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Title: Investigation of Solid Electrolyte Interphase Layer Formation and Electrochemical Reversibility of Magnetite, Fe 3 O 4 , Electrodes: A Combined X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy Study

Magnetite (Fe 3O 4) is a promising electrode material for the next generation of Li-ion batteries with multiple electron transfers per metal center and a theoretical capacity of 924 mAh/g. However, multiple phase conversions during (de)lithiation of Fe 3O 4 and formation of a surface electrolyte interphase (SEI) contribute to capacity fade. In this study, X-ray Absorption Spectroscopy (XAS), and X-ray Photoelectron Spectroscopy (XPS) were used to determine the surface chemistry, redox chemistry, and the impact on the electrochemical reversibility in the presence and absence of fluoroethylene carbonate (FEC) solvent. With FEC improved capacity retention and enhanced reversibility are observed. In contrast, electrodes cycled with no FEC exhibit decreased reversibility where the active material remains as reduced Fe 0. XPS results reveal LiF and lower quantities of oxygen containing species, especially carbonates at the electrode surface tested in FEC. The improvement in electrochemical reversibility with FEC is attributed to the formation of a solid electrolyte interphase which forms prior to initiation of the conversion reaction limiting SEI growth on the reduced products, Fe0 and Li 2O. In contrast, EC-based carbonate electrolyte forms SEI at a potential where formation of Fe0 and Li 2O has already initiated resulting in SEI formationmore » on Fe 0 nanograins.« less
Authors:
 [1] ;  [2] ;  [2] ; ORCiD logo [3] ; ORCiD logo [4] ; ORCiD logo [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Naval Surface Warfare Center (NSWC), West Bethesda, MD (United States)
  3. State Univ. of New York (SUNY), Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. State Univ. of New York (SUNY), Stony Brook, NY (United States)
Publication Date:
Report Number(s):
BNL-207984-2018-JAAM
Journal ID: ISSN 1932-7447
Grant/Contract Number:
SC0012704
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 26; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Li ion batteries; Fe3O4; SEI; FEC; XPS; XAS
OSTI Identifier:
1466625

Bock, David C., Waller, Gordon H., Mansour, Azzam N., Marschilok, Amy C., Takeuchi, Kenneth J., and Takeuchi, Esther S.. Investigation of Solid Electrolyte Interphase Layer Formation and Electrochemical Reversibility of Magnetite, Fe 3 O 4 , Electrodes: A Combined X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy Study. United States: N. p., Web. doi:10.1021/acs.jpcc.8b01970.
Bock, David C., Waller, Gordon H., Mansour, Azzam N., Marschilok, Amy C., Takeuchi, Kenneth J., & Takeuchi, Esther S.. Investigation of Solid Electrolyte Interphase Layer Formation and Electrochemical Reversibility of Magnetite, Fe 3 O 4 , Electrodes: A Combined X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy Study. United States. doi:10.1021/acs.jpcc.8b01970.
Bock, David C., Waller, Gordon H., Mansour, Azzam N., Marschilok, Amy C., Takeuchi, Kenneth J., and Takeuchi, Esther S.. 2018. "Investigation of Solid Electrolyte Interphase Layer Formation and Electrochemical Reversibility of Magnetite, Fe 3 O 4 , Electrodes: A Combined X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy Study". United States. doi:10.1021/acs.jpcc.8b01970.
@article{osti_1466625,
title = {Investigation of Solid Electrolyte Interphase Layer Formation and Electrochemical Reversibility of Magnetite, Fe 3 O 4 , Electrodes: A Combined X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy Study},
author = {Bock, David C. and Waller, Gordon H. and Mansour, Azzam N. and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S.},
abstractNote = {Magnetite (Fe3O4) is a promising electrode material for the next generation of Li-ion batteries with multiple electron transfers per metal center and a theoretical capacity of 924 mAh/g. However, multiple phase conversions during (de)lithiation of Fe3O4 and formation of a surface electrolyte interphase (SEI) contribute to capacity fade. In this study, X-ray Absorption Spectroscopy (XAS), and X-ray Photoelectron Spectroscopy (XPS) were used to determine the surface chemistry, redox chemistry, and the impact on the electrochemical reversibility in the presence and absence of fluoroethylene carbonate (FEC) solvent. With FEC improved capacity retention and enhanced reversibility are observed. In contrast, electrodes cycled with no FEC exhibit decreased reversibility where the active material remains as reduced Fe0. XPS results reveal LiF and lower quantities of oxygen containing species, especially carbonates at the electrode surface tested in FEC. The improvement in electrochemical reversibility with FEC is attributed to the formation of a solid electrolyte interphase which forms prior to initiation of the conversion reaction limiting SEI growth on the reduced products, Fe0 and Li2O. In contrast, EC-based carbonate electrolyte forms SEI at a potential where formation of Fe0 and Li2O has already initiated resulting in SEI formation on Fe0 nanograins.},
doi = {10.1021/acs.jpcc.8b01970},
journal = {Journal of Physical Chemistry. C},
number = 26,
volume = 122,
place = {United States},
year = {2018},
month = {6}
}