Stabilizing electrode–electrolyte interfaces to realize high-voltage Li||LiCoO2 batteries by a sulfonamide-based electrolyte

High-voltage lithium-metal batteries (LMBs) with LiCoO2 (LCO) as the cathode have high volumetric and gravimetric energy densities. However, it remains a challenge for stable cycling of LCO >4.5 VLi. Here we demonstrate that a rationally designed sulfonamide-based electrolyte can greatly improve the cycling stability at high voltages up to 4.7 VLi by stabilizing the electrode–electrolyte interfaces (EEIs) on both the Li-metal anode (LMA) and high-voltage LCO cathode. With the sulfonamide-based electrolyte, commercial LCO cathodes retain 89% and 85% of their capacities after 200 and 100 cycles under high charging voltages of 4.55 VLi and 4.6 VLi, respectively, significantly outperforming traditional carbonate-based electrolytes. The surface degradation, impedance growth, and detrimental side reactions in terms of gas evolution and Co dissolution are well suppressed. Our work demonstrates a promising strategy for designing new electrolytes to realize high-energy Li||LCO batteries.