Role of Polysulfide Anions in Solid-Electrolyte Interphase Formation at the Lithium Metal Surface in Li–S Batteries
Kie Hankins, Venkateshkumar Prabhakaran, Sungun Wi, V. Shutthanandan, Grant E. Johnson, Swadipta Roy, Hui Wang, Yuyan Shao, Suntharampillai Thevuthasan, Perla B. Balbuena, Karl T. Mueller, Vijayakumar Murugesan
Abstract
Delineating intricate interactions between highly reactive Li-metal electrodes and the diverse constituents of battery electrolytes has been a long-standing scientific challenge in materials design for advanced energy storage devices. Here, we isolated lithium polysulfide anions (LiS4–) from an electrolyte solution based on their mass-to-charge ratio and deposited them on Li-metal electrodes under clean vacuum conditions using ion soft landing (ISL), a highly controlled interface preparation technique. The molecular level precision in the construction of these model interfaces with ISL, coupled with in situ X-ray photoelectron spectroscopy and ab initio theoretical calculations, allowed us to obtain unprecedented insight into the parasitic reactions of well-defined polysulfides on Li-metal electrodes. Our study revealed that the oxide-rich surface layer, which is amenable to direct electron exchange, drives multielectron sulfur oxidation (S0 → S6+) processes. Our results have substantial implications for the rational design of future Li–S batteries with improved efficiency and durability.