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

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.

doi:10.1002/adfm.201907337

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

Journal Article · Wed Nov 20 04:00:00 EST 2019 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.201907337· OSTI ID:1580038

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Columbia Univ., New York, NY (United States); Univ. of California, Berkeley, CA (United States)
Stony Brook Univ., Stony Brook, NY (United States)
Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Columbia Univ., New York, NY (United States)

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 Fe₃O₄ nanocrystals. Adding complexity, the relaxed state for Li_xFe₃O₄ is observed to be a function of electrochemical discharge rate. The phases occurring on the first OCV plateau for the lithiation of Fe₃O₄ 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_xFe₃O₄. In contrast to the Li–Fe–O bulk phase thermodynamic pathway, Fe0 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 LiFe₃O₄, showing Li+Fe cation disorder. Here, the observed equilibrium concentration for conversion to Fe⁰ 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.

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Research Organization:: 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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division

Grant/Contract Number:: SC0012704; SC0012673; AC02-06CH11357

OSTI ID:: 1580038

Alternate ID(s):: OSTI ID: 1689951
OSTI ID: 1595869

Report Number(s):: BNL--212447-2019-JAAM

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 5 Vol. 30; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Electronic Structure and Elastic Properties of Strongly Correlated Metal Oxides from First Principles: LSDA + U, SIC-LSDA and EELS Study of UO2 and NiO Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. physica status solidi (a), Vol. 166, Issue 1 https://doi.org/10.1002/(SICI)1521-396X(199803)166:1<429::AID-PSSA429>3.0.CO;2-F	journal	March 1998
Insights into Ionic Transport and Structural Changes in Magnetite during Multiple-Electron Transfer Reactions Zhang, Wei; Bock, David C.; Pelliccione, Christopher J. Advanced Energy Materials, Vol. 6, Issue 10 https://doi.org/10.1002/aenm.201502471	journal	March 2016
EXAFS and diffraction Raoux, D. Zeitschrift f�r Physik B Condensed Matter, Vol. 61, Issue 4 https://doi.org/10.1007/BF01303543	journal	December 1985
Structural characterization of the lithiated iron oxides LixFe3O4 and LixFe2O3 (0 Thackeray, M. M.; David, W. I. F.; Goodenough, J. B. Materials Research Bulletin, Vol. 17, Issue 6 https://doi.org/10.1016/0025-5408(82)90029-0	journal	June 1982
Spinel electrodes for lithium batteries — A review Thackeray, M. M.; de Picciotto, L. A.; de Kock, A. Journal of Power Sources, Vol. 21, Issue 1 https://doi.org/10.1016/0378-7753(87)80071-X	journal	August 1987
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 Majzlan, J.; Navrotsky, A.; Schwertmann, U. Geochimica et Cosmochimica Acta, Vol. 68, Issue 5, p. 1049-1059 https://doi.org/10.1016/S0016-7037(03)00371-5	journal	March 2004
Thermo-Calc & DICTRA, computational tools for materials science Andersson, J-O; Helander, Thomas; Höglund, Lars Calphad, Vol. 26, Issue 2 https://doi.org/10.1016/S0364-5916(02)00037-8	journal	June 2002
Variation in the iron oxidation states of magnetite nanocrystals as a function of crystallite size: The impact on electrochemical capacity Menard, Melissa C.; Marschilok, Amy C.; Takeuchi, Kenneth J. Electrochimica Acta, Vol. 94 https://doi.org/10.1016/j.electacta.2013.02.012	journal	April 2013
Simulations of Lithium-Magnetite Electrodes Incorporating Phase Change Knehr, Kevin W.; Cama, Christina A.; Brady, Nicholas W. Electrochimica Acta, Vol. 238 https://doi.org/10.1016/j.electacta.2017.04.041	journal	June 2017
Galvanostatic interruption of lithium insertion into magnetite: Evidence of surface layer formation Brady, Nicholas W.; Knehr, K. W.; Cama, Christina A. Journal of Power Sources, Vol. 321 https://doi.org/10.1016/j.jpowsour.2016.04.117	journal	July 2016
Thermodynamics at the nanoscale: A new approach to the investigation of unique physicochemical properties of nanomaterials Yang, Chun Cheng; Mai, Yiu-Wing Materials Science and Engineering: R: Reports, Vol. 79 https://doi.org/10.1016/j.mser.2014.02.001	journal	May 2014
Equilibria and Rate Phenomena from Atomistic to Mesoscale: Simulation Studies of Magnetite Lininger, Christianna N.; Brady, Nicholas W.; West, Alan C. Accounts of Chemical Research, Vol. 51, Issue 3 https://doi.org/10.1021/acs.accounts.7b00531	journal	March 2018
Energetics of Lithium Insertion into Magnetite, Defective Magnetite, and Maghemite Lininger, Christianna N.; Cama, Christina A.; Takeuchi, Kenneth J. Chemistry of Materials, Vol. 30, Issue 21 https://doi.org/10.1021/acs.chemmater.8b03544	journal	October 2018
Lithiation of Magnetite (Fe ₃ O ₄ ): Analysis Using Isothermal Microcalorimetry and Operando X-ray Absorption Spectroscopy Huie, Matthew M.; Bock, David C.; Wang, Lei The Journal of Physical Chemistry C, Vol. 122, Issue 19 https://doi.org/10.1021/acs.jpcc.8b01681	journal	April 2018
Investigation of Solid Electrolyte Interphase Layer Formation and Electrochemical Reversibility of Magnetite, Fe ₃ O ₄ , Electrodes: A Combined X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy Study Bock, David C.; Waller, Gordon H.; Mansour, Azzam N. The Journal of Physical Chemistry C, Vol. 122, Issue 26 https://doi.org/10.1021/acs.jpcc.8b01970	journal	May 2018
Visualizing non-equilibrium lithiation of spinel oxide via in situ transmission electron microscopy He, Kai; Zhang, Sen; Li, Jing Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11441	journal	May 2016
Computational understanding of Li-ion batteries Urban, Alexander; Seo, Dong-Hwa; Ceder, Gerbrand npj Computational Materials, Vol. 2, Issue 1 https://doi.org/10.1038/npjcompumats.2016.2	journal	March 2016
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-58835-5	journal	February 2020
Magnetosomes could be protective shields against metal stress in magnetotactic bacteria Muñoz, D.; Marcano, L.; Martín-Rodríguez, R. Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-68183-z	journal	July 2020
Lithium and sodium battery cathode materials: computational insights into voltage, diffusion and nanostructural properties Islam, M. Saiful; Fisher, Craig A. J. Chem. Soc. Rev., Vol. 43, Issue 1 https://doi.org/10.1039/C3CS60199D	journal	January 2014
Size dependent behavior of Fe ₃ O ₄ crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation Bock, David C.; Pelliccione, Christopher J.; Zhang, Wei Physical Chemistry Chemical Physics, Vol. 19, Issue 31 https://doi.org/10.1039/C7CP03312E	journal	January 2017
First principles computational materials design for energy storage materials in lithium ion batteries Meng, Ying Shirley; Arroyo-de Dompablo, M. Elena Energy & Environmental Science, Vol. 2, Issue 6 https://doi.org/10.1039/b901825e	journal	January 2009
Structural and magnetic characterization of the lithiated iron oxide Li _x Fe ₃ O ₄ Fontcuberta, J.; Rodríguez, J.; Pernet, M. Journal of Applied Physics, Vol. 59, Issue 6 https://doi.org/10.1063/1.336420	journal	March 1986
JANAF thermochemical tables, 1975 supplement Chase, M. W.; Curnutt, J. L.; Prophet, H. Journal of Physical and Chemical Reference Data, Vol. 4, Issue 1 https://doi.org/10.1063/1.555517	journal	January 1975
Electron states, magnetism, and the Verwey transition in magnetite Zhang, Ze; Satpathy, Sashi Physical Review B, Vol. 44, Issue 24 https://doi.org/10.1103/PhysRevB.44.13319	journal	December 1991
Ab initio curved-wave x-ray-absorption fine structure Mustre de Leon, J.; Rehr, J. J.; Zabinsky, S. I. Physical Review B, Vol. 44, Issue 9 https://doi.org/10.1103/PhysRevB.44.4146	journal	September 1991
Band theory and Mott insulators: Hubbard U instead of Stoner I Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K. Physical Review B, Vol. 44, Issue 3, p. 943-954 https://doi.org/10.1103/PhysRevB.44.943	journal	July 1991
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Generalized gradient approximation for the exchange-correlation hole of a many-electron system Perdew, John P.; Burke, Kieron; Wang, Yue Physical Review B, Vol. 54, Issue 23 https://doi.org/10.1103/PhysRevB.54.16533	journal	December 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Formation enthalpies by mixing GGA and GGA + U calculations Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping Physical Review B, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevB.84.045115	journal	July 2011
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013
IFEFFIT : interactive XAFS analysis and FEFF fitting Newville, Matthew Journal of Synchrotron Radiation, Vol. 8, Issue 2 https://doi.org/10.1107/S0909049500016964	journal	March 2001
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Structure of Spinel Sickafus, Kurt E.; Wills, John M.; Grimes, Norman W. Journal of the American Ceramic Society, Vol. 82, Issue 12 https://doi.org/10.1111/j.1151-2916.1999.tb02241.x	journal	December 1999
Mesoscale Transport in Magnetite Electrodes for Lithium-Ion Batteries Knehr, K. W.; Brady, N. W.; Lininger, C. N. ECS Transactions, Vol. 69, Issue 1 https://doi.org/10.1149/06901.0007ecst	journal	September 2015
Effect of Particle Size on Lithium Intercalation into α-Fe[sub 2]O[sub 3] Larcher, D.; Masquelier, C.; Bonnin, D. Journal of The Electrochemical Society, Vol. 150, Issue 1 https://doi.org/10.1149/1.1528941	journal	January 2003
Nanocrystalline Magnetite: Synthetic Crystallite Size Control and Resulting Magnetic and Electrochemical Properties Zhu, Shali; Marschilok, Amy C.; Takeuchi, Esther S. Journal of The Electrochemical Society, Vol. 157, Issue 11 https://doi.org/10.1149/1.3478667	journal	January 2010
Sensitivity and Limitations of Structures from X-ray and Neutron-Based Diffraction Analyses of Transition Metal Oxide Lithium-Battery Electrodes Liu, Hao; Liu, Haodong; Lapidus, Saul H. Journal of The Electrochemical Society, Vol. 164, Issue 9 https://doi.org/10.1149/2.0271709jes	journal	January 2017
The Crystal Structure of γ-Fe ₂ O ₃ and γ-Al ₂ O ₃ Verwey, E. J. W. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 91, Issue 1-6 https://doi.org/10.1524/zkri.1935.91.1.65	journal	November 1935
Oxidation state and coordination of Fe in minerals: An Fe K- XANES spectroscopic study Wilke, Max; Farges, François; Petit, Pierre-Emmanuel American Mineralogist, Vol. 86, Issue 5-6 https://doi.org/10.2138/am-2001-5-612	journal	May 2001

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