Multi-scale thermal stability study of commercial lithium-ion batteries as a function of cathode chemistry and state-of-charge

Abstract

This paper takes a critical look at the materials aspects of thermal runaway of lithium-ion batteries and correlates contributions from individual cell components to thermal runaway trends.An accelerating rate calorimeter (ARC) was used to evaluate commercial lithium-ion cells based on LiCoO2 (LCO), LiFePO4 (LFP), and LiNixCoyAl1-x-yO2 (NCA) at various states of charge (SOC). Cells were disassembled and the component properties were evaluated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and temperature-resolved X-ray diffraction (TR-XRD).The whole cell thermal runaway onset temperature decreases and peak heating rate increases with SOC due to cathode destabilization. LCO and NCA cathodes are metastable, with NCA cells exhibiting the highest thermal runaway rates. By contrast, the LFP cathode is stable to >500 °C, even when charged. For anodes, the decomposition and whole cell self-heating onset temperature is generally independent of SOC. DSC exotherm onset temperatures of the anodes were generally within 10 °C of the onset of self-heating in whole cell ARC. However, onset temperatures of the cathodes were typically observed above the ARC onset of whole cell runaway. This systematic evaluation of component to whole cell degradation provides a scientific basis for future thermal modeling and design of safer cells.