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Title: The reaction mechanism of FeSb 2 as anode for sodium-ion batteries

Abstract

The electrochemical reaction of FeSb 2 with Na is reported for the first time. The first discharge (sodiation) potential profile of FeSb 2 is characterized by a gentle slope centered at 0.25 V. During charge (Na removal) and the subsequent discharge, the main reaction takes place near 0.7 V and 0.4 V, respectively. The reversible storage capacity amounts to 360 mA h g -1, which is smaller than the theoretical value of 537 mA h g -1. The reaction, studied by ex situ and in situ X-ray diffraction, is found to proceed by the consumption of crystalline FeSb 2 to form an amorphous phase. Upon further sodiation, the formation of nanocrystalline Na3Sb domains is evidenced. During desodiation, Na 3Sb domains convert into an amorphous phase. The chemical environment of Fe, probed by 57Fe Mo ssbauer spectroscopy, undergoes significant changes during the reaction. During sodiation, the well-resolved doublet of FeSb2 with an isomer shift around 0.45 mm s -1 and a quadrupole splitting of 1.26 mm s -1 is gradually converted into a doublet line centered at about 0.15 mm s1 along with a singlet line around 0 mm s -1. The former signal results from the formation of a Fe-richmore » FexSb alloy with an estimated composition of Fe4Sb while the latter signal corresponds to superparamagnetic Fe due to the formation of nanosized pure Fe domains. Interestingly the signal of Fe4Sb remains unaltered during desodiation. This mechanism is substantially different than that observed during the reaction with Li. The irreversible formation of a Fe-rich Fe 4Sb alloy and the absence of full desodiation of Sb domains explain the lower than theoretical practical storage capacity.« less

Authors:
 [1];  [2]; ;  [1];  [2];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of Tennessee Space Inst. (UTSI), Tullahoma, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1185578
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 16; Journal Issue: 20; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Sodium-ion battery; Iron antimony (FeSb2) anodes; Reaction mechanism; X-ray diffraction; 57Fe Mössbauer spectroscopy

Citation Formats

Baggetto, Loic, Hah, Hien-Yoong, Charles E. Johnson, Bridges, Craig A., Johnson, Jackie A., and Veith, Gabriel M. The reaction mechanism of FeSb2 as anode for sodium-ion batteries. United States: N. p., 2014. Web. doi:10.1039/c4cp00738g.
Baggetto, Loic, Hah, Hien-Yoong, Charles E. Johnson, Bridges, Craig A., Johnson, Jackie A., & Veith, Gabriel M. The reaction mechanism of FeSb2 as anode for sodium-ion batteries. United States. doi:10.1039/c4cp00738g.
Baggetto, Loic, Hah, Hien-Yoong, Charles E. Johnson, Bridges, Craig A., Johnson, Jackie A., and Veith, Gabriel M. Fri . "The reaction mechanism of FeSb2 as anode for sodium-ion batteries". United States. doi:10.1039/c4cp00738g. https://www.osti.gov/servlets/purl/1185578.
@article{osti_1185578,
title = {The reaction mechanism of FeSb2 as anode for sodium-ion batteries},
author = {Baggetto, Loic and Hah, Hien-Yoong and Charles E. Johnson and Bridges, Craig A. and Johnson, Jackie A. and Veith, Gabriel M.},
abstractNote = {The electrochemical reaction of FeSb2 with Na is reported for the first time. The first discharge (sodiation) potential profile of FeSb2 is characterized by a gentle slope centered at 0.25 V. During charge (Na removal) and the subsequent discharge, the main reaction takes place near 0.7 V and 0.4 V, respectively. The reversible storage capacity amounts to 360 mA h g-1, which is smaller than the theoretical value of 537 mA h g-1. The reaction, studied by ex situ and in situ X-ray diffraction, is found to proceed by the consumption of crystalline FeSb2 to form an amorphous phase. Upon further sodiation, the formation of nanocrystalline Na3Sb domains is evidenced. During desodiation, Na3Sb domains convert into an amorphous phase. The chemical environment of Fe, probed by 57Fe Mo ssbauer spectroscopy, undergoes significant changes during the reaction. During sodiation, the well-resolved doublet of FeSb2 with an isomer shift around 0.45 mm s-1 and a quadrupole splitting of 1.26 mm s-1 is gradually converted into a doublet line centered at about 0.15 mm s1 along with a singlet line around 0 mm s-1. The former signal results from the formation of a Fe-rich FexSb alloy with an estimated composition of Fe4Sb while the latter signal corresponds to superparamagnetic Fe due to the formation of nanosized pure Fe domains. Interestingly the signal of Fe4Sb remains unaltered during desodiation. This mechanism is substantially different than that observed during the reaction with Li. The irreversible formation of a Fe-rich Fe4Sb alloy and the absence of full desodiation of Sb domains explain the lower than theoretical practical storage capacity.},
doi = {10.1039/c4cp00738g},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 20,
volume = 16,
place = {United States},
year = {2014},
month = {4}
}

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Works referenced in this record:

Electrochemical synthesis of a three-dimensional porous Sb/Cu2Sb anode for Na-ion batteries
journal, February 2014


Sodium-Ion Batteries
journal, May 2012

  • Slater, Michael D.; Kim, Donghan; Lee, Eungje
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