Comprehensive reinvestigation on the initial coulombic efficiency and capacity fading mechanism of LiNi_0.5Mn_1.5O₄ at low rate and elevated temperature

Abstract

The effect of different membranes and aluminum current collectors on the initial coulombic efficiency of LiNi_0.5Mn_1.5O₄/Li was investigated, and the cycling performance at different rates and temperatures and the storage performance at 60 °C for a week are discussed for LiNi_0.5Mn_1.5O₄/Li. The results show that the lower initial coulombic efficiency is associated with the lower decomposition voltage of the commercial membrane and electrolyte, and the instability of aluminum current collector under the higher voltage. In addition, both versions of LiNi_0.5Mn_1.5O₄ can deliver about 115 mA h g⁻¹ of initial discharge capacity at 1 C at 25 °C and 60 °C; however, it retains only 61.57 % of its initial capacity after the 130th cycles at 60 °C, which is much lower than the 94.46 % rate observed for LiNi_0.5Mn_1.5O₄ at 25 °C, and the cycling performance of the material at 1 C is better than that at 0.5 C. Meanwhile, the initial discharge capacity at 0.1 C after storing at 60 °C is 119.3 mA h g⁻¹, which is only a little lower than 121.5 mA h g⁻¹ recorded before storing; moreover, the spinel structure and surface state of LiNi_0.5Mn_1.5O₄ after storing at 60 °C has not been changed basically. These results indicate that the electrochemical stability of electrolyte is also related to the temperature. The serious capacity fading of LiNi_0.5Mn_1.5O₄ at 60 °C is attributed to the severe oxidation decomposition and the thermal decomposition in the range of cut-off voltage of the materials, and then the decomposition products interact with active materials to form a solid interface phase, leading to the larger electrode polarization and irreversible capacity loss. Meanwhile, the worse cycling performance at 0.5 C than that at 1 C is attributed to the longer interaction time between the electrolyte and the active materials. However, the storage performance of LiNi_0.5Mn_1.5O₄ corresponds to the thermal stability of electrolyte to a certain extent.