Insights into the LiI Redox Mediation in Aprotic Li–O₂ Batteries: Solvation Effects and Singlet Oxygen Evolution

Lithium–oxygen aprotic batteries (aLOBs) are highly promising next-generation secondary batteries due to their high theoretical energy density. However, the practical implementation of these batteries is hindered by parasitic reactions that negatively impact their reversibility and cycle life. One of the challenges lies in the oxidation of Li₂O₂, which requires large overpotentials if not catalyzed. To address this issue, redox mediators (RMs) have been proposed to reduce the oxygen evolution reaction (OER) overpotentials. In this study, we focus on a lithium iodide RM and investigate its role on the degradation chemistry and the release of singlet oxygen in aLOBs, in different solvent environments. Specifically, we compare the impact of a polar solvent, dimethyl sulfoxide (DMSO), and a low polarity solvent, tetraglyme (G4). We demonstrate a strong interplay between solvation, degradation, and redox mediation in OER by LiI in aLOBs. The results show that LiI in DMSO-based electrolytes leads to extensive degradation and to ¹O₂ release, affecting the cell performance, while in G4-based electrolytes, the release of ¹O₂ appears to be suppressed, resulting in better cyclability.