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Charge regulation by ferromagnetic metal/LiF spin-polarized interface for high-performance Li metal anodes

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Abstract

The interfacial characteristics of the Li metal anode (LMA) play a crucial role in its overall performance. Despite various materials being applied to modify the interface, a comprehensive understanding of their specific mechanisms remains to be investigated. Herein, we have prepared carbon cloth (CC) frameworks with their surfaces modified using ferromagnetic metal/LiF heterogeneous films (TM-LiF-CC) as the substrate for LMA, which exhibit superior electrochemical performance. Utilizing ferromagnetic Co as a representative example, our study demonstrates that the enhanced performance of Co-LiF-CC, compared to bare CC, is attributed to the spin-polarized interface contributed by the Co/LiF heterostructure. Co and LiF play individual roles in redistributing electrons and Li+ to promote homogeneous Li deposition. Co nanoparticles play a crucial role in generating strong surface capacitance by storing electrons in spin-split bands, while LiF, with low surface diffusion barriers, ensures fast transportation of Li+. The Co-LiF-CC@Li electrodes deliver long lives of 7400 and 3600 h at 1 and 2 mA·cm−2 in symmetric cells, respectively; moreover, they enable full batteries with high and durable capacities, particularly when the N/P ratios are low (3.3 or even 1.7).

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摘要

锂金属负极（LMA）的界面特性对其整体性能起着至关重要的作用。尽管有多种材料被用于界面改性，但其作用的具体机制仍有待研究。在此项工作中，我们制备了表面由铁磁性金属/氟化锂异质膜修饰的碳布骨架（TM-LiF-CC）作为锂金属负极的基底，其表现出优异的电化学性能。以铁磁性Co为例，与裸CC相比，Co-LiF-CC性能的提升得益于Co/LiF异质结构产生的自旋极化界面。Co和LiF能够重新分配电子和Li+，促进锂的均匀沉积。Co纳米颗粒在自旋分裂带中存储电子产生了强表面电容，而具有低表面扩散势垒的LiF促进了Li+的快速传输。因此，使用Co-LiF-CC@Li复合负极组装的对称电池在1和2 mA·cm-2的条件下分别稳定循环超过了7400和3600 h。同时，低N/P比的锂金属全电池表现出优异的循环性能。

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Acknowledgments

This study was financially supported by the National Natural Science Foundation of China (No. 52002270) and the China Postdoctoral Science Foundation (No. 2020M670661).

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  1. Ming-Yang Feng and Shuang Zhou have contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Powder Metallurgy, School of Materials Science and Engineering, Central South University, Changsha, 410083, China

    Ming-Yang Feng, Shuang Zhou, Chun-Yan Fu, Jian-Wen Li, Yuan-Lang Wan & An-Qiang Pan

  2. State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Key Laboratory of Advanced Fibers and Energy Storage, School of Material Science and Engineering, Tiangong University, Tianjin, 300387, China

    Yi-Fang Zhang, Zhi-Jia Zhang & Yong Jiang

  3. School of Materials Science and Engineering, Hebei University of Technology, Tianjin, 300130, China

    Ya-Ping Wang

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Feng, MY., Zhou, S., Zhang, YF. et al. Charge regulation by ferromagnetic metal/LiF spin-polarized interface for high-performance Li metal anodes. Rare Met. 43, 995–1005 (2024). https://doi.org/10.1007/s12598-023-02517-4

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