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Title: Lithiation of Magnetite (Fe 3O 4): Analysis Using Isothermal Microcalorimetry and Operando X-ray Absorption Spectroscopy

Abstract

Conversion electrodes, such as magnetite (Fe 3O 4), offer high theoretical capacities (>900 mAh/g) because of multiple electron transfer per metal center. Capacity retention for conversion electrodes has been a challenge in part because of the formation of an insulating surface electrolyte interphase (SEI). This paper provides the first detailed analysis of the lithiation of Fe 3O 4 using isothermal microcalorimetry (IMC). The measured heat flow was compared with heat contributions predicted from heats of formation for the Faradaic reaction, cell polarization, and entropic contributions. The total measured energy output of the cell (7260 J/g Fe 3O 4) exceeded the heat of reaction predicted for full lithiation of Fe 3O 4 (5508 J/g). During initial lithiation (3.0–0.86 V), the heat flow was successfully modeled using polarization and entropic contributions. Heat flow at lower voltage (0.86–0.03 V) exceeded the predicted values for iron oxide reduction, consistent with heat generation attributable to electrolyte decomposition and surface electrolyte interphase (SEI). Operando X-ray absorption spectroscopy (XAS) indicated that the oxidation state of the Fe centers deviated from predicted values beginning at ~0.86 V, supportive of SEI onset in this voltage range. Finally and thus, these combined results from electrochemistry, IMC, and XAS indicate parasiticmore » reactions consistent with SEI formation at a moderate voltage and illustrate an approach for deconvoluting Faradaic and non-Faradaic contributions to heat, which should be broadly applicable to the study of energy-storage materials and systems.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [4]
  1. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
  3. Stony Brook Univ., NY (United States). Dept. of Chemistry
  4. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering. Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
  5. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering. Dept. of Chemistry
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1466641
Report Number(s):
BNL-207937-2018-JAAM
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
SC0012704; SC0012673
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 19; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Huie, Matthew M., Bock, David C., Wang, Lei, Marschilok, Amy C., Takeuchi, Kenneth J., and Takeuchi, Esther S. Lithiation of Magnetite (Fe3O4): Analysis Using Isothermal Microcalorimetry and Operando X-ray Absorption Spectroscopy. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b01681.
Huie, Matthew M., Bock, David C., Wang, Lei, Marschilok, Amy C., Takeuchi, Kenneth J., & Takeuchi, Esther S. Lithiation of Magnetite (Fe3O4): Analysis Using Isothermal Microcalorimetry and Operando X-ray Absorption Spectroscopy. United States. doi:10.1021/acs.jpcc.8b01681.
Huie, Matthew M., Bock, David C., Wang, Lei, Marschilok, Amy C., Takeuchi, Kenneth J., and Takeuchi, Esther S. Thu . "Lithiation of Magnetite (Fe3O4): Analysis Using Isothermal Microcalorimetry and Operando X-ray Absorption Spectroscopy". United States. doi:10.1021/acs.jpcc.8b01681. https://www.osti.gov/servlets/purl/1466641.
@article{osti_1466641,
title = {Lithiation of Magnetite (Fe3O4): Analysis Using Isothermal Microcalorimetry and Operando X-ray Absorption Spectroscopy},
author = {Huie, Matthew M. and Bock, David C. and Wang, Lei and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S.},
abstractNote = {Conversion electrodes, such as magnetite (Fe3O4), offer high theoretical capacities (>900 mAh/g) because of multiple electron transfer per metal center. Capacity retention for conversion electrodes has been a challenge in part because of the formation of an insulating surface electrolyte interphase (SEI). This paper provides the first detailed analysis of the lithiation of Fe3O4 using isothermal microcalorimetry (IMC). The measured heat flow was compared with heat contributions predicted from heats of formation for the Faradaic reaction, cell polarization, and entropic contributions. The total measured energy output of the cell (7260 J/g Fe3O4) exceeded the heat of reaction predicted for full lithiation of Fe3O4 (5508 J/g). During initial lithiation (3.0–0.86 V), the heat flow was successfully modeled using polarization and entropic contributions. Heat flow at lower voltage (0.86–0.03 V) exceeded the predicted values for iron oxide reduction, consistent with heat generation attributable to electrolyte decomposition and surface electrolyte interphase (SEI). Operando X-ray absorption spectroscopy (XAS) indicated that the oxidation state of the Fe centers deviated from predicted values beginning at ~0.86 V, supportive of SEI onset in this voltage range. Finally and thus, these combined results from electrochemistry, IMC, and XAS indicate parasitic reactions consistent with SEI formation at a moderate voltage and illustrate an approach for deconvoluting Faradaic and non-Faradaic contributions to heat, which should be broadly applicable to the study of energy-storage materials and systems.},
doi = {10.1021/acs.jpcc.8b01681},
journal = {Journal of Physical Chemistry. C},
number = 19,
volume = 122,
place = {United States},
year = {2018},
month = {4}
}

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