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Fluorinated hybrid interphases enable anti-corrosion and uniform zinc deposition for aqueous zinc metal batteries

构建富氟杂化界面实现水性锌电池负极的防腐和均匀锌沉积

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Abstract

Rechargeable aqueous zinc (Zn) metal batteries (AZMBs) have become the most promising option for large-scale energy storage systems because they utilize low-cost, high-safety aqueous electrolytes. However, the poor reversibility of the Zn anode due to inferior stability in aqueous electrolytes has severely impeded the practical applications of AZMBs. Herein, we propose a fluorine (F)-rich hybrid artificial solid electrolyte interphase (ASEI) to solve the above issue by coating Zn surface with fluorinated graphite and exploiting the interfacial reaction between fluorinated graphite and Zn. The interaction between the electrolyte and Zn was effectively restricted by the hydrophobic fluorinated graphite, thereby improving the corrosion resistance of the Zn anode. Furthermore, the F-rich hybrid interphase comprising fluorinated graphite and in situ generated ZnF2 facilitated the desolvation of Zn2+ and homogenized the Zn2+ flux, effectively inhibiting side reactions and dendrite growth. Consequently, the symmetric cell showed stable cycle performance for over 1400 h at 10 mA cm−2 and 1 mA h cm−2 and for 200 h at 30 mA cm−2 and 10 mA h cm−2, significantly exceeding the performance of the cell with a bare Zn anode. Moreover, the Zn/MnO2 full cell with the MnO2 loading of 6 mg cm−2 maintained more than 80% capacity after 2000 cycles at 1 A g−1. This strategy for constructing fluorinated hybrid ASEI is a promising approach for the design of high-performance AZMBs.

摘要

使用低成本、高安全性的水系电解液使二次锌金属电池 (AZMBs)成为大规模储能系统是最有前途的选择. 然而, 锌金属负极在 水系电解液中热力学稳定性较差, 严重阻碍了AZMBs的实际应用. 在 此, 我们通过在锌表面涂覆氟化石墨并利用氟化石墨和锌之间原位的 界面反应开发了一种富氟的杂化人工固体电解质界面来解决上述问 题. 疏水的氟化石墨可以有效地限制电解液和电极之间的接触, 从而显 著提高锌负极的抗腐蚀能力. 同时, 由氟化石墨和锌原位反应生成的 ZnF2共同组成的富氟杂化界面可以促进Zn2+的脱溶剂化作用, 并均匀 化锌离子通量, 从而有效地抑制了副反应发生和枝晶生长. 因此, 在苛 刻的测试条件下(10 mA cm−2, 1 mA h cm−2 和30 mA cm−2, 10 mA h cm−2), 对称电池可以分别稳定地循环1400和200小时以上, 远 远超过了裸锌的性能. 此外, 使用载量为6 mg cm−2的MnO2正极组装的 Zn/MnO2全电池在1 A g−1的条件下经过2000次循环, 仍能保持80%以上 的容量. 本文提出的这种构建富氟杂化ASEI的方法可以为设计高性能 AZMBs提供一种有效的潜在策略.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (22075048 and 52201201), Shaanxi Yanchang Petroleum Co., Ltd. (18529), Yiwu Research Institute of Fudan University (20-1-06), Shanghai International Collaboration Research Project (19520713900), and the State Key Lab of Advanced Metals and Materials (2022Z-11).

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Authors and Affiliations

  1. State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, 200438, China

    Lequan Wang  (王乐泉), Yuhuan Meng  (孟宇寰), Yixiang Zhang  (张逸翔), Junming Kang  (康峻铭), Huajing Li  (李华晶), Jiajia Zhang  (张佳佳), Zedong Zhao  (赵则栋) & Hongbin Lu  (卢红斌)

  2. Yiwu Research Institute of Fudan University, Yiwu, 322000, China

    Hongbin Lu  (卢红斌)

  3. School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing, 100083, China

    Long Zhang  (张隆)

  4. Xiaomi EV Technology Co., Ltd., Beijing, 100176, China

    Zedong Zhao  (赵则栋)

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  1. Lequan Wang  (王乐泉)
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  2. Long Zhang  (张隆)
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  7. Jiajia Zhang  (张佳佳)
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Contributions

Author contributions Wang L, Zhang L and Lu H conceived and designed this work. Wang L performed the experiments and wrote the paper, Meng Y, Kang J, Zhang Y and Zhang J provided valuable advice and participated in helpful discussions. All authors discussed the data and commented on the manuscript. The project was supervised by Zhang L and Lu H. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Corresponding authors

Correspondence to Long Zhang  (张隆) or Hongbin Lu  (卢红斌).

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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.

Lequan Wang received his Master’s degree from Sichuan University. He is currently a Doctor’s degree candidate at Fudan University. His research interest mainly focuses on the interfacial engineering of zinc anodes for high-performance aqueous zinc-ion batteries.

Long Zhang is currently an associate professor at the University of Science and Technology Beijing. He received his PhD degree from the State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University in 2019. He then worked as a postdoctoral fellow at the College of Engineering, Peking University from 2019 to 2021. During this period, he obtained the financial support of the Postdoctoral Innovation Talent Support Program. His research focuses on the design and chemical synthesis of functional nanomaterials in the fields of energy storage applications.

Hongbin Lu is a professor at the Department of Macromolecular Science, Fudan University, China. He received his PhD degree from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences in 1999. He worked as a postdoctoral fellow at the University of Southern California in America from 2001 to 2004. Currently, his research focuses on the synthesis of low-dimensional nanomaterials and their applications in energy storage, thermal management, catalysis and composite materials.

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40843_2023_2598_MOESM1_ESM.pdf

Supporting Information: Fluorinated hybrid interphases enable anti-corrosion and uniform zinc deposition for aqueous zinc metal batteries

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Wang, L., Zhang, L., Meng, Y. et al. Fluorinated hybrid interphases enable anti-corrosion and uniform zinc deposition for aqueous zinc metal batteries. Sci. China Mater. 66, 4595–4604 (2023). https://doi.org/10.1007/s40843-023-2598-0

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