Thermal characterization of Li-ion cells using calorimetric techniques

The thermal stability of Li-ion cells with intercalating carbon anodes and metal oxide cathodes was measured as a function of state of charge and temperature for two advanced cell chemistries. Cells of the 18650 design with Li_xCoO₂ cathodes (commercial Sony cells) and Li_xNi_0.8Co_0.2O₂ cathodes were measured for thermal reactivity. Accelerating rate calorimetry (ARC) was used to measure cell thermal runaway as a function of state of charge (SOC), microcalorimetry was used to measure the time dependence of thermal output, and differential scanning calorimetry (DSC) was used to study the thermal reactivity of the individual components. Thermal decomposition of the anode solid electrolyte interphase (SEI) layer occurred at low temperatures and contributes to the initiation of thermal runaway. Low temperature reactions from 40°C-70°C were observed during the ARC runs that were SOC dependent. These reactions measured in the microcalorimeter decayed over time with power-law dependence and were highly sensitive to SOC and temperature. ARC runs of aged and cycled cells showed complete absence of these low-temperature reactions but showed abrupt exothermic spikes between 105-135°C. These results suggest that during aging the anode SEI layer is decomposing from a metastable state to a stable composition that is breaking down at elevated temperatures