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

Jessica Nava-Avendaño, M. Elena Arroyo-De Dompablo, Carlos Frontera, José A. Ayllón, M. Rosa Palacín

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© 2015 Elsevier B.V. Abstract Na<inf>2</inf>MnF<inf>5</inf> and NaMnF<inf>3</inf> were prepared in aqueous media using Mn<inf>2</inf>O<inf>3</inf> and NaMnO<inf>4</inf>·H<inf>2</inf>O 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 = 4.07559 Å, b = 9.04090 Å and c = 6.77290 Å and Cccm space group which yielded NaMnF<inf>4</inf> upon dehydration. The feasibility of Na<sup>+</sup> 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 NaMnF<inf>3</inf>, for which he calculated density of states predicts a bang gap of 2.7 eV, its insulating character induces significant cell polarization thus electrochemical activity cannot not practically reached with the available electrolytes.
Idioma originalAnglès
Número d’article13680
Pàgines (de-a)106-113
RevistaSolid State Ionics
Volum278
DOIs
Estat de la publicacióPublicada - 22 de juny 2015

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