Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals

Abstract

Abstract Nanostructured materials can exhibit phase change behavior that deviates from the macroscopic phase behavior. This is exemplified by the ambiguity for the equilibrium phases driving the first open‐circuit voltage (OCV) plateau for the lithiation of Fe 3 O 4 nanocrystals. Adding complexity, the relaxed state for Li x Fe 3 O 4 is observed to be a function of electrochemical discharge rate. The phases occurring on the first OCV plateau for the lithiation of Fe 3 O 4 nanocrystals have been investigated with density functional theory (DFT) through the evaluation of stable, or hypothesized metastable, reaction pathways. Hypotheses are evaluated through the systematic combined refinement with X‐ray absorption spectroscopy (XAS), X‐ray diffraction (XRD) measurements, neutron‐diffraction measurements, and the measured OCV on samples lithiated to x = 2.0, 3.0, and 4.0 in Li x Fe 3 O 4 . In contrast to the Li–Fe–O bulk phase thermodynamic pathway, Fe 0 is not observed as a product on the first OCV plateau for 10–45 nm nanocrystals. The phase most consistent with the systematic refinement is LiFe 3 O 4 , showing Li+Fe cation disorder. The observed equilibrium concentration for conversion to Fe 0 occurs at x = 4.0. These definitive phasemore » identifications rely heavily on the systematic combined refinement approach, which is broadly applicable to other nano‐ and mesoscaled systems that have suffered from difficult or crystallite‐size‐dependent phase identification.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [5]
+ Show Author Affiliations
  1. Columbia Univ., New York, NY (United States); Univ. of California, Berkeley, CA (United States)
  2. Stony Brook Univ., Stony Brook, NY (United States)
  3. Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Columbia Univ., New York, NY (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1580038
Alternate Identifier(s):
OSTI ID: 1595869
Report Number(s):
BNL-212447-2019-JAAM
Journal ID: ISSN 1616-301X
Grant/Contract Number:  
SC0012704; SC0012673; C090171; ACI-1548562; TG-DMR160174; TG-DMR160128; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 5; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; batteries; lithium ions; nanomaterials; phase identification; thermodynamics

Citation Formats

Lininger, Christianna N., Bruck, Andrea M., Lutz, Diana M., Housel, Lisa M., Takeuchi, Kenneth J., Takeuchi, Esther S., Huq, Ashfia, Marschilok, Amy C., and West, Alan C. The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals. United States: N. p., 2019. Web. doi:10.1002/adfm.201907337.
Copy to clipboard
Lininger, Christianna N., Bruck, Andrea M., Lutz, Diana M., Housel, Lisa M., Takeuchi, Kenneth J., Takeuchi, Esther S., Huq, Ashfia, Marschilok, Amy C., & West, Alan C. The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals. United States. https://doi.org/10.1002/adfm.201907337
Copy to clipboard
Lininger, Christianna N., Bruck, Andrea M., Lutz, Diana M., Housel, Lisa M., Takeuchi, Kenneth J., Takeuchi, Esther S., Huq, Ashfia, Marschilok, Amy C., and West, Alan C. Wed . "The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals". United States. https://doi.org/10.1002/adfm.201907337. https://www.osti.gov/servlets/purl/1580038.
Copy to clipboard
@article{osti_1580038,
title = {The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals},
author = {Lininger, Christianna N. and Bruck, Andrea M. and Lutz, Diana M. and Housel, Lisa M. and Takeuchi, Kenneth J. and Takeuchi, Esther S. and Huq, Ashfia and Marschilok, Amy C. and West, Alan C.},
abstractNote = {Abstract Nanostructured materials can exhibit phase change behavior that deviates from the macroscopic phase behavior. This is exemplified by the ambiguity for the equilibrium phases driving the first open‐circuit voltage (OCV) plateau for the lithiation of Fe 3 O 4 nanocrystals. Adding complexity, the relaxed state for Li x Fe 3 O 4 is observed to be a function of electrochemical discharge rate. The phases occurring on the first OCV plateau for the lithiation of Fe 3 O 4 nanocrystals have been investigated with density functional theory (DFT) through the evaluation of stable, or hypothesized metastable, reaction pathways. Hypotheses are evaluated through the systematic combined refinement with X‐ray absorption spectroscopy (XAS), X‐ray diffraction (XRD) measurements, neutron‐diffraction measurements, and the measured OCV on samples lithiated to x = 2.0, 3.0, and 4.0 in Li x Fe 3 O 4 . In contrast to the Li–Fe–O bulk phase thermodynamic pathway, Fe 0 is not observed as a product on the first OCV plateau for 10–45 nm nanocrystals. The phase most consistent with the systematic refinement is LiFe 3 O 4 , showing Li+Fe cation disorder. The observed equilibrium concentration for conversion to Fe 0 occurs at x = 4.0. These definitive phase identifications rely heavily on the systematic combined refinement approach, which is broadly applicable to other nano‐ and mesoscaled systems that have suffered from difficult or crystallite‐size‐dependent phase identification.},
doi = {10.1002/adfm.201907337},
journal = {Advanced Functional Materials},
number = 5,
volume = 30,
place = {United States},
year = {Wed Nov 20 00:00:00 EST 2019},
month = {Wed Nov 20 00:00:00 EST 2019}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/adfm.201907337
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

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

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

Structure of Spinel
journal, December 1999

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

Generalized gradient approximation for the exchange-correlation hole of a many-electron system
journal, December 1996

Projector augmented-wave method
journal, December 1994

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

EXAFS and diffraction
journal, December 1985

  • Raoux, D.
  • Zeitschrift f�r Physik B Condensed Matter, Vol. 61, Issue 4
  • DOI: 10.1007/BF01303543

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

Thermodynamics of iron oxides: Part III. Enthalpies of formation and stability of ferrihydrite (∼Fe(OH)3), schwertmannite (∼FeO(OH)3/4(SO4)1/8), and ε-Fe2O3
journal, March 2004

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

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

Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020

Oxidation state and coordination of Fe in minerals: An Fe K- XANES spectroscopic study
journal, May 2001

  • Wilke, Max; Farges, François; Petit, Pierre-Emmanuel
  • American Mineralogist, Vol. 86, Issue 5-6
  • DOI: 10.2138/am-2001-5-612

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

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Thermodynamics at the nanoscale: A new approach to the investigation of unique physicochemical properties of nanomaterials
journal, May 2014

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

JANAF thermochemical tables, 1975 supplement
journal, January 1975

  • Chase, M. W.; Curnutt, J. L.; Prophet, H.
  • Journal of Physical and Chemical Reference Data, Vol. 4, Issue 1
  • DOI: 10.1063/1.555517

Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991

  • Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
  • Physical Review B, Vol. 44, Issue 3, p. 943-954
  • DOI: 10.1103/PhysRevB.44.943

First principles computational materials design for energy storage materials in lithium ion batteries
journal, January 2009

  • Meng, Ying Shirley; Arroyo-de Dompablo, M. Elena
  • Energy & Environmental Science, Vol. 2, Issue 6
  • DOI: 10.1039/b901825e

Computational understanding of Li-ion batteries
journal, March 2016

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

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

Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021

Equilibria and Rate Phenomena from Atomistic to Mesoscale: Simulation Studies of Magnetite
journal, March 2018

  • Lininger, Christianna N.; Brady, Nicholas W.; West, Alan C.
  • Accounts of Chemical Research, Vol. 51, Issue 3
  • DOI: 10.1021/acs.accounts.7b00531

Energetics of Lithium Insertion into Magnetite, Defective Magnetite, and Maghemite
journal, October 2018

  • Lininger, Christianna N.; Cama, Christina A.; Takeuchi, Kenneth J.
  • Chemistry of Materials, Vol. 30, Issue 21
  • DOI: 10.1021/acs.chemmater.8b03544

Electron states, magnetism, and the Verwey transition in magnetite
journal, December 1991

Sensitivity and Limitations of Structures from X-ray and Neutron-Based Diffraction Analyses of Transition Metal Oxide Lithium-Battery Electrodes
journal, January 2017

  • Liu, Hao; Liu, Haodong; Lapidus, Saul H.
  • Journal of The Electrochemical Society, Vol. 164, Issue 9
  • DOI: 10.1149/2.0271709jes

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

Lithium and sodium battery cathode materials: computational insights into voltage, diffusion and nanostructural properties
journal, January 2014

  • Islam, M. Saiful; Fisher, Craig A. J.
  • Chem. Soc. Rev., Vol. 43, Issue 1
  • DOI: 10.1039/C3CS60199D

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

Thermo-Calc & DICTRA, computational tools for materials science
journal, June 2002

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

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

Lithiation of Magnetite (Fe 3 O 4 ): Analysis Using Isothermal Microcalorimetry and Operando X-ray Absorption Spectroscopy
journal, April 2018

  • Huie, Matthew M.; Bock, David C.; Wang, Lei
  • The Journal of Physical Chemistry C, Vol. 122, Issue 19
  • DOI: 10.1021/acs.jpcc.8b01681

The Crystal Structure of γ-Fe 2 O 3 and γ-Al 2 O 3
journal, November 1935

  • Verwey, E. J. W.
  • Zeitschrift für Kristallographie - Crystalline Materials, Vol. 91, Issue 1-6
  • DOI: 10.1524/zkri.1935.91.1.65
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: