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

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‐Na0.8Cu0.22Li0.08Mn0.67O2 (NCLMO‐12h) 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‐12h 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.