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Title: Dynamic imaging of crystalline defects in lithium-manganese oxide electrodes during electrochemical activation to high voltage

Abstract

Crystalline defects are commonly generated in lithium-metal-oxide electrodes during cycling of lithium-ion batteries. Their role in electrochemical reactions is not yet fully understood because, until recently, there has not been an effective operando technique to image dynamic processes at the atomic level. In this study, two types of defects were monitored dynamically during delithiation and concomitant oxidation of oxygen ions by using in situ high-resolution transmission electron microscopy supported by density functional theory calculations. One stacking fault with a fault vector b/6[110] and low mobility contributes minimally to oxygen release from the structure. In contrast, dissociated dislocations with Burgers vector of c/2[001] have high gliding and transverse mobility; they lead to the formation, transport and release subsequently of oxygen related species at the surface of the electrode particles. This work advances the scientific understanding of how oxygen participates and the structural response during the activation process at high potentials.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [3];  [4];  [4];  [5]
  1. Wuhan Univ. of Technology, Hubei (China); Shanghai Univ., Shanghai (China); Northwestern Univ., Evanston, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States); Harvard Univ., Cambridge, MA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Northwestern Univ., Evanston, IL (United States)
  5. Wuhan Univ. of Technology, Hubei (China); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1510310
Alternate Identifier(s):
OSTI ID: 1542887
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Qianqian, Yao, Zhenpeng, Lee, Eungje, Xu, Yaobin, Thackeray, Michael M., Wolverton, Chris, Dravid, Vinayak P., and Wu, Jinsong. Dynamic imaging of crystalline defects in lithium-manganese oxide electrodes during electrochemical activation to high voltage. United States: N. p., 2019. Web. doi:10.1038/s41467-019-09408-2.
Li, Qianqian, Yao, Zhenpeng, Lee, Eungje, Xu, Yaobin, Thackeray, Michael M., Wolverton, Chris, Dravid, Vinayak P., & Wu, Jinsong. Dynamic imaging of crystalline defects in lithium-manganese oxide electrodes during electrochemical activation to high voltage. United States. doi:10.1038/s41467-019-09408-2.
Li, Qianqian, Yao, Zhenpeng, Lee, Eungje, Xu, Yaobin, Thackeray, Michael M., Wolverton, Chris, Dravid, Vinayak P., and Wu, Jinsong. Fri . "Dynamic imaging of crystalline defects in lithium-manganese oxide electrodes during electrochemical activation to high voltage". United States. doi:10.1038/s41467-019-09408-2. https://www.osti.gov/servlets/purl/1510310.
@article{osti_1510310,
title = {Dynamic imaging of crystalline defects in lithium-manganese oxide electrodes during electrochemical activation to high voltage},
author = {Li, Qianqian and Yao, Zhenpeng and Lee, Eungje and Xu, Yaobin and Thackeray, Michael M. and Wolverton, Chris and Dravid, Vinayak P. and Wu, Jinsong},
abstractNote = {Crystalline defects are commonly generated in lithium-metal-oxide electrodes during cycling of lithium-ion batteries. Their role in electrochemical reactions is not yet fully understood because, until recently, there has not been an effective operando technique to image dynamic processes at the atomic level. In this study, two types of defects were monitored dynamically during delithiation and concomitant oxidation of oxygen ions by using in situ high-resolution transmission electron microscopy supported by density functional theory calculations. One stacking fault with a fault vector b/6[110] and low mobility contributes minimally to oxygen release from the structure. In contrast, dissociated dislocations with Burgers vector of c/2[001] have high gliding and transverse mobility; they lead to the formation, transport and release subsequently of oxygen related species at the surface of the electrode particles. This work advances the scientific understanding of how oxygen participates and the structural response during the activation process at high potentials.},
doi = {10.1038/s41467-019-09408-2},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Fig. 1 Fig. 1 : The exitance form and motion of stacking faults in lithium extraction process. a Transmission electron microscopy (TEM) image of (001) stacking faults in pristine Li2MnO3 with fault vector of b/6[110], which are confirmed by a corresponding electron diffraction (b). During delithiation, the gliding of the b/6[110] partialmore » dislocation shears the stacking of the (001) plane from ABC1 in pristine Li2MnO3 (c), to AC2C1 (d), and AC2B (e) after 0, 301, and 408 s, respectively; corresponding density functional theory (DFT) structural models are provided of pristine Li2MnO3 (f) and generated defects (g, h), respectively. The scale bar is 5 nm« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.