Additive effects in high-voltage layered-oxide cells: A statistics of mixtures approach

Li1.03(Ni0.5Mn0.3Co0.2)0.97O2 (NMC)-based coin cells containing the electrolyte additives vinylene carbonate (VC) and tris(trimethylsilyl)phosphite (TMSPi) in the range of 0-2 wt% were cycled between 3.0 and 4.4 V. The changes in capacity at rates of C/10 and C/1 and resistance at 60% state of charge were found to follow linear-with-time kinetic rate laws. Further, the C/10 capacity and resistance data were amenable to modeling by a statistics of mixtures approach. Applying physical meaning to the terms in the empirical models indicated that the interactions between the electrolyte and additives were not simple. For example, there were strong, synergistic interactions between VC and TMSPi affecting C/10 capacity loss, as expected, but there were other, more subtle interactions between the electrolyte components. The interactions between these components controlled the C/10 capacity decline and resistance increase.