Revealing the Role of W-Doping in Enhancing the Electrochemical Performance of the LiNiCoMnO Cathode at 4.5 V.

More and more attention has been focused on Ni-rich ternary materials due to their superior specific capacity, but they still suffer inherent structural irreversibility and rapid capacity degradation under a high voltage. Oxidation of unstable oxygen will lead to the irreversible transformation of the structure. Taking into account the strong W-O bond, an appropriate amount of W-doping is studied to reinforce the thermal stability and electrochemical performance of LiNiCoMnO (NCM622) at 4.5 V. Combining experiments and theoretical calculations, it can be found that W-doping is most preferred at Co sites, and the average charge around O in the NiO octahedron becomes more negative after W-doping, which can successfully restrain the release of oxygen, thereby improving the stability of the crystal structure during deep delithiation. In addition, W-doping decreases the energy barrier of the Li migration slightly and boosts the kinetic diffusion of lithium ions. As a result, NCM622 doped with 0.5% W boasts an outstanding capacity retention of 96.7% at 1 C after 100 cycles and a discharge specific capacity of up to 152.8 mA h g at 5 C between 3.0 and 4.5 V. Furthermore, analysis of the cycled electrodes indicates that the lattice expansion and the formation of microcracks during long cycling are suppressed after W-doping, thereby elevating the structure and interface stability. Therefore, doping an appropriate amount of W via simple methods is helpful to obtain Ni-rich cathode materials with admirable performance.