High-Performance Lithium-Oxygen Batteries Using a Urea-Based Electrolyte with Kinetically Favorable One-Electron Li2 O2 Oxidation Pathways

Angew Chem Int Ed Engl. 2022 Sep 5;61(36):e202207570. doi: 10.1002/anie.202207570. Epub 2022 Jul 26.

Abstract

Glymes are the most widely used electrolyte solvents in lithium-oxygen batteries (LOBs) due to their relatively high stability. However, their associated LOBs have long been plagued by large charge overpotential, which is closely related to the sluggish two-electron Li2 O2 oxidation mechanism. Here, we report a new electrolyte solvent-1,1,3,3-tetramethylurea (TMU) for LOBs with high performance and an alternative mechanism, where a kinetically favorable one-electron Li2 O2 oxidation pathway can happen in the urea electrolyte system, thus leading to a much lower charge overpotential (≈0.51 V) compared to the tetraglyme-based LOBs (≈1.27 V). Besides, TMU also exhibits good stability since it does not contain any α-hydrogen atoms that are vulnerable to be attacked by superoxide species, thus suppressing the hydrogen abstraction side reactions. Consequently, the TMU-based LOBs can stably work for more than 135 cycles, which is four times that of the tetraglyme-based LOBs (≈28 cycles).

Keywords: 1,1,3,3-Tetramethylurea; Electrolyte Solvents; Hydrogen Abstraction; Li-O2 Batteries; Li2O2 Oxidation.