Thermal processes in the systems with Li-battery cathode materials and LiPF 6 -based organic solutions

Thermodynamic instability of positive electrodes (cathodes) in Li-ion batteries in humid air and battery solutions results in capacity fading and batteries degradation, especially at elevated temperatures. In this work, we studied thermal interactions between cathode materials Li 2 MnO 3 , x Li 2 MnO 3 . (1 − x )Li(MnNiCo)O 2 ,LiNi 0.33 Mn 0.33 Co 0.33 O 2 , LiNi 0.4 Mn 0.4 Co 0.2 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 LiMn 1.5 Ni 0.5 O 4 , LiMn(or Fe)PO 4 , and battery solutions containing ethylene carbonate (EC) or propylene carbonate (PC), dimethyl carbonate (DMC) or ethylmethyl carbonate (EMC) and LiPF 6 salt in the temperature range of 40–400 °C. It was found that these materials are stable chemically and well performing in LiPF 6 -based solutions up to 60 °C. The thermal decomposition of the electrolyte solutions starts >180 °C. The macro-structural transformations of cathode materials upon exothermic reactions were studied by transmission electron microscopy (TEM), X-ray difraction (XRD) and Raman spectroscopy. Differential scanning calorimetry (DSC) studies have shown that the exothermic reactions in the temperature range of 60–140 °C lead to partial decomposition of both the cathode material and electrolyte solution. The systems thus formed consisted of partially decomposed solutions and partially chemically delithiated cathode materials covered by reactions products. Thermal reactions terminate and this system reaches equilibrium at about 120 °C. It remains stable up to the beginning of the solution decomposition at about 180 °C. The increased content of surface Li 2 CO 3 is found to significantly affect the thermal processes at high temperature range due to extensive exothermic decomposition at low temperatures.