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Title: Discharge, Relaxation, and Charge Model for the Lithium Trivanadate Electrode: Reactions, Phase Change, and Transport

The electrochemical behavior of lithium trivanadate (LiV 3O 8) during lithiation, delithiation, and voltage recovery experiments is simulated using a crystal-scale model that accounts for solid-state diffusion, charge-transfer kinetics, and phase transformations. The kinetic expression for phase change was modeled using an approach inspired by the Avrami formulation for nucleation and growth. Numerical results indicate that the solid-state diffusion coefficient of lithium in LiV 3O 8 is ~ 10 -13 cm 2 s -1 and the equilibrium compositions in the two phase region (~2.5 V) are Li 2.5V 3O 8:Li 4V 3O 8. Agreement between the simulated and experimental results is excellent. Relative to the lithiation curves, the experimental delithiation curves show significantly less overpotential and at low levels of lithiation (end of charge). Simulations are only able to capture this result by assuming that the solid-state mass-transfer resistance is less during delithiation. The proposed rationale for this difference is that the (100) face is inactive during lithiation, but active during delithiation. Finally, by assuming non-instantaneous phase-change kinetics, estimates are made for the overpotential due to imperfect phase change (supersaturation).
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [4] ;  [4] ;  [5] ;  [6]
  1. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
  2. Stony Brook Univ., NY (United States). Dept. of Chemistry
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Stony Brook Univ., NY (United States). Dept. of Chemistry; Stony Brook Univ., NY (United States). Dept. of Materials Science and Engineering
  5. Stony Brook Univ., NY (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States). Dept. of Materials Science and Engineering
  6. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering; Columbia Univ., New York, NY (United States). Dept. of Earth and Environmental Engineering
Publication Date:
Report Number(s):
BNL-113780-2017-JA
Journal ID: ISSN 0013-4651
Grant/Contract Number:
SC0012704; SC0012673; 1144155
Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 163; Journal Issue: 14; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Cathode phase change; Lithium Trivanadate; Battery simulations; Voltage recovery; Shrinking-core; Phase change resistance; Nucleation and growth; Lithium-ion batteries; Current interrupt
OSTI Identifier:
1354637

Brady, Nicholas W., Zhang, Qing, Knehr, K. W., Liu, Ping, Marschilok, Amy C., J. Takeuchi, Kenneth, Takeuchi, Esther S., and West, Alan C.. Discharge, Relaxation, and Charge Model for the Lithium Trivanadate Electrode: Reactions, Phase Change, and Transport. United States: N. p., Web. doi:10.1149/2.0341614jes.
Brady, Nicholas W., Zhang, Qing, Knehr, K. W., Liu, Ping, Marschilok, Amy C., J. Takeuchi, Kenneth, Takeuchi, Esther S., & West, Alan C.. Discharge, Relaxation, and Charge Model for the Lithium Trivanadate Electrode: Reactions, Phase Change, and Transport. United States. doi:10.1149/2.0341614jes.
Brady, Nicholas W., Zhang, Qing, Knehr, K. W., Liu, Ping, Marschilok, Amy C., J. Takeuchi, Kenneth, Takeuchi, Esther S., and West, Alan C.. 2016. "Discharge, Relaxation, and Charge Model for the Lithium Trivanadate Electrode: Reactions, Phase Change, and Transport". United States. doi:10.1149/2.0341614jes. https://www.osti.gov/servlets/purl/1354637.
@article{osti_1354637,
title = {Discharge, Relaxation, and Charge Model for the Lithium Trivanadate Electrode: Reactions, Phase Change, and Transport},
author = {Brady, Nicholas W. and Zhang, Qing and Knehr, K. W. and Liu, Ping and Marschilok, Amy C. and J. Takeuchi, Kenneth and Takeuchi, Esther S. and West, Alan C.},
abstractNote = {The electrochemical behavior of lithium trivanadate (LiV3O8) during lithiation, delithiation, and voltage recovery experiments is simulated using a crystal-scale model that accounts for solid-state diffusion, charge-transfer kinetics, and phase transformations. The kinetic expression for phase change was modeled using an approach inspired by the Avrami formulation for nucleation and growth. Numerical results indicate that the solid-state diffusion coefficient of lithium in LiV3O8 is ~ 10-13 cm2 s-1 and the equilibrium compositions in the two phase region (~2.5 V) are Li2.5V3O8:Li4V3O8. Agreement between the simulated and experimental results is excellent. Relative to the lithiation curves, the experimental delithiation curves show significantly less overpotential and at low levels of lithiation (end of charge). Simulations are only able to capture this result by assuming that the solid-state mass-transfer resistance is less during delithiation. The proposed rationale for this difference is that the (100) face is inactive during lithiation, but active during delithiation. Finally, by assuming non-instantaneous phase-change kinetics, estimates are made for the overpotential due to imperfect phase change (supersaturation).},
doi = {10.1149/2.0341614jes},
journal = {Journal of the Electrochemical Society},
number = 14,
volume = 163,
place = {United States},
year = {2016},
month = {10}
}

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