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Structural characterization and electrochemical intercalation of Li+ in layered Na0.65Ni0.5Mn0.5O2 obtained by freeze-drying method

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Abstract

New data on the structure and reversible lithium intercalation properties of sodium-deficient nickel–manganese oxides are provided. Novel properties of oxides determine their potential for direct use as cathode materials in lithium-ion batteries. The studies are focused on Na x Ni0.5Mn0.5O2 with x = 2/3. Between 500 and 700 °C, new layered oxides Na0.65Ni0.5Mn0.5O2 with P3-type structure are obtained by a simple precursor method that consists in thermal decomposition of mixed sodium–nickel–manganese acetate salts obtained by freeze-drying. The structure, morphology, and oxidation state of nickel and manganese ions of Na0.65Ni0.5Mn0.5O2 are determined by powder X-ray diffraction, SEM and TEM analysis, and X-ray photoelectron spectroscopy (XPS). The lithium intercalation in Na0.65Ni0.5Mn0.5O2 is carried out in model two-electrode lithium cells of the type Li|LiPF6(EC:DMC)|Na0.65Ni0.5Mn0.5O2. A new structural feature of Na0.65Ni0.5Mn0.5O2 as compared with well-known O3–NaNi0.5Mn0.5O2 and P2–Na2/3Ni1/3Mn2/3O2 is the development of layer stacking ensuring prismatic site occupancy for Na+ ions with shared face on one side and shared edges on the other side with surrounding Ni/MnO6 octahedra. The reversible lithium intercalation in Na0.65Ni0.5Mn0.5O2 is demonstrated and discussed.

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Acknowledgments

This work was supported by ESF (grant BG051PO001-3.3.06-0050). Thanks are due to Dr. Diana Nihtianova (Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences).

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Authors and Affiliations

  1. Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113, Sofia, Bulgaria

    M. Kalapsazova, R. Stoyanova & E. Zhecheva

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  1. M. Kalapsazova
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  2. R. Stoyanova
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  3. E. Zhecheva
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Correspondence to M. Kalapsazova.

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Kalapsazova, M., Stoyanova, R. & Zhecheva, E. Structural characterization and electrochemical intercalation of Li+ in layered Na0.65Ni0.5Mn0.5O2 obtained by freeze-drying method. J Solid State Electrochem 18, 2343–2350 (2014). https://doi.org/10.1007/s10008-014-2399-x

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  • DOI: https://doi.org/10.1007/s10008-014-2399-x

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