Interlayer Entropy Engineering Inducing the Symmetry‐Broken Layered Oxide Cathodes to Activate Reversible High‐Voltage Redox Reaction

Abstract The as‐reported doping entropy engineering of electrode materials that are usually realized by the sharing of multiple metal elements with the metal element from the lattice body, potentially has three shortages of stringent synthesis conditions, large active element loss, and serious lattice distortion. Herein, an interlayer entropy engineering of layered oxide cathodes is proposed, where the multiple metal ions are simultaneously intercalated into the same interlayer sites, thus avoiding the three shortages. Concretely, a novel interlayer medium‐entropy V 2 O 5 ((MnCoNiMgZn) 0.26 V 2 O 5 ∙0.84H 2 O) is successfully constructed by a one‐step hydrothermal method. The interlayer medium‐entropy effect is revealed to be that five metal ions pre‐intercalation induces the local symmetry‐broken [VO 6 ] octahedra in bilayer V 2 O 5 , thus activating the reversible high‐voltage redox reaction, inhibiting the layer slip and following phase transformation by its pinning effect, and enhancing the charge transfer kinetics. As a result, the medium‐entropy cathode realizes the trade‐off between specific capacity and structural stability with a discharge capacity of 152 mAh g −1 at 0.1 A g −1 after 100 cycles, and a capacity retention rate of 98.7% at 0.5 A g −1 after 150 cycles for Li + storage. This engineering provides a new guideline for the rational design of high‐performance layered oxide cathodes.