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Hierarchical porous separator with excellent isotropic modulus enabling homogeneous Zn2+ flux for stable aqueous Zn battery

各向同性模量的分级多孔隔膜促进锌离子均匀扩散及水系锌离子电池循环稳定性

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Abstract

Low-cost, high-safety aqueous Zn-ion batteries show promise for large-scale energy storage, but the unsatisfactory cycling stability of Zn anodes and the lack of a suitable hydrophilic separator for rechargeable aqueous Zn batteries limit their practical applications. In this work, we report a scalable method for the preparation of a homogenous polyvinylidene fluoride-lithium bistrifluoromethanesulfonimide (LiTFSI) (PVDF-Li)-based separator for aqueous Zn batteries. The homogenously mixed LiTFSI salt interrupted the crystalline framework of PVDF with excellent mechanical strength and led to hierarchical pore structures for the rapid and uniform Zn2+ flux through the separator. Meanwhile, the PVDF-Li separator exhibited excellent wettability toward aqueous Zn electrolytes. With the advanced PVDF-Li separator, the Zn dendrite growth can be suppressed greatly, showing an improved cycle life. The Zn||V2O5 full cell with PVDF-Li separator exhibited a 27% higher initial capacity (324 mA h g−1) and considerably better capacity retention than the traditional glass fiber separator due to the uniform reaction on the V2O5 cathode and Zn anode sides. This work provides new insights into the development of high-performance aqueous batteries by regulating the reactions on the cathode and anode through functional separators.

摘要

水系锌离子电池具有低成本、 高安全的特点, 有望应用于大规模储能. 然而, 锌负极的循环稳定性仍不理想, 且水系电池缺少合适的亲水隔膜, 这限制了水系锌离子电池的实际应用. 在本文中, 我们报道了一种可用于水系电池的分级多孔的聚偏二氟乙烯-双三氟甲磺酰亚 胺锂(PVDF-LiTFSI) (PVDF-Li)隔膜. 均匀混合的LiTFSI盐降低了PVDF的结晶性, 使隔膜具有优异的机械强度, 并形成分级的孔隙结构. 这种LiTFSI诱导的分级多孔结构有助于实现Zn2+的快速传输和锌的均匀沉积, 同时保证隔膜在水系电解液中具有优异的润湿性. 这种先进的PVDF-Li隔膜能显著抑制锌枝晶的生长, 提高水系锌离子电池的循环寿命. 因此, 使用PVDF-Li隔膜的Zn||V2O5电池的初始容量达324 mA h g−1, 比传统玻璃纤维隔膜高27%, 且容量保持率也得到大幅提升. 该研究设计了一种功能隔膜来调控正负极反应的均匀性, 这为高性能水系电池的开发提供了新的思路.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22179117 and U21A2075) and the startup foundation for the Hundred-Talent Program of Zhejiang University. XRD and SEM measurements were performed at the Chemistry Instrument Center, Department of Chemistry, Zhejiang University. AFM was performed at the University of Science and Technology of China.

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Authors and Affiliations

  1. Department of Chemistry, Zhejiang University, Hangzhou, 310027, China

    Fenglin Zhang  (张丰麟), Renzhi Huang  (黄仁智), Ning Dong  (董宁) & Huilin Pan  (潘慧霖)

  2. Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, China

    Fanyang Huang  (黄凡洋), Shuhong Jiao  (焦淑红) & Ruiguo Cao  (曹瑞国)

  3. State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, 310027, China

    Huilin Pan  (潘慧霖)

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  1. Fenglin Zhang  (张丰麟)
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  2. Fanyang Huang  (黄凡洋)
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  3. Renzhi Huang  (黄仁智)
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  4. Ning Dong  (董宁)
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  5. Shuhong Jiao  (焦淑红)
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  6. Ruiguo Cao  (曹瑞国)
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  7. Huilin Pan  (潘慧霖)
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Contributions

Author contributions Zhang F conducted the experiment; Huang F, Jiao S and Cao R performed the AFM measurement. Huang R and Dong N performed some data analysis and offered helpful suggestions. Zhang F and Pan H designed this study, analyzed the data and wrote the paper. All authors contributed to the general discussion.

Corresponding author

Correspondence to Huilin Pan  (潘慧霖).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Supporting data are available in the online version of the paper.

Fenglin Zhang received his BS degree in chemistry from Xiamen University in 2020. He then joined the Department of Chemistry at Zhejiang University under the supervision of Prof. Huilin Pan. His research focuses on the design of new electrolytes and separators for energy storage devices.

Huilin Pan is a group leader for the energy storage material research at the Department of Chemistry, Zhejiang University. She received her PhD degree in condensed matter physics from the Institute of Physics, Chinese Academy of Sciences in 2013. In the past, she worked as a staff scientist at Pacific Northwest National Laboratory. Her research interest is primarily engaged in new energy storage battery materials and systems, including rechargeable aqueous Zn batteries, Na-ion batteries, and solid electrolyte interphases.

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40843_2022_2239_MOESM1_ESM.pdf

Hierarchical porous separator with excellent isotropic modulus enabling homogeneous Zn2+ flux for stable aqueous Zn battery

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Zhang, F., Huang, F., Huang, R. et al. Hierarchical porous separator with excellent isotropic modulus enabling homogeneous Zn2+ flux for stable aqueous Zn battery. Sci. China Mater. 66, 982–991 (2023). https://doi.org/10.1007/s40843-022-2239-8

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