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

Journal Article · · Chemistry of Materials
 [1];  [1];  [2];  [1];  [1]
  1. Univ. of Southern California, Los Angeles, CA (United States)
  2. Univ. of Bath (United Kingdom)
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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.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC02-06CH11357; AC05-00OR22725; FG02-11ER46826; DMR-1554204
OSTI ID:
1324795
Alternate ID(s):
OSTI ID: 1418544
Journal Information:
Chemistry of Materials, Vol. 28, Issue 12; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
ENGLISH
Citation Metrics:
Cited by: 32 works
Citation information provided by
Web of Science

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Cited By (4)

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 journal January 2020
Recent Progress in Iron-Based Electrode Materials for Grid-Scale Sodium-Ion Batteries journal January 2018
Polyanion-Type Electrode Materials for Sodium-Ion Batteries journal January 2017

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemical structure
physical and chemical processes
intercalation
lattices
ions