Excellent design of a thermal management system requires good understanding of the thermal behaviors of power batteries. In this study, the electrochemical and heat performances of a prismatic 40 Ah C/LiFePO4 battery are investigated with a focus on the influence of temperature on cell capacity in a mixed charge–discharge cycle. In addition, the heat generation and energy efficiency of a battery are determined during charge and discharge at different current rates. The experimental results indicate that in certain temperature ranges, both the charging and discharging capacities increase significantly as the temperature increases. In addition, the energy efficiency reaches more than 95% when the battery runs at a current rate of 0.33 C–2 C and temperature of 25–45 °C. A thermal mathematical model based on experimentally obtained internal resistances and entropy coefficients is developed. Using this model, the increase in the battery temperature is simulated based on specific heat values that are measured experimentally and calculated theoretically. The results from the simulation indicate that the temperature increase agrees well with the experimental values, the measured specific heat provides better results than the calculated specific heat and the heat generated decreases as the temperature increases.