The Electrochemical Sodiation of FeSb2: New Insights from Operando 57Fe Synchrotron Mössbauer and X-Ray Absorption Spectroscopy
Abstract
Operando Sb K–edge X–ray absorption spectroscopy and 57Fe Synchrotron Mössbauer Spectroscopy, used for the first time in the field of operando energy storage materials, assisted by operando magnetic measurements, were combined to clarify the role of iron and antimony in the electrochemical reaction mechanism of FeSb2 as negative electrode material for sodium–ion batteries (SIB). Both datasets were analyzed using an innovative chemometric approach involving principal component analysis (PCA) and multivariate curve resolution – alternating least square analysis (MCR–ALS) yielding new insights on the sodiation reaction. Our findings show that the reaction of Na with FeSb2 during discharge leads to the formation of Na3Sb along with superparamagnetic Fe amorphous nanoparticles which contain small amounts of Sb dissolved in their lattice. During the following desodiation, the pristine material FeSb2 is not recovered while iron nanoparticles grow in size, and continue growing also along the following discharge. Here, even though such iron nanoparticles remain electrochemically inactive, they play a key role in the reduction and stabilization of the polarization as well as in the reversibility of the electrochemical sodiation of antimony.
- Authors:
-
- ESRF-The European Synchrotron, Grenoble (France); Delft Univ. of Technology, Delft (Netherlands); Alistore European Research Institute, Amiens (France)
- ESRF-The European Synchrotron, Grenoble (France)
- Univ. Montpellier, Montpellier (France)
- Univ. Lìege, Lìege (Belgium)
- Bar Ilan Univ., Ramat Gan (Israel)
- Synchrotron Soleil, Gif-sur-Yvette (France)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Alistore European Research Institute, Amiens (France); Univ. Montpellier, Montpellier (France); Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amiens (France)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1560386
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Batteries & Supercaps
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 1; Journal ID: ISSN 2566-6223
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; anode materials; magnetism; sodium-ion batteries; synchrotron Mössbauer spectroscopy; X-ray absorption spectroscopy
Citation Formats
Fehse, Marcus, Bessas, Dimitrios, Darwiche, Ali, Mahmoud, Abdelfattah, Rahamim, Guy, La Fontaine, Camille, Hermann, Raphael P., Zitoun, David, Monconduit, Laure, Stievano, Lorenzo, and Sougrati, Moulay T. The Electrochemical Sodiation of FeSb2: New Insights from Operando 57Fe Synchrotron Mössbauer and X-Ray Absorption Spectroscopy. United States: N. p., 2018.
Web. doi:10.1002/batt.201800075.
Fehse, Marcus, Bessas, Dimitrios, Darwiche, Ali, Mahmoud, Abdelfattah, Rahamim, Guy, La Fontaine, Camille, Hermann, Raphael P., Zitoun, David, Monconduit, Laure, Stievano, Lorenzo, & Sougrati, Moulay T. The Electrochemical Sodiation of FeSb2: New Insights from Operando 57Fe Synchrotron Mössbauer and X-Ray Absorption Spectroscopy. United States. https://doi.org/10.1002/batt.201800075
Fehse, Marcus, Bessas, Dimitrios, Darwiche, Ali, Mahmoud, Abdelfattah, Rahamim, Guy, La Fontaine, Camille, Hermann, Raphael P., Zitoun, David, Monconduit, Laure, Stievano, Lorenzo, and Sougrati, Moulay T. Mon .
"The Electrochemical Sodiation of FeSb2: New Insights from Operando 57Fe Synchrotron Mössbauer and X-Ray Absorption Spectroscopy". United States. https://doi.org/10.1002/batt.201800075. https://www.osti.gov/servlets/purl/1560386.
@article{osti_1560386,
title = {The Electrochemical Sodiation of FeSb2: New Insights from Operando 57Fe Synchrotron Mössbauer and X-Ray Absorption Spectroscopy},
author = {Fehse, Marcus and Bessas, Dimitrios and Darwiche, Ali and Mahmoud, Abdelfattah and Rahamim, Guy and La Fontaine, Camille and Hermann, Raphael P. and Zitoun, David and Monconduit, Laure and Stievano, Lorenzo and Sougrati, Moulay T.},
abstractNote = {Operando Sb K–edge X–ray absorption spectroscopy and 57Fe Synchrotron Mössbauer Spectroscopy, used for the first time in the field of operando energy storage materials, assisted by operando magnetic measurements, were combined to clarify the role of iron and antimony in the electrochemical reaction mechanism of FeSb2 as negative electrode material for sodium–ion batteries (SIB). Both datasets were analyzed using an innovative chemometric approach involving principal component analysis (PCA) and multivariate curve resolution – alternating least square analysis (MCR–ALS) yielding new insights on the sodiation reaction. Our findings show that the reaction of Na with FeSb2 during discharge leads to the formation of Na3Sb along with superparamagnetic Fe amorphous nanoparticles which contain small amounts of Sb dissolved in their lattice. During the following desodiation, the pristine material FeSb2 is not recovered while iron nanoparticles grow in size, and continue growing also along the following discharge. Here, even though such iron nanoparticles remain electrochemically inactive, they play a key role in the reduction and stabilization of the polarization as well as in the reversibility of the electrochemical sodiation of antimony.},
doi = {10.1002/batt.201800075},
journal = {Batteries & Supercaps},
number = 1,
volume = 2,
place = {United States},
year = {Mon Sep 17 00:00:00 EDT 2018},
month = {Mon Sep 17 00:00:00 EDT 2018}
}
Web of Science
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