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

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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.

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Acknowledgements

The authors acknowledge financial supports provided by the National Natural Science Foundation of China (No. 52064049), Key Laboratory of Solid-State Ions for Green Energy of Yunnan University (2019), Analysis and Measurements Center of Yunnan University for the sample testing service, the Electron Microscope Center of Yunnan University for the support of this work, and the Postgraduate Research and Innovation Foundation of Yunnan University (No. KC-22221440). The authors would like to thank Jiao Kang and Shu-di Ren from Shiyanjia Lab (https://www.shiyanjia.com) for the NMR analysis.

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  1. 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

    Yongxin Yang, Conghui Zhang, Zhiyuan Mei, Yongjiang Sun, Qi An, Qi Jing, Genfu Zhao & Hong Guo

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  1. Yongxin Yang
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  2. Conghui Zhang
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Correspondence to Hong Guo.

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

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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 Res. 16, 9289–9298 (2023). https://doi.org/10.1007/s12274-023-5534-0

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