Lithium batteries for energy storage systems are a prominent solution for both stationary and mobile applications. Electro-thermal modelling of the cell is a useful tool for monitoring voltage and temperature in order to predict battery behaviour especially in cases of critical operative conditions. This paper provides a modelling approach focusing on the calibration of parameters of an electro-thermal model for large prismatic LFP lithium cells. The designed model is tuned by means of experimental tests that identify a set of parameters that are function of a cell’s state-of-charge and temperature. The model outputs are voltage, cell surface, and internal temperature profiles, which are validated against experimental data referring to realistic working conditions, even providing an intense level of thermal stress. The model accuracy is marked by a voltage mean average error lower than 1% and a mean cell surface temperature deviation lower than 1 K.