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 we reveal the essential role of Li content on the topological inhibition of oxygen loss in lithium-rich cathode materials, and the relationship between the migration networks of oxygen ions with the transition metal (TM) component. Utilizing first-principles calculations in combination with percolation theory and Monte Carlo simulations, we find that TM ions can effectively encage the oxidized oxygen species when the TM concentration in TM layer exceeds 5/6, thus hindering the formation of oxygen ion percolation 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. This article is protected by copyright. All rights reserved.