Cathode-Electrolyte Interphase in Lithium Batteries Revealed by Cryogenic Electron Microscopy
Abstract
Cathode electrolyte interphase (CEI), the intimate coating layer formed on the positive electrode, has been thought to be critical. However, many aspects of CEI remain unclear. This originates from the lack of effective tools to characterize structural and chemical properties of these sensitive interphases at nanoscale. Here, we develop a protocol to preserve the native state and directly visualize the interface on the positive electrode using cryogenic electron microscopy. We find that under normal operation conditions, there does not exist an intimate coating layer at the single-particle level in carbonate-based electrolyte. However, upon brief external electrical shorting, a solid-electrolyte interphase, which usually forms on anodes, could form on cathodes and be electrochemically converted into a stable, conformal CEI in situ. The conformal CEI helps improve Coulombic efficiency and overall capacity retention of the battery. This generates a different perspective of CEI in commercial carbonate-based electrolytes than previously understood.
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1708934
- Alternate Identifier(s):
- OSTI ID: 1768244
- Grant/Contract Number:
- AC02-76SF00515; ECCS-2026822
- Resource Type:
- Published Article
- Journal Name:
- Matter (Online)
- Additional Journal Information:
- Journal Name: Matter (Online) Journal Volume: 4 Journal Issue: 1; Journal ID: ISSN 2590-2385
- Publisher:
- Cell Press/Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; cathode-electrolyte interphase; cryo-EM; lithium-ion battery
Citation Formats
Zhang, Zewen, Yang, Jinlong, Huang, William, Wang, Hansen, Zhou, Weijiang, Li, Yanbin, Li, Yuzhang, Xu, Jinwei, Huang, Wenxiao, Chiu, Wah, and Cui, Yi. Cathode-Electrolyte Interphase in Lithium Batteries Revealed by Cryogenic Electron Microscopy. United States: N. p., 2021.
Web. doi:10.1016/j.matt.2020.10.021.
Zhang, Zewen, Yang, Jinlong, Huang, William, Wang, Hansen, Zhou, Weijiang, Li, Yanbin, Li, Yuzhang, Xu, Jinwei, Huang, Wenxiao, Chiu, Wah, & Cui, Yi. Cathode-Electrolyte Interphase in Lithium Batteries Revealed by Cryogenic Electron Microscopy. United States. https://doi.org/10.1016/j.matt.2020.10.021
Zhang, Zewen, Yang, Jinlong, Huang, William, Wang, Hansen, Zhou, Weijiang, Li, Yanbin, Li, Yuzhang, Xu, Jinwei, Huang, Wenxiao, Chiu, Wah, and Cui, Yi. Fri .
"Cathode-Electrolyte Interphase in Lithium Batteries Revealed by Cryogenic Electron Microscopy". United States. https://doi.org/10.1016/j.matt.2020.10.021.
@article{osti_1708934,
title = {Cathode-Electrolyte Interphase in Lithium Batteries Revealed by Cryogenic Electron Microscopy},
author = {Zhang, Zewen and Yang, Jinlong and Huang, William and Wang, Hansen and Zhou, Weijiang and Li, Yanbin and Li, Yuzhang and Xu, Jinwei and Huang, Wenxiao and Chiu, Wah and Cui, Yi},
abstractNote = {Cathode electrolyte interphase (CEI), the intimate coating layer formed on the positive electrode, has been thought to be critical. However, many aspects of CEI remain unclear. This originates from the lack of effective tools to characterize structural and chemical properties of these sensitive interphases at nanoscale. Here, we develop a protocol to preserve the native state and directly visualize the interface on the positive electrode using cryogenic electron microscopy. We find that under normal operation conditions, there does not exist an intimate coating layer at the single-particle level in carbonate-based electrolyte. However, upon brief external electrical shorting, a solid-electrolyte interphase, which usually forms on anodes, could form on cathodes and be electrochemically converted into a stable, conformal CEI in situ. The conformal CEI helps improve Coulombic efficiency and overall capacity retention of the battery. This generates a different perspective of CEI in commercial carbonate-based electrolytes than previously understood.},
doi = {10.1016/j.matt.2020.10.021},
journal = {Matter (Online)},
number = 1,
volume = 4,
place = {United States},
year = {Fri Jan 01 00:00:00 EST 2021},
month = {Fri Jan 01 00:00:00 EST 2021}
}
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Works referenced in this record:
Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries
journal, August 2018
- Zachman, Michael J.; Tu, Zhengyuan; Choudhury, Snehashis
- Nature, Vol. 560, Issue 7718
Correlating Structure and Function of Battery Interphases at Atomic Resolution Using Cryoelectron Microscopy
journal, October 2018
- Li, Yuzhang; Huang, William; Li, Yanbin
- Joule, Vol. 2, Issue 10
Examining Solid Electrolyte Interphase Formation on Crystalline Silicon Electrodes: Influence of Electrochemical Preparation and Ambient Exposure Conditions
journal, September 2012
- Schroder, Kjell W.; Celio, Hugo; Webb, Lauren J.
- The Journal of Physical Chemistry C, Vol. 116, Issue 37
Phosphorus Enrichment as a New Composition in the Solid Electrolyte Interphase of High-Voltage Cathodes and Its Effects on Battery Cycling
journal, October 2015
- Yang, Pengfei; Zheng, Jianming; Kuppan, Saravanan
- Chemistry of Materials, Vol. 27, Issue 21
Electrode/Electrolyte Interface Reactivity in High-Voltage Spinel LiMn 1.6 Ni 0.4 O 4 /Li 4 Ti 5 O 12 Lithium-Ion Battery
journal, May 2010
- Dedryvère, R.; Foix, D.; Franger, S.
- The Journal of Physical Chemistry C, Vol. 114, Issue 24
Study of the Cathode–Electrolyte Interface of LiMn[sub 1.5]Ni[sub 0.5]O[sub 4] Synthesized by a Sol–Gel Method for Li-Ion Batteries
journal, January 2010
- Duncan, Hugues; Abu-Lebdeh, Yaser; Davidson, Isobel J.
- Journal of The Electrochemical Society, Vol. 157, Issue 4
Dynamic evolution of cathode electrolyte interphase (CEI) on high voltage LiCoO2 cathode and its interaction with Li anode
journal, September 2018
- Zhang, Jie-Nan; Li, Qinghao; Wang, Yi
- Energy Storage Materials, Vol. 14
Evolution of the LiFePO4 positive electrode interface along cycling monitored by MAS NMR
journal, February 2013
- Cuisinier, Marine; Dupré, Nicolas; Martin, Jean-Frédéric
- Journal of Power Sources, Vol. 224
Mechanisms of Degradation and Strategies for the Stabilization of Cathode–Electrolyte Interfaces in Li-Ion Batteries
journal, January 2018
- Cabana, Jordi; Kwon, Bob Jin; Hu, Linhua
- Accounts of Chemical Research, Vol. 51, Issue 2
Chemical and Structural Stability of Lithium-Ion Battery Electrode Materials under Electron Beam
journal, July 2014
- Lin, Feng; Markus, Isaac M.; Doeff, Marca M.
- Scientific Reports, Vol. 4, Issue 1
Investigations on the Fundamental Process of Cathode Electrolyte Interphase Formation and Evolution of High-Voltage Cathodes
journal, December 2019
- Li, Qinghao; Wang, Yi; Wang, Xuelong
- ACS Applied Materials & Interfaces, Vol. 12, Issue 2
Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries
journal, January 2013
- Wei Seh, Zhi; Li, Weiyang; Cha, Judy J.
- Nature Communications, Vol. 4, Article No. 1331
Dynamic Behavior at the Interface between Lithium Cobalt Oxide and an Organic Electrolyte Monitored by Neutron Reflectivity Measurements
journal, September 2016
- Minato, Taketoshi; Kawaura, Hiroyuki; Hirayama, Masaaki
- The Journal of Physical Chemistry C, Vol. 120, Issue 36
Cathode Modification for Improved Performance of Rechargeable Lithium∕Composite Polymer Electrolyte-Pyrite Battery
journal, January 1999
- Strauss, E.
- Electrochemical and Solid-State Letters, Vol. 2, Issue 3
Dynamic Structure and Chemistry of the Silicon Solid-Electrolyte Interphase Visualized by Cryogenic Electron Microscopy
journal, November 2019
- Huang, William; Wang, Jiangyan; Braun, Michael R.
- Matter, Vol. 1, Issue 5
Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries
journal, August 2000
- Aurbach, Doron
- Journal of Power Sources, Vol. 89, Issue 2
Theory of SEI Formation in Rechargeable Batteries: Capacity Fade, Accelerated Aging and Lifetime Prediction
journal, December 2012
- Pinson, Matthew B.; Bazant, Martin Z.
- Journal of The Electrochemical Society, Vol. 160, Issue 2
Anode-originated SEI migration contributes to formation of cathode-electrolyte interphase layer
journal, January 2018
- Fang, Shuyu; Jackson, David; Dreibelbis, Mark L.
- Journal of Power Sources, Vol. 373
Film Formation at Positive Electrodes in Lithium-Ion Batteries
journal, January 2005
- Würsig, Andreas; Buqa, Hilmi; Holzapfel, Michael
- Electrochemical and Solid-State Letters, Vol. 8, Issue 1
In Situ Visualized Cathode Electrolyte Interphase on LiCoO 2 in High Voltage Cycling
journal, May 2017
- Lu, Wei; Zhang, Jiansheng; Xu, Jingjing
- ACS Applied Materials & Interfaces, Vol. 9, Issue 22
High-Concentration Ether Electrolytes for Stable High-Voltage Lithium Metal Batteries
journal, March 2019
- Ren, Xiaodi; Zou, Lianfeng; Jiao, Shuhong
- ACS Energy Letters, Vol. 4, Issue 4
Operando Investigation into Dynamic Evolution of Cathode–Electrolyte Interfaces in a Li-Ion Battery
journal, February 2019
- Chen, Dongchang; Mahmoud, Mahmoud A.; Wang, Jeng-Han
- Nano Letters, Vol. 19, Issue 3
Conversion Reaction Mechanisms in Lithium Ion Batteries: Study of the Binary Metal Fluoride Electrodes
journal, November 2011
- Wang, Feng; Robert, Rosa; Chernova, Natasha A.
- Journal of the American Chemical Society, Vol. 133, Issue 46
Chemical versus Electrochemical Electrolyte Oxidation on NMC111, NMC622, NMC811, LNMO, and Conductive Carbon
journal, September 2017
- Jung, Roland; Metzger, Michael; Maglia, Filippo
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 19
Capacity Fade Mechanisms and Side Reactions in Lithium-Ion Batteries
journal, January 1998
- Arora, Pankaj; White, Ralph E.; Doyle, Marc
- Journal of The Electrochemical Society, Vol. 145, Issue 10, p. 3647-3667
New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM
journal, November 2017
- Wang, Xuefeng; Zhang, Minghao; Alvarado, Judith
- Nano Letters, Vol. 17, Issue 12
Aging of the LiNi[sub 1∕2]Mn[sub 1∕2]O[sub 2] Positive Electrode Interface in Electrolyte
journal, January 2009
- Dupré, Nicolas; Martin, Jean-Frédéric; Oliveri, Julie
- Journal of The Electrochemical Society, Vol. 156, Issue 5
Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014
- Xu, Kang
- Chemical Reviews, Vol. 114, Issue 23
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy
journal, October 2017
- Li, Yuzhang; Li, Yanbin; Pei, Allen
- Science, Vol. 358, Issue 6362
Review on electrode–electrolyte solution interactions, related to cathode materials for Li-ion batteries
journal, March 2007
- Aurbach, Doron; Markovsky, Boris; Salitra, Gregory
- Journal of Power Sources, Vol. 165, Issue 2
Stable cycling of high-voltage lithium metal batteries in ether electrolytes
journal, July 2018
- Jiao, Shuhong; Ren, Xiaodi; Cao, Ruiguo
- Nature Energy, Vol. 3, Issue 9
Extending the Service Life of High-Ni Layered Oxides by Tuning the Electrode-Electrolyte Interphase
journal, September 2018
- Li, Jianyu; Li, Wangda; You, Ya
- Advanced Energy Materials, Vol. 8, Issue 29
Ethylene Sulfite as Electrolyte Additive for Lithium-Ion Cells with Graphitic Anodes
journal, January 1999
- Wrodnigg, Gerhard H.
- Journal of The Electrochemical Society, Vol. 146, Issue 2
Review—SEI: Past, Present and Future
journal, January 2017
- Peled, E.; Menkin, S.
- Journal of The Electrochemical Society, Vol. 164, Issue 7
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model
journal, January 1979
- Peled, E.
- Journal of The Electrochemical Society, Vol. 126, Issue 12
Evolution of the Solid–Electrolyte Interphase on Carbonaceous Anodes Visualized by Atomic-Resolution Cryogenic Electron Microscopy
journal, July 2019
- Huang, William; Attia, Peter M.; Wang, Hansen
- Nano Letters, Vol. 19, Issue 8