Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy
Abstract
Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. In this study, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge–discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed for the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Lastly, our results show that electrochemically induced solid–solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.
- Authors:
-
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1265168
- Report Number(s):
- SAND2016-6066J
Journal ID: ISSN 1936-0851; 644958
- Grant/Contract Number:
- AC04-94AL85000; SC0001160
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 6; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; 36 MATERIALS SCIENCE; batteries; energy storage; in situ TEM; liquid-cell electron microscopy; phase transformations
Citation Formats
Leenheer, Andrew J., Jungjohann, Katherine L., Zavadil, Kevin R., and Harris, Charles T. Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy. United States: N. p., 2016.
Web. doi:10.1021/acsnano.6b02200.
Leenheer, Andrew J., Jungjohann, Katherine L., Zavadil, Kevin R., & Harris, Charles T. Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy. United States. https://doi.org/10.1021/acsnano.6b02200
Leenheer, Andrew J., Jungjohann, Katherine L., Zavadil, Kevin R., and Harris, Charles T. Tue .
"Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy". United States. https://doi.org/10.1021/acsnano.6b02200. https://www.osti.gov/servlets/purl/1265168.
@article{osti_1265168,
title = {Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy},
author = {Leenheer, Andrew J. and Jungjohann, Katherine L. and Zavadil, Kevin R. and Harris, Charles T.},
abstractNote = {Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. In this study, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge–discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed for the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Lastly, our results show that electrochemically induced solid–solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.},
doi = {10.1021/acsnano.6b02200},
journal = {ACS Nano},
number = 6,
volume = 10,
place = {United States},
year = {Tue May 31 00:00:00 EDT 2016},
month = {Tue May 31 00:00:00 EDT 2016}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 50 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Alloy Negative Electrodes for Li-Ion Batteries
journal, October 2014
- Obrovac, M. N.; Chevrier, V. L.
- Chemical Reviews, Vol. 114, Issue 23
Spontaneous evolution of bicontinuous nanostructures in dealloyed Li-based systems
journal, August 2013
- Chen, Qing; Sieradzki, Karl
- Nature Materials, Vol. 12, Issue 12
Evolution of nanoporosity in dealloying
journal, March 2001
- Erlebacher, Jonah; Aziz, Michael J.; Karma, Alain
- Nature, Vol. 410, Issue 6827, p. 450-453
Materials science principles related to alloys of potential use in rechargeable lithium cells
journal, May 1989
- Huggins, Robert A.
- Journal of Power Sources, Vol. 26, Issue 1-2
25th Anniversary Article: Understanding the Lithiation of Silicon and Other Alloying Anodes for Lithium-Ion Batteries
journal, August 2013
- McDowell, Matthew T.; Lee, Seok Woo; Nix, William D.
- Advanced Materials, Vol. 25, Issue 36
Theory of Coherent Nucleation in Phase-Separating Nanoparticles
journal, May 2013
- Cogswell, Daniel A.; Bazant, Martin Z.
- Nano Letters, Vol. 13, Issue 7
The thermodynamic origin of hysteresis in insertion batteries
journal, April 2010
- Dreyer, Wolfgang; Jamnik, Janko; Guhlke, Clemens
- Nature Materials, Vol. 9, Issue 5
Phase Transformation Dynamics in Porous Battery Electrodes
journal, November 2014
- Ferguson, Todd R.; Bazant, Martin Z.
- Electrochimica Acta, Vol. 146
Intercalation Pathway in Many-Particle LiFePO 4 Electrode Revealed by Nanoscale State-of-Charge Mapping
journal, February 2013
- Chueh, William C.; El Gabaly, Farid; Sugar, Joshua D.
- Nano Letters, Vol. 13, Issue 3
A Sealed Liquid Cell for In Situ Transmission Electron Microscopy of Controlled Electrochemical Processes
journal, August 2015
- Leenheer, Andrew J.; Sullivan, John P.; Shaw, Michael J.
- Journal of Microelectromechanical Systems, Vol. 24, Issue 4
Lithium Electrodeposition Dynamics in Aprotic Electrolyte Observed in Situ via Transmission Electron Microscopy
journal, February 2015
- Leenheer, Andrew J.; Jungjohann, Katherine L.; Zavadil, Kevin R.
- ACS Nano, Vol. 9, Issue 4
In situ TEM electrochemistry of anode materials in lithium ion batteries
journal, January 2011
- Liu, Xiao Hua; Huang, Jian Yu
- Energy & Environmental Science, Vol. 4, Issue 10
Demonstration of an Electrochemical Liquid Cell for Operando Transmission Electron Microscopy Observation of the Lithiation/Delithiation Behavior of Si Nanowire Battery Anodes
journal, November 2013
- Gu, Meng; Parent, Lucas R.; Mehdi, B. Layla
- Nano Letters, Vol. 13, Issue 12
Morphological changes in and around Sn electrodes during Li ion cycling characterized by in situ environmental TEM
journal, November 2013
- Noh, Kyong Wook; Dillon, Shen J.
- Scripta Materialia, Vol. 69, Issue 9
On the origin of the capacity fading for aluminium negative electrodes in Li-ion batteries
journal, December 2014
- Oltean, Gabriel; Tai, Cheuk-Wai; Edström, Kristina
- Journal of Power Sources, Vol. 269
Electrochemical formation of lithium-aluminium alloys in propylene carbonate electrolytes
journal, April 1981
- Frazer, E. J.
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 121
Size Effects in the Electrochemical Alloying and Cycling of Electrodeposited Aluminum with Lithium
journal, January 2012
- Hudak, Nicholas S.; Huber, Dale L.
- Journal of The Electrochemical Society, Vol. 159, Issue 5
Lithiation and Delithiation Mechanisms of Gold Thin Film Model Anodes for Lithium Ion Batteries: Electrochemical Characterization
journal, May 2015
- Bach, P.; Stratmann, M.; Valencia-Jaime, I.
- Electrochimica Acta, Vol. 164
First Principles Model of Amorphous Silicon Lithiation
journal, January 2009
- Chevrier, V. L.; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 156, Issue 6
Two-Phase Electrochemical Lithiation in Amorphous Silicon
journal, January 2013
- Wang, Jiang Wei; He, Yu; Fan, Feifei
- Nano Letters, Vol. 13, Issue 2
The Al−Li (Aluminum−Lithium) system
journal, September 1982
- McAlister, A. J.
- Bulletin of Alloy Phase Diagrams, Vol. 3, Issue 2
In Situ Transmission Electron Microscopy Observation of Pulverization of Aluminum Nanowires and Evolution of the Thin Surface Al 2 O 3 Layers during Lithiation–Delithiation Cycles
journal, October 2011
- Liu, Yang; Hudak, Nicholas S.; Huber, Dale L.
- Nano Letters, Vol. 11, Issue 10
A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes
journal, February 2014
- Liu, Nian; Lu, Zhenda; Zhao, Jie
- Nature Nanotechnology, Vol. 9, Issue 3
High-rate aluminium yolk-shell nanoparticle anode for Li-ion battery with long cycle life and ultrahigh capacity
journal, August 2015
- Li, Sa; Niu, Junjie; Zhao, Yu Cheng
- Nature Communications, Vol. 6, Issue 1
Electrochemical behavior and passivation of current collectors in lithium-ion batteries
journal, January 2011
- Myung, Seung-Taek; Hitoshi, Yashiro; Sun, Yang-Kook
- Journal of Materials Chemistry, Vol. 21, Issue 27
Reversible Nanopore Formation in Ge Nanowires during Lithiation–Delithiation Cycling: An In Situ Transmission Electron Microscopy Study
journal, September 2011
- Liu, Xiao Hua; Huang, Shan; Picraux, S. Tom
- Nano Letters, Vol. 11, Issue 9
The Au−Li (Gold-Lithium) system
journal, June 1986
- Pelton, A. D.
- Bulletin of Alloy Phase Diagrams, Vol. 7, Issue 3
Direct in situ measurements of Li transport in Li-ion battery negative electrodes
journal, January 2010
- Harris, Stephen J.; Timmons, Adam; Baker, Daniel R.
- Chemical Physics Letters, Vol. 485, Issue 4-6
Direct In Situ Observation and Numerical Simulations of Non-Shrinking-Core Behavior in an MCMB Graphite Composite Electrode
journal, January 2012
- Harris, Stephen J.; Rahani, Ehsan Kabiri; Shenoy, Vivek B.
- Journal of The Electrochemical Society, Vol. 159, Issue 9
Deformation, Stress State, and Thermodynamic Force for a Transforming Spherical Inclusion in an Elastic-Plastic Material
journal, February 2000
- Fischer, F. D.; Oberaigner, E. R.
- Journal of Applied Mechanics, Vol. 67, Issue 4
Mechanical-energy influences to electrochemical phenomena in lithium-ion batteries
journal, January 2011
- Ichitsubo, T.; Yukitani, S.; Hirai, K.
- Journal of Materials Chemistry, Vol. 21, Issue 8
Large Plastic Deformation in High-Capacity Lithium-Ion Batteries Caused by Charge and Discharge: Large Plastic Deformation in Lithium-Ion Batteries
journal, March 2011
- Zhao, Kejie; Pharr, Matt; Cai, Shengqiang
- Journal of the American Ceramic Society, Vol. 94
Stochastic Analysis of Diffusion Induced Damage in Lithium-Ion Battery Electrodes
journal, January 2013
- Barai, Pallab; Mukherjee, Partha P.
- Journal of The Electrochemical Society, Vol. 160, Issue 6, p. A955-A967
Plastic deformation associated with phase transformations during lithiation/delithiation of Sn
journal, December 2014
- Mukhopadhyay, Amartya; Kali, Ravi; Badjate, Shubham
- Scripta Materialia, Vol. 92
Nanoscale Imaging of Lithium Ion Distribution During In Situ Operation of Battery Electrode and Electrolyte
journal, February 2014
- Holtz, Megan E.; Yu, Yingchao; Gunceler, Deniz
- Nano Letters, Vol. 14, Issue 3
In Situ Study of Lithiation and Delithiation of MoS 2 Nanosheets Using Electrochemical Liquid Cell Transmission Electron Microscopy
journal, July 2015
- Zeng, Zhiyuan; Zhang, Xiaowei; Bustillo, Karen
- Nano Letters, Vol. 15, Issue 8
Probing the Degradation Mechanisms in Electrolyte Solutions for Li-Ion Batteries by in Situ Transmission Electron Microscopy
journal, February 2014
- Abellan, Patricia; Mehdi, B. Layla; Parent, Lucas R.
- Nano Letters, Vol. 14, Issue 3
Works referencing / citing this record:
In Situ Transmission Electron Microscopy for Energy Materials and Devices
journal, June 2019
- Fan, Zheng; Zhang, Liqiang; Baumann, Daniel
- Advanced Materials, Vol. 31, Issue 33
Review of Recent Development of In Situ/Operando Characterization Techniques for Lithium Battery Research
journal, May 2019
- Liu, Dongqing; Shadike, Zulipiya; Lin, Ruoqian
- Advanced Materials, Vol. 31, Issue 28
Current Status of Liquid-cell Transmission Electron Microscopy
journal, December 2019
- Hong, Jaeyoung; Chun, Dong Won
- Ceramist, Vol. 22, Issue 4
Review—Promises and Challenges of In Situ Transmission Electron Microscopy Electrochemical Techniques in the Studies of Lithium Ion Batteries
journal, January 2017
- Xie, Zhi-Hui; Jiang, Zimin; Zhang, Xueyuan
- Journal of The Electrochemical Society, Vol. 164, Issue 9
Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy
journal, August 2017
- Yuan, Yifei; Amine, Khalil; Lu, Jun
- Nature Communications, Vol. 8, Issue 1
In Situ Transmission Electron Microscopy Studies of Electrochemical Reaction Mechanisms in Rechargeable Batteries
journal, June 2019
- Wu, Xiaoyu; Li, Songmei; Yang, Bin
- Electrochemical Energy Reviews, Vol. 2, Issue 3
Real-time monitoring of stress development during electrochemical cycling of electrode materials for Li-ion batteries: overview and perspectives
journal, January 2019
- Jangid, Manoj K.; Mukhopadhyay, Amartya
- Journal of Materials Chemistry A, Vol. 7, Issue 41
Using in situ and operando methods to characterize phase changes in charged lithium nickel cobalt aluminum oxide cathode materials
journal, January 2020
- Hwang, Sooyeon; Stach, Eric A.
- Journal of Physics D: Applied Physics, Vol. 53, Issue 11
Operando Observations of SEI Film Evolution by Mass‐Sensitive Scanning Transmission Electron Microscopy
journal, October 2019
- Hou, Chen; Han, Jiuhui; Liu, Pan
- Advanced Energy Materials, Vol. 9, Issue 45
Effects of residual stress on overpotentials and mechanical integrity during electrochemical Li-alloying of Al film electrodes
journal, February 2017
- Kali, Ravi; Badjate, Shubham; Mukhopadhyay, Amartya
- Journal of Applied Electrochemistry, Vol. 47, Issue 4
Advanced Transmission Electron Microscopy for Electrode and Solid-Electrolyte Materials in Lithium-Ion Batteries
journal, June 2018
- Liu, Xiaozhi; Gu, Lin
- Small Methods, Vol. 2, Issue 8
Cryogenic specimens for nanoscale characterization of solid–liquid interfaces
journal, December 2019
- Zachman, Michael J.; de Jonge, Niels; Fischer, Robert
- MRS Bulletin, Vol. 44, Issue 12
Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy
journal, August 2017
- Yuan, Yifei; Amine, Khalil; Lu, Jun
- Nature Communications, Vol. 8, Issue 1