Non‐Flammable Ester Electrolyte with Boosted Stability Against Li for High‐Performance Li Metal Batteries

In traditional non‐flammable electrolytes a trade‐off always exists between non‐flammability and battery performance. Previous research focused on reducing free solvents and forming anion‐derived solid‐electrolyte interphase. However, the contribution of solvated anions in boosting the stability of electrolyte has been overlooked. Here, we resolve this via introducing anions into Li(+) solvation sheaths using anions with similar Gutmann donor number (DN) to that of solvents. Taking trimethyl phosphate fire‐retardant (DN=23.0 kcal mol(−1)) and NO(3) (−) (DN=22.2 kcal mol(−1)) as an example, NO(3) (−) is readily involved in the Li(+) solvation sheath and reduces the polarity of solvent. This results in boosted stability of electrolyte against Li. The developed non‐flammable electrolyte has low viscosity, high ionic conductivity and is low cost. The reversibility of Li‐Cu cell was improved to 99.49 % and the lifespan of practical LMBs was extended by >100 %.