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Title: Size dependent behavior of Fe 3O 4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation

Abstract

Here, the iron oxide magnetite, Fe 3O 4, is a promising conversion type lithium ion battery anode material due to its high natural abundance, low cost and high theoretical capacity. While the close packing of ions in the inverse spinel structure of Fe 3O 4 enables high energy density, it also limits the kinetics of lithium ion diffusion in the material. Nanosizing of Fe 3O 4 to reduce the diffusion path length is an effective strategy for overcoming this issue and results in improved rate capability. However, the impact of nanosizing on the multiple structural transformations that occur during the electrochemical (de)lithiation reaction in Fe 3O 4 is poorly understood. In this study, the influence of crystallite size on the lithiation-conversion mechanisms in Fe 3O 4 is investigated using complementary X-ray techniques along with transmission electron microscopy (TEM) and continuum level simulations on electrodes of two different Fe 3O 4 crystallite sizes. In situ X-ray diffraction (XRD) measurements were utilized to track the changes to the crystalline phases during (de)lithiation. X-ray absorption spectroscopy (XAS) measurements at multiple points during the (de)lithiation processes provided local electronic and atomic structural information. Tracking the crystalline and nanocrystalline phases during the first (de)lithiation providesmore » experimental evidence that (1) the lithiation mechanism is non-uniform and dependent on crystallite size, where increased Li + diffusion length in larger crystals results in conversion to Fe 0 metal while insertion of Li + into spinel-Fe 3O 4 is still occurring, and (2) the disorder and size of the Fe metal domains formed when either material is fully lithiated impacts the homogeneity of the FeO phase formed during the subsequent delithiation.« less

Authors:
 [1];  [1];  [1];  [2];  [3];  [3];  [1];  [4];  [2]; ORCiD logo [5];  [2]; ORCiD logo [2]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Stony Brook Univ., Stony Brook, NY (United States)
  3. Columbia Univ., New York, NY (United States)
  4. American Physical Society, Ridge, NY (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1402423
Report Number(s):
BNL-114433-2017-JA
Journal ID: ISSN 1463-9076; PPCPFQ; TRN: US1703237
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 31; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Bock, David C., Pelliccione, Christopher J., Zhang, Wei, Timoshenko, Janis, Knehr, K. W., West, Alan C., Wang, Feng, Li, Yan, Frenkel, Anatoly I., Takeuchi, Esther S., Takeuchi, Kenneth J., and Marschilok, Amy C. Size dependent behavior of Fe3O4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation. United States: N. p., 2017. Web. doi:10.1039/c7cp03312e.
Bock, David C., Pelliccione, Christopher J., Zhang, Wei, Timoshenko, Janis, Knehr, K. W., West, Alan C., Wang, Feng, Li, Yan, Frenkel, Anatoly I., Takeuchi, Esther S., Takeuchi, Kenneth J., & Marschilok, Amy C. Size dependent behavior of Fe3O4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation. United States. doi:10.1039/c7cp03312e.
Bock, David C., Pelliccione, Christopher J., Zhang, Wei, Timoshenko, Janis, Knehr, K. W., West, Alan C., Wang, Feng, Li, Yan, Frenkel, Anatoly I., Takeuchi, Esther S., Takeuchi, Kenneth J., and Marschilok, Amy C. Mon . "Size dependent behavior of Fe3O4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation". United States. doi:10.1039/c7cp03312e. https://www.osti.gov/servlets/purl/1402423.
@article{osti_1402423,
title = {Size dependent behavior of Fe3O4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation},
author = {Bock, David C. and Pelliccione, Christopher J. and Zhang, Wei and Timoshenko, Janis and Knehr, K. W. and West, Alan C. and Wang, Feng and Li, Yan and Frenkel, Anatoly I. and Takeuchi, Esther S. and Takeuchi, Kenneth J. and Marschilok, Amy C.},
abstractNote = {Here, the iron oxide magnetite, Fe3O4, is a promising conversion type lithium ion battery anode material due to its high natural abundance, low cost and high theoretical capacity. While the close packing of ions in the inverse spinel structure of Fe3O4 enables high energy density, it also limits the kinetics of lithium ion diffusion in the material. Nanosizing of Fe3O4 to reduce the diffusion path length is an effective strategy for overcoming this issue and results in improved rate capability. However, the impact of nanosizing on the multiple structural transformations that occur during the electrochemical (de)lithiation reaction in Fe3O4 is poorly understood. In this study, the influence of crystallite size on the lithiation-conversion mechanisms in Fe3O4 is investigated using complementary X-ray techniques along with transmission electron microscopy (TEM) and continuum level simulations on electrodes of two different Fe3O4 crystallite sizes. In situ X-ray diffraction (XRD) measurements were utilized to track the changes to the crystalline phases during (de)lithiation. X-ray absorption spectroscopy (XAS) measurements at multiple points during the (de)lithiation processes provided local electronic and atomic structural information. Tracking the crystalline and nanocrystalline phases during the first (de)lithiation provides experimental evidence that (1) the lithiation mechanism is non-uniform and dependent on crystallite size, where increased Li+ diffusion length in larger crystals results in conversion to Fe0 metal while insertion of Li+ into spinel-Fe3O4 is still occurring, and (2) the disorder and size of the Fe metal domains formed when either material is fully lithiated impacts the homogeneity of the FeO phase formed during the subsequent delithiation.},
doi = {10.1039/c7cp03312e},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 31,
volume = 19,
place = {United States},
year = {Mon Jul 17 00:00:00 EDT 2017},
month = {Mon Jul 17 00:00:00 EDT 2017}
}

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