The effect of LiPO2F2 as an electrolyte additive in Li[Ni0.5Mn0.3Co0.2]O-2 (NMC532)/graphite pouch cells was examined using ultra high precision coulometry (UHPC), electrochemical impedance spectroscopy (EIS), storage testing, gas evolution measurements, isothermal calorimetry and long term charge-discharge cycling. Comparisons to the well-known additive, vinylene carbonate (VC) were made. LiPO2F2 is an effective additive for NMC532/graphite pouch cells since it was found to improve coulombic efficiency, decrease parasitic heat flow, improve charge-discharge cycle lifetime and decrease impedance growth. The composition of the solid electrolyte interphases (SEI) on both electrodes was examined by X-ray photoelectron spectroscopy in cases where LiPO2F2 was used or not used. The effect of combining methyl acetate, as a co-solvent to improve rate capability, and LiPO2F2 was also investigated using long term cycling testing at 20 degrees C. Overall, LiPO2F2 is shown to be an extremely valuable electrolyte additive, more effective than VC in these cells. (C) The Author(s) 2018. Published by ECS.