Thermal management is one of the key factors to keep lithium-ion cells in optimum electrical performance, under safe working conditions and into a reasonably low ageing process. This issue is becoming particularly relevant due to the heterogeneous heat generation along the cell. Cell working temperature is determined by ambient temperature, heat generation and evacuation capacity. Therefore, thermal management is established by: i) the intrinsic thermal properties (heat capacity & thermal conductivity) and ii) the heat generation electro-thermal parameters (internal resistance, open circuit voltage & entropic factor). In this research, different methods - calculated and experimental - are used to characterize the main heat properties of a 14Ah -LiFePO4/graphite-commercial large sizes pouch cell. In order to evaluate the accuracy of methods, two comparisons were performed. First, Newman heat generation estimations were compared with experimental heat measurements. Secondly, empirical thermal cell behaviour was match with 1D electro-thermal model response. Finally, considering the results, the most adequate methodology to evaluate the key thermal parameters of a large size Lithium-ion pouch cell are proposed to be: i) pulse method for internal resistance, ii)heat loss method for entropic factor; and iii)experimental measurement (ARC calorimeter and C-177-97 standard method) for heat capacity and thermal conductivity.