Electrolyte additive tris(trimethylsilyl) phosphite (TMSPi) was used to promote the electrochemical performances of LiNi[Formula: see text]Co[Formula: see text]Mn[Formula: see text]O2 (NCM523) at elevated voltage (4.5 V) and temperature (55[Formula: see text]C). The NCM523 in 2.0 wt.% TMSPi-added electrolyte exhibited a much higher capacity (166.8 mAh/g) than that in the baseline electrolyte (118.3 mAh/g) after 100 cycles under 4.5 V at 30[Formula: see text]C. Simultaneously, the NCM523 with 2.0 wt.% TMSPi showed superior rate capability compared to that without TMSPi. Besides, after 100 cycles at 55[Formula: see text]C under 4.5 V, the discharge capacity retention reached 87.4% for the cell with 2.0 wt.% TMSPi, however, only 24.4% of initial discharge capacity was left for the cell with the baseline electrolyte. A series of analyses (TEM, XPS and EIS) confirmed that TMSPi-derived solid electrolyte interphase (SEI) stabilized the electrode/electrolyte interface and hindered the increase of interface impedance, resulting in obviously enhanced electrochemical performances of NCM523 cathode materials under elevated voltage and/or temperature.
