Unexpected Elevated Working Voltage by Na+/Vacancy Ordering and Stabilized Sodium‐Ion Storage by Transition‐Metal Honeycomb Ordering

Abstract Na + /vacancy ordering in sodium‐ion layered oxide cathodes is widely believed to deteriorate the structural stability and retard the Na + diffusion kinetics, but its unexplored potential advantages remain elusive. Herein, we prepared a P2‐Na 0.8 Cu 0.22 Li 0.08 Mn 0.67 O 2 (NCLMO‐12 h) material featuring moderate Na + /vacancy and transition‐metal (TM) honeycomb orderings. The appropriate Na + /vacancy ordering significantly enhances the operating voltage and the TM honeycomb ordering effectively strengthens the layered framework. Compared with the disordered material, the well‐balanced dual‐ordering NCLMO‐12 h cathode affords a boosted working voltage from 2.85 to 3.51 V, a remarkable ~20 % enhancement in energy density, and a superior cycling stability (capacity retention of 86.5 % after 500 cycles). The solid‐solution reaction with a nearly “zero‐strain” character, the charge compensation mechanisms, and the reversible inter‐layer Li migration upon sodiation/desodiation are unraveled by systematic in situ/ex situ characterizations. This study breaks the stereotype surrounding Na + /vacancy ordering and provides a new avenue for developing high‐energy and long‐durability sodium layered oxide cathodes.