Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping

Lithium cobalt oxides (LiCoO2) possess a high theoretical specific capacity of 274 mAh g–1. However, cycling LiCoO2-based batteries to voltages greater than 4.35 V versus Li/Li+ causes significant structural instability and severe capacity fade. Consequently, commercial LiCoO2 exhibits a maximum capacity of only ~165 mAh g–1. Here, we develop a doping technique to tackle this long-standing issue of instability and thus increase the capacity of LiCoO2. La and Al are concurrently doped into Co-containing precursors, followed by high-temperature calcination with lithium carbonate. The dopants are found to reside in the crystal lattice of LiCoO2, where La works as a pillar to increase the c axis distance and Al as a positively charged centre, facilitating Li+ diffusion, stabilizing the structure and suppressing the phase transition during cycling, even at a high cut-off voltage of 4.5 V. This doped LiCoO2 displays an exceptionally high capacity of 190 mAh g–1, cyclability with 96% capacity retention over 50 cycles and significantly enhanced rate capability. Lithium cobalt oxides are used as a cathode material in batteries for mobile devices, but their high theoretical capacity has not yet been realized. Here, the authors present a doping method to enhance diffusion of Li ions as well as to stabilize structures during cycling, leading to impressive electrochemical performance.