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Title: Simulations of Lithium-Magnetite Electrodes Incorporating Phase Change

In this work, the phase changes occurring in magnetite (Fe 3O 4) during lithiation and voltage recovery experiments are modeled using a model that simulates the electrochemical performance of a Fe 3O 4 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 xFe 3O 4 to β-Li 4Fe 3O 4. In addition, the long voltage plateau at ~1.2 V observed during lithiation of electrodes is attributed to conversion from α-Li xFe 3O 4 to γ-(4 Li 2O + 3 Fe). Simulations for the lithiation of 6 and 32 nm Fe 3O 4 suggest the rate of conversion to γ-(4 Li 2O + 3 Fe) decreases with decreasing crystal size.
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [3] ;  [4] ;  [1]
  1. Columbia Univ., New York, NY (United States). Department of Chemical Engineering
  2. Stony Brook Univ., NY (United States). Dept. of Chemistry
  3. Stony Brook Univ., NY (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering
  4. 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
Publication Date:
Report Number(s):
BNL-114104-2017-JA
Journal ID: ISSN 0013-4686
Grant/Contract Number:
SC0012704; SC0012673
Type:
Accepted Manuscript
Journal Name:
Electrochimica Acta
Additional Journal Information:
Journal Volume: 238; Journal ID: ISSN 0013-4686
Publisher:
Elsevier
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; Nucleation and growth; voltage recovery; current interrupt; lithium-ion batteries; Avrami
OSTI Identifier:
1376153
Alternate Identifier(s):
OSTI ID: 1413354

Knehr, Kevin W., Cama, Christina A., Brady, Nicholas W., Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., and West, Alan C.. Simulations of Lithium-Magnetite Electrodes Incorporating Phase Change. United States: N. p., Web. doi:10.1016/j.electacta.2017.04.041.
Knehr, Kevin W., Cama, Christina A., Brady, Nicholas W., Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., & West, Alan C.. Simulations of Lithium-Magnetite Electrodes Incorporating Phase Change. United States. doi:10.1016/j.electacta.2017.04.041.
Knehr, Kevin W., Cama, Christina A., Brady, Nicholas W., Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., and West, Alan C.. 2017. "Simulations of Lithium-Magnetite Electrodes Incorporating Phase Change". United States. doi:10.1016/j.electacta.2017.04.041. https://www.osti.gov/servlets/purl/1376153.
@article{osti_1376153,
title = {Simulations of Lithium-Magnetite Electrodes Incorporating Phase Change},
author = {Knehr, Kevin W. and Cama, Christina A. and Brady, Nicholas W. and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S. and West, Alan C.},
abstractNote = {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-LixFe3O4 to β-Li4Fe3O4. In addition, the long voltage plateau at ~1.2 V observed during lithiation of electrodes is attributed to conversion from α-LixFe3O4 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.},
doi = {10.1016/j.electacta.2017.04.041},
journal = {Electrochimica Acta},
number = ,
volume = 238,
place = {United States},
year = {2017},
month = {4}
}