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Title: The Electrochemical Sodiation of Sb Investigated by Operando X-ray Absorption and 121Sb Mössbauer Spectroscopy: What Does One Really Learn?

In this study, we want to highlight the assets and restrictions of X-ray absorption spectroscopy (XAS) and Mössbauer spectroscopy for investigating the mechanism of the electrochemical reaction of antimony electrode materials vs. Na. For this, operando XAS was carried out during the first one and a half cycles, and the whole set of measured data was analysed using a statistical-chemometric approach, while low temperature Mössbauer spectroscopy measurements were carried out ex situ on selected samples stopped at different points of the electrochemical reaction. Complementary ab initio calculations were performed to support the experimental findings. Both techniques show that, upon the first sodiation, most Sb reacts with Na to form disordered Na 3 Sb. This step is accompanied by the formation of amorphous Sb as an intermediate. Upon inversion of the current Na 3 Sb is desodiated and an amorphous Sb phase, distinct from the pristine bulk Sb state, is gradually formed. However, both XAS and Mössbauer spectroscopy were unable to spot the formation of intermediate Na x Sb phases, which were evinced in previous works by operando Pair Distribution Function analyses. The results shown here clearly assign such failure to the intrinsic inability of both techniques to identify these intermediates.
Authors:
 [1] ; ORCiD logo [2] ;  [3] ;  [4] ;  [1] ; ORCiD logo [5] ;  [6] ;  [7] ; ORCiD logo [7] ;  [8] ; ORCiD logo [9]
  1. Université de Montpellier, CNRS (France). ICGM
  2. Dutch-Belgian (DUBBLE), ESRF-The European Synchrotron, Grenoble (France); Delft Univ. of Technology (Netherlands). Faculty of Applied Sciences; Université de Picardie Jules Verne (France). Alistore European Research Institute
  3. University of Liège (Belgium). GreenMat, CESAM, Institute of Chemistry
  4. Synchrotron Soleil, Saint-Aubin (France)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  6. Université de Montpellier, CNRS (France). ICGM; Université de Picardie Jules Verne (France). Alistore European Research Institute; Reseau sur le Stockage Electrochimique de l’Energie (RS2E), CNRS (France)
  7. Université de Montpellier, CNRS (France). ICGM; Université de Picardie Jules Verne (France). Alistore European Research Institute; Reseau sur le Stockage Electrochimique de l’Energie (RS2E), CNRS (France)
  8. Université de Montpellier, CNRS (France). ICGM; Université de Picardie Jules Verne (France). Alistore European Research Institute
  9. Dutch-Belgian (DUBBLE), ESRF-The European Synchrotron, Grenoble (France); Université de Picardie Jules Verne (France). Alistore European Research Institute; Reseau sur le Stockage Electrochimique de l’Energie (RS2E), CNRS (France)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Batteries
Additional Journal Information:
Journal Volume: 4; Journal Issue: 2; Journal ID: ISSN 2313-0105
Publisher:
MDPI
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; X-ray absorption spectroscopy; Mössbauer spectroscopy; DFT calculations; chemometrics; MCR-ALS; Na-ion batteries; alloy reaction; Sb
OSTI Identifier:
1471851

Darwiche, Ali, Fehse, Marcus, Mahmoud, Abdelfattah, La Fontaine, Camille, Fraisse, Bernard, Hermann, Raphael, Doublet, Marie-Liesse, Monconduit, Laure, Sougrati, Moulay, Ben Yahia, Mouna, and Stievano, Lorenzo. The Electrochemical Sodiation of Sb Investigated by Operando X-ray Absorption and 121Sb Mössbauer Spectroscopy: What Does One Really Learn?. United States: N. p., Web. doi:10.3390/batteries4020025.
Darwiche, Ali, Fehse, Marcus, Mahmoud, Abdelfattah, La Fontaine, Camille, Fraisse, Bernard, Hermann, Raphael, Doublet, Marie-Liesse, Monconduit, Laure, Sougrati, Moulay, Ben Yahia, Mouna, & Stievano, Lorenzo. The Electrochemical Sodiation of Sb Investigated by Operando X-ray Absorption and 121Sb Mössbauer Spectroscopy: What Does One Really Learn?. United States. doi:10.3390/batteries4020025.
Darwiche, Ali, Fehse, Marcus, Mahmoud, Abdelfattah, La Fontaine, Camille, Fraisse, Bernard, Hermann, Raphael, Doublet, Marie-Liesse, Monconduit, Laure, Sougrati, Moulay, Ben Yahia, Mouna, and Stievano, Lorenzo. 2018. "The Electrochemical Sodiation of Sb Investigated by Operando X-ray Absorption and 121Sb Mössbauer Spectroscopy: What Does One Really Learn?". United States. doi:10.3390/batteries4020025. https://www.osti.gov/servlets/purl/1471851.
@article{osti_1471851,
title = {The Electrochemical Sodiation of Sb Investigated by Operando X-ray Absorption and 121Sb Mössbauer Spectroscopy: What Does One Really Learn?},
author = {Darwiche, Ali and Fehse, Marcus and Mahmoud, Abdelfattah and La Fontaine, Camille and Fraisse, Bernard and Hermann, Raphael and Doublet, Marie-Liesse and Monconduit, Laure and Sougrati, Moulay and Ben Yahia, Mouna and Stievano, Lorenzo},
abstractNote = {In this study, we want to highlight the assets and restrictions of X-ray absorption spectroscopy (XAS) and Mössbauer spectroscopy for investigating the mechanism of the electrochemical reaction of antimony electrode materials vs. Na. For this, operando XAS was carried out during the first one and a half cycles, and the whole set of measured data was analysed using a statistical-chemometric approach, while low temperature Mössbauer spectroscopy measurements were carried out ex situ on selected samples stopped at different points of the electrochemical reaction. Complementary ab initio calculations were performed to support the experimental findings. Both techniques show that, upon the first sodiation, most Sb reacts with Na to form disordered Na 3 Sb. This step is accompanied by the formation of amorphous Sb as an intermediate. Upon inversion of the current Na 3 Sb is desodiated and an amorphous Sb phase, distinct from the pristine bulk Sb state, is gradually formed. However, both XAS and Mössbauer spectroscopy were unable to spot the formation of intermediate Na x Sb phases, which were evinced in previous works by operando Pair Distribution Function analyses. The results shown here clearly assign such failure to the intrinsic inability of both techniques to identify these intermediates.},
doi = {10.3390/batteries4020025},
journal = {Batteries},
number = 2,
volume = 4,
place = {United States},
year = {2018},
month = {5}
}

Works referenced in this record:

Density‐functional thermochemistry. III. The role of exact exchange
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  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
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