A Hybrid-Salt Strategy for Modulating the Li+ Solvation Sheathes and Constructing Robust SEI in Non-Flammable Electrolyte Lithium Metal Batteries

Abstract

The electrode interface determines the performance of an electrochemical energy storage system. Using traditional electrolyte organic additives and high-concentration electrolyte emerging recently are two generally strategies for improving the electrode interface. Here, a hybrid-salt electrolyte strategy is proposed for constructing the stable electrode interface. Through the solubilization effect of phosphate ester on LiNO₃, a hybrid-salts-based non-flammable phosphate ester electrolyte system (HSPE) with LiPF₆ and LiNO₃ as Li salts has been developed. By the strong interaction between NO₃⁻ and Li⁺, the Li⁺ solvation sheath and solvent behaviors have been modulated, thus the undesirable effects of phosphate ester are eliminated and a robust SEI is formed. Experimental results and theoretical calculations illustrate that NO₃⁻ as a kind of strongly coordinating anion can reduce the number of TEP molecules and lower the reduction reactivity of TEP. The reconfigured Li⁺ solvation structure allows the formation of an inorganic-rich SEI on the electrode surface. As a result, in the designed HSPE, the average coulombic efficiency of lithium plating/stripping is increased to 99.12 %. This work explored a new approach to construct the electrode interface and addressing the poor interface performance issue of phosphate esters.