Some Lewis acid-base adducts involving boron trifluoride as electrolyte additives for lithium ion cells

Describes several Lewis acid-base adducts as electrolyte additives. Pyridine boron trifluoride is the best adduct studied here. Pyridine boron trifluoride improved storage, impedance and long-term cycling. a b s t r a c t Three complexes with boron trifluoride (BF 3) as the Lewis acid and different Lewis bases were synthe-sized and used as electrolyte additives in Li[Ni 1/3 Mn 1/3 Co 1/3 ]O 2 /graphite and Li[Ni 0.42 Mn 0.42 Co 0.16 ]O 2 / graphite pouch cells. Lewis acid-base adducts with a boron-oxygen (BeO) bond were trimethyl phos-phate boron trifluoride (TMP-BF) and triphenyl phosphine oxide boron trifluoride (TPPO-BF). These were compared to pyridine boron trifluoride (PBF) which has a boron-nitrogen (BeN) bond. The experimental results showed that cells with PBF had the least voltage drop during storage at 4.2 V, 4.4 V and 4.7 V at 40 C and the best capacity retention during long-term cycling at 55 C compared to cells with the other additives. Charge-hold-discharge cycling combined with simultaneous electrochemical impedance spectroscopy measurements showed that impedance growth in TMP-BF and TPPO-BF containing cells was faster than cells containing 2%PBF, suggesting that PBF is useful for impedance control at high voltages (>4.4 V). XPS analysis of the SEI films highlighted a specific reactivity of the PBF-derived SEI species that apparently hinders the degradation of both LiPF 6 and solvent during formation and charge-hold-discharge cycling. The modified SEI films may explain the improved impedance, the smaller voltage drop during storage and the improved capacity retention during cycling of cells containing the PBF additive.