A cell-resolved model that simulates the dynamic thermal behavior of a Vanadium Redox Flow Battery during charge and discharge is presented. It takes into account, at a cell level, the reversible entropic heat of the electrochemical reactions, irreversible heat due to overpotentials, self-discharge reactions due to ion crossover, and shunt current losses. The model accounts for the heat transfer between cells and toward the environment, the pump hydraulic losses and the heat transfer of piping and tanks. It provides the electrolyte temperature in each cell, at the stack inlet and outlet, along the piping and in the tanks. Validation has been carried out against the charge/discharge measurements from a 9kW/27 kWh VRFB test facility. The model has been applied to study a VRFB with the same stack but a much larger capacity, operating at ±400 A for 8 h, in order to identify critical thermal conditions which may occur in next-generation industrial VRFB stacks capable to operating at high current density. The most critical condition has been found at the end of a long discharge, when temperatures above 50 °C appeared, possibly resulting in V O 2 + precipitation and battery faults. These results call for heat exchangers tailored to assist high-power VRFB systems.