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Title: Lithium Insertion Mechanism in Iron‐Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis

Abstract

Abstract The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)‐type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer‐sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF‐type electrodes, upon de‐lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re‐oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties.

Authors:
 [1];  [2];  [3];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Sorbonne Universités UPMC Univ. Paris 06 UMR 8234 PHENIX 75005 Paris France, CNRS UMR 8234 PHENIX 75005 Paris France
  2. X-ray Science Division Advanced Photon Source Argonne National Laboratory Argonne IL 60439 USA
  3. Sorbonne Universités UPMC Univ. Paris 06 UMR 8234 PHENIX 75005 Paris France, CNRS UMR 8234 PHENIX 75005 Paris France, CNRS Univ. Bordeaux ICMCB UPR 9048 33600 Pessac France
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1222371
Alternate Identifier(s):
OSTI ID: 1212713; OSTI ID: 1786436
Grant/Contract Number:  
AC02-06CH11357; FP7/2007-2013; [321879]
Resource Type:
Published Article
Journal Name:
ChemistryOpen
Additional Journal Information:
Journal Name: ChemistryOpen Journal Volume: 4 Journal Issue: 4; Journal ID: ISSN 2191-1363
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; anionic partitioning; cathode materials; ferric fluoride; pair distribution function

Citation Formats

Dambournet, Damien, Chapman, Karena W., Duttine, Mathieu, Borkiewicz, Olaf, Chupas, Peter J., and Groult, Henri. Lithium Insertion Mechanism in Iron‐Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis. Germany: N. p., 2015. Web. doi:10.1002/open.201500031.
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Dambournet, Damien, Chapman, Karena W., Duttine, Mathieu, Borkiewicz, Olaf, Chupas, Peter J., & Groult, Henri. Lithium Insertion Mechanism in Iron‐Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis. Germany. https://doi.org/10.1002/open.201500031
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Dambournet, Damien, Chapman, Karena W., Duttine, Mathieu, Borkiewicz, Olaf, Chupas, Peter J., and Groult, Henri. Thu . "Lithium Insertion Mechanism in Iron‐Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis". Germany. https://doi.org/10.1002/open.201500031.
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@article{osti_1222371,
title = {Lithium Insertion Mechanism in Iron‐Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis},
author = {Dambournet, Damien and Chapman, Karena W. and Duttine, Mathieu and Borkiewicz, Olaf and Chupas, Peter J. and Groult, Henri},
abstractNote = {Abstract The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)‐type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer‐sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF‐type electrodes, upon de‐lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re‐oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties.},
doi = {10.1002/open.201500031},
journal = {ChemistryOpen},
number = 4,
volume = 4,
place = {Germany},
year = {Thu Jun 25 00:00:00 EDT 2015},
month = {Thu Jun 25 00:00:00 EDT 2015}
}
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https://doi.org/10.1002/open.201500031
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