Effect of Sodium Content on the Electrochemical Performance of Li-Substituted, Manganese-Based, Sodium-Ion Layered Oxide Cathodes

Li-substituted, manganese-based, layered oxides Na_xLi_0.18Mn_0.66Co_0.17Ni_0.17O_2+δ (x = 0.54, 0.66, 0.78, and 0.90) have been investigated as one kind of high-performance cathode materials for sodium ion batteries (SIBs). Phase compositions and local structures of the cathode materials with varying sodium content were elucidated by powder X-ray diffraction (PXRD) and atomic-scale high angle annular dark field scanning transmission electron microscope (HAADF-STEM), which demonstrates that a Li-O'3 phase was aroused in P2-type sodium layered oxide matrix forming a Na-P2/Li-O'3 hybrid structure. More importantly, the effect of sodium content on the preferential exposure of (102) and (104) facets and surface morphology of the cathode particles has been comprehensively studied, as well as their relationship with electrochemical performance. It reveals that, in addition to the preferential growth of (102) and (104) facets that has been proved to enhance the capacity and rate performance of the layered oxides, the smooth surface finish of the particles also plays a vital role in deciding the electrochemical performance. The layered sodium cathode material with a sodium content of 0.66 possesses sufficient exposure of (102) and (104) facets and smooth side surface, resulting in the superior capacities under various C rates (187 mAh/g at 0.2 C and 114 mAh/g at 5 C) comparing to the cathode materials with all other sodium contents. The mechanism has also been proposed in this study. These findings presented herein open up new strategies to design high performance sodium layered oxide cathode.