The effect of the electrolyte additive fluoroethylene carbonate (FEC) for Li-ion batteries has been widely discussed in literature in recent years. Here, the additive is studied for the high-voltage cathode LiNi0.5Mn1.5O4 (LNMO) coupled to Li4Ti5O12 (LTO) to specifically study its effect on the cathode side. Electrochemical performance of full cells prepared by using a standard electrolyte (LP40) with different concentrations of FEC (0, 1 and 5 wt%) were compared and the surface of cycled positive electrodes were analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The results show that addition of FEC is generally of limited use for this battery system. Addition of 5 wt% FEC results in relatively poor cycling performance, while the cells with 1 wt% FEC showed similar behavior compared to reference cells prepared without FEC. SEM and XPS analysis did not indicate the formation of thick surface layers on the LNMO cathode, however, an increase in layer thickness with increased FEC content in the electrolyte could be observed. XPS analysis on LTO electrodes showed that the electrode interactions between positive and negative electrodes occurred as Mn and Ni were detected on the surface of LTO already after 1 cycle. (C) The Author(s) 2017. Published by ECS. All rights reserved.