenylene ether) (BPPO) was prepared, and its conductivity was enhanced by phosphoric acid selective swelling-induced microphase separation. The study found that the cross-linked structure formed by BPPO as a cross-linking agent and PyPEK significantly improved the swelling resistance and mechanical strength of the membrane. For example, the ultimate tensile strength of the POPEK-3 membrane was 45.8 MPa, the swelling ratio was reduced to 6.56% in 3 mol/L H2SO4, and it exhibited excellent membrane selectivity. The POPEK-1 membrane exhibited superior energy efficiency compared to the Nafion 212 membrane at the same current density in VRFB applications. For example, the POPEK-1 membrane achieved an energy efficiency of 90.99% at 80 mA/cm2, significantly bettered than the Nafion 212 membrane’s energy efficiency (81.87%). The POPEK membrane demonstrates excellent VRFB cell performance, providing new insights for the design and optimization of high-performance VRFB membranes.

基金项目：

国家自然科学基金项目(21706164); 辽宁省自然科学基金面上项目(2023-MS-236)

作者简介：

何靖俊（1999-），男，辽宁本溪人，硕士研究生，研究方向为钒液流电池用离子交换膜

参考文献：

［1］Lyu T, Yang Q, Deng X, et al. Generation expansion planning considering the output and flexibility requirement of renewable energy: the case of Jiangsu Province［J］. Front Energy Res, 2020, 8:00039.
［2］Zhu M, Sun Y, Lu Y, et al. The value of energy storage in facilitating renewables: a northeast area analysis［J/OL］. Processes, 2023, 11: 3449.
［3］Yuan Z, Zheng K, Xu J, et al. An aqueous organic flow battery integrating a high-capacity hexaazatrinaphthylene anode with a phenazine anolyte for hybrid energy storage［J］. J Energy Storage, 2025, 128: 117251.
［4］Brahma K, Nayak R, Verma S K, et al. Recent advances in development and application of polymer nanocomposite ion exchange membrane for high performance vanadium redox flow battery[J]. J Energy Storage, 2024, 97: 112850.
［5］Zhang L, Yu G. Recent developments in materials and chemistries for redox flow batteries［J］. ACS Materials Lett, 2023, 5(11): 3007-3009.
［6］Aristizábal S L, Upadhyaya L, Falca G, et al. Acid-free fabrication of polyaryletherketone membranes ［J］. J Membr Sci, 2022, 660: 120798.
［7］Yap T, Heathman N, Phillips T, et al. Additive manufacturing of polyaryletherketone (PAEK) polymers and their composites［J］. Composites Part B: Eng, 2023, 266: 111019.
［8］Yang Y, Zhang B, Liu Q, et al. Enhanced stability of pyridine-containing poly(arylene ether) membranes for vanadium redox flow battery: influence of backbone structure ［J］. Adv Membr, 2026, 6: 100181.
［9］Jing Y, Wang G, Wei S, et al. A novel sulfonated polyimide membranes inserting flexible decane chain and rigid triptycene-based crosslinked network for vanadium redox flow batteries ［J］. J Membr Sci, 2025, 734: 124454.
［10］Maurya S, Abad S D, Park E J, et al. Phosphoric acid pre-treatment to tailor polybenzimidazole membranes for vanadium redox flow batteries［J］. J Membr Sci, 2023, 668: 121233.
［11］Zhang B, Zhang X, Liu Q, et al. Robust selective swelling-induced pyridine-containing membranes with advanced conductivity for vanadium redox flow batteries［J］. J Power Sources, 2023, 580: 233610.
［12］Ban T, Wang Y, Xu Y, et al. Constructing high-performance poly(terphenyl pyridinium) membranes through efficient acid doping and controllable crosslinking for vanadium flow batteries ［J］. Chem Eng J, 2025, 504: 158925.
［13］Li T, Zhang B, Liu Q, et al. Conductivity-enhanced swelling-induced pyridine-containing poly(aryl ether ketone) membranes for vanadium redox flow batteries ［J］. J Energy Storage, 2025, 134: 118154.
［14］Huang L, Wang Q, Wang Z, et al. One-pot preparation of crosslinked network membranes via knitting strategy for application in high-temperature proton-exchange membrane fuel cells ［J］. J Mater Chem A, 2024, 12(22): 13364-13373.
［15］Zhang B, Yang Z, Liu Q, et al. Swelling-induced cross-linked pyridine-containing membranes with high stability and conductivity for vanadium redox flow batteries ［J］. ACS Sustain Chem Eng, 2023, 11(31): 11601-11612.
［16］Yu L, Wang L, Yu L, et al. Aliphatic/aromatic sulfonated polyimide membranes with cross-linked structures for vanadium flow batteries ［J］. J Membr Sci, 2019, 572: 119-127.
［17］Xia Y, Yu H, Yuan C, et al. Crosslinked sulfonated poly (arylene ether sulfone)/sulfonated poly (vinyl alcohol) membrane formed by in situ casting and reaction for vanadium redox flow battery application［J］. Chem Eng J, 2021, 425: 131448.
［18］Kim J, Han J, Kim H, et al. Thermally cross-linked sulfonated poly(ether ether ketone) membranes containing a basic polymer-grafted graphene oxide for vanadium redox flow battery application［J］. J Energy Storage, 2022, 45: 103784.
［19］Shi M, Lu W, Li X. A sub-10 μm ion conducting membrane with an ultralow area resistance for a high-power density vanadium flow battery［J］. ACS Appl Energy Mater, 2024, 7(18): 7576-7583.
［20］Dai Q, Liu Z, Huang L, et al. Thin-film composite membrane breaking the trade-off between conductivity and selectivity for a flow battery［J］. Nat Commun, 2020, 11(1): 13.
［21］Xu J, Dong S, Li P, et al. Novel ether-free sulfonated poly(biphenyl) tethered with tertiary amine groups as highly stable amphoteric ionic exchange membranes for vanadium redox flow battery［J］. Chem Eng J, 2021, 424: 130314.
［22］Di M, Sun X, Hu L, et al. Hollow COF selective layer based flexible composite membranes constructed by an integrated “casting-precipitation-evaporation” strategy［J］. Adv Funct Mater, 2022, 32(22): 2111594.
［23］Liang D, Wang S, Ma W, et al. A low vanadium permeability sulfonated polybenzimidazole membrane with a metal-organic framework for vanadium redox flow batteries［J］. Electrochimica Acta, 2022, 405: 139795.
［24］Li J, Xu W, Huang W, et al. Stable covalent cross-linked polyfluoro sulfonated polyimide membranes with high proton conductance and vanadium resistance for application in vanadium redox flow batteries［J］. J Mater Chem A, 2021, 9(43): 24704-24711.
［25］Zhao Y, Zhang D, Zhao L, et al. Excellent ion selectivity of Nafion membrane modified by PBI via acid-base pair effect for vanadium flow battery［J］. Electrochim Acta, 2021, 394: 139144.
［26］Zhang D, Xin L, Xia Y, et al. Advanced Nafion hybrid membranes with fast proton transport channels toward high-performance vanadium redox flow battery［J］. J Membr Sci, 2021, 624: 119047.
［27］Bui T T, Shin M, Abbas S, et al. Sulfonated para-polybenzimidazole membranes for use in vanadium redox flow batteries［J］. Adv Energy Mater, 2025, 15(25): 2401375.
［28］Zhang M, Wang G, Li F, et al. High conductivity membrane containing polyphosphazene derivatives for vanadium redox flow battery［J］. J Membr Sci, 2021, 630: 119322.
［29］Jiang S, Zhang B, Liu Q, et al. Conductivity-enhanced swelling-induced triphenylphosphine-functionalized adamantane-containing poly(aryl ether ketone) membranes for vanadium redox flow batteries［J］. J Membr Sci, 2024, 707: 123023.
［30］Zhang M, Lyu P, Wang L, et al. Ether-free poly(arylene methylimidazole) membranes with high performance for vanadium redox flow battery applications［J］. ACS Appl Polym Mater, 2025, 7(5): 3164-3173.
［31］Duburg J C, Avaro J, Krupnik L, et al. Design principles for high-performance meta-polybenzimidazole membranes for vanadium redox flow batteries［J］. Energy Environ Mater, 2025, 8(1): e12793.
［32］Ye J, Zhao X, Ma Y, et al. Hybrid membranes dispersed with superhydrophilic TiO2 nanotubes toward ultra-stable and high-performance vanadium redox flow batteries［J］. Adv Energy Mater, 2020, 10(22): 1904041.
［33］Su Y, Liu S, Yuan H, et al. Optimizing proton transfer of polybenzimidazole membrane through Grotthuss mechanism by an acid swelling strategy［J］. Chem Eng J, 2025, 521: 166773.
［34］Ikhsan M M, Abbas S, Do X H, et al. Sulfonated polystyrene/polybenzimidazole bilayer membranes for vanadium redox flow batteries［J］. Adv Energy Mater, 2025, 15(25): 2400139.
［35］Ban T, Xu Y, Shen K, et al. Functional integration in tailored polymers enables zwitterionic membranes with selective ion transport and enhanced stability ［J］. Adv Funct Mater, 2025, 36(18): e17813.

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