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Research Article

Interfacial engineering of perfluoroalkyl functionalized covalent organic framework achieved ultra-long cycled and dendrite-free lithium anodes

Yongxin Yang, Conghui Zhang, Zhiyuan Mei, Yongjiang Sun, Qi An, Qi Jing, Genfu Zhao, Hong Guo( )
International Joint Research Center for Advanced Energy Materials of Yunnan Province, Yunnan Key Laboratory of Carbon Neutrality and Green Low-carbon Technologies, School of Materials and Energy, Yunnan University, Kunming 650091, China
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Graphical Abstract

The strong electron-withdrawing effect of perfluoroalkyl covalent organic framework (COF-F6) promotes dissociation of lithium bis(trifluoromethanesulphonyl)imide (LiTFSI) and Li+ desolvation to inhibit Li dendrites.

Abstract

The finite lithium-ion utilization, short cycling life, and lower capacity retention caused by irreversible dendrite growth become the maximum dilemma in lithium metal batteries’ (LMBs’) commercialization. Herein, a perfluoroalkyl-functionalized covalent organic framework (COF-F6) equipped with high stability and supernal proton conduction is introduced as an artificial solid electrolyte interface to stable the lithium metal anode. Benefiting from the strong electron-withdrawing effect of perfluoroalkyl, Li+ will be freed more by the competition of electronegative fluorine (F) and bis(trifluoromethanesulphonyl)imide anion (TFSI−). The dissociation of LiTFSI and process of Li+ desolvation are easier to achieve. In addition, high electronegative fluorine can also regulate local electron-cloud density to induce the fast immigration of Li+. All the above roles contribute to improving the Li+ transfer number (0.7) and achieving the goal of inhibiting Li dendrite. As a result, the perfluoroalkyl COF-F6 modified LMB presents outstanding cycling stability. The symmetric batteries accomplish an overlong life-span of more than 5000 h with a lower hysteresis voltage (11 mV) at 5 mA·cm−2. Also, no dendrites are observed when using an in-situ optical microscope to learn the process of Li deposition. Therefore, this dendrite-free protection tactic holds broad prospects for the practical application of Li metal anodes.

Keywords

perfluoroalkyl-functionalized covalent organic framework (COF-F6)artificial solid electrolyte interfacestrong electron-withdrawing effectdendrite-freelithium metal anode

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Nano Research
Volume 16 Issue 7,
July 2023
Pages 9289-9298
DOI: 10.1007/s12274-023-5534-0
Cite this article:
Yang Y, Zhang C, Mei Z, et al. Interfacial engineering of perfluoroalkyl functionalized covalent organic framework achieved ultra-long cycled and dendrite-free lithium anodes. Nano Research, 2023, 16(7): 9289-9298. https://doi.org/10.1007/s12274-023-5534-0
Topics:
Lithium batteries

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Received: 20 December 2022
Revised: 14 January 2023
Accepted: 30 January 2023
Published: 19 February 2023
© Tsinghua University Press 2023
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