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Title: Influence of Rotational Distortions on Li+- and Na+-Intercalation in Anti-NASICON Fe2(MoO4)3

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. Furthermore, 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.

Authors:
 [1];  [1];  [2];  [1];  [1]
+ Show Author Affiliations
  1. Univ. of Southern California, Los Angeles, CA (United States)
  2. Univ. of Bath (United Kingdom)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1324795
Alternate Identifier(s):
OSTI ID: 1418544
Grant/Contract Number:  
AC02-06CH11357; AC05-00OR22725; FG02-11ER46826; DMR-1554204
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 12; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical structure; physical and chemical processes; intercalation; lattices; ions

Citation Formats

Zhou, Shiliang, Barim, Gözde, Morgan, Benjamin J., Melot, Brent C., and Brutchey, Richard L. Influence of Rotational Distortions on Li+- and Na+-Intercalation in Anti-NASICON Fe2(MoO4)3. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b01806.
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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. United States. https://doi.org/10.1021/acs.chemmater.6b01806
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Zhou, Shiliang, Barim, Gözde, Morgan, Benjamin J., Melot, Brent C., and Brutchey, Richard L. Fri . "Influence of Rotational Distortions on Li+- and Na+-Intercalation in Anti-NASICON Fe2(MoO4)3". United States. https://doi.org/10.1021/acs.chemmater.6b01806. https://www.osti.gov/servlets/purl/1324795.
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@article{osti_1324795,
title = {Influence of Rotational Distortions on Li+- and Na+-Intercalation in Anti-NASICON Fe2(MoO4)3},
author = {Zhou, Shiliang and Barim, Gözde and Morgan, Benjamin J. and Melot, Brent C. and Brutchey, Richard L.},
abstractNote = {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. Furthermore, 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.},
doi = {10.1021/acs.chemmater.6b01806},
journal = {Chemistry of Materials},
number = 12,
volume = 28,
place = {United States},
year = {Fri May 27 00:00:00 EDT 2016},
month = {Fri May 27 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acs.chemmater.6b01806
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    Works referencing / citing this record:

    Challenges and Perspectives for NASICON-Type Electrode Materials for Advanced Sodium-Ion Batteries
    journal, June 2017

    Facile aqueous synthesis of high performance Na 2 FeM(SO 4 ) 3 (M = Fe, Mn, Ni) alluaudites for low cost Na-ion batteries
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    • Plewa, Anna; Kulka, Andrzej; Hanc, Emil
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    Recent Progress in Iron-Based Electrode Materials for Grid-Scale Sodium-Ion Batteries
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    Polyanion-Type Electrode Materials for Sodium-Ion Batteries
    journal, January 2017

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