Facile Synthesis of O3-Type NaNi0.5Mn0.5O2 Single Crystals with Improved Performance in Sodium-Ion Batteries

Sodium-ion batteries can be a practical alternative to lithium-ion batteries due to the relatively high abundance of sodium and the projected scarcity of lithium. Both of these factors are critical considerations for grid-scale energy storage, but the central challenge to implementing sodium layered oxides in sodium-ion batteries is their relatively poor cycle life. Single-crystal particles with micrometer size can mitigate several failure mechanisms related to sodium layered oxides and can improve performance when compared to the commonly used polycrystalline particles. This work demonstrates a novel two-step molten-salt synthesis method using sodium chloride and metal oxides to form "single crystals" of a mixed-phase, spinel/rock-salt intermediate that crystallizes as micron-sized truncated octahedra. The mixed-phase spinel/rock-salt material is effectively used as a precursor to form O3-type NaNi_0.5Mn_0.5O₂ with large primary particles and substantially improved cycle life. This synthesis route offers the added benefit of using simple metal oxides instead of hydroxide precursors, eliminating the need for coprecipitation. Particle morphology is found to be a critical factor in mitigating the structural damages incurred during phase transformations and maintaining the electrochemical performance.