Constructing a Stable Interface Layer by Tailoring Solvation Chemistry in Carbonate Electrolytes for High‐Performance Lithium‐Metal Batteries

Lithium-metal batteries (LMBs) are considered as promising next-generation batteries due to their high energy density. However, commercial carbonate electrolytes cannot be used in LMBs due to their poor compatibility with the lithium-metal anode and detrimental hydrogen fluoride (HF) generation by lithium hexafluorophosphate decomposition. By introducing lithium nitrate additive and a small amount of tetramethylurea as a multifunctional cosolvent to a commercial carbonate electrolyte, NO3- , which is usually insoluble, can be introduced into the solvation structure of Li+ to form a conductive and stable solid electrolyte interface. At the same time, HF generation is suppressed by manipulating the solvation structure and a scavenging effect. As a result, the Coulombic efficiency (CE) of Li||Cu half cells using the designed carbonate electrolyte can reach 98.19% at room temperature and 96.14% at low temperature (-15 °C), and Li||LiFePO4 cells deliver a high capacity retention of 94.9% with a high CE of 99.6% after 550 cycles. This work provides a simple and effective way to extend the use of commercial carbonate electrolytes for next-generation battery systems.