A sulfur-based compound, 1,3,2-dioxathiolane-2,2-dioxide (DTD) is utilized as a cathode film forming additive for high voltage (4.5 V) Li/LiNi0.5Mn0.3Co0.2O2 cell. Electrochemical performance of Li/LiNi0.5Mn0.3Co0.2O2 cell with 1.0 MLiPF6 EC/EMC (3/7, v/v) with/without DTD additive electrolyte has been evaluated. Linear sweep voltammetry (LSV) result demonstrates that DTD is preferably oxidized on the cathode surface to the LiPF6/carbonate bulk electrolyte. After 100 cycles at high voltage (4.5 V, vs. Li/Li+), the discharge capacity retention of the Li/LiNi0.5Co0.2Mn0.3O2 cell with baseline electrolyte is 68%, whereas the cell with 2.0 wt% DTD added electrolyte maintains 84% of its initial discharge capacity. Moreover, the cells with DTD additive exhibits superior rate performance and negligible self-discharge behavior. Ex-situ surface analysis on the cycled cathode and lithium metal was conducted with multiple advanced-techniques, including scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), inductive coupled plasma spectroscopy (ICP-MS) and transmission electron microscope (TEM) as well. Ex-situ surface analysis of the cathode after cycling confirms that the improved electrochemical performances of the cells can be ascribed to more stable and robust surface layer built-up on cathode surface via the sacrificial decomposition of the DTD additive. This tailored stable and robust cathode layer can effectively prevent the detrimental reactions on the cathode/electrolyte interface, mitigate electrolyte decomposition on the cathode surface, and inhibit transition metal dissolution from the bulk cathode material upon cycling at high voltage. (C) 2017 The Electrochemical Society. All rights reserved.