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

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/2.0341614jes· OSTI ID:1354637
 [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
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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).

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); National Science Foundation (NSF)
Grant/Contract Number:
SC0012704; SC0012673; 1144155
OSTI ID:
1354637
Report Number(s):
BNL-113780-2017-JA
Journal Information:
Journal of the Electrochemical Society, Vol. 163, Issue 14; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

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Cited By (2)

Quantitative Parameter Estimation, Model Selection, and Variable Selection in Battery Science journal August 2019
Operando Study of LiV 3 O 8 Cathode: Coupling EDXRD Measurements to Simulations journal January 2018

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Related Subjects

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