Spatial dynamics of lithiation and lithium plating during high-rate operation of graphite electrodes
Abstract
The principal inhibitor of fast charging lithium ion cells is the graphite negative electrode, where favorable conditions for lithium plating occur at high charge rates, causing accelerated degradation and safety concerns. The local response of graphite, both at the electrode and particle level, when exposed to fast charging conditions of around 6C is not well understood. Consequently, the conditions that lead to the onset of lithium plating, as well as the local dynamics of lithium plating and stripping, have also remained elusive. Here, we use high-speed (100 Hz) pencil-beam X-ray diffraction to repeatedly raster along the depth of a 101 μm thick graphite electrode in 3 μm steps during fast (up to 6C) charge and discharge conditions. Consecutive depth profiles from separator to current collector were each captured in 0.5 seconds, giving an unprecedented spatial and temporal description of the state of the electrode and graphite's staging dynamics during high rate conditions. The electrode is preferentially activated near the separator, and the non-uniformity increases with rate and is influenced by free-energy barriers between graphite's lithiation stages. The onset of lithium plating and stripping was quantified, occurring only within the first 15 μm from the separator. The presence of lithium platingmore »
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- National Renewable Energy Laboratory, Golden, USA
- Centre for Materials and Nanotechnology, University of Oslo, 0315 Oslo, Norway
- Electrochemical Innovation Laboratory, Department of Chemical Engineering, University College London, London, UK, The Faraday Institution
- Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, USA
- ESRF-The European Synchrotron, 38000 Grenoble, France
- MAX IV Laboratory, University of Lund, Lund, Sweden
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; The Faraday Institution
- OSTI Identifier:
- 1638545
- Alternate Identifier(s):
- OSTI ID: 1660156
- Report Number(s):
- NREL/JA-5400-77537
Journal ID: ISSN 1754-5692; EESNBY
- Grant/Contract Number:
- AC36-08GO28308; EP/S003053/1
- Resource Type:
- Published Article
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Name: Energy & Environmental Science Journal Volume: 13 Journal Issue: 8; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; fast charging; graphite electrodes; lithium ion cells; X-ray diffraction
Citation Formats
Finegan, Donal P., Quinn, Alexander, Wragg, David S., Colclasure, Andrew M., Lu, Xuekun, Tan, Chun, Heenan, Thomas M. M., Jervis, Rhodri, Brett, Dan J. L., Das, Supratim, Gao, Tao, Cogswell, Daniel A., Bazant, Martin Z., Di Michiel, Marco, Checchia, Stefano, Shearing, Paul R., and Smith, Kandler. Spatial dynamics of lithiation and lithium plating during high-rate operation of graphite electrodes. United Kingdom: N. p., 2020.
Web. doi:10.1039/D0EE01191F.
Finegan, Donal P., Quinn, Alexander, Wragg, David S., Colclasure, Andrew M., Lu, Xuekun, Tan, Chun, Heenan, Thomas M. M., Jervis, Rhodri, Brett, Dan J. L., Das, Supratim, Gao, Tao, Cogswell, Daniel A., Bazant, Martin Z., Di Michiel, Marco, Checchia, Stefano, Shearing, Paul R., & Smith, Kandler. Spatial dynamics of lithiation and lithium plating during high-rate operation of graphite electrodes. United Kingdom. https://doi.org/10.1039/D0EE01191F
Finegan, Donal P., Quinn, Alexander, Wragg, David S., Colclasure, Andrew M., Lu, Xuekun, Tan, Chun, Heenan, Thomas M. M., Jervis, Rhodri, Brett, Dan J. L., Das, Supratim, Gao, Tao, Cogswell, Daniel A., Bazant, Martin Z., Di Michiel, Marco, Checchia, Stefano, Shearing, Paul R., and Smith, Kandler. Wed .
"Spatial dynamics of lithiation and lithium plating during high-rate operation of graphite electrodes". United Kingdom. https://doi.org/10.1039/D0EE01191F.
@article{osti_1638545,
title = {Spatial dynamics of lithiation and lithium plating during high-rate operation of graphite electrodes},
author = {Finegan, Donal P. and Quinn, Alexander and Wragg, David S. and Colclasure, Andrew M. and Lu, Xuekun and Tan, Chun and Heenan, Thomas M. M. and Jervis, Rhodri and Brett, Dan J. L. and Das, Supratim and Gao, Tao and Cogswell, Daniel A. and Bazant, Martin Z. and Di Michiel, Marco and Checchia, Stefano and Shearing, Paul R. and Smith, Kandler},
abstractNote = {The principal inhibitor of fast charging lithium ion cells is the graphite negative electrode, where favorable conditions for lithium plating occur at high charge rates, causing accelerated degradation and safety concerns. The local response of graphite, both at the electrode and particle level, when exposed to fast charging conditions of around 6C is not well understood. Consequently, the conditions that lead to the onset of lithium plating, as well as the local dynamics of lithium plating and stripping, have also remained elusive. Here, we use high-speed (100 Hz) pencil-beam X-ray diffraction to repeatedly raster along the depth of a 101 μm thick graphite electrode in 3 μm steps during fast (up to 6C) charge and discharge conditions. Consecutive depth profiles from separator to current collector were each captured in 0.5 seconds, giving an unprecedented spatial and temporal description of the state of the electrode and graphite's staging dynamics during high rate conditions. The electrode is preferentially activated near the separator, and the non-uniformity increases with rate and is influenced by free-energy barriers between graphite's lithiation stages. The onset of lithium plating and stripping was quantified, occurring only within the first 15 μm from the separator. The presence of lithium plating changed the behavior of the underlying graphite, such as causing co-existence of LiC6 and graphite in the fully discharged state. Finally, the staging behavior of graphite at different rates was quantified, revealing a high dependency on rate and drastic hysteresis between lithiation and delithiation.},
doi = {10.1039/D0EE01191F},
journal = {Energy & Environmental Science},
number = 8,
volume = 13,
place = {United Kingdom},
year = {Wed Jul 08 00:00:00 EDT 2020},
month = {Wed Jul 08 00:00:00 EDT 2020}
}
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https://doi.org/10.1039/D0EE01191F
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