Study of sodium manganese fluorides as positive electrodes for Na-ion batteries

Study of sodium manganese fluorides as positive electrodes for Na-ion batteries Na2MnF5 and NaMnF3 were prepared in aqueous media using Mn2O3 and NaMnO4·H2O as Mn precursors and characterized by XRPD, ATR-IR and ICP-OES/ICP-MS. Additionally, a new metastable hydrated oxyfluoride was prepared, with a diffraction pattern (neutron and SXRPD data) consistent with an orthorhombic cell with a=4.07559Å, b=9.04090Å and c=6.77290Å and Cccm space group which yielded NaMnF4 upon dehydration. The feasibility of Na+ deintercalation was experimentally tested in electrochemical cells against sodium metal counter electrodes under different conditions, and also investigated by first principles methods. Experimental results were confronted to blank experiments performed with electrodes containing only carbon black and allowed to conclude that the redox processes observed were not related to active materials but to electrolyte/carbon black reactivity. DFT results point at the electrochemical activity of such compounds taking place at high potential values, in some cases well outside the electrolyte stability window. In the case of NaMnF3, for which he calculated density of states predicts a bang gap of 2.7eV, its insulating character induces significant cell polarization thus electrochemical activity cannot not practically reached with the available electrolytes. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Solid State Ionics Elsevier

Study of sodium manganese fluorides as positive electrodes for Na-ion batteries

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Publisher
Elsevier
Copyright
Copyright © 2015 Elsevier B.V.
ISSN
0167-2738
eISSN
1872-7689
D.O.I.
10.1016/j.ssi.2015.05.023
Publisher site
See Article on Publisher Site

Abstract

Na2MnF5 and NaMnF3 were prepared in aqueous media using Mn2O3 and NaMnO4·H2O as Mn precursors and characterized by XRPD, ATR-IR and ICP-OES/ICP-MS. Additionally, a new metastable hydrated oxyfluoride was prepared, with a diffraction pattern (neutron and SXRPD data) consistent with an orthorhombic cell with a=4.07559Å, b=9.04090Å and c=6.77290Å and Cccm space group which yielded NaMnF4 upon dehydration. The feasibility of Na+ deintercalation was experimentally tested in electrochemical cells against sodium metal counter electrodes under different conditions, and also investigated by first principles methods. Experimental results were confronted to blank experiments performed with electrodes containing only carbon black and allowed to conclude that the redox processes observed were not related to active materials but to electrolyte/carbon black reactivity. DFT results point at the electrochemical activity of such compounds taking place at high potential values, in some cases well outside the electrolyte stability window. In the case of NaMnF3, for which he calculated density of states predicts a bang gap of 2.7eV, its insulating character induces significant cell polarization thus electrochemical activity cannot not practically reached with the available electrolytes.

Journal

Solid State IonicsElsevier

Published: Oct 1, 2015

References

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    Nava-Avendaño, J.; Frontera, C.; Ayllón, J.A.; Oró-Solé, J.; Senguttuvan, P.; Palacín, M.R.
  • J. Power Sources
    Kitajou, A.; Komatsu, H.; Chihara, K.; Gocheva, I.D.; Okada, S.; Yamaki, J.
  • Phys. Rev. Lett.
    Perdew, J.P.; Burke, K.; Ernzerhof, M.
  • Phys. Status Solidi
    Dudarev, S.L.; Botton, G.A.; Savrasov, S.Y.; Szotek, Z.; Temmerman, W.M.; Sutton, A.P.
  • J. Power Sources
    Gocheva, I.D.; Nishijima, M.; Doi, T.; Okada, S.; Yamaki, J.; Nishida, T.

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