PNNL

Abstract

To enable next-generation high-energy-density lithium (Li) metal batteries (LMBs), an electrolyte that has simultaneous high Li metal Coulombic efficiency (CE) and high anodic stability on cathodes is of significant importance. Sulfones are known for their high dielectric constants, low flammability and in particular strong resistance against oxidation, but their application in LMBs is restricted due to their poor compatibility with Li metal anode. Uncontrolled Li plating in sulfones results in poor Li CE and induces catastrophic battery failure, and their high viscosity and poor wettability towards electrodes and separators introduce serious issues for the practical applications. Here, we demonstrate that stable Li plating/stripping cycles can be achieved in concentrated sulfone-based electrolytes at a high CE over 98%, where nodule instead of dendritic Li deposition occurs. Furthermore, the viscosity and wettability issues of sulfones could be resolved by the addition of a fluorinated ether, which is a poor solvating agent for ionic species but well miscible with sulfones at microscopic scale. This localized high-concentration electrolyte (LHCE) not only provides further improvement in Li CE (to 98.8%), but also remains anodically stable with high voltage cathode and enables LMBs to operate in a wide temperature range. As a result, significantly improved cycling performance of LMBs using sulfone-based LHCE has been realized.