Thermal Stability Enhancement through Structure Modification on the Microsized Crystalline Grain Surface of Lithium-Rich Layered Oxides.

Lithium-rich layered oxides have been considered as the most promising candidate for offering a high specific capacity and energy density for lithium-ion batteries. However, their practical applications are still suffered by the cycle instability and also closely related thermal stability. Here, microsized crystalline grains with good dispersion of lithium-rich layered oxides are prepared by a molten-salt method, while a spinel structure is also introduced on a grain surface by following chemical oxidation and annealing process, and their thermal performance with different cutoff voltages during the charge process is systematically studied using differential scanning calorimetry method. Results have shown that thermal stability of microsized crystalline grains is better than that of spherical secondary agglomerates, the spinel structure introduction on the grain surface of microsized crystalline grains can contribute obviously to their thermal stability, in which the onset temperature of the exothermic peak has been increased by 103 °C, and the thermal release value can be reduced as much as about 40% when the battery was charged to 4.8 V. Furthermore, the electrochemical performance, especially cycle stability under a high temperature, has also been enhanced for spinel-modified microsized crystalline grains. This work not only develops the microsized crystalline grains with good dispersion of lithium-rich layered oxides, confirming the advantages of these materials compared to spherical secondary agglomerates, but also reveals the method to improve their thermal stability by grain surface structure modification, opening the way to optimize the comprehensive performance of electrode materials for batteries.