The Anionic Chemistry in Regulating the Reductive Stability of Electrolytes for Lithium Metal Batteries

• Published in: Angewandte Chemie International Edition Vol. 61; no. 52; pp. e202210859 - n/a
• Main Authors: Yao, Nan, Sun, Shu‐Yu, Chen, Xiang, Zhang, Xue‐Qiang, Shen, Xin, Fu, Zhong‐Heng, Zhang, Rui, Zhang, Qiang
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 23.12.2022
• Edition: International ed. in English
• Subjects: anionic chemistry; Anions; Batteries; Chemistry; Computer applications; electrolyte stability; Electrolytes; Lithium; Lithium batteries; lithium metal battery; Metals; Molecular orbitals; multi-scale simulation; Sheaths; Solvation; solvation chemistry; Stability; Structural stability; Structure-function relationships; anionic chemistry; electrolyte stability; multi-scale simulation; lithium metal battery; solvation chemistry
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202210859

Advanced electrolyte design is essential for building high‐energy‐density lithium (Li) batteries, and introducing anions into the Li+ solvation sheaths has been widely demonstrated as a promising strategy. However, a fundamental understanding of the critical role of anions in such electrolytes is very lacking. Herein, the anionic chemistry in regulating the electrolyte structure and stability is probed by combining computational and experimental approaches. Based on a comprehensive analysis of the lowest unoccupied molecular orbitals, the solvents and anions in Li+ solvation sheaths exhibit enhanced and decreased reductive stability compared with free counterparts, respectively, which agrees with both calculated and experimental results of reduction potentials. Accordingly, new strategies are proposed to build stable electrolytes based on the established anionic chemistry. This work unveils the mysterious anionic chemistry in regulating the structure–function relationship of electrolytes and contributes to a rational design of advanced electrolytes for practical Li metal batteries. The participation of anions in the solvation sheath of lithium ions promotes the reductive stability of solvents. Simultaneously, anions themselves tend to get reduced more easily and induce the formation of inorganic‐rich solid electrolyte interphase, which is beneficial to stabilizing lithium metal anodes.