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Suppression of Fe-cation migration by indium substitution in LiFe2–xInxSbO6 cathode materials

DOI: 10.1021/acs.chemmater.2c03418 DOI Help

Authors: Xabier Martinez De Irujo-Labalde (University of Oxford; The Faraday Institution) , Heather Grievson (The Faraday Institution; University of Sheffield) , Josie-May Mortimer (The Faraday Institution; University of Sheffield) , Samuel G. Booth (The Faraday Institution; University of Sheffield) , Alex Scrimshire (Sheffield Hallam University) , Paul A. Bingham (Sheffield Hallam University) , Emmanuelle Suard (Institut Laue-Langevin) , Serena A. Cussen (The Faraday Institution; University of Sheffield) , Michael A. Hayward (University of Oxford; The Faraday Institution)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry Of Materials

State: Published (Approved)
Published: December 2022
Diamond Proposal Number(s): 25166

Open Access Open Access

Abstract: Cation migration on electrochemical cycling can significantly influence the performance of li-ion cathode materials. Phases of composition LiFe2–xInxSbO6 (0 < x <1) adopt crystal structures described in space group Pnnm, consisting of a hexagonally close-packed array of oxide ions, with Fe/In and Sb cations ordered on octahedral sites, and lithium cations located within partially occupied tetrahedral sites. NPD, SXRD, and 57Fe Mössbauer data indicate that on reductive lithium insertion (either chemically or electrochemically), LiFe2SbO6 is converted to Li2Fe2SbO6 accompanied by large-scale cation migration, to form a partially Fe/Li cation-ordered and Fe2+/Fe3+ charge-ordered phase from which lithium cations cannot be easily removed, either chemically or electrochemically. Partial substitution of Fe with In suppresses the degree of cation migration that occurs on lithium insertion such that no structural change is observed when LiFeInSbO6 is converted into Li1.5FeInSbO6, allowing the system to be repeatedly electrochemically cycled between these two compositions. Phases with intermediate levels of In substitution exhibit low levels of Fe migration on Li insertion and electrochemical capacities which evolve on cycling. The mechanism by which the In3+ cations suppress the migration of Fe cations is discussed along with the cycling behavior of the LiFe1.5In0.5SbO6–Li1.75Fe1.5In0.5SbO6.

Diamond Keywords: Batteries; Lithium-ion

Subject Areas: Chemistry, Materials, Energy

Instruments: B18-Core EXAFS , I11-High Resolution Powder Diffraction

Added On: 24/12/2022 09:17


Discipline Tags:

Energy Storage Energy Physical Chemistry Energy Materials Chemistry Materials Science Chemical Engineering Engineering & Technology

Technical Tags:

Diffraction Spectroscopy X-ray Powder Diffraction X-ray Absorption Spectroscopy (XAS) X-ray Absorption Near Edge Structure (XANES)