In this experimental investigation, we studied the safety and thermal runaway behavior of commercial lithium-ion batteries of type 21700. The different cathode materials NMC, NCA and LFP were compared, as well as high power and high energy cells. After characterization of all relevant components of the batteries to assure comparability, two abuse methods were applied: thermal abuse by the heat-wait-seek test and mechanical abuse by nail penetration, both in an accelerating rate calorimeter. Several critical temperatures and temperature rates, as well as exothermal data, were determined. Furthermore, the grade of destruction, mass loss and, for the thermal abuse scenario, activation energy and enthalpy, were calculated for critical points. It was found that NMC cells reacted first, but NCA cells went into thermal runaway a little earlier than NMC cells. LFP cells reacted, as expected, more slowly and at significantly higher temperatures, making the cell chemistry considerably safer. For mechanical abuse, no thermal runaway was observed for LFP cells, as well as at state of charge (SOC) zero for the other chemistries tested. For thermal abuse, at SOC 0 and SOC 30 for LFP cells and at SOC 0 for the other cell chemistries, no thermal runaway occurred until 350 °C. In this study, the experimental data are provided for further simulation approaches and system safety design.

The purpose of this study was to investigate the calendar aging of lithium-ion batteries by using both open circuit and floating current measurements. Existing degradation studies usually focus on commercial cells. The initial electrolyte composition and formation protocol for these cells is often unknown. This study investigates the role of electrolyte additives, specifically, vinylene carbonate (VC) and fluoroethylene carbonate (FEC), in the aging process of lithium-ion batteries. The results showed that self-discharge plays a significant role in determining the severity of aging for cells without additives. Interestingly, the aging was less severe for the cells without additives as they deviated more from their original storage state of charge. It was also observed that the addition of VC and FEC had an effect on the formation and stability of the solid electrolyte interphase (SEI) layer on the surface of the carbonaceous anode. By gaining a better understanding of the aging processes and the effects of different electrolyte additives, we can improve the safety and durability of lithium-ion batteries, which is critical for their widespread adoption in various applications.

Since Sony launched the commercial lithium-ion cell in 1991, the composition of the liquid electrolytes has changed only slightly. The electrolyte consists of highly flammable solvents and thus poses a safety risk. Solid-state ion conductors, classified as non-combustible and safe, are being researched worldwide. However, they still have a long way to go before being available for commercial cells. As an alternative, this study presents glyceryl tributyrate (GTB) as a flame retardant and eco-friendly solvent for liquid electrolytes for lithium-ion cells. The remarkably high flashpoint ($T_{\mathrm{FP}}=174{}^{°}$C) and the boiling point ($T_{\mathrm{BP}}=287{}^{°}$C) of GTB are approximately 150 K higher than that of conventional linear carbonate components, such as ethyl methyl carbonate (EMC) or diethyl carbonate (DEC). The melting point ($T_{\mathrm{MP}}=-75{}^{°}$C) is more than 100 K lower than that of ethylene carbonate (EC). A life cycle test of graphite/NCM with 1 M LiTFSI dissolved in GTB:EC (85:15 wt) achieved a Coulombic efficiency of above 99.6% and the remaining capacity resulted in 97% after 50 cycles ($C/4$) of testing. The flashpoint of the created electrolyte is $T_{\mathrm{FP}}=172{}^{°}$C and, therefore, more than 130 K higher than that of state-of-the-art liquid electrolytes. Furthermore, no thermal runaway was observed during thermal abuse tests. Compared to the reference electrolyte LP40, the conductivity of the GTB-based is reduced, but the electrochemical stability is highly improved. GTB-based electrolytes are considered an interesting alternative for improving the thermal stability and safety of lithium-ion cells, especially in low power-density applications.

The demand for safer, thermally stable lithium-ion batteries (LIBs) has driven the search for advanced electrolyte systems. This study introduces an electrolyte based on propylene glycol diacetate (PGDA) to improve thermal safety and stability. The optimized PGDA-based solvent mixture increases the flash point to 100 °C, which is approximately 63 K higher than that of the reference electrolyte LP40 (1 M LiPF ₆ in EC:DEC 1:1 wt). While the flash point is primarily determined by the solvent composition, the onset of exothermic reactions depends on the conducting salt. Replacing lithium hexafluorophosphate (LiPF ₆ ) with lithium bis(oxalato)borate (LiBOB) significantly improves thermal stability, cycling performance, and safety, as cells with LiBOB retain over 97% of their capacity after 100 cycles at 40 °C at C-rates up to 1C. Thermal abuse tests up to 300 °C exhibit no exothermic reactions, thereby preventing dangerous thermal runaways. These findings underscore the potential of PGDA-based electrolytes, especially when paired with LiBOB, for safer and more robust LIB applications.

Temperature plays a crucial role during the initial SEI formation in lithium-ion batteries. While formation at 80 °C results in lower initial capacity, it improves the cycle lifetime substantially. This is attributed to a more stable SEI.