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

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.

Automated summary

This study investigates the role of anionic chemistry in regulating the structure and stability of electrolytes through computational and experimental approaches. The research reveals that introducing anions into the Li+ solvation sheaths can enhance the reductive stability of solvents while decreasing the reductive stability of anions. Based on these findings, new strategies for building stable electrolytes are proposed. This work provides insights into the mysterious anionic chemistry and contributes to the rational design of advanced electrolytes for practical Li metal batteries.