Ultrahigh‐Voltage LiCoO2 at 4.7 V by Interface Stabilization and Band Structure Modification

Lithium cobalt oxide (LCO) is widely used in Li‐ion batteries due to its high volumetric energy density, which is generally charged to 4.3 V. Lifting the cut‐off voltage of LCO from 4.3 V to 4.7 V will increase the specific capacity from 150 to 230 mAh g‐1 with a significant improvement of 53%. However, LCO suffers serious problems of H1‐3/O1 phase transformation, unstable interface between cathode and electrolyte, and irreversible oxygen redox reaction at 4.7 V. Herein, interface stabilization and band structure modification are proposed to strengthen the crystal structure of LCO for stable cycling of LCO at an ultrahigh voltage of 4.7 V. Gradient distribution of magnesium and uniform doping of nickel in Li layers inhibit the harmful phase transitions of LCO, while uniform LiMgxNi1−xPO4 coating stabilizes the LCO‐electrolyte interface during cycles. Moreover, the modified band structure improves the oxygen redox reaction reversibility and electrochemical performance of the modified LCO. As a result, the modified LCO has a high capacity retention of 78% after 200 cycles at 4.7 V in the half cell and 63% after 500 cycles at 4.6 V in the full cell. This work makes the capacity of LCO one step closer to its theoretical specific capacity. The modified LCO has a gradient doping of Mg, uniform doping of Ni in Li layers, and uniform LiMgxNi1−xPO4 coating. The doping and coating simultaneously modify the band structure to improve the oxygen redox reversibility during cycles. Therefore, the modified LCO shows excellent cycling performance both at 4.6 V and 4.7 V.