The increment of battery temperature during the operation caused by internal heat generation is one of the main issues to face in the management of storage systems for automotive and power generation applications. The temperature strongly affects the battery efficiency, granting the best performance in a limited range. The investigation and testing of materials for the improvement of heat dissipation are crucial for modern battery systems that must provide high power and energy density. This study presents an analysis of the thermal behavior of a lithium-polymer cell, which can be stacked in a battery pack for electric vehicles. The cell is sheltered with layers of two different materials: carbon and graphene, used in turn, to dissipate the heat generated during the operation in natural convection. Optical diagnostics in the infrared band is used to evaluate the battery surface temperature and the effect of the coatings. Experiments are performed in two operating conditions varying the current demand. Moreover, two theoretical correlations are used to estimate the thermal parameters of the battery with a reverse-logic approach. The convective heat transfer coefficient h and the specific heat capacity cp of the battery are evaluated and provided for the Li-ion battery under investigation for different coatings’ conductivity. The results highlight the advantage of using a coating and the effect of the coating properties to reduce the battery temperature under operation. In particular, graphene is preferable because it provides the lowest battery temperature in the most intense operating condition.