Simulations of Lithium-Magnetite Electrodes Incorporating Phase Change

Knehr, Kevin W.; Cama, Christina A.; Brady, Nicholas W.; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.; West, Alan C.

doi:10.1016/j.electacta.2017.04.041

Title: Simulations of Lithium-Magnetite Electrodes Incorporating Phase Change

Journal Article · Sun Apr 09 00:00:00 EDT 2017 · Electrochimica Acta

DOI:https://doi.org/10.1016/j.electacta.2017.04.041· OSTI ID:1376153

Knehr, Kevin W. ^[1]; Cama, Christina A. ^[2]; Brady, Nicholas W. ^[1]; Marschilok, Amy C. ^[3]; Takeuchi, Kenneth J. ^[3]; Takeuchi, Esther S. ^[4]; West, Alan C. ^[1]

Columbia Univ., New York, NY (United States). Department of Chemical Engineering
Stony Brook Univ., NY (United States). Dept. of Chemistry
Stony Brook Univ., NY (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering
Stony Brook Univ., NY (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate

In this work, the phase changes occurring in magnetite (Fe₃O₄) during lithiation and voltage recovery experiments are modeled using a model that simulates the electrochemical performance of a Fe₃O₄ electrode by coupling the lithium transport in the agglomerate and nano-crystal length-scales to thermodynamic and kinetic expressions. Phase changes are described using kinetic expressions based on the Avrami theory for nucleation and growth. Also, simulated results indicate that the slow, linear voltage change observed at long times during the voltage recovery experiments can be attributed to a slow phase change from α-Li_xFe₃O₄ to β-Li₄Fe₃O₄. In addition, the long voltage plateau at ~1.2 V observed during lithiation of electrodes is attributed to conversion from α-Li_xFe₃O₄ to γ-(4 Li₂O + 3 Fe). Simulations for the lithiation of 6 and 32 nm Fe₃O₄ suggest the rate of conversion to γ-(4 Li₂O + 3 Fe) decreases with decreasing crystal size.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; SC0012673

OSTI ID:: 1376153

Alternate ID(s):: OSTI ID: 1413354

Report Number(s):: BNL-114104-2017-JA

Journal Information:: Electrochimica Acta, Vol. 238; ISSN 0013-4686

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 9 works

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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
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. Advanced Functional Materials, Vol. 30, Issue 5 https://doi.org/10.1002/adfm.201907337	journal	November 2019

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