The high temperature reactions of I M LiPF6 EC:DEC and LiCoO2, Li(Ni1/3CO1/3Mn1/3)O-2 (NCM) or Li(Ni0.8Co0.15Al0.05)O-2 (NCA) charged to 4.2 V and 4.4 V, respectively, were studied by accelerating rate calorimetry (ARC). The results indicate that NCM shows better thermal stability than both LiCoO2 and NCA. The state-of-the-art NCA sample shows better safety properties than LiCoO2. The reactivity of the samples depends on the electrolyte: active material ratio used during ARC testing. Electrode materials charged to 4.4 V are more reactive than the electrode materials charged to 4.2 V. These results should be useful for Li-ion battery researchers interested in maximizing the safety of high energy density cells and also as a benchmark for other researchers using ARC. (C) 2007 Elsevier B.V. All rights reserved.