In this work, various electrolyte additives designed for enhanced performance at high voltages were evaluated with elevated temperature potentiostatic holds with LiNi 0.5 Co 0.2 Mn 0.3 /Li 4 Ti 5 O 12 full cells to determine their effect on the high voltage stability. Of the additives investigated, many showed increased oxidation current through the 60 hour potentiostatic holds test, and adversely affected both the capacity retention and interfacial impedance. Improved high voltage performance was observed with two additives, vinylene carbonate (VC) and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), which was attributed to two different mechanisms of improvement. This work investigates some conclusions in the available literature of an additive molecule that decomposes on the charged cathode surface and passivates the surface against electrolyte oxidation. With the goal of increasing battery energy density for transportation applications, layered transition metal oxides cathodes of the form LiMO 2 (M = Ni, Co, Mn) have received significant attention.1-7 While these cathode materials have a high theoretical gravimetric capacity of ∼280 mAh/g, 8 achieving the high capacity of these materials requires very high charging voltages (>4.5V vs. Li + /Li), 2-4 above the stability range of conventional carbonate electrolytes.9,10 Enabling the additional high voltage capacity of the cathode materials requires new electrolytes that provide additional stability at high voltages at the charged cathode surface.The approach to creating compatible electrolytes has mainly fallen along two separate paths: either increasing the intrinsic anodic stability of the electrolyte, [11][12][13][14][15][16][17] or using a sacrificial component in small amounts (an additive) to "passivate" the cathode surface and inhibit continual electrolyte oxidation.18 20,32 have shown evidence of decomposition on various high voltage cathode surfaces through a variety of surface characterization techniques, including attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS).However, this cathode "passivation" is conventionally inferred through a combination of experimental results, such as increased capacity retention, voltammetric methods indicating a lower anodic stability attributed to additive oxidation, changes to the XPS and/or FTIR spectra of the cathode that include components of the additive, and decreased impedance after cycling. While the results provided by the previously mentioned characterization methods can be reconciled with the conclusion that cathode "passivation" led to the improvement, this mechanistic process can be more accurately evaluated by monitoring the electrolyte oxidation current at a charged cathode surface through potentiostatic holds. A passivation layer will limit electron transfer from the electrolyte to the charged cathode surface. By this definition, this layer must have both a minimal electron conductivity as well as a minimal diffusio...