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Title: Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes

Abstract

The performance of lithium ion electrodes is hindered by unfavorable chemical heterogeneities that pre-exist or develop during operation. Time-resolved spatial descriptions are needed to understand the link between such heterogeneities and a cell's performance. Here, operando high-resolution X-ray diffraction-computed tomography is used to spatially and temporally quantify crystallographic heterogeneities within and between particles throughout both fresh and degraded Li xMn 2O 4 electrodes. This imaging technique facilitates identification of stoichiometric differences between particles and stoichiometric gradients and phase heterogeneities within particles. Through radial quantification of phase fractions, the response of distinct particles to lithiation is found to vary; most particles contain localized regions that transition to rock salt LiMnO 2 within the first cycle. Other particles contain monoclinic Li 2MnO 3 near the surface and almost pure spinel LixMn2O4 near the core. Following 150 cycles, concentrations of LiMnO 2 and Li 2MnO 3 significantly increase and widely vary between particles.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [3];  [4];  [5];  [6];  [7]; ORCiD logo [8];  [3];  [3]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. European Synchrotron Radiation Facility (ESRF), Grenoble (France); Finden Limited, Abingdon (United Kingdom); Univ. College London (United Kingdom)
  3. Univ. College London (United Kingdom); The Faraday Inst. (United Kingdom)
  4. Univ. College London (United Kingdom)
  5. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
  6. European Synchrotron Radiation Facility (ESRF), Grenoble (France)
  7. Finden Limited, Abingdon (United Kingdom)
  8. Finden Limited, Abingdon (United Kingdom); Univ. College London (United Kingdom); Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab. (RAL)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); European Union Horizon 2020 Research and Innovation Program; Royal Academy of Engineering; The Faraday Institution
OSTI Identifier:
1601577
Report Number(s):
[NREL/JA-5400-75809]
[Journal ID: ISSN 2041-1723]
Grant/Contract Number:  
[AC36-08GO28308; 679933; EP/S003053/1]
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
[ Journal Volume: 11; Journal Issue: 1]; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; lithium ion batteries; x-ray diffraction; computed tomography; crystallography

Citation Formats

Finegan, Donal P., Vamvakeros, Antonis, Tan, Chun, Heenan, Thomas M. M., Daemi, Sohrab R., Seitzman, Natalie, Di Michiel, Marco, Jacques, Simon, Beale, Andrew M., Brett, Dan J. L., Shearing, Paul R., and Smith, Kandler. Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes. United States: N. p., 2020. Web. doi:10.1038/s41467-020-14467-x.
Finegan, Donal P., Vamvakeros, Antonis, Tan, Chun, Heenan, Thomas M. M., Daemi, Sohrab R., Seitzman, Natalie, Di Michiel, Marco, Jacques, Simon, Beale, Andrew M., Brett, Dan J. L., Shearing, Paul R., & Smith, Kandler. Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes. United States. doi:10.1038/s41467-020-14467-x.
Finegan, Donal P., Vamvakeros, Antonis, Tan, Chun, Heenan, Thomas M. M., Daemi, Sohrab R., Seitzman, Natalie, Di Michiel, Marco, Jacques, Simon, Beale, Andrew M., Brett, Dan J. L., Shearing, Paul R., and Smith, Kandler. Fri . "Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes". United States. doi:10.1038/s41467-020-14467-x. https://www.osti.gov/servlets/purl/1601577.
@article{osti_1601577,
title = {Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes},
author = {Finegan, Donal P. and Vamvakeros, Antonis and Tan, Chun and Heenan, Thomas M. M. and Daemi, Sohrab R. and Seitzman, Natalie and Di Michiel, Marco and Jacques, Simon and Beale, Andrew M. and Brett, Dan J. L. and Shearing, Paul R. and Smith, Kandler},
abstractNote = {The performance of lithium ion electrodes is hindered by unfavorable chemical heterogeneities that pre-exist or develop during operation. Time-resolved spatial descriptions are needed to understand the link between such heterogeneities and a cell's performance. Here, operando high-resolution X-ray diffraction-computed tomography is used to spatially and temporally quantify crystallographic heterogeneities within and between particles throughout both fresh and degraded LixMn2O4 electrodes. This imaging technique facilitates identification of stoichiometric differences between particles and stoichiometric gradients and phase heterogeneities within particles. Through radial quantification of phase fractions, the response of distinct particles to lithiation is found to vary; most particles contain localized regions that transition to rock salt LiMnO2 within the first cycle. Other particles contain monoclinic Li2MnO3 near the surface and almost pure spinel LixMn2O4 near the core. Following 150 cycles, concentrations of LiMnO2 and Li2MnO3 significantly increase and widely vary between particles.},
doi = {10.1038/s41467-020-14467-x},
journal = {Nature Communications},
number = [1],
volume = [11],
place = {United States},
year = {2020},
month = {1}
}

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