| Multiscale synergistic design of high-performance membranes for flow batteries |
| Authors： ZHAO Peihong, GUO Sheng |
| Units： School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China |
| KeyWords： flow-battery membrane; multiscale synergistic design; conductivity; selectivity; scale-up |
| ClassificationCode：TQ152 |
| year,volume(issue):pagination： 2026,46(1):178-198 |
|
Abstract： |
| As a key component of future green energy systems, energy storage plays a critical role in achieving the strategic goals of carbon peaking and carbon neutrality. Among various energy storage technologies, flow batteries stand out for their intrinsic safety, long cycle life, and independent tuning of power and energy capacities, making them particularly promising for long-duration energy storage. The overall performance of flow batteries is largely governed by membrane properties, including ionic conductivity, chemical stability, and the ability to suppress active species crossover. Among these, the intrinsic trade-off between achieving high ionic conductivity and effectively inhibiting the crossover of redox-active species remains one of the most critical bottlenecks hindering large-scale deployment. This review provides a comprehensive analysis of the correlations between membrane properties and battery performance, systematically summarizes multiscale optimization strategies ranging from molecular structure design to macroscopic architectural engineering, and highlights the current challenges associated with scale-up and industrial implementation. We further propose that multiscale synergistic design should serve as a central guiding principle for developing next-generation, low-cost, high-performance membranes for flow batteries, offering both theoretical insights and technological pathways to accelerate the commercialization of flow battery technologies. |
|
Funds： |
| 中央高校青年教师科研创新能力支持项目(2025300472) |
|
AuthorIntro： |
| 赵佩鈜（2004-），江苏南京人，主要从事离子交换膜的研究 |
|
Reference： |
|
[1]Dunn B, Kamath H, Tarascon J M. Electrical energy storage for the grid: a battery of choices[J]. Science, 2011, 334(6058): 928-935. [2]Gür T M. Review of electrical energy storage technologies, materials and systems: challenges and prospects for large-scale grid storage[J]. Energ Environ Sci, 2018, 11(10): 2696-2767. [3]国家能源局能源节约和科技装备司, 电力规划设计总院. 中国新型储能发展报告2025[M].北京: 人民日报出版社, 2025. [4]Li X F, Zhang H M, Mai Z S, et al. Ion exchange membranes for vanadium redox flow battery (VRB) applications[J]. Energ Environ Sci, 2011, 4(4): 1147-1160. [5]Zhao Z, Zhang C, Li X. Opportunities and challenges of organic flow battery for electrochemical energy storage technology[J]. J Energy Chem, 2022, 67: 621-639. [6]周凡宇, 曾晋珏, 王学斌. 碳中和目标下电化学储能技术进展及展望[J]. J Chinese Soc Power Eng, 2024, 44: 396-405. [7]Amini K, Shocron A N, Suss M E, et al. Pathways to high-power-density redox flow batteries[J]. ACS Energy Lett, 2023, 8(8): 3526-3535. [8]Peng K, Zhang C, Fang J, et al. Constructing microporous ion exchange membranes via simple hypercrosslinking for pH-neutral aqueous organic redox flow batteries[J]. Angew Chem Int Ed, 2024, 63(37): e202407372. [9]Song W, Peng K, Xu W, et al. Upscaled production of an ultramicroporous anion-exchange membrane enables long-term operation in electrochemical energy devices[J]. Nat Commun, 2023, 14(1): 2732. [10]Zuo P, Ye C, Jiao Z, et al. Near-frictionless ion transport within triazine framework membranes[J]. Nature, 2023, 617(7960): 299-305. [11]He G H, Li L, Xu H, et al. A polymer membrane with integrated microphase separation and intrinsic microporosity for aqueous organic redox flow batteries[J]. Joule, 2025, 9(7):101976. [12]Wang A, Breakwell C, Foglia F, et al. Selective ion transport through hydrated micropores in polymer membranes[J]. Nature, 2024, 635(8038): 353-358. [13]Wong T, Yang Y, Tan R, et al. Sulfonated poly(ether-ether-ketone) membranes with intrinsic microporosity enable efficient redox flow batteries for energy storage[J]. Joule, 2025, 9(2):101795. [14]Xin L, Zhang D Z, Qu K, et al. Zr-MOF-enabled controllable ion sieving and proton conductivity in flow battery membrane[J]. Adv Funct Mater, 2021, 31(42):2104629. [15]Wu J, Liao C, Li T, et al. Metal-coordinated polybenzimidazole membranes with preferential K+ transport[J]. Nat Commun, 2023, 14(1): 1149. [16]Lu W J, Yuan Z Z, Li M R, et al. Solvent-induced rearrangement of ion-transport channels: A way to create advanced porous membranes for vanadium flow batteries[J]. Adv Funct Mater, 2017, 27(4):1604587. [17]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. [18]Huang K, Mu F, Hou X, et al. Porous ceramic metal-based flow battery composite membrane[J]. Angew Chem Int Ed Engl, 2024, 63(19): e202401558. [19]Liu X N, Shi M Q, Liao C Y, et al. Ultrathin membranes prepared through interfacial polymer cross-linking for selective and fast ion transport[J]. Nat Chem Eng, 2025, 2(6): 369-378. [20]Lu W J, Li X F. Advanced membranes boost the industrialization of flow battery[J]. Accounts Mater Res, 2023, 4(8): 681-692. [21]Ye J, Xia L, Li H, et al. The critical analysis of membranes toward sustainable and efficient vanadium redox flow batteries[J]. Adv Mater, 2024, 36(28): e2402090. [22]Xiao S S, Xiong P, Sheng Z T, 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. [23]He G H, Yu R, Xu H, et al. Synthetic membranes for aqueous organic redox flow batteries (AORFBs): Towards high conductive and selective ion channels[J]. Chemistry, 2025,31(57): e02116. [24]Tsehaye M T, Mourouga G, Schmidt T J, et al. Towards optimized membranes for aqueous organic redox flow batteries: Correlation between membrane properties and cell performance[J]. Renew Sust Energ Rev, 2023, 173:113059. [25]Dai L H, Huang K, Xu F, et al. Emerging porous conductive ion-selective membranes for sustainable energy devices[J]. Angew Chem Int Edit, 2025, 64(30):e202504134. [26]Wang F, Mu D, Lu Y C. Ion-conducting membranes for long-duration energy storage[J]. ACS Energy Lett, 2025, 10(7): 3096-3111. [27]Machado C A, Brown G O, Yang R, et al. Redox flow battery membranes: Improving battery performance by leveraging structure-property relationships[J]. ACS Energy Lett, 2020, 6(1): 158-176. [28]Xiong P, Zhang L Y, Chen Y Y, et al. A chemistry and microstructure perspective on ion-conducting membranes for redox flow batteries[J]. Angew Chem Int Edit, 2021, 60(47): 24770-24798. [29]Wang Y Q, Hong H, Wei Z Q, et al. Pathways to realize high-energy density aqueous redox flow batteries[J]. Adv Funct Mater, 2025,35(48):2507320. [30]孙丹宁. 百兆瓦级大连液流电池储能调峰电站并网发电 [Z]. 中国科学院大连化学物理研究所, 2022.dicp.cas.cn/xwdt/kyjz/202210/t20221031_6541871.html. [31]袁治章, 刘宗浩, 李先锋. 液流电池储能技术研究进展[J]. 储能科学与技术, 2022, 11: 2944-2958. [32]Noack J. Standards for flow batteries[M]//Roth C, Noack J, Skyllas M. Flow Batteries. Weinheim: Wiley-VCH, 2023: 155-174. [33]姚祯, 王锐, 阳雪, 等. 锌铁液流电池研究现状及展望[J]. 储能材料与器件, 2022, 11: 78-88. [34]Xu P C, Yuan Z Z, Li X F. Progress on zinc-based flow batteries[J]. Chinese Science Bulletin-Chinese, 2024, 69(21): 3110-3121. [35]Yuan Z Z, Liang L X, Dai Q, et al. Low-cost hydrocarbon membrane enables commercial-scale flow batteries for long-duration energy storage[J]. Joule, 2022, 6(4): 884-905. [36]Yuan Z, Liu X, Xu W, et al. Negatively charged nanoporous membrane for a dendrite-free alkaline zinc-based flow battery with long cycle life[J]. Nat Commun, 2018, 9(1): 3731. [37]Wang P. Molecular design and redox chemistries for aqueous organic redox flow batteries (AORFBs)[J]. Angew Chem Int Ed Engl, 2025,64(51): e202515639. [38]Hu L, Gao L, Di M T, et al. Ion/molecule-selective transport nanochannels of membranes for redox flow batteries[J]. Energy Storage Mater, 2021, 34: 648-668. [39]Wang J H, Xu Z Y, Chen J, et al. Mesoscale simulation on the hydrated morphologies of SPEEK membrane[J]. Macromol Theor Simul, 2021, 30(4):2100006. [40]Li L, Wang H, Wei Q, et al. Homogeneous-strengthened SPEEK membrane with ultrahigh conductivity regulated by main/side-chain bisulfonated PEEK for vanadium flow battery[J]. J Membrane Sci, 2024, 701:122790. [41]Yuan Z, Li X, Hu J, et al. Degradation mechanism of sulfonated poly(ether ether ketone) (SPEEK) ion exchange membranes under vanadium flow battery medium[J]. Phys Chem Chem Phys, 2014, 16(37): 19841-19847. [42]Li Y, Liu Y, Xu Z, et al. Poly(phenylene oxide)-based ion-exchange membranes for aqueous organic redox flow battery[J]. Ind Eng Chem Res, 2019, 58(25): 10707-10712. [43]Xiao Y, Hu L, Gao L, et al. Enabling high anion-selective conductivity in membrane for high-performance neutral organic based aqueous redox flow battery by microstructure design[J]. Chem Eng J, 2022, 432:134268. [44]Zhang M C, Lyu P R, Wang L 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. [45]Zhang H Q, Xu W, Song W J, et al. High-performance spiro-branched polymeric membranes for sustainability applications[J]. Nat Sustain, 2024, 7(7):910-919. [46]Wang Q, Zhang Z J, Lyu P R, et al. Poly(terphenyl pyridine) based amphoteric and anion exchange membranes with high ionic selectivity for vanadium redox flow batteries[J]. Chem Eng J, 2025, 505:158922. [47]Shi N, Wang G, Wang Q, et al. Acid doped branched poly(biphenyl pyridine) membranes for high temperature proton exchange membrane fuel cells and vanadium redox flow batteries[J]. Chem Eng J, 2024, 489:151121. [48]Zhu Q, Ni L, Peng K, et al. Fluorine-engineered membranes break the conductivity-selectivity trade-off in aqueous organic redox flow batteries[J]. Angew Chem Int Ed Engl, 2025, 64(42): e202510497. [49]Song W J, Ge X L, Wu L, et al. Bottlenecks of commercializing anion exchange membranes for energy devices[J]. Joule, 2025, 9(8):102051. [50]Ye C, Tan R, Wang A, et al. Long-life aqueous organic redox flow batteries enabled by amidoxime-functionalized ion-selective polymer membranes[J]. Angew Chem Int Ed Engl, 2022, 61(38): e202207580. [51]Qian P, Wang H, Jiang Y, et al. High-performance composite membrane based on synergistic main-chain/side-chain proton conduction channels for the vanadium redox flow battery[J]. J Mater Chem A, 2021, 9(7): 4240-4252. [52]Chai S C, He S Q, Li Z X, et al. Supramolecular modification of Nafion ion channels for high-performance vanadium redox flow batteries[J]. Chem Eng J, 2025, 514:163174. [53]Gan R J, Ma Y J, Li S S, et al. Facile fabrication of amphoteric semi-interpenetrating network membranes for vanadium flow battery applications[J]. J Energy Chem, 2018, 27(4): 1189-1197. [54]Liang W, Ghasemiestahbanati E, Eden N T, et al. Flow battery with remarkably stable performance at high current density: Development of a nonfluorinated separator with concurrent rejection and conductivity[J]. Angew Chem Int Ed, 2025, 64(25): e202505383. [55]Zhang H, Liu J Q, Zhang K, et al. Unlocking ion selectivity and stability in ion exchange membranes for vanadium flow batteries via functionalized vermiculite nanosheets[J]. Chem Eng J, 2025, 517:164409. [56]Di M T, 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. [57]Zhang D H, Yu W J, Zhang Y, et al. Reconstructing proton channels via Zr-MOFs realizes highly ion- selective and proton-conductive SPEEK-based hybrid membrane for vanadium flow battery[J]. J Energy Chem, 2022, 75(12): 448-456. [58]Xu W Y, Wang Y X, Wu Y L, et al. Sub-2-nm channels within covalent triazine framework enable fast proton-selective transport in flow Battery membrane[J]. Adv Funct Mater, 2023, 33(21):2300138. [59]Kumar P, Suhag S, Mandal J R, et al. Partial fluorinated zwitterionic PVDF-co-HFP copolymer membrane doped with acid-functionalized graphene oxide for vanadium redox flow batteries[J]. ACS Appl Energ Mater, 2025, 8(11): 7371-7383. [60]Xu J, He M R, Jin H R, et al. Nano-sponge in concomitant swelling membrane for redox flow batteries with high operational stability[J]. Adv Energy Mater, 2025,15(37):e02374. [61]Huang K, Lin S H, Xia Y, et al. Highly conductive proton selectivity membrane enabled by hollow carbon sieving nanospheres for energy storage devices[J]. Engineering, 2023, 28: 69-78. [62]Cao H Y, Hong H Y, Cai Y K, et al. Upscaled production of high-performance hollow ZSM-5 zeolite flow battery hybrid membrane[J]. Ind Eng Chem Res, 2025, 64(23): 11551-11557. [63]Chen Y Y, Xiong P, Xiao S S, et al. Ion conductive mechanisms and redox flow battery applications of polybenzimidazole-based membranes[J]. Energy Storage Mater, 2022, 45: 595-617. [64]Liu X Y, Zeng D Q, Huang W H, et al. Porous branched polybenzimidazole membranes with high ion conductivity and selectivity for vanadium flow battery[J]. J Membr Sci, 2025, 736:124725. [65]Zhou Q, Zhang X H, Zhang Y B, et al. Tailored porous PBI membranes featuring efficient proton conduction pathways and multi-barrier systems for high-rate vanadium flow batteries[J]. J Membrane Sci, 2025, 719:123769. [66]Dai Q, Xing F, Liu X N, et al. High-performance PBI membranes for flow batteries: From the transport mechanism to the pilot plant[J]. Energ Environ Sci, 2022, 15(4): 1594-1600. [67]Ikhsan M M, Abbas S, Do X H, et al. Polybenzimidazole membranes for vanadium redox flow batteries: Effect of sulfuric acid doping conditions[J]. Chem Eng J, 2022, 435:134902. [68]Liu J, Song Z, Gao L, et al. A soluble highly-sulfonated polybenzimidazole with high molecular weight as membrane for vanadium flow battery with enhanced performance and long-term stability[J]. J Membrane Sci, 2024, 710:123114. [69]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. [70]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. [71]Ban T, Wang Z H, Wang Y F, et al. Phosphoric acid pre-swelling strategy constructing acid-doped fluoropoly (aryl pyridinium) membranes to enable high-performance vanadium flow batteries[J]. Chem Eng J, 2024, 494:153231. [72]Xiong P, Peng S S, Zhang L Y, et al. Supramolecular interactions enable pseudo-nanophase separation for constructing an ion-transport highway[J]. Chem, 2023, 9(3):592-606. [73]Zhang H Z, Zhang H M, Li X F, et al. Nanofiltration (NF) membranes: the next generation separators for all vanadium redox flow batteries (VRBs)?[J]. Energ Environ Sci, 2011, 4(5): 1676-1679. [74]Lu W J, Yuan Z Z, Zhao Y Y, et al. High-performance porous uncharged membranes for vanadium flow battery applications created by tuning cohesive and swelling forces[J]. Energ Environ Sci, 2016, 9(7): 2319-2325. [75]Lu W J, Yuan Z Z, Zhao Y 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. [76]Qiao L, Zhang H M, Lu W J, et al. Advanced porous membranes with slit-like selective layer for flow battery[J]. Nano Energy, 2018, 54: 73-81. [77]Shi M Q, Dai Q, Li F, et al. Membranes with well-defined selective layer regulated by controlled solvent diffusion for high power density flow battery[J]. Adv Energy Mater, 2020, 10(34):2001382. [78]鲁文静, 李先锋. 液流电池多孔复合离子传导膜研究进展[J]. CIESC Journal, 2024, 75: 3870-3882. [79]Hu J, Wang P, Hu J, et al. Chitosan composite membrane with efficient hydroxide ion transport via nano-confined hydrogen bonding network for alkaline zinc-based flow batteries[J]. Adv Sci, 2024, 11(23): e2401404. [80]Yuan Z, Zhu X, Li M, et al. A highly ion-selective zeolite flake layer on porous membranes for flow battery applications[J]. Angew Chem Int Ed, 2016, 55(9): 3058-3062. [81]Tan R, Wang A, Ye C, et al. Thin film composite membranes with regulated crossover and water migration for long-life aqueous redox flow batteries[J]. Adv Sci, 2023, 10(20): e2206888. [82]Huang Y, Liao C, Song Q, et al. Chemically cross-linked polybenzimidazole membranes with ion-conductive sub-nanometer channels for zinc-iron flow batteries[J]. Angew Chem Int Ed Engl, 2025, 64(37): e202511744. [83]Yuan Z Z, Duan Y Q, Zhang H Z, et al. Advanced porous membranes with ultra-high selectivity and stability for vanadium flow batteries[J]. Energ Environ Sci, 2016, 9(2): 441-447. [84]Di M T, Sun X J, 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. [85]Zhang D, Huang K, Xia Y, et al. Two-dimensional MFI-Type zeolite flow battery membranes[J]. Angew Chem Int Ed Engl, 2023, 62(43): e202310945. [86]Hu J, Tang X, Dai Q, et al. Layered double hydroxide membrane with high hydroxide conductivity and ion selectivity for energy storage device[J]. Nat Commun, 2021, 12(1): 3409. [87]Hu J, Yuan C G, Zhi L P, et al. In situ defect-free vertically aligned layered double hydroxide composite membrane for high areal capacity and long-cycle zinc-based flow battery[J]. Adv Funct Mater, 2021, 31(31):2102167. [88]Do X H, Abbas S, Ikhsan M M, et al. Membrane assemblies with soft protective layers: Dense and gel-type polybenzimidazole membranes and their use in vanadium redox flow batteries[J]. Small, 2022, 18(50): e2206284. [89]Bui T 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(7):e473. [90]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. [91]Wu Y, Zhang F, Wang T, et al. A submillimeter bundled microtubular flow battery cell with ultrahigh volumetric power density[J]. Proc Natl Acad Sci U S A, 2023, 120(2): e2213528120. [92]Deng C, Zheng Z, Chen S, et al. Highly stable polybenzimidazole composite membrane with a durable separation layer by interfacial polymerization[J]. ACS Appl Mater Interfaces, 2025, 17(28): 40594-40604. [93]Stolze C, Janoschka T, Winsberg J, et al. Micro-tubular flow cell design utilizing commercial hollow fiber dialysis membranes for size-exclusion based flow batteries[J]. Energy Technol, 2018, 6(11): 2296-2310. [94]Brandes F, Ressel S, Kuhn P, et al. Redox flow stacks with tubular cell design-feasibility and performance[J]. J Power Sources, 2025, 628:235839. [95]Yang Y C, Zhang B G, 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. [96]Zhou J H, Liu Y H, Zuo P P, et al. Highly conductive and vanadium sieving microporous Trger’s Base Membranes for vanadium redox flow battery[J]. J Membr Sci, 2021, 620:118832. [97]Ye J, Yu S, Zheng C, et al. Advanced hybrid membrane for vanadium redox flow battery created by polytetrafluoroethylene layer and functionalized silicon carbide nanowires[J]. Chem Eng J, 2022, 427:131413. [98]Ye J Y, Zhao X L, Ma Y L, 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. [99]Zhang Y X, Liu M, Liu H J, et al. High ion-selective SPEEK-based composite membrane containing zwitterionic polymer-modified MOFs for vanadium redox flow battery[J]. Chem Eng J, 2025, 516:164246. [100]Xu J F, Zhao H, Li W H, et al. Facile strategy for preparing a novel reinforced blend membrane with high cycling stability for vanadium redox flow batteries[J]. Chem Eng J, 2022, 433:133197. [101]Zhang D H, Zhang X H, Luan C, et al. Zwitterionic interface engineering enables ultrathin composite membrane for high-rate vanadium flow battery[J]. Energy Storage Mater, 2022, 49: 471-480. [102]Zhao Y Y, Li M R, Yuan Z Z, et al. Advanced charged sponge-like membrane with ultrahigh stability and selectivity for vanadium flow batteries[J]. Adv Funct Mater, 2016, 26(2): 210-218. [103]Ye C, Wang A, Breakwell C, et al. Development of efficient aqueous organic redox flow batteries using ion-sieving sulfonated polymer membranes[J]. Nat Commun, 2022, 13(1): 3184. [104]Xia Y S, Hou X X, Chen X Y, et al. Membrane with horizontally rigid zeolite nanosheet arrays against zinc dendrites in zinc-based flow battery[J]. Chem Eng J, 2023, 465:142912. [105]Li T Y, Lu W J, Yuan Z Z, et al. A data-driven and DFT assisted theoretic guide for membrane design in flow batteries[J]. J Mater Chem A, 2021, 9(25): 14545-14552. [106]Wei W, Nan S, Wang H, et al. Design and preparation of sulfonated polymer membranes for Zn/MnO2 flow batteries with assistance of machine learning[J]. J Membrane Sci, 2023, 672:121453. [107]Bamgbopa M O, Fetyan A, Vagin M, et al. Towards eco-friendly redox flow batteries with all bio-sourced cell components[J]. J Energy Storage, 2022, 50:104352. [108]Gao L, Ding Y, He G, et al. Bio-derived and cost-effective membranes with high selectivity for redox flow batteries based on host-guest chemistry[J]. Small, 2022, 18(43): e2107055. |
|
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
京公网安备11011302000819号