Pinning Effect Enhanced Structural Stability toward a Zero‐Strain Layered Cathode for Sodium‐Ion Batteries

Abstract Layered oxides as the cathode materials of sodium‐ion batteries are receiving extensive attention due to their high capacity and flexible composition. However, the layered cathode tends to be thermodynamically and electrochemically unstable during (de)sodiation. Herein, we propose the pinning effect and controllable pinning point in sodium storage layered cathodes to enhance the structural stability and achieve optimal electrochemical performance. 0 %, 2.5 % and 7.3 % transition‐metal occupancies in Na‐site as pinning points are obtained in Na 0.67 Mn 0.5 Co 0.5− x Fe x O 2 . 2.5 % Na‐site pinned by Fe 3+ is beneficial to restrain the potential slab sliding and enhance the structural stability, resulting in an ultra‐low volume variation of 0.6 % and maintaining the smooth two‐dimensional channel for Na‐ion transfer. The Na 0.67 Mn 0.5 Co 0.4 Fe 0.1 O 2 cathode with the optimal Fe 3+ pinning delivers outstanding cycle performance of over 1000 cycles and superior rate capability up to 10 C.