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Title: Kinetic Phase Evolution of Spinel Cobalt Oxide during Lithiation

Authors:
 [1];  [2];  [2];  [3];  [4];  [2];  [2];  [2];  [2];  [4];  [2];  [2]
  1. Brookhaven National Laboratory, Upton, New York 11973, United States; Department of Materials Science and Engineering, Stony Brook University, Stony Brook, New York 11720, United States
  2. Brookhaven National Laboratory, Upton, New York 11973, United States
  3. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States
  4. Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742, United States
Publication Date:
Research Org.:
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)
OSTI Identifier:
1388494
DOE Contract Number:
SC0012673
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Nano; Journal Volume: 10; Journal Issue: 10; Related Information: m2M partners with Stony Brook University (lead); Brookhaven National Laboratory; Columbia University; Georgia Institute of Technology; Oak Ridge National Laboratory; Rensselaer Polytechnic Institute; University of California, Berkeley; University of North Carolina at Chapel Hill
Country of Publication:
United States
Language:
English
Subject:
energy storage (including batteries and capacitors), charge transport, mesostructured materials

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. 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., and Su, Dong. Tue . "Kinetic Phase Evolution of Spinel Cobalt Oxide during Lithiation". United States. doi:10.1021/acsnano.6b04958.
@article{osti_1388494,
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 = {},
doi = {10.1021/acsnano.6b04958},
journal = {ACS Nano},
number = 10,
volume = 10,
place = {United States},
year = {Tue Sep 20 00:00:00 EDT 2016},
month = {Tue Sep 20 00:00:00 EDT 2016}
}
  • 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 intercalationmore » 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.« less
  • In this study, the structural changes of FeOxF2-x/C during the first discharge and recharge cycles were studied by ex situ electron microscopy techniques including annular dark field scanning transmission electron microscopy (DF-STEM) imaging, selected area electron diffraction (SAED) and electron energy loss spectroscopy (EELS) as well as by in situ X-ray absorption spectroscopy (XAS). The evolution of the valence state of Fe was determined by combined EELS using the Fe-L edge and XAS using the Fe-K edge. The results of this investigation show that the conversion reaction path during 1st lithiation is very different from the re-conversion path during 1stmore » delithiation. During lithiation, intercalation is first observed followed by conversion into a lithiated rocksalt (Li–Fe–O–F) structure, and metallic Fe and LiF phases. During delithiation, the rocksalt phase does not disappear, but co-exists with an amorphous (rutile type) phase formed initially by the reaction of LiF and Fe. However, a de-intercalation stage is still observed at the end of reconversion similar to a single phase process despite the coexistence of these two (rocksalt and amorphous) phases.« less