The effects of four fluorinated carbonates including fluoroethylene carbonate, difluoroethylene carbonate, bis(2,2,2-trifluoroethyl) carbonate and 2,2,3,4,4,4-hexafluorobutyl methyl carbonate as electrolyte additives were studied in Li(Ni 0.4 Mn 0.4 Co 0.2 )O 2 /graphite pouch cells using ultra-high precision coulometry, in situ measurements of gas evolution, gas chromatography, electrochemical impedance spectroscopy, and long-term cycling experiments. The differential capacity vs. voltage curves during formation showed that fluoroethylene carbonate and difluoroethylene carbonate are solid electrolyte interphase (SEI) forming additives, while bis(2,2,2-trifluoroethyl) carbonate and 2,2,3,4,4,4-hexafluorobutyl methyl carbonate do not alter the SEI on the negative electrode during formation. Cells containing difluoroethylene carbonate have the highest coulombic efficiency and lowest charge end point capacity slippage rate at both 4.2 and 4.4 V. However the performance was not as good as that of cells containing a state of the art additive blend. Long-term cycle-hold-rest tests at 55 • C showed that at 4.4 V all cells with fluorinated additives that gave promising capacity retention generated unacceptable quantities of gas. Only difluoroethylene carbonate during cycling tests to 4.2 V at 55 • C provided promising capacity retention and moderate gas generation. These results suggest that the use of only these fluorinated additives in Therefore NMC422 is a suitable material to use to test electrolytes proposed for high voltage NMC Li-ion cells. The cycling stability of NMC442/graphite cells is quite poor when charged to cutoff voltages higher than 4.4 V. 6 As an example, Nelson et al. 7 have shown that NMC442/graphite cells can be cycled aggressively at 4.4 V using state-of-the-art electrolyte additives in conventional solvents, but the same cells fail rapidly when the upper cutoff is increased to 4.5 V. Nelson et al. 7 used an electrolyte consisting of 1 M LiPF 6 in ethylene carbonate (EC): ethyl methyl carbonate (EMC) 3:7 (by wt) with 2% prop-1-ene,1,3,sultone (PES), 2% 1,3,2-dioxathiolane-2,2-dioxide (DTD, also called ethylene sulfate) and 2% tris-trimethylsilyl phosphite (TTSPi). This electrolyte, called PES222, was very successful at 4.4 V, even though fluorinated solvents and additives were not used. Based on work by Xia et al.,8 fluorinated solvents appear to extend the voltage range of NMC442/graphite cells. The purpose of this paper is to compare the effectiveness of a variety of fluorinated additives in EC:EMC electrolyte and also to compare those to PES222 and to a related additive blend PES211 which has 2% PES + 1% DTD + 1% TTSPi.Fluoroethylene carbonate (FEC) has been used as an solid electrolyte interphase (SEI)-forming additive and as an electrolyte solvent in Li-ion cells.9-13 The addition of small amounts of FEC to electrolyte significantly improves the cycling stability of graphite, silicon, silicon-alloy and other anode materials.14-19 Difluoroethylene carbonate (DiFEC), is less well known.20 DiFEC...