Stable Non‐flammable Phosphate Electrolyte for Lithium Metal Batteries via Solvation Regulation by the Additive

Abstract The application of lithium metal batteries (LMBs) is impeded by safety concerns. Employing non‐flammable electrolytes can improve battery reliability while the cost and performance deterioration limit their popularization. Herein, a high‐performance non‐flammable electrolyte is designed, 1.5 m LiTFSI in propylene carbonate (PC)/triethyl phosphate (TEP) (4:1 by vol.) with 4‐nitrophenyl trifluoroacetate (TFANP) as the additive, which can facilitate the construction of LiF‐rich solid electrolyte interphase (SEI) on Li anode surface and cathode electrolyte interphase (CEI) on cathode surface through its prioritized decomposition. In TFANP‐containing electrolyte, the decreased TEP coordination number in the solvation sheath relieves the adverse effect of active TEP on both the SEI and CEI for suppressing the growth of Li dendrites and reducing the continuous electrolyte consumption. Thus, the Li||LiNi 0.6 Co 0.2 Mn 0.2 O 2 battery with such an electrolyte can deliver 132 mAh g −1 after 150 cycles with high coulombic efficiency (99.5%) and superior rate performance (110 mAh g −1 at 5 C, 1 C = 200 mA g −1 ). This work provides a new additive insight on non‐flammable electrolyte for reliable LMBs.