Influence of rotational distortions on Li+- and Na+- intercalation in anti-NASICON Fe2(MoO4)3

Shiliang Zhou, Gözde Barim, Benjamin J. Morgan, Brent C. Melot, Richard L. Brutchey

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Abstract

Anti-NASICON Fe2(MoO4)3 (P21/c) shows significant structural and electrochemical differences in the intercalation of Li+ and Na+ ions. To understand the origin of this behavior, we have used a combination of in-situ X-ray and high-resolution neutron diffraction, total scattering, electrochemical measurements, density functional theory calculations, and symmetry-mode analysis. We find that for Li+-intercalation, which proceeds via a two-phase monoclinic-to-orthorhombic (Pbcn) phase transition, the host lattice undergoes a concerted rotation of rigid polyhedral subunits driven by strong interactions with the Li+ ions, leading to an ordered lithium arrangement. Na+- intercalation, which proceeds via a two-stage solid solution insertion into the monoclinic structure, similarly produces rotations of the lattice polyhedral subunits. However, using a combination of total neutron scattering data and density-functional theory calculations, we find that while these rotational distortions upon Na+ intercalation are fundamentally the same as for Li+ intercalation, they result in a far less coherent final structure, with this difference attributed to the substantial difference between the ionic radii of the two alkali metals.
Original languageEnglish
Pages (from-to)4492-4500
JournalChemistry of Materials
Volume28
Issue number2
Early online date27 May 2016
DOIs
Publication statusPublished - 28 Jun 2016

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Intercalation
Density functional theory
Ions
Alkali Metals
Alkali metals
Neutron diffraction
Neutron scattering
Lithium
Solid solutions
Phase transitions
Scattering
X rays

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Influence of rotational distortions on Li+- and Na+- intercalation in anti-NASICON Fe2(MoO4)3. / Zhou, Shiliang; Barim, Gözde; Morgan, Benjamin J.; Melot, Brent C.; Brutchey, Richard L.

In: Chemistry of Materials, Vol. 28, No. 2, 28.06.2016, p. 4492-4500.

Research output: Contribution to journalArticle

Zhou, Shiliang ; Barim, Gözde ; Morgan, Benjamin J. ; Melot, Brent C. ; Brutchey, Richard L. / Influence of rotational distortions on Li+- and Na+- intercalation in anti-NASICON Fe2(MoO4)3. In: Chemistry of Materials. 2016 ; Vol. 28, No. 2. pp. 4492-4500.
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