U.S. Department of EnergyOffice of Scientific and Technical Information
Kinetic phase evolution of spinel cobalt oxide during lithiation
Abstract
Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalation reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Harvard Univ., Cambridge, MA (United States)
- Univ. of Maryland, College Park, MD (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1328370
- Report Number(s):
- BNL-112671-2016-JA
Journal ID: ISSN 1936-0851; KC0403020
- Grant/Contract Number:
- SC0012704; SC0012673
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Name: ACS Nano; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 29 ENERGY PLANNING, POLICY, AND ECONOMY; Co3O4 nanoparticles; lithium ion battery; in situ TEM; Center for Functional Nanomaterials
Citation Formats
Li, Jing, He, Kai, Meng, Qingping, Li, Xin, Zhu, Yizhou, Hwang, Sooyeon, Sun, Ke, Gan, Hong, Zhu, Yimei, Mo, Yifei, Stach, Eric A., and Su, Dong. Kinetic phase evolution of spinel cobalt oxide during lithiation. United States: N. p., 2016.
Web. doi:10.1021/acsnano.6b04958.
Li, Jing, He, Kai, Meng, Qingping, Li, Xin, Zhu, Yizhou, Hwang, Sooyeon, Sun, Ke, Gan, Hong, Zhu, Yimei, Mo, Yifei, Stach, Eric A., & Su, Dong. Kinetic phase evolution of spinel cobalt oxide during lithiation. United States. https://doi.org/10.1021/acsnano.6b04958
Li, Jing, He, Kai, Meng, Qingping, Li, Xin, Zhu, Yizhou, Hwang, Sooyeon, Sun, Ke, Gan, Hong, Zhu, Yimei, Mo, Yifei, Stach, Eric A., and Su, Dong. 2016.
"Kinetic phase evolution of spinel cobalt oxide during lithiation". United States. https://doi.org/10.1021/acsnano.6b04958. https://www.osti.gov/servlets/purl/1328370.
@article{osti_1328370,
title = {Kinetic phase evolution of spinel cobalt oxide during lithiation},
author = {Li, Jing and He, Kai and Meng, Qingping and Li, Xin and Zhu, Yizhou and Hwang, Sooyeon and Sun, Ke and Gan, Hong and Zhu, Yimei and Mo, Yifei and Stach, Eric A. and Su, Dong},
abstractNote = {Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalation reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.},
doi = {10.1021/acsnano.6b04958},
url = {https://www.osti.gov/biblio/1328370},
journal = {ACS Nano},
issn = {1936-0851},
number = ,
volume = ,
place = {United States},
year = {Thu Sep 15 00:00:00 EDT 2016},
month = {Thu Sep 15 00:00:00 EDT 2016}
}
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