Characterizing the Cathode Degradation Process from Thermal Abuse in Solid State Batteries

Abstract

With an ever-increasing reliance on batteries for all aspects of life, safety of energy storage is a growing concern as reported instances of lithium-ion battery (LIB) fires and even a solid-state battery (SSB) fire arise. However, the understanding of battery safety from a fundamental materials level is not well understood. As the push for higher energy density batteries in the electrification of transportation continues, it is imperative to understand how underlying material degradation and failure affects the safety of current and next-generation lithium battery technology.In this study, heat release and corresponding degradation due to external heating are explored for the following battery configurations: All solid-state batteries (ASSBs), SSBs containing a low amount of liquid electrolyte, and LIBs. NMC532 cathode was used in all battery configurations, Ta-doped LLZO was used for the solid electrolyte, and LiPF6 in EC/EMC was used as the liquid electrolyte in the SSB and LIB configurations. Differential scanning calorimetry (DSC) was used to raise microcells to definitive temperatures of interest depending upon their respective exotherm profile. LIB sample heat release was significantly higher than the heat release of the ASSB and SSB, even though the heating temperature range and final temperature were lower for the LIB samples. The disassembled microcell components were then analyzed using X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD analysis revealed the LIB samples did not show the presence of the fully degraded rock salt crystalline phase after peak heat release, whereas ASSB and SSB configurations revealed the presence of the rock salt phase. Additionally, SEM image analysis shows no degradation of the LIB particles, while ASSB and SSB samples show surface degradation of the high temperature samples. Decomposition of NMC to the rock salt phase involves the release of oxygen, which may undergo an exothermic reaction inside the SSB. These investigations shed light into the expected extent of NMC decomposition at key temperatures and exothermic heat flow peaks for each battery composition. Future work combining these results with further elemental characterization experiments will pave the way for a materials-level understanding that can be incorporated into the initial design and development stages of next generation lithium batteries, impacting the creation of energy storage devices by ensuring commitment to safety from the ground up.