Internal Electron‐Donation Allocation Design for Intrinsic Solubilization of Lithium Nitrate in Ester Electrolyte for Stable Lithium Metal Batteries

Lithium metal batteries (LMBs) have become a hot topic in the research of next‐generation advanced battery technology due to their high specific energy. However, the high reaction activity between lithium metal and electrolyte is considered one of the key bottlenecks limiting large‐scale applications of LMBs. As a classic electrolyte additive, LiNO3 significantly improves the stability of lithium metal in ether‐based electrolytes. However, its solubility in carbonate‐based electrolytes widely used in lithium‐ion batteries is extremely low, and its protective effect on lithium metal is limited, which has become a key obstacle to the commercial application of lithium metal batteries. Here, we enhanced the local negative charge density of carbonyl oxygen atoms in carbonate molecules by introducing electron donors, making it easier for them to coordinate with Li+, thereby weakening the interaction between Li+ and NO3−, and significantly increasing the solubility of LiNO3 in ester electrolytes. The modified ester solvent promotes the derivatization and decomposition of salt anions, leading to the formation of a dense SEI layer rich in LiF and LiNxOy. This significantly improves the stability of lithium metal in ester‐based electrolytes. The assembled Li||Li symmetric battery shows excellent cycling performance of over 4000 hours.