This chapter proposes an advanced thermal model for lithium-ion battery technology. The model is able to predict the surface temperature of lithium-ion battery cell accurately. The model exists of electrical components such as thermal capacitance, inside thermal resistance and convective thermal resistance. In this chapter, a new methodology is presented that allows to determine the parameters of the thermal model. Then, the model has been calibrated and validated at different environmental conditions. According to the validations results, the error of the simulation compared to experimental results is less than 1 °C. Furthermore, the model has been extended to a novel electrothermal model for enhancing of the model performances. Particularly, the association of the electrical model with the thermal model is of high importance due to the change of the battery parameters such as internal resistance in function of state of charge, temperature and current rates.