Ensuring the safety of lithium-ion batteries is paramount given their widespread applications and the potential risk of fire and explosion. To improve our understanding of thermal runaway behavior, we conducted in-depth research focusing on the electrolyte and two commonly used film forming additives, vinylene carbonate (VC) and fluoroethylene carbonate (FEC).Dry cells were filled with a control electrolyte (EC:EMC, 3:7 wt%, 1M LiPF6). In addition, 5 wt% of either VC or FEC was added to the electrolyte. After formation, the cells were subjected to 10 initial cycles and a characterization test, consisting of a capacity check and a pulse test for the determination of the internal resistance. The negative electrode is graphite and the positive electrode is LiNi0.6Mn0.2Co0.2O2 (NMC622). All cells showed a stable capacity of more than 1 Ah. After the characterization test, the electrodes and separator were extracted from some cells in an argon-filled glove box (H2O and O2 < 0.1 ppm) for further analysis. The thermal behavior of the individual electrodes in combination with the electrolyte was measured using highly sensitive Tian-Calvet calorimeters (Setaram) in the temperature range of 30 to 300°C. Safety testing on the full cells was performed using the Heat-Wait-Seek (HWS) method with fully charged cells (SoC100) inside an ES-ARC (Thermal Hazard Technologies).VC and FEC additives decompose before ethylene carbonate (EC) from the electrolyte during initial charging, as evidenced by peaks in the differential capacity analysis at voltages of 2.4 V and 2.6 V, respectively. Conversely, decomposition without additives begins just before 2.8 V. VC and FEC are used to create a more stable solid electrolyte interface (SEI) at the anode. The thermal stability of the separator was tested with a Differential Scanning Calorimeter DSC204 (Netzsch). The melting of the separator started at 119°C, which is typical for polymer separators used in lithium-ion batteries.In the HWS test, the cells are heated in 5°C increments inside the Accelerating Rate Calorimeter (ARC), followed by a waiting period to ensure thermal equilibrium. The ARC then looks for self-heating of the battery. When a threshold of 0.02°C/min is reached, the ARC switches to a quasi-adiabatic mode and tracks the temperature of the cell. During thermal abuse, cells without additives showed an earlier onset of exothermic reactions, with thermal runaway observed in all cells tested between 195°C and 205°C.A thorough understanding of thermal runaway is critical to the safety of lithium-ion batteries. An accurate understanding of the electrolyte composition provides a deeper insight into its safety implications. Future research will further investigate the effects of aged cells with the same electrolyte combinations.
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