膜科学与技术

Position：Home >> Abstract

Research progress of polybenzimidazole-based membranes
in acidic aqueous flow batteries

Authors： HU Lei1,2, YAN Xiaoming1, HE Gaohong1

Units： 1. State Key Laboratory of Fine Chemicals, Research and Development Center of Membrane Science and Technology, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China; 2. Canmax Technologies Co., Ltd., Suzhou 215121, China

KeyWords： acidic aqueous flow batteries; polybenzimidazole; ion transport channels; membranes

ClassificationCode：TQ028

year,volume(issue):pagination： 2026,46(2):178-190

Abstract：

Acidic aqueous flow batteries (AAFBs) have emerged as one of the preferred technologies for power system energy storage, thanks to their inherent safety, long cycle life, high efficiency, and environmental friendliness. As a key component of AAFBs, the membrane directly determines the overall operational efficiency of battery. However, commercial ion exchange membranes are difficult to simultaneously have high ion conductivity and high ion selectivity, which restricts the large-scale commercial application of AAFBs. Polybenzimidazole (PBI)-based membranes have been extensively researched and applied in AAFB due to excellent ion separation performance and stability under harsh conditions. This review systematically elaborates on the core characteristics and basic requirements of PBI-based membranes for AAFBs, focuses on summarizing the construction strategies of ion-transport channels in PBI-based membranes, and points out the key future development directions of PBI-based membranes, thereby advancing the industrialization of high-performance and low-cost AAFB technologies.

Funds：

辽宁滨海实验室颠覆性技术类基金项目（LBLE-2023-03）；国家自然科学基金项目（2253000382）；中国博士后科学基金资助项目（2024M762321）；江苏省基础研究计划资助（BK20250444）

AuthorIntro：

胡磊（1994-），男，四川内江人，工程师，博士，研究方向为液流电池膜

Reference：

[1]Zhao Z, Liu X, Zhang M, et al. Development of flow battery technologies using the principles of sustainable chemistry[J]. Chem Soc Rev, 2023, 52: 6031-6074.
[2]Xiong P, Zhang L, Chen Y, et al. A chemistry and microstructure perspective on ion-conducting membranes for redox flow batteries[J]. Angew Chem Int Ed, 2021, 60: 24770-24798.
[3]Xia Y, Cao H, Xu F, et al. Polymeric membranes with aligned zeolite nanosheets for sustainable energy storage[J]. Nat Sustain, 2022, 5: 1080-1091.
[4]Chen Y, Xiong P, Xiao S, et al. Ion conductive mechanisms and redox flow battery applications of polybenzimidazole-based membranes[J]. Energy Storage Mater, 2022, 45: 595-617.
[5]Noh C, Jung M, Henkensmeier D, et al. Vanadium redox flow batteries using meta-polybenzimidazole-based membranes of different thicknesses[J]. ACS Appl Mater Interf, 2017, 9: 36799-36809.
[6]Zhou J, Zhong X, Takada K, et al. Auto-homogenization of polybenzimidazole composites with enhanced mechanical performance by air incorporation[J]. Langmuir, 2024, 40: 23780-23787.
[7]Xu Z, Wang Q, Guo L, et al. Porphyrin helical nanochannel-assembled polybenzimidazole membranes doped with phosphoric acid for fuel cells operating in a temperature Range of 25~200 ℃[J]. Adv Funct Mater, 2023, 34: 2310762.
[8]Zhou X, Zhao T, An L, et al. The use of polybenzimidazole membranes in vanadium redox flow batteries leading to increased coulombic efficiency and cycling performance[J]. Electrochim Acta, 2015, 153: 492-498.
[9]冯美佳, 刘功益, 张崇印,等. 一种新型聚苯并咪唑阴离子交换膜的制备与性能研究[J]. 化工新型材料, 2022, 50: 109-116.
[10]Shanahan B, Bhm T, Britton B, et al. 30 μm thin hexamethyl-p-terphenyl poly(benzimidazolium) anion exchange membrane for vanadium redox flow batteries[J]. Electrochem Commun, 2019, 102: 37-40.
[11]Tang W, Yang Y, Liu X, et al. Long side-chain quaternary ammonium group functionalized polybenzi-midazole based anion exchange membranes and their applications[J]. Electrochim Acta, 2021, 391: 138919.
[12]Du Y, Gao L, Hu L, et al. The synergistic effect of protonated imidazole-hydroxyl-quaternary ammonium on improving performances of anion exchange membrane assembled flow batteries[J]. J Membr Sci, 2020, 603: 118011.
[13]Ren X, Zhao L, Che X, et al. Quaternary ammonium groups grafted polybenzimidazole membranes for vanadium redox flow battery applications[J]. J Power Sources, 2020, 457: 228037.
[14]Jiang B, Hu L, Yan X, et al. A new long-side-chain sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) / polybenzimidazole (PBI) amphoteric membrane for vanadium redox flow battery[J]. Chin J Chem Eng, 2020, 28: 1918-1924.
[15]Hu L, Du Y, Gao L, et al. Nanoscale solid superacid-coupled polybenzimidazole membrane with high ion selectivity for flow batteries[J]. ACS Sustain Chem Eng, 2020, 8: 16493-16502.
[16]Wang J, Xu W, Xu F, et al. A polybenzimidazole-covalent organic framework hybrid membrane with highly efficient proton-selective transport channels for vanadium redox flow battery[J]. J Membr Sci, 2024, 695: 122470.
[17]Yan H, Wei W, Li X, et al. Sulfonated ether-free polybenzimidazole membrane with fast and selective ion transport enabling ultrahigh cycle stability in vanadium redox flow batteries[J]. Nano Energy, 2026, 147: 111570.
[18]Bui T, Shin M, Abbas S, et al. Sulfonated para-polybenzimidazole membranes for use in vanadium redox flow batteries[J]. Adv Energy Mater, 2024, 15: e473.
[19]Yan X, Dong Z, Di M, et al. A highly proton-conductive and vanadium-rejected long-side-chain sulfonated polybenzimidazole membrane for redox flow battery[J]. J Membr Sci, 2020, 596: 117616.
[20]房庭旭, 逄博, 崔福军,等. 高分散COF基离子传导膜提高全钒液流电池性能[J]. 膜科学与技术, 2025, 45（4）: 95-103, 112.
[21]李慧婷, 刘希阳, 龙俊,等.面向全钒液流电池用磺化支化聚苯并咪唑膜的构筑[J]. 材料工程, 2025, 53（7）: 201-211.
[22]Dong Z, Di M, Hu L, et al. Hydrophilic/hydrophobic-bi-comb-shaped amphoteric membrane for vanadium redox flow battery[J]. J Membr Sci, 2020, 608: 118179.
[23]Chen D, Qi H, Sun T, et al. Polybenzimidazole membrane with dual proton transport channels for vanadium flow battery applications[J]. J Membr Sci, 2019, 586: 202-210.
[24]Peng S, Wu X, Yan X, et al. Polybenzimidazole membranes with nanophase-separated structure induced by non-ionic hydrophilic side chains for vanadium flow batteries[J]. J Mater Chem A, 2018, 6: 3895-3905.
[25]Chen Y, Li A, Xiong P, et al. Three birds with one stone: Microphase separation induced by densely grafted short chains in ion conducting membranes[J]. J Membr Sci, 2022, 664: 121119.
[26]Hu L, Gao L, Di M, et al. Pyridine-extended proton sponge enabling high-performance membrane for flow batteries[J]. J Membr Sci, 2023, 669: 121290.
[27]Hu L, Gao L, Yan X, et al. Proton delivery through a dynamic 3D H-bond network constructed from dense hydroxyls for advanced ion-selective membranes[J]. J Mater Chem A, 2019, 7: 15137-15144.
[28]Hu L, Gao L, Zhang C, et al. “Fishnet-like” ion-selective nanochannels in advanced membranes for flow batteries[J]. J Mater Chem A, 2019, 7: 21112-21119.
[29]Xiong P, Peng S, Zhang L, et al. Supramolecular interactions enable pseudo-nanophase separation for constructing an ion-transport highway[J]. Chem, 2023, 9: 592-606.
[30]Xiao S, Xiong P, Sheng Z, et al. Overcoming the conductivity-selectivity trade-off in flow battery membranes via weak supramolecular interaction mediated pseudo-nanophase separation[J]. Energy Storage Mater, 2024, 66: 103226.
[31]Wan Y, Sun J, Jian Q, et al. A detachable sandwiched polybenzimidazole-based membrane for high-performance aqueous redox flow batteries[J]. J Power Sources, 2022, 526: 231139.
[32]Bui T, Shin M, Rahimi M, et al. Highly efficient vanadium redox flow batteries enabled by a trilayer polybenzimidazole membrane assembly[J]. Carbon Energy, 2024, 6: e473.
[33]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, 2023, 7: 7576-7583.
[34]王亚辉, 刘金宇, 王丽华,等.不同酸质子化聚苯并咪唑膜的制备及钒电池应用[J]. 膜科学与技术, 2019, 39（6）: 129-137.
[35]Peng S, Yan X, Zhang D, et al. A H3PO4 preswelling strategy to enhance the proton conductivity of a H2SO4-doped polybenzimidazole membrane for vanadium flow batteries[J]. RSC Adv, 2016, 6: 23479-23488.
[36]Ikhsan M M, Abbas S, Do X, et al. Polybenzimi-dazole membranes for vanadium redox flow batteries: Effect of sulfuric acid doping conditions[J]. Chem Eng J, 2022, 435: 134902.
[37]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.
[38]Noh C, Serhiichuk D, Malikah N, et al. Optimizing the performance of meta-polybenzimidazole membranes in vanadium redox flow batteries by adding an alkaline pre-swelling step[J]. Chem Eng J, 2021, 407: 126574.
[39]Hampson E, Duburg J, Casella J, et al. A simple approach to balancing conductivity and capacity fade in vanadium redox flow batteries by the tunable pretreatment of polybenzimidazole membranes[J]. Chem Eng J, 2024, 485: 149930.
[40]Di M, Hu L, Gao L, et al. Covalent organic framework (COF) constructed proton permselective membranes for acid supporting redox flow batteries[J]. Chem Eng J, 2020, 399: 125833.
[41]Zhen Y, Xu Z, Cao Q, et al. Self-standing covalent organic polymer membrane with high stability and enhanced ion-sieving effect for flow battery[J]. Angew Chem Int Ed, 2024, 64: e202413046.
[42]Yuan Z, Duan Y, Zhang H, et al. Advanced porous membranes with ultra-high selectivity and stability for vanadium flow batteries[J]. Energy Environ Sci, 2016, 9(2): 441-447.
[43]Luo T, David O, Gendel Y, et al. Porous poly(benzimidazole) membrane for all vanadium redox flow battery[J]. J Power Sources, 2016, 312: 45-54.
[44]Qiao L, Zhang H, Lu W, et al. Advanced porous membranes with tunable morphology regulated by ionic strength of nonsolvent for flow battery[J]. ACS Appl Mater Interf, 2019, 11: 24107-24113.
[45]Liu X, Zeng D, Huang W, et al. Porous branched polybenzimidazole membranes with high ion conductivity and selectivity for vanadium flow battery[J]. J Membr Sci, 2025, 736: 124725.
[46]Lu W, Yuan Z, Zhao Y, et al. Advanced porous PBI membranes with tunable performance induced by the polymer-solvent interaction for flow battery application[J]. Energy Storage Mater, 2018, 10: 40-47.
[47]Zhou Q, Zhang X, Zhang Y, et al. Tailored porous PBI membranes featuring efficient proton conduction pathways and multi-barrier systems for high-rate vanadium flow batteries[J]. J Membr Sci, 2025, 719: 123769.
[48]Che X, Zhao H, Ren X, et al. Porous polybenzi-midazole membranes with high ion selectivity for the vanadium redox flow battery[J]. J Membr Sci, 2020, 611: 118359.
[49]Peng S, Yan X, Wu X, et al. Thin skinned asymmetric polybenzimidazole membranes with readily tunable morphologies for high-performance vanadium flow batteries[J]. RSC Adv, 2017, 7: 1852-1862.
[50]Yang E, Wang Y, Guo T, et al. Asymmetric porous polybenzimidazole membrane with tunable morphology for vanadium flow battery (VFB)[J]. J Membr Sci, 2025, 713: 123281.
[51]Pang B, Chen W, Li T, et al. A hierarchical nano/sub-nano hybrid ion conduction channel induced by ion-cluster-confined hydrolysis for high ion selectivity in vanadium redox flow batteries[J]. ACS Energy Lett, 2025, 10: 4418-4427.
[52]Liu X, Shi M, Liao C, et al. Ultrathin membranes prepared through interfacial polymer cross-linking for selective and fast ion transport[J]. Nat Chem Eng, 2025, 2: 369-378.
[53]Hu L, Gao L, Di M, et al. Nanocage-oriented induction for highly ion-selective sub-1-nanometer channels of membranes[J]. J Mater Chem A, 2022, 10: 3430-3435.
[54]Wang Y, Geng K, Tan Q, et al. Highly ion selective proton exchange membrane based on sulfonated polybenzimidazoles for iron-chromium redox flow battery[J]. ACS Appl Energy Mater, 2022, 5: 15918-15927.
[55]Song P, Zhang Y, Du H, et al. Simply designed sulfonated polybenzimidazole membranes for iron-chromium redox flow battery[J]. J Membr Sci, 2025, 719: 123745.
[56]Park G, Eun S, Lee W, et al. Polybenzimidazole membrane based aqueous redox flow batteries using anthraquinone-2,7-disulfonic acid and vanadium as redox couple[J]. J Power Sources, 2023, 569: 233015.
[57]Chen D, Liu G, Liu J, et al. Porous polybenzi-midazole membranes with positive charges enable an excellent anti-fouling ability for vanadium-methylene blue flow battery[J]. J Energy Chem, 2022, 68: 247-254.

Service：

【Download】【Collect】

《膜科学与技术》编辑部 Address: Bluestar building, 19 east beisanhuan road, chaoyang district, Beijing; 100029 Postal code; Telephone：010-80492417/010-80485372; Fax：010-80485372 ; Email：mkxyjs@163.com