The conventional heating materials of thermal battery have the disadvantages of low combustion rate and less heat release, so it is necessary to develop new heating materials. Al/Ni Reactive Multilayer Foils (RMFs) is an ideal heat source due to its high heat release, fast burning speed and no gas generated during combustion. Al/Ni RMFs were prepared by magnetron sputtering, and the heat transfer process of thermal battery using Al/Ni RMFs as heating material was simulated by the COMSOL MULTIPHYSICS simulation. The Al/Ni RMFs combustion reaction mechanism with different Al/Ni ratios was proposed according to DSC and XRD results. The effects of Al/Ni atomic ratio of RMFs on the melting time of electrolyte were investigated, and the temperature distribution during the activation was obtained, indicating the rapid activation process of the thermal battery.