Electrochemical Na extraction/insertion of Na3V 2O2x(PO4)2F3-2 x

Paula Serras, Verónica Palomares, Javier Alonso, Neeraj Sharma, Juan Miguel López Del Amo, Pierre Kubiak, María Luisa Fdez-Gubieda, Teófilo Rojo

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Abstract

A mixed-valence V3+/V4+ composite material belonging to the Na3V2O2x(PO4)2F 3-2x/C family is synthesized and the electrochemical Na extraction/insertion mechanism is determined using a combination of high-resolution synchrotron X-ray diffraction (XRD) data, X-ray absorption spectroscopy (XAS), 23Na and 19F solid state nuclear magnetic resonance (NMR), double titration (for the elucidation of the vanadium oxidation state), and electrochemical measurements. The vanadium oxidation state is found to be +3.8 for the as-prepared sample. Detailed analysis of the cathode structural evolution illustrated that the V4+/V5+ couple is active in this compound during electrochemical cycling between 2.8 V and 4.3 V. This study demonstrates how the sodium-ion extraction and insertion pathways in cathode materials can be followed (and verified) using several experimental techniques, especially when multiple potential oxidation states are present in the parent compound.

Original languageEnglish
Pages (from-to)4917-4925
Number of pages9
JournalChemistry of Materials
Volume25
Issue number24
DOIs
Publication statusPublished - 23 Dec 2013
Externally publishedYes

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Keywords

  • electrochemistry
  • mixed valence sodium vanadium fluorophosphate
  • sodium ion batteries
  • X-ray diffraction and X-ray absorption near edge structure

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Serras, P., Palomares, V., Alonso, J., Sharma, N., López Del Amo, J. M., Kubiak, P., Fdez-Gubieda, M. L., & Rojo, T. (2013). Electrochemical Na extraction/insertion of Na3V 2O2x(PO4)2F3-2 x Chemistry of Materials, 25(24), 4917-4925. https://doi.org/10.1021/cm403679b