Fire and deflagration are extreme manifestation of thermal runaway (TR) of Li-ion cells, and they are characterized for fully charged LiNiCoAlO2 (LNCA) 18650 cells in this investigation. The cells are over-heated using a cone calorimeter under different incident heat fluxes. When the cells are exposed to the incident heat flux larger than 35 kW m−2, both fire and deflagration present. The pressure valve opens when the temperature of the cell is higher than 132 °C. The fire occurs with the valve opening when the concentration of the venting vapour in the air is higher than the lower flammability limit. The deflagration happens after the cell temperature arrives about 200 °C, and is mainly arising from the cathode decomposition, the combustion of solvents and the anode relevant thermal reactions. The extreme temperatures of the cell and the flame during deflagration are over than 820 and 1035 °C, respectively. The production of COx, mass loss, heat release rate (HRR) are quantitative identified, and are found increase as the increasing incident heat flux. Based on revised oxygen consumption method, the HRR and liberated heat during the fire and deflagration for the cells are up to 11.8 ± 0.05 kW and 163.1 ± 1.5 kJ, respectively
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