Influence of Li Content on the Topological Inhibition of Oxygen Loss in Li‐Rich Cathode Materials

Lithium-rich layer oxide cathodes are promising energy storage materials due to their high energy densities. However, the oxygen loss during cycling limits their practical applications. Here, the essential role of Li content on the topological inhibition of oxygen loss in lithium-rich cathode materials and the relationship between the migration network of oxygen ions and the transition metal (TM) component are revealed. Utilizing first-principles calculations in combination with percolation theory and Monte Carlo simulations, it is found that TM ions can effectively encage the oxidized oxygen species when the TM concentration in TM layer exceeds 5/6, which hinders the formation of a percolating oxygen migration network. This study demonstrates the significance of rational compositional design in lithium-rich cathodes for effectively suppressing irreversible oxygen release and enhancing cathode cycling performance.