The O3-Na3Ni2SbO6 compound, with its hexagonal honeycomb cationic ordering, is a promising sodium-ion battery (SIB) cathode due to its phase transition steps and high average voltage. In this study, various concentrations of cobalt (Co) are doped into Na3Ni2SbO6 to replace nickel (Ni), increasing disorder within the transition metal layers. Co doping introduced specific stacking faults along the c-axis direction, resulting in an ambiguous configuration of Sb/Ni(Co) within each transition metal layer, while maintaining the honeycomb order. This disorderly arrangement optimized the electronic structure and reduced the energy barrier for reactions. Na3Ni1.6Co0.4SbO6 exhibited superior performance, with a higher initial discharge capacity (137.8 mAh g-1 at 0.1 C) and better rate performance (87 mAh g-1 at 5 C) compared to Na3Ni2SbO6 (113.6 mAh g-1 at 0.1 C, 74 mAh g-1 at 5 C), including improved long-term cyclic stability. The findings demonstrate that electrochemical performance can be significantly enhanced through atomic layer stacking disorder and the Na coordination environment, which is influenced by Na ion extraction and insertion, resulting in more gradual and smaller variations in lattice parameters, electronic structure, and crystal defects. This study provides a foundation for future designs of sodium-ion battery cathode materials with improved performance.
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