Experimental Analysis of Thermal Runaway in 18650 Cylindrical Li-Ion Cells Using an Accelerating Rate Calorimeter

TLDR

The study investigates the thermal behavior of commercial 18650 Li‑ion cells with LiMn₂O₄, LiFePO₄, and Li(Ni₀.₃₃Mn₀.₃₃Co₀.₃₃)O₂ cathodes under abuse conditions using an accelerating rate calorimeter. New procedures were developed to measure external and internal pressure changes, employing a gas‑tight cylinder to detect venting and a pressure transducer inserted into the cell. Thermal runaway experiments revealed three stages—low, medium, and high rate reactions—whose pressure and temperature signatures allowed estimation of onset temperatures and activation energies from Arrhenius plots.

Abstract

In this work, commercial 18650 lithium-ion cells with LiMn2O4, LiFePO4, and Li(Ni0.33Mn0.33Co0.33)O2 cathodes were exposed to external heating in an accelerating rate calorimeter (es-ARC, Thermal Hazard Technology (THT), Bletchley, UK), to investigate the thermal behavior under abuse conditions. New procedures for measuring the external and internal pressure change of cells were developed. The external pressure was measured utilizing a gas-tight cylinder inside the calorimeter chamber, in order to detect the venting of the cells. For internal pressure measurements, a pressure line connected to a pressure transducer was directly inserted into the cell. During the thermal runaway experiments, three stages (low rate, medium rate, and high rate reactions) were observed. Both the pressure and temperature change indicated different stages of exothermic reactions, which produced gases or/and heat. The onset temperature of the thermal runaway was estimated according to the temperature and pressure changes. Moreover, the different activation energies for the exothermic reactions could be derived from Arrhenius plots.