Sulfonated polybenzimidazole membrane crosslinked by a star crosslinker with stable operation of high-performance all-vanadium flow batteries

doi:10.19799/j.cnki.2095-4239.2024.1013

Abstract

Abstract:

All-vanadium flow batteries are essential for long-term energy storage owing to their high power density, intrinsic safety, and the decoupling of capacity and energy. However, commercial applications are hindered by issues such as low energy efficiency and poor cycle stability, which are primarily attributed to the poor ion selectivity of commonly used Nafion membrane materials. To address these limitations, this study prepared a crosslinked sulfonated polybenzimidazole microporous proton exchange membrane (tbt-SP-110) using a star crosslinker. This star crosslinker was introduced into the sulfonated polybenzimidazole membrane to construct an ion transport channel. This channel accelerated proton conduction while containing water molecules to limit the swelling of the membrane material. Combined with the inherently high ion selectivity of polybenzimidazole, this approach facilitates rapid and selective proton transport. Owing to the excellent properties of the developed membrane material, the Coulomb efficiency and energy efficiency reached 99.45% and 79.06%, respectively, at a current density of 250 mA/cm². Under a current density of 200 mA/cm², the capacity retention rate was maintained at 72% after 100 cycles. These results highlight the potential of the membrane for use in high-performance all-vanadium flow batteries.

Key words: star crosslinker, polybenzimidazole microporous film, low surface resistance, high ion selectivity, all-vanadium flow battery

CLC Number:

TM 911

Xiaohu SHI, Yixin HUANG, Tao ZOU, Yiting YUAN. Sulfonated polybenzimidazole membrane crosslinked by a star crosslinker with stable operation of high-performance all-vanadium flow batteries[J]. Energy Storage Science and Technology, 2025, 14(4): 1377-1385.

Figures/Tables 9

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References 11

1	王贝, 李宾宾, 孙广星, 等. 新型储能技术与产业发展研究[J]. 能源与节能, 2023(11): 8-13. DOI: 10.16643/j.cnki.14-1360/td.2023.11.053.
	WANG B, LI B B, SUN G X, et al. Technologies and industrial development of new-type energy storage[J]. Energy and Energy Conservation, 2023(11): 8-13. DOI: 10.16643/j.cnki.14-1360/td.2023.11.053.
2	李建林, 邸文峰, 李雅欣, 等. 长时储能技术及典型案例分析[J]. 热力发电, 2023, 52(11): 85-94. DOI: 10.19666/j.rlfd.202301003.
	LI J L, DI W F, LI Y X, et al. Analysis of long-term energy storage technologies and typical case studies[J]. Thermal Power Generation, 2023, 52(11): 85-94. DOI: 10.19666/j.rlfd.202301003.
3	胡磊, 高莉, 焉晓明, 等. 全钒液流电池膜离子选择性传导通道构建的研究进展[J]. 化工进展, 2020, 39(6): 2079-2092. DOI: 10.16085/j.issn.1000-6613.2019-2111.
	HU L, GAO L, YAN X M, et al. Progress in construction of ion-selective transport channels in membranes for vanadium flow batteries[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2079-2092. DOI: 10.16085/j.issn.1000-6613.2019-2111.
4	严川伟. 大规模长时储能与全钒液流电池产业发展[J]. 太阳能, 2022(5): 14-22. DOI: 10.19911/j.1003-0417.tyn20220404.01.
	YAN C W. Large energy storage and vanadium flow battery industrialization[J]. Solar Energy, 2022(5): 14-22. DOI: 10.19911/j.1003-0417.tyn20220404.01.
5	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]. Advanced Energy Materials, 2020, 10(22): 1904041. DOI: 10.1002/aenm.201904041.
6	XIA Y F, YU H L, YUAN C Y, 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]. Chemical Engineering Journal, 2021, 425: 131448. DOI: 10.1016/j.cej.2021.131448.
7	白恩瑞, 谢小银, 朱昊天, 等. 全钒液流电池隔膜Nafion与SPEEK改性研究进展[J]. 化工矿物与加工, 2024, 53(1): 60-68. DOI: 10.16283/j.cnki.hgkwyjg.2024.01.008.
	BAI E R, XIE X Y, ZHU H T, et al. Research progress on Nafion and SPEEK modification of all vanadium redox flow battery separator[J]. Industrial Minerals & Processing, 2024, 53(1): 60-68. DOI: 10.16283/j.cnki.hgkwyjg.2024.01.008.
8	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]. Journal of Energy Chemistry, 2022, 75: 448-456. DOI: 10.1016/j.jechem.2022.08.043.
9	WANG Y X, GENG K, TAN Q, et al. Highly ion selective proton exchange membrane based on sulfonated polybenzimidazoles for iron-chromium redox flow battery[J]. ACS Applied Energy Materials, 2022, 5(12): 15918-15927. DOI: 10.1021/acsaem.2c03471.
10	CHE X F, ZHAO H, REN X R, et al. Porous polybenzimidazole membranes with high ion selectivity for the vanadium redox flow battery[J]. Journal of Membrane Science, 2020, 611: 118359. DOI: 10.1016/j.memsci.2020.118359.
11	ZHOU S Y, SUN Y X, XUE B X, et al. Controlled superacid-catalyzed self-cross-linked polymer of intrinsic microporosity for high-performance CO₂ separation[J]. Macromolecules, 2020, 53(18): 7988-7996. DOI: 10.1021/acs.macromol.0c01590.

[1]	Hong WANG, Kaiyue ZHANG. Study on thermal treatment activation of carbon felt electrode for all-vanadium flow batteries [J]. Energy Storage Science and Technology, 2025, 14(2): 488-496.
[2]	Mengyao QI, Yichen HOU, Lei CHEN, Lijun YANG. Numerical simulation of a novel radial all-vanadium flow battery cell [J]. Energy Storage Science and Technology, 2022, 11(10): 3209-3220.
[3]	SHEN Haifeng, ZHU Xinjian, CAO Hongfei, SHAO Mengchen. Dynamic modeling of all-vanadium flow battery [J]. Energy Storage Science and Technology, 2018, 7(1): 135-.