Transition metal oxide cathodes for Li-ion batteries offer high energy density and high voltage. Composites of these materials have shown excellent life expectancy and improved thermal performance. In the present work, a comprehensive non-isothermal electrochemical model for a Lithium ion cell with a composite cathode is developed. The present work builds on lithium concentration-dependent diffusivity and thermal gradient of cathode potential, obtained from experiments. The model validation is performed for a wide range of temperature and discharge rates. Excellent agreement is found for high and room temperature with moderate success at low temperatures, which can be attributed to the low fidelity of material properties at low temperature. Although the cell operation is limited by electronic conductivity of NCA at room temperature, at low temperatures a shift in controlling process is seen, and operation is limited by electrolyte transport. At room temperature, the lithium transport in Cathode appears to be the main source of heat generation with entropic heat as the primary contributor at low discharge rates and ohmic heat at high discharge rates respectively. Improvement in electronic conductivity of the cathode is expected to improve the performance of these composite cathodes and pave way for its wider commercialization. (C) 2015 Elsevier B.V. All rights reserved.