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Vol. 17 (2025)

Revisiting Dipole-Induced Fluorinated-Anion Decomposition Reaction for Promoting a LiF-Rich Interphase in Lithium-Metal Batteries

https://doi.org/10.1007/s40820-024-01637-5
Liu Wang
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003, People’s Republic of China
Jiahui Guo
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003, People’s Republic of China
Qi Qi
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Xiaotong Li
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Yuanmeng Ge
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003, People’s Republic of China
Haoyi Li
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003, People’s Republic of China
Yunfeng Chao
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003, People’s Republic of China
Jiang Du
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Xinwei Cui
Henan Institutes of Advanced Technology, Zhengzhou University, Zhengzhou 450003, People’s Republic of China

Corresponding Author: Xinwei Cui

xinweic@zzu.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 111

Abstract

Building anion-derived solid electrolyte interphase (SEI) with enriched LiF is considered the most promising strategy to address inferior safety features and poor cyclability of lithium-metal batteries (LMBs). Herein, we discover that, instead of direct electron transfer from surface polar groups to bis(trifluoromethanesulfonyl)imide (TFSI−) for inducing a LiF-rich SEI, the dipole-induced fluorinated-anion decomposition reaction begins with the adsorption of Li ions and is highly dependent on their mobility on the polar surface. To demonstrate this, a single-layer graphdiyne on MXene (sGDY@MXene) heterostructure has been successfully fabricated and integrated into polypropylene separators. It is found that the adsorbed Li ions connect electron-donating sGDY@MXene to TFSI−, facilitating interfacial charge transfer for TFSI− decomposition. However, this does not capture the entire picture. The sGDY@MXene also renders the adsorbed Li ions with high mobility, enabling them to reach optimal reaction sites and expedite their coordination processes with O on O=S=O and F on the broken –CF3−, facilitating bond cleavage. In contrast, immobilized Li ions on the more lithiophilic pristine MXene retard these cleavage processes. Consequently, the decomposition reaction is accelerated on sGDY@MXene. This work highlights the dedicate balance between lithiophilicity and Li-ion mobility in effectively promoting a LiF-rich SEI for the long-term stability of LMBs.


Highlights:
1 Single-layer graphdiyne on MXene (sGDY@MXene) heterostructure was fabricated and integrated into polypropylene separators, directing a LiF-rich solid electrolyte interphase and long-term stability of lithium-metal anode.
2 Instead of direct electron transfer from surface polar groups to fluorinated anions, the adsorbed Li ions on sGDY@MXene act as dynamic bridges collaboratively connecting the electron-donating heterostructure to the anion and its derivatives, facilitating interface charge transfer.
3 Dedicate balance between lithiophilicity and high Li-ion mobility is the key to promote the dipole-induced fluorinated-anion decomposition.

Keywords

LiF-rich SEI Li-ion mobility Lithiophilicity MXene Graphdiyne
Wang, Liu, Jiahui Guo, Qi Qi, Xiaotong Li, Yuanmeng Ge, Haoyi Li, Yunfeng Chao, Jiang Du, and Xinwei Cui. 2025. “Revisiting Dipole-Induced Fluorinated-Anion Decomposition Reaction for Promoting a LiF-Rich Interphase in Lithium-Metal Batteries”. Nano-Micro Letters 17 (January):111. https://doi.org/10.1007/s40820-024-01637-5.
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