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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

Abstract

Crystal and atomic structural changes of Fe3O4upon electrochemical (de)lithiation were determined.

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 Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1402423
Alternate Identifier(s):
OSTI ID: 1425178
Report Number(s):
BNL-114433-2017-JA; BNL-114491-2017-JAAM
Journal ID: ISSN 1463-9076; PPCPFQ; TRN: US1703237
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
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. https://doi.org/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. https://doi.org/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 = {Crystal and atomic structural changes of Fe3O4upon electrochemical (de)lithiation were determined.},
doi = {10.1039/c7cp03312e},
journal = {Physical Chemistry Chemical Physics. PCCP},
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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

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Cited by: 39 works
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Figures / Tables:

Figure 1 Figure 1: a) Representative voltage vs. electron equivalent profiles for Fe3O4-S and Fe3O4-C electrodes lithiated and delithiated at a 0.1C rate in the voltage range 0.2 – 3.0 V.

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Works referenced in this record:

Spinel electrodes for lithium batteries — A review
journal, August 1987


A Tunable 3D Nanostructured Conductive Gel Framework Electrode for High-Performance Lithium Ion Batteries
journal, March 2017


What Happens Structurally and Electronically during the Li Conversion Reaction of CoFe 2 O 4 Nanoparticles: An Operando XAS and XRD Investigation
journal, January 2016


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


The Electrochemistry of Fe 3 O 4 /Polypyrrole Composite Electrodes in Lithium-Ion Cells: The Role of Polypyrrole in Capacity Retention
journal, December 2016

  • Bruck, Andrea M.; Gannett, Cara N.; Bock, David C.
  • Journal of The Electrochemical Society, Vol. 164, Issue 1
  • DOI: 10.1149/2.0361701jes

Magnetoresistance of magnetite
journal, February 1998

  • Coey, J. M. D.; Berkowitz, A. E.; Balcells, Ll.
  • Applied Physics Letters, Vol. 72, Issue 6
  • DOI: 10.1063/1.120859

Structural characterization of the lithiated iron oxides LixFe3O4 and LixFe2O3 (0<x<2)
journal, June 1982


Crystallite Size Control and Resulting Electrochemistry of Magnetite, Fe[sub 3]O[sub 4]
journal, January 2009

  • Zhu, Shali; Marschilok, Amy C.; Takeuchi, Esther S.
  • Electrochemical and Solid-State Letters, Vol. 12, Issue 4
  • DOI: 10.1149/1.3078076

Structural and magnetic characterization of the lithiated iron oxide Li x Fe 3 O 4
journal, March 1986

  • Fontcuberta, J.; Rodríguez, J.; Pernet, M.
  • Journal of Applied Physics, Vol. 59, Issue 6
  • DOI: 10.1063/1.336420

Ab initio curved-wave x-ray-absorption fine structure
journal, September 1991


A View from the Inside:  Complexity in the Atomic Scale Ordering of Supported Metal Nanoparticles
journal, December 2001

  • Frenkel, Anatoly I.; Hills, Charles W.; Nuzzo, Ralph G.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 51
  • DOI: 10.1021/jp012769j

SnO reduction in lithium cells: study by X-ray absorption, 119Sn Mössbauer spectroscopy and X-ray diffraction
journal, December 2000


Insights into Ionic Transport and Structural Changes in Magnetite during Multiple-Electron Transfer Reactions
journal, March 2016

  • Zhang, Wei; Bock, David C.; Pelliccione, Christopher J.
  • Advanced Energy Materials, Vol. 6, Issue 10
  • DOI: 10.1002/aenm.201502471

A Review on the Structural Studies of Batteries and Host Materials by X-Ray Absorption Spectroscopy
journal, January 2013


GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013


Mesoscale Transport in Magnetite Electrodes for Lithium-Ion Batteries
journal, September 2015


The Scherrer Formula for X-Ray Particle Size Determination
journal, November 1939


Modeling the Mesoscale Transport of Lithium-Magnetite Electrodes Using Insight from Discharge and Voltage Recovery Experiments
journal, January 2015

  • Knehr, K. W.; Brady, Nicholas W.; Cama, Christina A.
  • Journal of The Electrochemical Society, Vol. 162, Issue 14
  • DOI: 10.1149/2.0961514jes

Determination of crystallite size in a magnetic nanocomposite using extended x-ray absorption fine structure
journal, July 2003

  • Calvin, S.; Miller, M. M.; Goswami, R.
  • Journal of Applied Physics, Vol. 94, Issue 1
  • DOI: 10.1063/1.1581344

In Situ X-ray Absorption Spectroscopy Study of the Capacity Fading Mechanism in Hybrid Sn 3 O 2 (OH) 2 /Graphite Battery Anode Nanomaterials
journal, January 2015

  • Pelliccione, Christopher J.; Timofeeva, Elena V.; Segre, Carlo U.
  • Chemistry of Materials, Vol. 27, Issue 2
  • DOI: 10.1021/cm504101h

Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts
journal, August 2016

  • Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12582

EXAFS study of size dependence of atomic structure in palladium nanoparticles
journal, April 2014

  • Srabionyan, Vasiliy V.; Bugaev, Aram L.; Pryadchenko, Vasiliy V.
  • Journal of Physics and Chemistry of Solids, Vol. 75, Issue 4
  • DOI: 10.1016/j.jpcs.2013.12.012

Theoretical x-ray absorption fine structure standards
journal, July 1991

  • Rehr, J. J.; Mustre de Leon, J.; Zabinsky, S. I.
  • Journal of the American Chemical Society, Vol. 113, Issue 14
  • DOI: 10.1021/ja00014a001

X-ray diffraction and EXAFS analysis of materials for lithium-based rechargeable batteries
journal, December 2013


Lithium insertion into Fe3O4
journal, November 1988


Progress in the theory and interpretation of XANES
journal, January 2005


Electrochemical and In Situ X‐Ray Diffraction Studies of Lithium Intercalation in LixCoO2
journal, January 1992

  • Reimers, Jan N.; Dahn, J. R.
  • Journal of The Electrochemical Society, Vol. 139, Issue 8, p. 2091-2097
  • DOI: 10.1149/1.2221184

In Situ XRD and Electrochemical Study of the Reaction of Lithium with Amorphous Silicon
journal, January 2004

  • Hatchard, T. D.; Dahn, J. R.
  • Journal of The Electrochemical Society, Vol. 151, Issue 6
  • DOI: 10.1149/1.1739217

XLI. Precision measurements of crystal parameters
journal, February 1933

  • Owen, E. A.; Yates, E. L.
  • The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 15, Issue 98
  • DOI: 10.1080/14786443309462199

Holy Grails in Chemistry: Investigating and Understanding Fast Electron/Cation Coupled Transport within Inorganic Ionic Matrices
journal, March 2017

  • Smith, Paul F.; Takeuchi, Kenneth J.; Marschilok, Amy C.
  • Accounts of Chemical Research, Vol. 50, Issue 3
  • DOI: 10.1021/acs.accounts.6b00540

Investigating the Complex Chemistry of Functional Energy Storage Systems: The Need for an Integrative, Multiscale (Molecular to Mesoscale) Perspective
journal, April 2016


In Situ XAFS Study of the Capacity Fading Mechanisms in ZnO Anodes for Lithium-Ion Batteries
journal, January 2015

  • Pelliccione, Christopher J.; Ding, Yujia; Timofeeva, Elena V.
  • Journal of The Electrochemical Society, Vol. 162, Issue 10
  • DOI: 10.1149/2.1011509jes

Effect of Particle Size on Lithium Intercalation into α-Fe[sub 2]O[sub 3]
journal, January 2003

  • Larcher, D.; Masquelier, C.; Bonnin, D.
  • Journal of The Electrochemical Society, Vol. 150, Issue 1
  • DOI: 10.1149/1.1528941

Electron/Ion Transport Enhancer in High Capacity Li-Ion Battery Anodes
journal, September 2016


Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries
journal, September 2000

  • Poizot, P.; Laruelle, S.; Grugeon, S.
  • Nature, Vol. 407, Issue 6803, p. 496-499
  • DOI: 10.1038/35035045

Synthesis and rate performance of Fe3O4-based Cu nanostructured electrodes for Li ion batteries
journal, May 2011


Phase transitions in lithiated Cu2Sb anodes for lithium batteries: an in situ X-ray diffraction study
journal, July 2001

  • Fransson, L. M. L.; Vaughey, J. T.; Benedek, R.
  • Electrochemistry Communications, Vol. 3, Issue 7, p. 317-323
  • DOI: 10.1016/S1388-2481(01)00140-0

Electrochemical discharge of nanocrystalline magnetite: structure analysis using X-ray diffraction and X-ray absorption spectroscopy
journal, January 2013

  • Menard, Melissa C.; Takeuchi, Kenneth J.; Marschilok, Amy C.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 42
  • DOI: 10.1039/c3cp52870g

Visualizing non-equilibrium lithiation of spinel oxide via in situ transmission electron microscopy
journal, May 2016

  • He, Kai; Zhang, Sen; Li, Jing
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11441

X-ray diffraction and extended x-ray absorption fine-structure characterization of nonspherical crystallographic grains in iron thin films
journal, December 2004

  • Jiménez-Villacorta, F.; Muñoz-Martín, A.; Prieto, C.
  • Journal of Applied Physics, Vol. 96, Issue 11
  • DOI: 10.1063/1.1810636

Galvanostatic interruption of lithium insertion into magnetite: Evidence of surface layer formation
journal, July 2016


The structure of magnetite: Symmetry of cubic spinels
journal, March 1986


Electrochemical activity of nanocrystalline Fe3O4 in aprotic Li and Na salt electrolytes
journal, September 2008


Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure
journal, September 1998


In situ X-ray diffraction and X-ray absorption studies of high-rate lithium-ion batteries
journal, January 2001


Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy
journal, January 2016

  • Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 25
  • DOI: 10.1039/C6CP02974D

Comparison of extended x-ray absorption fine structure and Scherrer analysis of x-ray diffraction as methods for determining mean sizes of polydisperse nanoparticles
journal, December 2005

  • Calvin, S.; Luo, S. X.; Caragianis-Broadbridge, C.
  • Applied Physics Letters, Vol. 87, Issue 23
  • DOI: 10.1063/1.2137872

Carbon-Encapsulated Fe 3 O 4 Nanoparticles as a High-Rate Lithium Ion Battery Anode Material
journal, April 2013

  • He, Chunnian; Wu, Shan; Zhao, Naiqin
  • ACS Nano, Vol. 7, Issue 5
  • DOI: 10.1021/nn401059h

Electrochemical and In Situ X-Ray Diffraction Studies of the Reaction of Lithium with Tin Oxide Composites
journal, January 1997

  • Courtney, Ian A.; Dahn, J. R.
  • Journal of The Electrochemical Society, Vol. 144, Issue 6, p. 2045-2052
  • DOI: 10.1149/1.1837740

Magnetite/carbon core-shell nanorods as anode materials for lithium-ion batteries
journal, December 2008


Electrochemical Insertion of Li and Na Ions into Nanocrystalline Fe[sub 3]O[sub 4] and α-Fe[sub 2]O[sub 3] for Rechargeable Batteries
journal, January 2010

  • Komaba, Shinichi; Mikumo, Takashi; Yabuuchi, Naoaki
  • Journal of The Electrochemical Society, Vol. 157, Issue 1
  • DOI: 10.1149/1.3254160

Nanocrystalline Magnetite: Synthetic Crystallite Size Control and Resulting Magnetic and Electrochemical Properties
journal, January 2010

  • Zhu, Shali; Marschilok, Amy C.; Takeuchi, Esther S.
  • Journal of The Electrochemical Society, Vol. 157, Issue 11
  • DOI: 10.1149/1.3478667

Solving the structure of nanoparticles by multiple-scattering EXAFS analysis
journal, May 1999


2D Cross Sectional Analysis and Associated Electrochemistry of Composite Electrodes Containing Dispersed Agglomerates of Nanocrystalline Magnetite, Fe 3 O 4
journal, June 2015

  • Bock, David C.; Kirshenbaum, Kevin C.; Wang, Jiajun
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 24
  • DOI: 10.1021/acsami.5b02478

Toward Uniformly Dispersed Battery Electrode Composite Materials: Characteristics and Performance
journal, January 2016

  • Kwon, Yo Han; Huie, Matthew M.; Choi, Dalsu
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 5
  • DOI: 10.1021/acsami.5b11938

The Chemistry of the Oxychlorination Catalyst: an In Situ, Time-Resolved XANES Study
journal, July 2002


Crystallographic Data 186. Lithium
journal, December 1959

  • Nadler, M. R/.; Kempier, C. P.
  • Analytical Chemistry, Vol. 31, Issue 12
  • DOI: 10.1021/ac60156a007

Dispersion of Nanocrystalline Fe 3 O 4 within Composite Electrodes: Insights on Battery-Related Electrochemistry
journal, April 2016

  • Bock, David C.; Pelliccione, Christopher J.; Zhang, Wei
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 18
  • DOI: 10.1021/acsami.6b01134

IFEFFIT  : interactive XAFS analysis and FEFF fitting
journal, March 2001


Theoretical approaches to x-ray absorption fine structure
journal, July 2000


Variation in the iron oxidation states of magnetite nanocrystals as a function of crystallite size: The impact on electrochemical capacity
journal, April 2013


An X‐Ray Study of the Wüstite (FeO) Solid Solutions
journal, January 1933

  • Jette, Eric R.; Foote, Frank
  • The Journal of Chemical Physics, Vol. 1, Issue 1
  • DOI: 10.1063/1.1749215

Simulations of Lithium-Magnetite Electrodes Incorporating Phase Change
journal, June 2017


EXAFS as a tool to interrogate the size and shape of mono and bimetallic catalyst nanoparticles
journal, January 2010

  • Beale, Andrew M.; Weckhuysen, Bert M.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 21
  • DOI: 10.1039/b925206a

Water-oxidation catalysis by manganese in a geochemical-like cycle
journal, May 2011

  • Hocking, Rosalie K.; Brimblecombe, Robin; Chang, Lan-Yun
  • Nature Chemistry, Vol. 3, Issue 6
  • DOI: 10.1038/nchem.1049

Discovery of Amorphous Iron Hydrides via Novel Quiescent Reaction in Aqueous Solution
journal, April 2020


Magnetosomes could be protective shields against metal stress in magnetotactic bacteria
journal, July 2020


The Chemistry of the Oxychlorination Catalyst: an In Situ, Time-Resolved XANES Study
journal, July 2002


Modeling the Mesoscale Transport of Lithium-Magnetite Electrodes Using Insight from Discharge and Voltage Recovery Experiments
text, January 2015

  • Knehr, K. W.; Brady, Nicholas William; Cama, Christina A.
  • Columbia University
  • DOI: 10.7916/d83r0tcd

Works referencing / citing this record:

The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals
journal, November 2019

  • Lininger, Christianna N.; Bruck, Andrea M.; Lutz, Diana M.
  • Advanced Functional Materials, Vol. 30, Issue 5
  • DOI: 10.1002/adfm.201907337

In Situ Probing Multiple-Scale Structures of Energy Materials for Li-Ion Batteries
journal, May 2019


Synthesis and structural characterization of iron-cementite nanoparticles encapsulated in carbon matrix
journal, January 2020

  • Avakyan, Leon; Manukyan, Aram; Bogdan, Alena
  • Journal of Nanoparticle Research, Vol. 22, Issue 1
  • DOI: 10.1007/s11051-019-4698-8

Multi-electron transfer enabled by topotactic reaction in magnetite
journal, April 2019


Probing enhanced lithium-ion transport kinetics in 2D holey nanoarchitectured electrodes
journal, August 2018


Application of Operando X-ray Diffractometry in Various Aspects of the Investigations of Lithium/Sodium-Ion Batteries
journal, November 2018

  • Zhu, Wen; Wang, Yuesheng; Liu, Dongqiang
  • Energies, Vol. 11, Issue 11
  • DOI: 10.3390/en11112963