A family of organophosphorus compounds including triphenyl phosphite (TPP), trimethyl phosphite (TMP), tris(2,2,2-trifluoroethyl) phosphite (TFEP), and tris(trimethylsily1) phosphite (TMSP) is investigated as additives for the stabilization of high-voltage LiNi0.5Mn1.5O4 (LNMO) cathode-electrolyte interface. Our investigation reveals that the cycling performance of Li/LNMO half cells with the TMP, TFEP or TMSP additive is drastically improved at 60 degrees C compared to the baseline electrolyte. Among the various phosphite-based additives tested, TMSP additive enables facile Li ion transport at high C rates and significantly enhances the storage performance of the Li/LNMO cells at 60 degrees C. To understand the effects of the phosphite-based additives on electrolyte oxidative decomposition at high voltages, the surface chemistry of the cathode after precycling is investigated via ex-situ X-ray photoelectron spectroscopy (XPS). Additionally, the roles of phosphite-based additives to suppress LiPF6 hydrolysis and to remove HE are examined via F-19 and P-31 NMR spectroscopies. (C) 2015 Elsevier B.V. All rights reserved.