skip to main content

DOE PAGESDOE PAGES

This content will become publicly available on July 16, 2019

Title: Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging

Lithium-rich layered oxides (LRLO) are among the leading candidates for the next-generation cathode material for energy storage, delivering 50% excess capacity over commercially used compounds. Despite excellent prospects, voltage fade has prevented effective use of the excess capacity, and a major challenge has been a lack of understanding of the mechanisms underpinning the voltage fade. Here, using operando three-dimensional Bragg coherent diffractive imaging, we directly observe the nucleation of a mobile dislocation network in LRLO nanoparticles. The dislocations form more readily in LRLO as compared with a classical layered oxide, suggesting a link between the defects and voltage fade. We show microscopically how the formation of partial dislocations contributes to the voltage fade. The insights allow us to design and demonstrate an effective method to recover the original high-voltage functionality. Furthermore, our findings reveal that the voltage fade in LRLO is reversible and call for new paradigms for improved design of oxygen-redox active materials.
Authors:
 [1] ;  [2] ;  [2] ;  [2] ;  [2] ;  [2] ; ORCiD logo [3] ;  [3] ;  [3] ;  [4] ;  [2] ;  [2] ;  [2] ;  [5] ;  [6] ;  [7] ;  [7] ;  [2] ;  [2]
  1. Univ. of California-San Diego, La Jolla, CA (United States); Cornell Univ., Ithaca, NY (United States)
  2. Univ. of California-San Diego, La Jolla, CA (United States)
  3. Chinese Academy of Sciences, Zhejiang (China)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  6. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); European XFEL GmbH, Schenefeld (Germany)
  7. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 3; Journal Issue: 8; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE
OSTI Identifier:
1481914

Singer, A., Zhang, M., Hy, S., Cela, D., Fang, C., Wynn, T. A., Qiu, B., Xia, Y., Liu, Z., Ulvestad, A., Hua, N., Wingert, J., Liu, H., Sprung, M., Zozulya, A. V., Maxey, E., Harder, R., Meng, Y. S., and Shpyrko, O. G.. Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging. United States: N. p., Web. doi:10.1038/s41560-018-0184-2.
Singer, A., Zhang, M., Hy, S., Cela, D., Fang, C., Wynn, T. A., Qiu, B., Xia, Y., Liu, Z., Ulvestad, A., Hua, N., Wingert, J., Liu, H., Sprung, M., Zozulya, A. V., Maxey, E., Harder, R., Meng, Y. S., & Shpyrko, O. G.. Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging. United States. doi:10.1038/s41560-018-0184-2.
Singer, A., Zhang, M., Hy, S., Cela, D., Fang, C., Wynn, T. A., Qiu, B., Xia, Y., Liu, Z., Ulvestad, A., Hua, N., Wingert, J., Liu, H., Sprung, M., Zozulya, A. V., Maxey, E., Harder, R., Meng, Y. S., and Shpyrko, O. G.. 2018. "Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging". United States. doi:10.1038/s41560-018-0184-2.
@article{osti_1481914,
title = {Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging},
author = {Singer, A. and Zhang, M. and Hy, S. and Cela, D. and Fang, C. and Wynn, T. A. and Qiu, B. and Xia, Y. and Liu, Z. and Ulvestad, A. and Hua, N. and Wingert, J. and Liu, H. and Sprung, M. and Zozulya, A. V. and Maxey, E. and Harder, R. and Meng, Y. S. and Shpyrko, O. G.},
abstractNote = {Lithium-rich layered oxides (LRLO) are among the leading candidates for the next-generation cathode material for energy storage, delivering 50% excess capacity over commercially used compounds. Despite excellent prospects, voltage fade has prevented effective use of the excess capacity, and a major challenge has been a lack of understanding of the mechanisms underpinning the voltage fade. Here, using operando three-dimensional Bragg coherent diffractive imaging, we directly observe the nucleation of a mobile dislocation network in LRLO nanoparticles. The dislocations form more readily in LRLO as compared with a classical layered oxide, suggesting a link between the defects and voltage fade. We show microscopically how the formation of partial dislocations contributes to the voltage fade. The insights allow us to design and demonstrate an effective method to recover the original high-voltage functionality. Furthermore, our findings reveal that the voltage fade in LRLO is reversible and call for new paradigms for improved design of oxygen-redox active materials.},
doi = {10.1038/s41560-018-0184-2},
journal = {Nature Energy},
number = 8,
volume = 3,
place = {United States},
year = {2018},
month = {7}
}

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996
  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode
journal, December 2010

Redox-Based Resistive Switching Memories - Nanoionic Mechanisms, Prospects, and Challenges
journal, July 2009
  • Waser, Rainer; Dittmann, Regina; Staikov, Georgi
  • Advanced Materials, Vol. 21, Issue 25-26, p. 2632-2663
  • DOI: 10.1002/adma.200900375