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Lithiation of Magnetite (Fe3O4): Analysis Using Isothermal Microcalorimetry and Operando X-ray Absorption Spectroscopy

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [4];  [5];  [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
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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.
Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M); Stony Brook Univ., NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012673; SC0012704
OSTI ID:
1466641
Report Number(s):
BNL--207937-2018-JAAM
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 19 Vol. 122; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals journal November 2019
Revisiting the Electrochemical Lithiation Mechanism of Aluminum and the Role of Li‐rich Phases (Li 1+ x Al) on Capacity Fading journal April 2019
Revisiting the Electrochemical Lithiation Mechanism of Aluminum and the Role of Li‐rich Phases (Li 1+ x Al) on Capacity Fading journal May 2019

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