Conformal Coating of a High-Voltage Spinel to Stabilize LiCoO2 at 4.6 V

The ever-growing demand for portable electronic devices has put forward higher requirements on the energy density of layered LiCoO₂ (LCO). The unstable surface structure and side reactions with electrolytes at high voltages (>4.5 V) however hinder its practical applications. Here, considering the high-voltage stability and three-dimensional lithium-ion transport channel of the high-voltage Li-containing spinel (M = Ni and Co) LiM_xMn_2-xO₄, we design a conformal and integral LiNi_xCo_yMn_2-x-yO₄ spinel coating on the surface of LCO via a sol-gel method. The accurate structure of the coating layer is identified to be a spinel solid solution with gradient element distribution, which compactly covers the LCO particle. The coated LCO exhibits significantly improved cycle performance (86% capacity remained after 100 cycles at 0.5C in 3-4.6 V) and rate performance (150 mAh/g at a high rate of 5C). The characterizations of the electrodes from the bulk to surface suggest that the conformal spinel coating acts as a physical barrier to inhibit the side reactions and stabilize the cathode-electrolyte interface (CEI). In addition, the artificially designed spinel coating layer is well preserved on the surface of LCO after prolonged cycling, preventing the formation of an electrochemically inert Co₃O₄ phase and ensuring fast lithium transport kinetics. This work provides a facile and effective method for solving the surface problems of LCO operated at high voltages.