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Succinonitrile (SN) has been used as functional additive to improve the thermal stability and broaden the oxidation electrochemical window of commercial electrolyte 1 M LiPF6/EC/DEC (1:1, by volume) for highvoltage LIBs (cathode: Li1.2Ni0.2Mn0.6O2, anode: Li). 1 wt % SN-based electrolyte showed a wide electrochemical oxidation window of 5.4 V vs Li รพ /Li and excellent thermal stability demonstrated by thermogravimetry (TG) and X-ray photoelectron spectroscopy (XPS), as well as theoretical analysis according to molecular orbital theory. The LNMO (Li1.2Ni0.2Mn0.6O2) battery with 1 wt % SN-based electrolyte showed better cyclability and capacity retention when charged to higher cut-off voltage. The improved battery performance is mainly attributed to the formation of uniform cathode electrolyte interface (CEI)