Abstract:In this work, commercial 18650 lithium-ion cells with LiMn 2 O 4 , LiFePO 4 , and Li(Ni 0.33 Mn 0.33 Co 0.33 )O 2 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.

In this study, novel electrolyte mixtures for Li-ion cells are presented with highly improved safety features. The electrolyte formulations are composed of ethylene carbonate/dimethyl sulfone (80:20 wt/wt) as the solvent mixture and LiBF4 , lithium bis(trifluoromethanesulfonyl)azanide, and lithium bis(oxalato)borate as the conducting salts. Initially, the electrolytes are characterized with regard to their physical properties, their lithium transport properties, and their electrochemical stability. The key advantages of the electrolytes are high flash points of >140 °C, which enhance significantly the intrinsic safety of Li-ion cells containing these electrolytes. This has been quantified by measurements in an accelerating rate calorimeter. By using the newly developed electrolytes, which are liquid down to T=-10 °C, it is possible to achieve C-rates of up to 1.5 C with >80 % of the initial specific capacity. During 100 cycles in cell tests (graphite||LiNi1/3 Co1/3 Mn1/3 O2 ), it is proven that the retention of the specific capacity is >98 % of the third discharge cycle with dependence on the conducting salt. The best electrolyte mixture yields a capacity retention of >96 % after 200 cycles in coin cells.

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, THT Company) to investigate the thermal behavior under abuse conditions. New procedures for measuring 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 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 reaction) have been observed. Both pressure and temperature change indicated different stages of exothermic reactions, which produced gases or/and heat. The onset temperature of thermal runaway was estimated according to temperature and pressure changes. Moreover, the different activation energies for the exothermic reactions could be derived from Arrhenius plots.

The thermal runaway of a single Li-ion battery (LIB) in larger battery package is the worst case scenario which must be avoided under all circumstances. In this work the electrochemical-thermal model for a LIB based on porous electrode theory is extended with contribution coming from exothermic side reactions to model the abuse mechanisms in Li-ion batteries with respect to the temperature which could lead to a thermal runaway. The electrochemical-thermal model is extended with several new contributions which occur in several temperature regimes. In detail the heat source in the corresponding heat equation is extended  with the heat generated by various exothermic reactions, for example at the surface-electrolyte interface at temperatures in the interval T=[T1, T2],  reactions between anode resp. cathode and the electrolyte between temperatures in the interval T=[T3, T4]  and the destruction of the electrolyte above the temperature T>T5, where T1<T2 ≤T3<T4 ≤T5. These extensions will be modeled with a solid fuel or a constant fuel model as simplification coming from combustion theory. For this extended model simulations are performed for specified current profiles and exterior temperature profiles to simulate an oven trial and cell cycling.  In the simulations a cylindrical 18650 LIB is investigated with a LiCoO2 cathode.  The purpose of the simulations is to compute the temperature-field during the time evolution of a thermal runaway, therefore the cross section in horizontal and vertical direction are considered as well as the one-dimensional temperature profiles along these directions. Finally the time evolution of the overall mean cell temperature T is used to classify the different stages of a thermal runaway in a T-dT/dt-plot. The results will be compared with experimental ARC-measurements in pure oven experiments and cycling experiments.