This paper examines the effect of flowrate, cell number, tank dimension and environment temperature on the thermal behaviour of the vanadium redox flow battery. Simulations are carried out under a power arbitrage scenario for two different types of membranes. It was found that at high flowrates the thermal behaviour of the stack is similar to that of the storage tanks. Increasing the number of cells in the stack does not change the shape of the general thermal gradient across the cells, but changing the tank dimensions can affect the system temperature significantly. The environment temperature has a significant impact on the system thermal behaviour as does the types of membrane used. This study shows that by altering the parameters, the thermal behaviour of the system can be regulated and even, in some cases, controlled within desirable ranges to prevent vanadium salt precipitation at temperature extremes.