Building a fast lane for Mg diffusion in α-MoO3 by fluorine doping

Liwen F. Wan, Jared T. Incorvati, Kenneth R Poeppelmeier, David Prendergast

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Following previous experimental work examining a layered oxyfluoride as cathode material for Mg-ion batteries [ Incorvati et al., Chem. Mater. 2016, 28, 17 ], we study the role of fluorination on the structural and electronic properties of molybdenum trioxide and its impact on Mg intercalation and diffusion using first-principles methods. Although bulk α-MoO3 is a 2D layered compound, we find that it provides 3D channels for Mg diffusion. When F atoms are incorporated into the α-MoO3 lattice, they replace the O atoms sitting at a specific crystallographic site that is linked by two nearest Mo atoms within a single Mo-O layer. As a consequence of F substitution, the local Mo-anion bonds are distorted, which leads to closure of the electronic band gap. From the analysis of zone center phonon vibrational frequencies, it is found that the local Mo-anion bonding strength is weakened by replacing O2- with F-, which ultimately facilitates Mg diffusion through the F-substituted lattice. For example, it is shown that upon fluorination the activation barriers for Mg diffusion along selected pathways can be lowered by as much as 0.6 eV, estimated from our nudged elastic band simulations at 0K. Our results imply that direct anion doping can be a viable approach toward improving ion diffusivity in Mg-ion battery cathodes.

Original languageEnglish
Pages (from-to)6900-6908
Number of pages9
JournalChemistry of Materials
Volume28
Issue number19
DOIs
Publication statusPublished - Oct 11 2016

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Fluorine
Doping (additives)
Anions
Fluorination
Negative ions
Ions
Atoms
Cathodes
Vibrational spectra
Intercalation
Electronic properties
Molybdenum
Structural properties
Energy gap
Substitution reactions
Chemical activation
molybdenum trioxide

ASJC Scopus subject areas

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

Cite this

Building a fast lane for Mg diffusion in α-MoO3 by fluorine doping. / Wan, Liwen F.; Incorvati, Jared T.; Poeppelmeier, Kenneth R; Prendergast, David.

In: Chemistry of Materials, Vol. 28, No. 19, 11.10.2016, p. 6900-6908.

Research output: Contribution to journalArticle

Wan, Liwen F. ; Incorvati, Jared T. ; Poeppelmeier, Kenneth R ; Prendergast, David. / Building a fast lane for Mg diffusion in α-MoO3 by fluorine doping. In: Chemistry of Materials. 2016 ; Vol. 28, No. 19. pp. 6900-6908.
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