Abstract
As a promising secondary battery system, lithium—sulfur (Li—S) batteries have attracted extensive attention due to their high energy density. However, the development of Li—S batteries is hindered by the detrimental shuttling of soluble lithium polysulfides (LiPs) in traditional liquid electrolytes. In this work, we fabricate a functional gel polymer electrolyte for Li—S batteries. This electrolyte consists of poly(vinylidene fluoride-co-hexaflfluoropropylene) (PVDF-HFP) polymer matrix and a continuous γ-Al2O3 three-dimensional skeleton with structural and thermal stability. PVDF-HFP offers lithium-ion transport pathways and equips the electrolyte with flexibility, whereas the inorganic γ-Al2O3 skeleton as Lewis acid can suppress the shuttling of LiPs through strong Lewis acid-base interactions between γ-Al2O3 and LiPs. In addition, γ-Al2O3 has an effect on the Lewis base of bis(trifluoromethanesulphony)imide anion, facilitating the dissociation of lithium salts and leading to a high lithium-ion transference number. Moreover, γ-Al2O3 can improve the ionic conductivity by reacting with LiF to partly form the lithium-ion conductors of LiAlO2 and Li3AlF6. Benefiting from the synergistic effect of PVDF-HFP and γ-Al2O3, Li—S cells with this gel polymer electrolyte present improved cycling stability in terms of cathode capacity retention and anode morphology. This work provides a promising strategy for fabricating multifunctional gel electrolytes for high-energy Li—S batteries.
摘要
锂硫电池作为一种极具前景的二次电池系统受到了广泛关注. 然而, 传统液态电解质中多硫化锂的穿梭效应阻碍了其发展. 在本工作中, 我们制备了用于锂硫电池的功能性凝胶电解质. 该电解质由聚偏氟乙烯-六氟丙烯(PVDF-HFP)和连续γ-Al2O3三维骨架组成. PVDF-HFP提供锂离子传输路径, 使电解质具有良好的柔性; γ-Al2O3为路易斯酸, 可通过与多硫化锂之间的路易斯酸碱相互作用抑制穿梭效应. 而且, γ-Al2O3与路易斯碱TFSI−有相互作用, 可促进锂盐解离, 提高锂离子迁移数. 此外, 部分γ-Al2O3可以与LiF反应形成锂离子导体LiAlO2和Li3AlF6 来提高离子电导率. 使用该凝胶电解质的锂硫电池在正极容量保持和负极形貌方面展现出良好的稳定性. 该项研究为制备高能量锂硫电池的多功能凝胶电解质提供了一种有前景的策略.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (21935006, 22075151, and 22279064) and the Fundamental Research Funds for the Central Universities of China.
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Author contributions Liu S and Gao XP conceived the idea and supervised the research. Wang HM designed the experimental part and performed most of the experiments. Wang HM and Wang ZY analyzed the data. Wang HM wrote the manuscript. Liu S and Zhou C revised the manuscript. Li GR and Gao XP commented on the manuscript. All authors contributed to the general discussion.
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Hui-Min Wang is currently pursuing her doctorate degree in Prof. Xue-Ping Gao’s group at the School of Materials Science and Engineering, Nankai University, China. She got her bachelor’s degree from Xiangtan University. Her research interests mainly include Li-S and Li-ion batteries.
Sheng Liu is an associate professor at the Institute of New Energy Material Chemistry, School of Materials Science and Engineering, Nankai University, China. He received his doctorate degree from Nankai University in 2012. His main research focuses on new energy materials and chemical power sources, including Li-S batteries, lithium-ion batteries, and new systems of secondary batteries.
Xue-Ping Gao is a professor at the Institute of New Energy Material Chemistry, Nankai University, China. He received his PhD degree from Nankai University in 1995. He worked as a visiting research fellow at Kogakuin University in Japan from 1997 to 1999. Currently, his main research focuses on energy storage materials for power sources, including Li-S, Li-ion, and solar rechargeable batteries.
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Wang, HM., Wang, ZY., Zhou, C. et al. A gel polymer electrolyte with Al2O3 nanofibers skeleton for lithium—sulfur batteries. Sci. China Mater. 66, 913–922 (2023). https://doi.org/10.1007/s40843-022-2252-1
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DOI: https://doi.org/10.1007/s40843-022-2252-1