Regulating Dynamic Evolution of Interfacial Electrolyte Configuration via Inert Cation Induced Anion Anchoring to Stabilize Lithium‐Metal Anode

J Junhao Wang (Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering) Y Yaopeng Li W Wenbin Tu (State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering Xiamen University Xiamen P. R. China) H Haitang Zhang X Xiaoyu Yu Y Yuran Yang (State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering) H Haiyan Luo (State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering) Q Qingao Zhao Y Yaxin Ru (State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering) M Ming Chen Y Yuhao Hong J Jinyu Ye (State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering) J Jian‐Feng Li (College of Materials State Key Laboratory of Physical Chemistry of Solid Surfaces iChEM College of Chemistry and Chemical Engineering College of Energy and College of Physical Science and Technology Xiamen University Xiamen China) N Na Liu C Chuying Ouyang H Hansen Wang (Fujian Science & Technology Innovation Laboratory for Energy Devices (21C-Lab)) Y Yeguo Zou (State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering) G Guang Feng Y Yu Qiao S Shi‐Gang Sun (State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen P. R. China)

Abstract

Abstract Interfacial stability in high‐energy‐density lithium metal batteries (LMBs) hinges on precise regulation of dynamic interfacial electrolyte configuration. Although inert cations are frequently employed to stabilize Li‐metal anode, their interfacial adsorption behavior and the resultant evolution of the electrolyte/electrode interface remain elusive. Herein, using in‐situ spectroscopy, we visualized the adsorption of inert cations, exemplified by tetrabutylammonium (TBA + ). Furthermore, the inherent anion‐lean, solvent‐rich interface formed during desolvation was mitigated by the electrostatic interaction between TBA + and anions. This anion‐anchoring effect promotes preferential anion decomposition, thereby suppressing parasitic reactions associated with solvent decomposition. Consequently, the cycling stability and reversibility of Li stripping/plating are significantly enhanced. This work not only refreshes the understanding of inert cations on regulating the interfacial electrolyte configuration, but also highlights the close relationship between the interfacial solvation configuration and the SEI architecture, offering fundamental insights for potential electrolyte design.

Article Details

Volume / Issue Vol. 64, Issue 42
Published October 13, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (20)

J

Junhao Wang

Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering

Y

Yaopeng Li

W

Wenbin Tu

State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering Xiamen University Xiamen P. R. China

H

Haitang Zhang

X

Xiaoyu Yu

Y

Yuran Yang

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering

H

Haiyan Luo

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering

Q

Qingao Zhao

Y

Yaxin Ru

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering

M

Ming Chen

Y

Yuhao Hong

J

Jinyu Ye

State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering

J

Jian‐Feng Li

College of Materials State Key Laboratory of Physical Chemistry of Solid Surfaces iChEM College of Chemistry and Chemical Engineering College of Energy and College of Physical Science and Technology Xiamen University Xiamen China

N

Na Liu

C

Chuying Ouyang

H

Hansen Wang

Fujian Science & Technology Innovation Laboratory for Energy Devices (21C-Lab)

Y

Yeguo Zou

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering

G

Guang Feng

Y

Yu Qiao

S

Shi‐Gang Sun

State Key Laboratory of Physical Chemistry of Solid Surfaces College of Chemistry and Chemical Engineering Xiamen University Xiamen P. R. China