Abstract
| Original language | English |
|---|---|
| Pages (from-to) | 4492-4500 |
| Journal | Chemistry of Materials |
| Volume | 28 |
| Issue number | 2 |
| Early online date | 27 May 2016 |
| DOIs | |
| Publication status | Published - 28 Jun 2016 |
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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 journal › Article
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TY - JOUR
T1 - Influence of rotational distortions on Li+- and Na+- intercalation in anti-NASICON Fe2(MoO4)3
AU - Zhou, Shiliang
AU - Barim, Gözde
AU - Morgan, Benjamin J.
AU - Melot, Brent C.
AU - Brutchey, Richard L.
PY - 2016/6/28
Y1 - 2016/6/28
N2 - 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.
AB - 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.
UR - http://dx.doi.org/10.1021/acs.chemmater.6b01806
U2 - 10.1021/acs.chemmater.6b01806
DO - 10.1021/acs.chemmater.6b01806
M3 - Article
VL - 28
SP - 4492
EP - 4500
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 2
ER -