High‐Entropy Phase Stabilization Engineering Enables High‐Performance Layered Cathode for Sodium‐Ion Batteries

O3‐type layered oxides are considered as one of the most promising cathode materials for rechargeable sodium‐ion batteries (SIBs) due to their appealing energy density and feasible synthesis. Nevertheless, it undergoes complicated phase transitions and pronounced structural degradation during the cycling of charge/discharge process, rendering severe volumetric strain and poor cycling performance. Herein, a zero‐strain high‐entropy NaNi0.2Fe0.2Mn0.35Cu0.05Zn0.1Sn0.1O2 cathode for SIBs is presented by high‐entropy phase stabilization engineering. It is verified that this low‐nickel cobalt‐free high‐entropy cathode can deliver a highly reversible phase evolution, zero volumetric strain, and a significantly improved cycling performance in full cells (87% capacity retention after 500 cycles at 3.0 C). Combining X‐ray absorption spectra and first‐principles calculations, the varied elemental functions in the high‐entropy framework are clearly elucidated, namely, Ni/Fe/Cu acts as charge compensators, while Mn/Zn/Sn serve as interlayer slipping inhibitors through enhanced charge localization besides their stable valence states. By addressing the volumetric strain and cycling instability concerns for O3‐type cathode materials, this work presents a promising strategy for inhibiting irreversible phase transitions and structural degradation in intercalation electrodes, which significantly boosts the development of commercially feasible cathodes for high‐performance SIBs. A zero‐strain layered cathode for sodium‐ion batteries is presented by high‐entropy phase stabilization engineering. By solving the drastic volumetric strain and cycling instability concerns for O3‐type cathode materials, this low‐nickel cobalt‐free high‐entropy cathode delivers highly reversible phase transition, zero volumetric strain, and significantly improved cycling stability.