Electrochemical properties and structural evolution of O3-type layered sodium mixed transition metal oxides with trivalent nickel
- Author(s): Vassilaras, P
- Kwon, DH
- Dacek, ST
- Shi, T
- Seo, DH
- Ceder, G
- Kim, JC
- et al.
Published Web Locationhttps://doi.org/10.1039/c6ta09220a
© The Royal Society of Chemistry. The electrochemical properties of NaNi0.5Co0.5O2and NaNi0.5Fe0.5O2and their structural transitions as a function of Na extraction associated with redox reactions are investigated in this work. Synthesized in the O3-type layered structure, both materials show reasonable electrochemical activities at room temperature, delivering approximately 0.5 Na per formula unit at C/10 discharge. More Na can be reversibly cycled in NaNi0.5Co0.5O2at elevated temperature and/or in an extended voltage window, while NaNi0.5Fe0.5O2shows significant capacity fading at a high voltage cutoff which is likely due to Fe4+migration. In situ X-ray diffraction shows that the structural changes in the two materials upon desodiation are very different. NaNi0.5Co0.5O2goes through many different two-phase reactions including three different O3-type and three different P3-type structures during cycling, producing a voltage profile with multiple plateau-like features. In contrast, NaNi0.5Fe0.5O2has a smooth voltage profile and shows the typical O3-P3 phase transition without lattice distortion seen in other materials. This different structural evolution upon desodiation and re-sodiation can be explained by the electronic structure of the mixed transition metals and how it perturbs the ordering between Na ions differently.
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