Lithium-ion batteries (LIBs) are widely used as the energy carrier in our daily life. However, the higher energy density of LIBs results in poor safety performance. Thermal runaway (TR) is the critical problem which hinders the further application of LIBs. Clarifying the mechanism of TR evolution is beneficial to safer cell design and safety management. In this paper, liquid nitrogen spray is proved to be an effective way to stop the violent reaction of LIBs during the TR process. Based on extended-volume accelerating rate calorimetry, the liquid nitrogen ceasing combined with non-atmospheric exposure analysis is used to investigate the TR evolution about LiFePO₄/graphite batteries at critical temperature. Specifically, the geometrical shape, voltage, and impedance change are monitored during the TR process on the cell level. The morphologies/constitution of electrodes and separators are presented on the component level. Utilizing the gas analysis, the failure mechanism of the prismatic LiFePO₄/graphite battery is studied comprehensively.