Layered transition-metal oxides are one kind of the most promising cathode materials for sodium-ion batteries. In this study, we propose a strategy to enhance the electrochemical properties of P3-type manganese-based layered oxide cathode by introducing a small amount of layered P2 and Li-O'3 phases. Powder X-ray diffraction (PXRD) structural refinement and aberration-corrected scanning transmission electron microscopy (STEM) are performed to confirm the microstructures of different samples. PXRD refinement results show that the elevated annealing temperature leads to a partial conversion of the P3 phase to the P2 phase and the addition of lithium results in the formation of a new O'3 phase in the P3/P2-layered matrix. STEM results identify the intergrowth of P3/P2 and P3/P2/O'3 in biphasic and triphasic materials, respectively. Electron energy loss spectroscopy verifies that the alkali metal layer in the O'3 phase is occupied by the lithium ion. The intergrowth of biphasic and triphasic materials in these layered P3/P2 and P3/P2/O'3 hybrid structures brings forth a positive effect on the electrochemical properties. In particular, the formation of P3/P2/O'3-intergrown hybrid structures greatly improves the cycling stability of the P3 phase that the capacity retention of P3/P2/O'3 hybrid structures remains 78%, while capacity retention of the pure P3 phase is only 54.1% after 50 cycles at a rate of 0.2 C, and the rate performance of the P3 phase has also been enhanced.

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http://dx.doi.org/10.1021/acs.inorgchem.8b02931DOI Listing

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