The flammability and volatility of conventional lithium hexafluorophosphate (LiPF
6)-based electrolytes with organic carbonate solvents remain critical issues to the safety and thermal stability of lithium-ion batteries (LIBs). This study investigates the incorporation of phosphate-based additives including ammonium dihydrogen phosphate (ADP), trimethyl
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The flammability and volatility of conventional lithium hexafluorophosphate (LiPF
6)-based electrolytes with organic carbonate solvents remain critical issues to the safety and thermal stability of lithium-ion batteries (LIBs). This study investigates the incorporation of phosphate-based additives including ammonium dihydrogen phosphate (ADP), trimethyl phosphate (TMP), and trimethyl phosphite (TMPi) into LiPF
6 electrolytes for improving the ionic conductivity, safety, and electrochemical performance of LIBs. Self-extinguishing time (SET) measurements demonstrated that the ADP-based LiPF
6 electrolyte significantly reduced flammability, achieving a shorter SET of 04 min 53 s, compared to 12 min for the pristine LiPF
6 electrolyte. The ADP-based LiPF
6 electrolyte possessed the highest ionic conductivity (14.08 mS·cm
−1) with an excellent lithium-ion transference number of 0.0076. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (C-V) analyses demonstrated that ADP lowered interfacial resistance and stabilized long-term cycling behavior. In particular, the 1% ADP-based LiPF
6 electrolyte maintained improved charge-discharge profiles and Coulombic efficiency over 200 cycles. These results highlight ADP’s dual functionality in suppressing gas-phase flammability and enhancing condensed-phase electrochemical stability, making it a promising candidate for next-generation, high-safety, high-performance LIB electrolytes.
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