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Vol. 17 (2025)

A LiF-Pie-Structured Interphase for Silicon Anodes

https://doi.org/10.1007/s40820-025-01832-y
Weiping Li
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Shiwei Xu
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Cong Zhong
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Qiu Fang
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Suting Weng
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Yinzi Ma
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Bo Wang
State Key Laboratory of Space Power‑Sources, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, People’s Republic of China
Yejing Li
Department of Energy Storage Science and Engineering, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, People’s Republic of China
Zhaoxiang Wang
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
Xuefeng Wang
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China

Corresponding Author: Xuefeng Wang

wxf@iphy.ac.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 322

Abstract

Silicon (Si) is a promising anode material for rechargeable batteries due to its high theoretical capacity and abundance, but its practical application is hindered by the continuous growth of porous solid-electrolyte interphase (SEI), leading to capacity fade. Herein, a LiF-Pie structured SEI is proposed, with LiF nanodomains encapsulated in the inner layer of the organic cross-linking silane matrix. A series of advanced techniques such as cryogenic electron microscopy, time-of-flight secondary ion mass spectrometry, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry have provided detailed insights into the formation mechanism, nanostructure, and chemical composition of the interface. With such SEI, the capacity retention of LiCoO2||Si is significantly improved from 49.6% to 88.9% after 300 cycles at 100 mA g−1. These findings provide a desirable interfacial design principle with enhanced (electro) chemical and mechanical stability, which are crucial for sustaining Si anode functionality, thereby significantly advancing the reliability and practical application of Si-based anodes.


Article Highlights:
1 A novel hierarchical solid electrolyte interface (SEI) structure is developed, featuring a lithium fluoride (LiF)-rich inner layer and a silane-based cross-linked matrix.
2 A comprehensive suite of advanced characterization techniques provides multi-scale insights into the structural and chemical composition of the LiF-Pie SEI.
3 The proposed SEI design significantly enhances cycling stability, achieving a capacity retention of LiCoO2||Si increase from 49.6% to 88.9% after 300 cycles at a current density of 100 mA g−1.

Keywords

Si anodes Solid electrolyte interface Electrolyte additive
Li, Weiping, Shiwei Xu, Cong Zhong, Qiu Fang, Suting Weng, Yinzi Ma, Bo Wang, Yejing Li, Zhaoxiang Wang, and Xuefeng Wang. 2025. “A LiF-Pie-Structured Interphase for Silicon Anodes”. Nano-Micro Letters 17 (July):322. https://doi.org/10.1007/s40820-025-01832-y.
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