Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters
Abstract
The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase formation and Li electrodeposition from a standard battery electrolyte, we use in situ electrochemical scanning transmission electron microscopy for controlled potential sweep-hold electrochemical measurements with simultaneous BF and ADF STEM image acquisition. Through a combined quantitative electrochemical measurement and quantitative STEM imaging approach, based upon electron scattering theory, we show that chemically sensitive ADF STEM imaging can be used to estimate the density of evolving SEI constituents and distinguish contrast mechanisms of Li-bearing components in the liquid cell.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1185816
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Nano Letters
- Additional Journal Information:
- Journal Volume: 15; Journal Issue: 3; Journal ID: ISSN 1530-6984
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; In situ ec-S/TEM; Li-ion batteries; solid electrolyte interface; Li deposition
Citation Formats
Sacci, Robert L, Black, Jennifer M., Wisinger, Nina, Dudney, Nancy J., More, Karren Leslie, and Unocic, Raymond R. Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters. United States: N. p., 2015.
Web. doi:10.1021/nl5048626.
Sacci, Robert L, Black, Jennifer M., Wisinger, Nina, Dudney, Nancy J., More, Karren Leslie, & Unocic, Raymond R. Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters. United States. https://doi.org/10.1021/nl5048626
Sacci, Robert L, Black, Jennifer M., Wisinger, Nina, Dudney, Nancy J., More, Karren Leslie, and Unocic, Raymond R. 2015.
"Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters". United States. https://doi.org/10.1021/nl5048626. https://www.osti.gov/servlets/purl/1185816.
@article{osti_1185816,
title = {Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters},
author = {Sacci, Robert L and Black, Jennifer M. and Wisinger, Nina and Dudney, Nancy J. and More, Karren Leslie and Unocic, Raymond R.},
abstractNote = {The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase formation and Li electrodeposition from a standard battery electrolyte, we use in situ electrochemical scanning transmission electron microscopy for controlled potential sweep-hold electrochemical measurements with simultaneous BF and ADF STEM image acquisition. Through a combined quantitative electrochemical measurement and quantitative STEM imaging approach, based upon electron scattering theory, we show that chemically sensitive ADF STEM imaging can be used to estimate the density of evolving SEI constituents and distinguish contrast mechanisms of Li-bearing components in the liquid cell.},
doi = {10.1021/nl5048626},
url = {https://www.osti.gov/biblio/1185816},
journal = {Nano Letters},
issn = {1530-6984},
number = 3,
volume = 15,
place = {United States},
year = {Mon Feb 23 00:00:00 EST 2015},
month = {Mon Feb 23 00:00:00 EST 2015}
}
Web of Science
Works referenced in this record:
Building better batteries
journal, February 2008
- Armand, M.; Tarascon, J.-M.
- Nature, Vol. 451, Issue 7179, p. 652-657
Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism
journal, March 2013
- Ding, Fei; Xu, Wu; Graff, Gordon L.
- Journal of the American Chemical Society, Vol. 135, Issue 11, p. 4450-4456
A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions
journal, June 2002
- Aurbach, D.
- Solid State Ionics, Vol. 148, Issue 3-4
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
SEI on lithium, graphite, disordered carbons and tin-based alloys
book, May 2004
- Peled, Emanuel; Golodnitsky, Diana
- Lithium-Ion Batteries
Fabrication and characterization of amorphous lithium electrolyte thin films and rechargeable thin-film batteries
journal, March 1993
- Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.
- Journal of Power Sources, Vol. 43, Issue 1-3, p. 103-110
Lithium anode for lithium-air secondary batteries
journal, December 2008
- Imanishi, Nobuyuki; Hasegawa, Satoshi; Zhang, Tao
- Journal of Power Sources, Vol. 185, Issue 2
Polymer solid electrolytes: Stability domain
journal, August 1981
- Armand, M.; Duclot, M.; Rigaud, P.
- Solid State Ionics, Vol. 3-4
Electrochemistry of Anodes in Solid-State Li-Ion Polymer Batteries
journal, January 1998
- Zaghib, K.
- Journal of The Electrochemical Society, Vol. 145, Issue 9
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
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004
- Xu, Kang
- Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418
Dendritic growth mechanisms in lithium/polymer cells
journal, September 1999
- Brissot, C.; Rosso, M.; Chazalviel, J. -N.
- Journal of Power Sources, Vol. 81-82
Onset of dendritic growth in lithium/polymer cells
journal, July 2001
- Rosso, M.; Gobron, T.; Brissot, C.
- Journal of Power Sources, Vol. 97-98
Suppression of Dendrite Formation via Pulse Charging in Rechargeable Lithium Metal Batteries
journal, December 2012
- Mayers, Matthew Z.; Kaminski, Jakub W.; Miller, Thomas F.
- The Journal of Physical Chemistry C, Vol. 116, Issue 50
Protection of lithium metal surfaces using tetraethoxysilane
journal, January 2011
- Umeda, Grant A.; Menke, Erik; Richard, Monique
- J. Mater. Chem., Vol. 21, Issue 5
Stabilization of lithium metal anodes using silane-based coatings
journal, December 2011
- Thompson, Rebecca S.; Schroeder, David J.; López, Carmen M.
- Electrochemistry Communications, Vol. 13, Issue 12
Lithium surface protection by polyacetylene in situ polymerization
journal, May 2006
- Belov, D. G.; Yarmolenko, O. V.; Peng, A.
- Synthetic Metals, Vol. 156, Issue 9-10
Electrochemical behaviors of a Li3N modified Li metal electrode in secondary lithium batteries
journal, October 2011
- Wu, Meifen; Wen, Zhaoyin; Liu, Yu
- Journal of Power Sources, Vol. 196, Issue 19
Dynamic microscopy of nanoscale cluster growth at the solid–liquid interface
journal, July 2003
- Williamson, M. J.; Tromp, R. M.; Vereecken, P. M.
- Nature Materials, Vol. 2, Issue 8
In Situ Transmission Electron Microscopy of Lead Dendrites and Lead Ions in Aqueous Solution
journal, June 2012
- White, Edward R.; Singer, Scott B.; Augustyn, Veronica
- ACS Nano, Vol. 6, Issue 7
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
Quantitative Electrochemical Measurements Using In Situ ec-S/TEM Devices
journal, March 2014
- Unocic, Raymond R.; Sacci, Robert L.; Brown, Gilbert M.
- Microscopy and Microanalysis, Vol. 20, Issue 2
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
Direct visualization of initial SEI morphology and growth kinetics during lithium deposition by in situ electrochemical transmission electron microscopy
journal, January 2014
- Sacci, Robert L.; Dudney, Nancy J.; More, Karren L.
- Chemical Communications, Vol. 50, Issue 17
Visualization of Electrode–Electrolyte Interfaces in LiPF 6 /EC/DEC Electrolyte for Lithium Ion Batteries via in Situ TEM
journal, March 2014
- Zeng, Zhiyuan; Liang, Wen-I; Liao, Hong-Gang
- Nano Letters, Vol. 14, Issue 4
In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode
journal, December 2010
- Huang, J. Y.; Zhong, L.; Wang, C. M.
- Science, Vol. 330, Issue 6010, p. 1515-1520
In Situ TEM Study of Lithiation Behavior of Silicon Nanoparticles Attached to and Embedded in a Carbon Matrix
journal, August 2012
- Gu, Meng; Li, Ying; Li, Xiaolin
- ACS Nano, Vol. 6, Issue 9
Direct Visualization of Solid Electrolyte Interphase Formation in Lithium-Ion Batteries with In Situ Electrochemical Transmission Electron Microscopy
journal, July 2014
- Unocic, Raymond R.; Sun, Xiao-Guang; Sacci, Robert L.
- Microscopy and Microanalysis, Vol. 20, Issue 4
Structural and spectroscopic studies of a commercial glassy carbon
journal, December 2013
- Parker, Stewart F.; Imberti, Silvia; Callear, Samantha K.
- Chemical Physics, Vol. 427
Investigation of the Electrochemical Windows of Aprotic Alkali Metal (Li, Na, K) Salt Solutions
journal, January 2001
- Moshkovich, M.; Gofer, Y.; Aurbach, D.
- Journal of The Electrochemical Society, Vol. 148, Issue 4
Why is the Solid-Electrolyte-Interphase Selective? Through-Film Ferrocenium Reduction on Highly Oriented Pyrolytic Graphite
journal, January 2012
- Tang, Maureen; Newman, John
- Journal of The Electrochemical Society, Vol. 159, Issue 12
Chemical Distribution and Bonding of Lithium in Intercalated Graphite: Identification with Optimized Electron Energy Loss Spectroscopy
journal, January 2011
- Wang, Feng; Graetz, Jason; Moreno, M. Sergio
- ACS Nano, Vol. 5, Issue 2
Consequences of air exposure on the lithiated graphite SEI
journal, August 2013
- Malmgren, Sara; Ciosek, Katarzyna; Lindblad, Rebecka
- Electrochimica Acta, Vol. 105
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
X-ray photoelectron spectroscopy of negative electrodes from high-power lithium-ion cells showing various levels of power fade
journal, November 2004
- Herstedt, M.; Abraham, D. P.; Kerr, J. B.
- Electrochimica Acta, Vol. 49, Issue 28
Underpotential Deposition of Metals: Structural and Thermodynamic Considerations
journal, March 2002
- Sudha, V.; Sangaranarayanan, M. V.
- The Journal of Physical Chemistry B, Vol. 106, Issue 10
Underpotential Deposition of Metals from Thermodynamic and Structural Considerations. 2. Nonaqueous Solvents
journal, April 2003
- Sudha, V.; Sangaranarayanan, M. V.
- The Journal of Physical Chemistry B, Vol. 107, Issue 16
Z-contrast stem for materials science
journal, June 1989
- Pennycook, S. J.
- Ultramicroscopy, Vol. 30, Issue 1-2
Comparison of the growth of lithium filaments and dendrites under different conditions
journal, January 2015
- Steiger, Jens; Richter, Gunther; Wenk, Moritz
- Electrochemistry Communications, Vol. 50
Effect of Electrolyte Composition on Lithium Dendrite Growth
journal, January 2008
- Crowther, Owen; West, Alan C.
- Journal of The Electrochemical Society, Vol. 155, Issue 11
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
Structural and Morphological Evolution of Lead Dendrites during Electrochemical Migration
journal, November 2013
- Sun, Minghua; Liao, Hong-Gang; Niu, Kaiyang
- Scientific Reports, Vol. 3, Issue 1
Gas evolution from cathode materials: A pathway to solvent decomposition concomitant to SEI formation
journal, October 2013
- Browning, Katie L.; Baggetto, Loïc; Unocic, Raymond R.
- Journal of Power Sources, Vol. 239
Electron energy-loss spectrometry on lithiated graphite
journal, July 2000
- Hightower, A.; Ahn, C. C.; Fultz, B.
- Applied Physics Letters, Vol. 77, Issue 2
Electron microscopy of whole cells in liquid with nanometer resolution
journal, January 2009
- Jonge, N. d.; Peckys, D. B.; Kremers, G. J.
- Proceedings of the National Academy of Sciences, Vol. 106, Issue 7
Liquid scanning transmission electron microscopy: Nanoscale imaging in micrometers-thick liquids
journal, February 2014
- Schuh, Tobias; de Jonge, Niels
- Comptes Rendus Physique, Vol. 15, Issue 2-3, p. 214-223
The study of the anodic stability of alkyl carbonate solutions by in situ FTIR spectroscopy, EQCM, NMR and MS
journal, February 2001
- Moshkovich, M.; Cojocaru, M.; Gottlieb, H. E.
- Journal of Electroanalytical Chemistry, Vol. 497, Issue 1-2
Works referencing / citing this record:
Liquid-Phase Transmission Electron Microscopy for Studying Colloidal Inorganic Nanoparticles
journal, November 2017
- Kim, Byung Hyo; Yang, Jiwoong; Lee, Donghoon
- Advanced Materials, Vol. 30, Issue 4
Designing solid-state interfaces on lithium-metal anodes: a review
journal, September 2019
- Zhao, Chen-Zi; Duan, Hui; Huang, Jia-Qi
- Science China Chemistry, Vol. 62, Issue 10
Emerging Electron Microscopy Techniques for Probing Functional Interfaces in Energy Materials
journal, October 2019
- Zachman, Michael J.; Hachtel, Jordan A.; Idrobo, Juan Carlos
- Angewandte Chemie, Vol. 132, Issue 4
Reviving the lithium metal anode for high-energy batteries
journal, March 2017
- Lin, Dingchang; Liu, Yayuan; Cui, Yi
- Nature Nanotechnology, Vol. 12, Issue 3
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
Impact of External Pressure and Electrolyte Transport Properties on Lithium Dendrite Growth
journal, January 2018
- Barai, Pallab; Higa, Kenneth; Srinivasan, Venkat
- Journal of The Electrochemical Society, Vol. 165, Issue 11
Lithium Silicide Surface Enrichment: A Solution to Lithium Metal Battery
journal, July 2018
- Tang, Wei; Yin, Xuesong; Kang, Sujin
- Advanced Materials, Vol. 30, Issue 34
Safe Lithium‐Metal Anodes for Li−O 2 Batteries: From Fundamental Chemistry to Advanced Characterization and Effective Protection
journal, May 2019
- Hong, Yan‐Shuai; Zhao, Chen‐Zi; Xiao, Ye
- Batteries & Supercaps, Vol. 2, Issue 7
In situ plasmonic optical fiber detection of the state of charge of supercapacitors for renewable energy storage
journal, July 2018
- Lao, Jiajie; Sun, Peng; Liu, Fu
- Light: Science & Applications, Vol. 7, Issue 1
Constructing first-principles phase diagrams of amorphous Li x Si using machine-learning-assisted sampling with an evolutionary algorithm
journal, June 2018
- Artrith, Nongnuch; Urban, Alexander; Ceder, Gerbrand
- The Journal of Chemical Physics, Vol. 148, Issue 24
Real-time mass spectrometric characterization of the solid–electrolyte interphase of a lithium-ion battery
journal, January 2020
- Zhou, Yufan; Su, Mao; Yu, Xiaofei
- Nature Nanotechnology, Vol. 15, Issue 3
Synergistic Effects of Salt Concentration and Working Temperature towards Dendrite-Free Lithium Deposition
journal, October 2019
- Li, Panlong; Li, Chao; Yang, Yang
- Research, Vol. 2019
Liquid K-Na Alloy Anode Enables Dendrite-Free Potassium Batteries
journal, September 2016
- Xue, Leigang; Gao, Hongcai; Zhou, Weidong
- Advanced Materials, Vol. 28, Issue 43
Reviving Lithium-Metal Anodes for Next-Generation High-Energy Batteries
journal, June 2017
- Guo, Yanpeng; Li, Huiqiao; Zhai, Tianyou
- Advanced Materials, Vol. 29, Issue 29
Current Density Distribution in Electrochemical Cells with Small Cell Heights and Coplanar Thin Electrodes as Used in ec-S/TEM Cell Geometries
journal, January 2019
- Stricker, Elizabeth A.; Ke, Xinyou; Wainright, Jesse S.
- Journal of The Electrochemical Society, Vol. 166, Issue 4
In Situ Volume Change Studies of Lithium Metal Electrode under Different Pressure
journal, January 2019
- Zhang, Chaofan; Liu, Yangyang; Jiao, Xingxing
- Journal of The Electrochemical Society, Vol. 166, Issue 15
The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries
journal, October 2016
- Mehdi, B. Layla; Stevens, Andrew; Qian, Jiangfeng
- Scientific Reports, Vol. 6, Issue 1
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
In Situ Techniques for Developing Robust Li-S Batteries
journal, August 2018
- Li, Ming; Amirzadeh, Zhila; De Marco, Roland
- Small Methods, Vol. 2, Issue 11
New Insights into the Electrochemistry Superiority of Liquid Na–K Alloy in Metal Batteries
journal, February 2019
- Huang, Man; Xi, Baojuan; Feng, Zhenyu
- Small, Vol. 15, Issue 12
Operando monitoring the lithium spatial distribution of lithium metal anodes
journal, June 2018
- Lv, Shasha; Verhallen, Tomas; Vasileiadis, Alexandros
- Nature Communications, Vol. 9, Issue 1
A Review of Solid Electrolyte Interphases on Lithium Metal Anode
journal, November 2015
- Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi
- Advanced Science, Vol. 3, Issue 3
N -Methyl- N -propyl pyrrolidine bromide (MPPBr) as a bi-functional redox mediator for rechargeable Li–O 2 batteries
journal, January 2019
- Zheng, Cheng; Ding, Wenwen; Wang, Cheng
- Journal of Materials Chemistry A, Vol. 7, Issue 11
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
Recent Developments of the Lithium Metal Anode for Rechargeable Non-Aqueous Batteries
journal, July 2016
- Zhang, Kai; Lee, Gi-Hyeok; Park, Mihui
- Advanced Energy Materials, Vol. 6, Issue 20
Automated analysis of evolving interfaces during in situ electron microscopy
journal, February 2016
- Schneider, Nicholas M.; Park, Jeung Hun; Norton, Michael M.
- Advanced Structural and Chemical Imaging, Vol. 2, Issue 1
Template‐Assisted Synthesis of Honeycomb‐Like CoFe 2 O 4 /CNTs/rGO Composite as Anode Material for Li/Na‐Ion Batteries
journal, July 2019
- Zhao, Min; Xiong, Jian; Yang, Yang
- ChemElectroChem, Vol. 6, Issue 13
In situ formation of a multicomponent inorganic-rich SEI layer provides a fast charging and high specific energy Li-metal battery
journal, January 2019
- Sun, Ho-Hyun; Dolocan, Andrei; Weeks, Jason A.
- Journal of Materials Chemistry A, Vol. 7, Issue 30
Model systems for screening and investigation of lithium metal electrode chemistry and dendrite formation
journal, January 2020
- Kamphaus, Ethan P.; Hight, Karoline; Dermott, Micah
- Physical Chemistry Chemical Physics, Vol. 22, Issue 2
Emerging Electron Microscopy Techniques for Probing Functional Interfaces in Energy Materials
journal, January 2020
- Zachman, Michael J.; Hachtel, Jordan A.; Idrobo, Juan Carlos
- Angewandte Chemie International Edition, Vol. 59, Issue 4
A Review of Solid Electrolyte Interphases on Lithium Metal Anode
journal, November 2015
- Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi
- Advanced Science, Vol. 3, Issue 3
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 plasmonic optical fiber detection of the state of charge of supercapacitors for renewable energy storage
journal, July 2018
- Lao, Jiajie; Sun, Peng; Liu, Fu
- Light: Science & Applications, Vol. 7, Issue 1
The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries
journal, October 2016
- Mehdi, B. Layla; Stevens, Andrew; Qian, Jiangfeng
- Scientific Reports, Vol. 6, Issue 1
Synergistic Effects of Salt Concentration and Working Temperature towards Dendrite-Free Lithium Deposition
journal, October 2019
- Li, Panlong; Li, Chao; Yang, Yang
- Research, Vol. 2019