Tuning Co/O Redox Chemistry via Fermi Level Regulation for Stable High-Voltage LiCoO₂

Abstract

LiCoO2 (LCO) is ideal for 3C electronics due to its high tap density. However, the excessive O → Co charge transfer at high delithiation leads to irreversible Co reduction, O release, and structural degradation, deteriorating the high-voltage performance of LCO. Herein, we propose to regulate the intrinsic Fermi level via uneven trace Zr/Mg doping. First, the increase of electron density in the Fermi level mitigates both the O oxidation/coupled Co reduction through alleviating the O → Co charge transfer, restraining the formations of Co2+ and O2. This elevates Co redox activity and reduces O redox activity. In addition, the structural evolution of the cathode at delithiation is simplified. The modulated LCO delivers a high discharge capacity and a high cycling stability with 4.5 and 4.6 V ceilings. This study sheds new light on the modulation of Co/O redox chemistry and the reliable large-scale production of high-voltage LiCoO2.