An electrochemical–thermal coupling model is developed to describe the LiFePO4/graphite battery discharge and charge processes. Various heat generations/consumptions including Joule heat, reversible entropy heat, contact resistance heat, irreversible electrochemical reaction heat, ionic migration heat, and convective heat release to the ambient during charge or discharge processes are calculated in detail. The developed model is first validated by experimental data. Then systematic and comprehensive thermal analyses with respect to various discharge processes are performed based on the simulated results. For the specific cell considered, the irreversible electrochemical reaction heat and contact resistance heat are found to be the two main heat generation sources; for discharge processes of higher C-rate, the contact resistance heat take more proportion of the total heat generation as it is directly proportional to the squared discharge current density; the ionic migration heat is a sink with magnitude being about 1/3 of the Joule heat. The reversible entropy heat changes its sign from a negative heat sink to a positive heat source during a discharge process and its changing magnitude may be comparable to the irreversible electrochemical reaction heat for all the discharge processes of different C-rates.