Direct Evidence of Reversible Changes in Electrolyte and its Interplay with LiO2 Intermediate in Li‐O2 Batteries

Abstract

AbstractLithium‐oxygen batteries show promising energy storage potential with high theoretical energy density; however, further investigation of chemical reactions is required. In this study, experimental Raman and theoretical analyzes are performed for a Li‐O2 battery with LiClO4/dimethyl sulfoxide (DMSO) electrolyte and carbon cathode to understand the role of intermediate species in the reactional mechanism of the cell using a high donor number solvent. Operando Raman results reveal reversible changes in the DMSO bands, in addition to the formation and decomposition of Li2O2. On discharge, a decrease in DMSO polarizability is observed and bands of DMSO‐Li+‐anion interactions are evidenced and supported by ab initio density functional theory (DFT) calculations. Molecular dynamics (MD) force field simulations and operando Raman show that DMSO interacts with LiO2(sol), highlighting the stability of the electrolyte compared to the interaction with reactive . On charging, the presence of Li+ indicates the formation of a lithium‐deficient phase, followed by the release of Li+ and oxygen. Therefore, this study contributes to understanding the discharge/charge chemistry of a Li‐O2 cell, employing a common carbon cathode and DMSO electrolyte. The combination of a simple characterization technique in operando mode and theoretical studies provides essential information on the mechanism of Li‐O2 system.