Mn-based layered oxide cathodes are pivotal for advancing sodium-ion batteries, yet their practical deployment is hindered by structural instability and complex phase transformations during cycling. This review provides a systematic overview of recent strategies aimed at rational design and performance enhancement of these materials. It begins with fundamental thermodynamic principles governing phase formation, particularly P2/O3 structural dichotomy, and highlights the critical roles of sodium content, transition metal chemistry, and ionic potential in determining crystal stability. The emergence of high-entropy engineering is examined as a powerful approach to suppress detrimental phase transitions through configurational entropy stabilization, lattice distortion, and synergistic multi-element interactions. Furthermore, the integration of machine learning with multidimensional descriptors including electronegativity-weighted entropy and cationic potential enables more accurate predictions of phase behavior in complex compositional spaces. The review also highlights the decisive influence of synthesis protocols, where precise control over calcination conditions, atmosphere, and local elemental distribution enables the formation of targeted phase architectures, such as P2/O3 intergrowth, which exhibit superior electrochemical robustness. Collectively, these advances illustrate a shift from empirical trial and error toward a theory-guided, data-informed framework for designing high-performance layered oxide cathodes.
Dong et al. (Mon,) studied this question.