Core–Shell Nanocomposites for Improving the Structural Stability of Li-Rich Layered Oxide Cathode Materials for Li-Ion Batteries

The structural stability of Li-rich layered oxide cathode materials is the ultimate frontier to allow the full development of these family of electrode materials. Here, first-principles calculations coupled with cluster expansion are presented to investigate the electrochemical activity of phase-separation, core-shell-structured xLi₂MnO₃·(1 - x)LiNiCoMnO₂ nanocomposites. The detrimental surface effects of the core region can be countered by the Li₂MnO₃ shell, which stabilizes the nanocomposites. The operational voltage windows are accurately determined to avoid the electrochemical activation of the shell and the subsequent structural evolution. In particular, the dependence of the activation voltage with the shell thickness shows that relatively high voltages can still be obtained to meet the energy density needs of Li-ion battery applications. Finally, activation energies of Li migration at the core-shell interface must also be analyzed carefully to avoid the outbreak of a phase transformation, thus making the nanocomposites suitable from a structural viewpoint.