Elastic Lattice Enabling Reversible Tetrahedral Li Storage Sites in a High‐Capacity Manganese Oxide Cathode

Abstract The key to breaking through the capacity limitation imposed by intercalation chemistry lies in the ability to harness more active sites that can reversibly accommodate more ions (e.g., Li + ) and electrons within a finite space. However, excessive Li‐ion insertion into the Li layer of layered cathodes results in fast performance decay due to the huge lattice change and irreversible phase transformation. In this study, an ultrahigh reversible capacity is demonstrated by a layered oxide cathode purely based on manganese. Through a wealth of characterizations, it is clarified that the presence of low‐content Li 2 MnO 3 domains not only reduces the amount of irreversible O loss; but also regulates Mn migration in LiMnO 2 domains, enabling elastic lattice with high reversibility for tetrahedral sites Li‐ion storage in Li layers. This work utilizes bulk cation disorder to create stable Li‐ion‐storage tetrahedral sites and an elastic lattice for layered materials, with a reversible capacity of 600 mA h g −1 , demonstrated in th range 0.6–4.9 V versus Li/Li + at 10 mA g −1 . Admittedly, discharging to 0.6 V might be too low for practical use, but this exploration is still of great importance as it conceptually demonstrates the limit of Li‐ions insertion into layered oxide materials.