Pentafluorophenyl diethoxy phosphate: An electrolyte additive for high-voltage cathodes of lithium-ion batteries

Increasing the upper limit of the charging voltage in commercial lithium-ion batteries (LIBs) can enable them to have a higher energy density, but during high-voltage charging and discharging, the electrolyte will accelerate the decomposition, and the interfacial adverse reaction among the cathode and electrolyte is serious, which corrodes the cathode active material and consumes excessive electrolyte, and ultimately lead to a shorter service life of lithium-ion batteries. To address this issue, an electrolyte additive with properties suitable for high voltage cathodes, named pentafluorophenyl diethoxy phosphate (FPOP), was synthesized in this work and successfully applied to LiNi0.8Co0.1Mn0.1O2 cathode (NCM-811). Density Functional Theory (DFT) computations reveal that the FPOP additive undergoes preferential oxidation and self-polymerizes on the NCM-811 cathode surface to establishing a safeguarding film at the cathode-electrolyte interface (CEI). This film effectively inhibits detrimental side reactions. The electrochemical performance test data indicated that the retention rate of discharge-specific capacity in batteries was markedly enhanced with 0.1 wt% of FPOP when added to the standard electrolyte. Specifically, after subjecting the batteries to 200 cycles at a current of 0.2C and under voltages ranging from 4.2 V to 4.5 V, the retention of discharge ratio capacity increased by 37.6 %, 39.2 %, 26.9 %, and 37.1 % correspondingly. Morphology characterization and spectroscopic characterization showed that FPOP could not only construct a stable CEI film by oxidation during the first stages of lithium precipitation but also remove HF by strongly binding to the HF in the electrolyte or dissociating H+ and F− from HF, which ultimately enhanced the batteries' capacity to operate effectively at elevated voltage levels. Therefore, incorporating FPOP as an additive in electrolyte presents a cost-efficient approach to achieving elevated energy density.