Commercial Li-ion batteries with high energy densities and promising rate performance are highly desired to meet the increasing demand for portable electronic devices and electric vehicles. LiCoO2, as the first generation of commercial cathode materials, still dominants the 3C electronic market owing to its advantages of a high theoretical capacity, a fast Li ion conductivity and a high energy density. Although the theoretical capacity of the LiCoO2 can reach up to 274 mAh g -1 , only a half capacity can be utilized during the discharging process, which greatly limits practical applications. Tremendous efforts have been devoted to improve the practical capacity. Expanding the voltage window to a high voltage is a common strategy to achieve this goal. For example, a 4.6 V versus Li/Li + gives a ~27% increase in the capacity, corresponding the value of 220 mAh g -1 . However, a high state of charge (SOC) means more Li ions are extracted from the layered structure, which could cause serious issues such as internal cracks generations, structural phase transitions and degradations. Extensive previous studies show that the structural degradation is caused by the transition metal (TM) cation migrations from the TM layer to the Li layer when Li ions are gradually extracted. Migrations of the TM cation lead to the blocking effect on the Li ion diffusion and thus the loss of the irreversible capacity, which is detrimental to the battery performance. On the other hand, once the migrations of the TM cation occur, it will inevitably be accompanied by the precipitation of the oxygen owing to the formation of TM vacancies, which could lead to potential safety problems for the battery. Experimentally, many strategies have been devoted to promote the structural stability of the LiCoO2 at the high SOC. The introduction of dopants is regarded as a promising and effective way to improve the electrochemical stability of the LiCoO2 material. However, the thermodynamic and kinetic effects of the dopant are rarely reported. For example, earlier studies investigated the TM migration paths in the LiMnO2 and LiNi0.6Co0.2Mn0.2O2 systems using ab-initio calculations combined with the climbing-image nudged-elastic-band (CI-NEB) method. Very recently, Sannyal et al. revealed the dopants' impact on the TM migration barrier in the doped NCM cathode. Although those studies provided a relatively clear understanding for the TM migration paths, the migration dynamics is still lacking. More importantly, a complete dynamic process of the oxygen dimer formation induced by the TM migrations needs a sufficiently long simulation time, thus is difficult to be clarified owing to the huge computational cost of the traditional ab-initio method. Therefore, it is crucial to reveal the dynamic correlations between the TM cation migrations and the associated oxygen dimer formations, and to understand the dopant's effect on the structural stability.