Impact of Selected LiPF₆ Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells

Diverse LiPF 6 hydrolysis products evolve during lithium-ion battery cell operation at elevated operation temperatures and high operation voltages. However, their impact on the formation and stability of the electrode/electrolyte interfaces is not yet investigated and understood. In this work, literature-known hydrolysis products of LiPF 6 dimethyl fluorophosphate (DMFP) and diethyl fluorophosphate (DEFP) were synthesized and characterized. The use of DMFP and DEFP as electrolyte additive in 1 M LiPF 6 in EC:EMC (1:1, by wt) was investigated in LiNi 1/3 Mn 1/3 Co 1/3 O 2 /Li half cells. When charged to a cutoff potential of 4.6 V vs Li/Li +, the additive containing cells showed improved cycling stability, increased Coulombic efficiencies, and prolonged shelf life. Furthermore, low amounts (1 wt % in this study) of the aforementioned additives did not show any negative effect on the cycling stability of graphite/Li half cells. DMFP and DEFP are susceptible to oxidation and contribute to the formation of an effective cathode/electrolyte interphase as confirmed by means of electrochemical stability window determination, and X-ray photoelectron spectroscopy characterization of pristine and cycled electrodes, and they are supported by computational calculations.