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

Bock, David C.; Waller, Gordon H.; Mansour, Azzam N.; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.

doi:10.1021/acs.jpcc.8b01970

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

Journal Article · Tue Jun 05 00:00:00 EDT 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b01970· OSTI ID:1466625

Bock, David C. ^[1]; Waller, Gordon H. ^[2]; Mansour, Azzam N. ^[2];

^[3];

^[4];

^[3]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Naval Surface Warfare Center (NSWC), West Bethesda, MD (United States)
State Univ. of New York (SUNY), Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
State Univ. of New York (SUNY), Stony Brook, NY (United States)

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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1466625

Report Number(s):: BNL-207984-2018-JAAM

Journal Information:: Journal of Physical Chemistry. C, Vol. 122, Issue 26; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 33 works

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25 ENERGY STORAGE
Li ion batteries
Fe3O4
SEI
FEC
XPS
XAS

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

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