Auger Electrons as Probes for Composite Micro- and Nano- structured Materials: Application to Solid Electrolyte Interphases in Graphite and Silicon-Graphite Electrodes
Abstract
In this study, Auger electron spectroscopy (AES) combined with ion sputtering profilometry, Xray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) have been used in a complementary fashion to examine chemical and microstructural changes in graphite (Gr) and silicon/graphite (Si/Gr) blends contained in the negative electrodes of lithium-ion cells. We demonstrate how AES can be used to characterize morphology of the solid-electrolyte interphase (SEI) deposits in such heterogeneous media, complementing well-established methods, such as XPS and SEM. In this way we demonstrate that the SEI does not consist of uniformly thick layers on the graphite and silicon; the thickness of the SEI layers in cycle-life aged electrodes follows an exponential distribution with a mean of ca. 13 nm for the graphite and ca. 20-25 nm for the silicon nanoparticles (with a crystalline core of 50-70 nm in diameter). Furthermore, a “sticky-sphere” model, in which Si nanoparticles are covered with a layer of polymer binder (that is replaced by the SEI during cycling) of variable thickness is introduced to account for the features observed.
- Authors:
-
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Illinois at Urbana-Champaign, Urbana, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
- OSTI Identifier:
- 1411171
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Auger electron spectroscopy; photoelectron spectroscopy; lithium ion battery; silicon anode; solid electrolyte interphase
Citation Formats
Kalaga, Kaushik, Shkrob, Ilya A., Haasch, Richard T., Peebles, Cameron, Bareno, Javier, and Abraham, Daniel P. Auger Electrons as Probes for Composite Micro- and Nano- structured Materials: Application to Solid Electrolyte Interphases in Graphite and Silicon-Graphite Electrodes. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.7b08279.
Kalaga, Kaushik, Shkrob, Ilya A., Haasch, Richard T., Peebles, Cameron, Bareno, Javier, & Abraham, Daniel P. Auger Electrons as Probes for Composite Micro- and Nano- structured Materials: Application to Solid Electrolyte Interphases in Graphite and Silicon-Graphite Electrodes. United States. https://doi.org/10.1021/acs.jpcc.7b08279
Kalaga, Kaushik, Shkrob, Ilya A., Haasch, Richard T., Peebles, Cameron, Bareno, Javier, and Abraham, Daniel P. Thu .
"Auger Electrons as Probes for Composite Micro- and Nano- structured Materials: Application to Solid Electrolyte Interphases in Graphite and Silicon-Graphite Electrodes". United States. https://doi.org/10.1021/acs.jpcc.7b08279. https://www.osti.gov/servlets/purl/1411171.
@article{osti_1411171,
title = {Auger Electrons as Probes for Composite Micro- and Nano- structured Materials: Application to Solid Electrolyte Interphases in Graphite and Silicon-Graphite Electrodes},
author = {Kalaga, Kaushik and Shkrob, Ilya A. and Haasch, Richard T. and Peebles, Cameron and Bareno, Javier and Abraham, Daniel P},
abstractNote = {In this study, Auger electron spectroscopy (AES) combined with ion sputtering profilometry, Xray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) have been used in a complementary fashion to examine chemical and microstructural changes in graphite (Gr) and silicon/graphite (Si/Gr) blends contained in the negative electrodes of lithium-ion cells. We demonstrate how AES can be used to characterize morphology of the solid-electrolyte interphase (SEI) deposits in such heterogeneous media, complementing well-established methods, such as XPS and SEM. In this way we demonstrate that the SEI does not consist of uniformly thick layers on the graphite and silicon; the thickness of the SEI layers in cycle-life aged electrodes follows an exponential distribution with a mean of ca. 13 nm for the graphite and ca. 20-25 nm for the silicon nanoparticles (with a crystalline core of 50-70 nm in diameter). Furthermore, a “sticky-sphere” model, in which Si nanoparticles are covered with a layer of polymer binder (that is replaced by the SEI during cycling) of variable thickness is introduced to account for the features observed.},
doi = {10.1021/acs.jpcc.7b08279},
journal = {Journal of Physical Chemistry. C},
number = ,
volume = 121,
place = {United States},
year = {Thu Oct 05 00:00:00 EDT 2017},
month = {Thu Oct 05 00:00:00 EDT 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 20 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
Li-alloy based anode materials for Li secondary batteries
journal, January 2010
- Park, Cheol-Min; Kim, Jae-Hun; Kim, Hansu
- Chemical Society Reviews, Vol. 39, Issue 8, p. 3115-3141
Silicon-based materials as high capacity anodes for next generation lithium ion batteries
journal, December 2014
- Liang, Bo; Liu, Yanping; Xu, Yunhua
- Journal of Power Sources, Vol. 267
Electrode Behavior RE-Visited: Monitoring Potential Windows, Capacity Loss, and Impedance Changes in Li 1.03 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.97 O 2 /Silicon-Graphite Full Cells
journal, January 2016
- Klett, Matilda; Gilbert, James A.; Trask, Stephen E.
- Journal of The Electrochemical Society, Vol. 163, Issue 6
Performance of Full Cells Containing Carbonate-Based LiFSI Electrolytes and Silicon-Graphite Negative Electrodes
journal, December 2015
- Trask, Stephen E.; Pupek, Krzysztof Z.; Gilbert, James A.
- Journal of The Electrochemical Society, Vol. 163, Issue 3
Layered Oxide, Graphite and Silicon-Graphite Electrodes for Lithium-Ion Cells: Effect of Electrolyte Composition and Cycling Windows
journal, October 2016
- Klett, Matilda; Gilbert, James A.; Pupek, Krzysztof Z.
- Journal of The Electrochemical Society, Vol. 164, Issue 1
Toward Silicon Anodes for Next-Generation Lithium Ion Batteries: A Comparative Performance Study of Various Polymer Binders and Silicon Nanopowders
journal, July 2013
- Erk, Christoph; Brezesinski, Torsten; Sommer, Heino
- ACS Applied Materials & Interfaces, Vol. 5, Issue 15
Influence of inactive electrode components on degradation phenomena in nano-Si electrodes for Li-ion batteries
journal, September 2016
- Jeschull, Fabian; Lindgren, Fredrik; Lacey, Matthew J.
- Journal of Power Sources, Vol. 325
Lithium Polyacrylate (LiPAA) as an Advanced Binder and a Passivating Agent for High-Voltage Li-Ion Batteries
journal, September 2015
- Pieczonka, Nicholas P. W.; Borgel, Valentina; Ziv, Baruch
- Advanced Energy Materials, Vol. 5, Issue 23
SEI-component formation on sub 5 nm sized silicon nanoparticles in Li-ion batteries: the role of electrode preparation, FEC addition and binders
journal, January 2015
- Jaumann, Tony; Balach, Juan; Klose, Markus
- Physical Chemistry Chemical Physics, Vol. 17, Issue 38
Multiprobe Study of the Solid Electrolyte Interphase on Silicon-Based Electrodes in Full-Cell Configuration
journal, April 2016
- Dupré, N.; Moreau, P.; De Vito, E.
- Chemistry of Materials, Vol. 28, Issue 8
Understanding interfacial chemistry and stability for performance improvement and fade of high-energy Li-ion battery of LiNi0.5Co0.2Mn0.3O2//silicon-graphite
journal, January 2016
- Nguyen, Dan-Thien; Kang, Joonsup; Nam, Kyoung-Mo
- Journal of Power Sources, Vol. 303
Improved Performances of Nanosilicon Electrodes Using the Salt LiFSI: A Photoelectron Spectroscopy Study
journal, June 2013
- Philippe, Bertrand; Dedryvère, Rémi; Gorgoi, Mihaela
- Journal of the American Chemical Society, Vol. 135, Issue 26
Role of the LiPF 6 Salt for the Long-Term Stability of Silicon Electrodes in Li-Ion Batteries – A Photoelectron Spectroscopy Study
journal, January 2013
- Philippe, Bertrand; Dedryvère, Rémi; Gorgoi, Mihaela
- Chemistry of Materials, Vol. 25, Issue 3
Improved Performance of the Silicon Anode for Li-Ion Batteries: Understanding the Surface Modification Mechanism of Fluoroethylene Carbonate as an Effective Electrolyte Additive
journal, March 2015
- Xu, Chao; Lindgren, Fredrik; Philippe, Bertrand
- Chemistry of Materials, Vol. 27, Issue 7
Nanosilicon Electrodes for Lithium-Ion Batteries: Interfacial Mechanisms Studied by Hard and Soft X-ray Photoelectron Spectroscopy
journal, February 2012
- Philippe, Bertrand; Dedryvère, Rémi; Allouche, Joachim
- Chemistry of Materials, Vol. 24, Issue 6
The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling
journal, August 2016
- An, Seong Jin; Li, Jianlin; Daniel, Claus
- Carbon, Vol. 105
The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes
journal, August 2015
- Schroder, Kjell; Alvarado, Judith; Yersak, Thomas A.
- Chemistry of Materials, Vol. 27, Issue 16
Systematic Investigation of Binders for Silicon Anodes: Interactions of Binder with Silicon Particles and Electrolytes and Effects of Binders on Solid Electrolyte Interphase Formation
journal, May 2016
- Nguyen, Cao Cuong; Yoon, Taeho; Seo, Daniel M.
- ACS Applied Materials & Interfaces, Vol. 8, Issue 19
Solid Electrolyte Interphase Growth and Capacity Loss in Silicon Electrodes
journal, June 2016
- Michan, Alison L.; Divitini, Giorgio; Pell, Andrew J.
- Journal of the American Chemical Society, Vol. 138, Issue 25
Elucidating the Surface Reactions of an Amorphous Si Thin Film as a Model Electrode for Li-Ion Batteries
journal, October 2016
- Ferraresi, Giulio; Czornomaz, Lukas; Villevieille, Claire
- ACS Applied Materials & Interfaces, Vol. 8, Issue 43
In Situ Observation and Long-Term Reactivity of Si/C/CMC Composites Electrodes for Li-Ion Batteries
journal, January 2011
- Bridel, J-S.; Azaïs, T.; Morcrette, M.
- Journal of The Electrochemical Society, Vol. 158, Issue 6
Voltage Dependent Solid Electrolyte Interphase Formation in Silicon Electrodes: Monitoring the Formation of Organic Decomposition Products
journal, December 2015
- Michan, Alison L.; Leskes, Michal; Grey, Clare P.
- Chemistry of Materials, Vol. 28, Issue 1
Identification of Li-Ion Battery SEI Compounds through 7 Li and 13 C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry
journal, December 2015
- Huff, Laura A.; Tavassol, Hadi; Esbenshade, Jennifer L.
- ACS Applied Materials & Interfaces, Vol. 8, Issue 1
In Situ Investigations of SEI Layer Growth on Electrode Materials for Lithium-Ion Batteries Using Spectroscopic Ellipsometry
journal, January 2012
- McArthur, M. A.; Trussler, S.; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 159, Issue 3
Determination of the Solid Electrolyte Interphase Structure Grown on a Silicon Electrode Using a Fluoroethylene Carbonate Additive
journal, July 2017
- Veith, Gabriel M.; Doucet, Mathieu; Sacci, Robert L.
- Scientific Reports, Vol. 7, Issue 1
In Situ and Quantitative Characterization of Solid Electrolyte Interphases
journal, February 2014
- Cresce, Arthur v.; Russell, Selena M.; Baker, David R.
- Nano Letters, Vol. 14, Issue 3
Evolution of the 3D Microstructure of a Si-Based Electrode for Li-Ion Batteries Investigated by FIB/SEM Tomography
journal, January 2016
- Etiemble, Aurélien; Tranchot, Alix; Douillard, Thierry
- Journal of The Electrochemical Society, Vol. 163, Issue 8
Quantifying microstructural dynamics and electrochemical activity of graphite and silicon-graphite lithium ion battery anodes
journal, September 2016
- Pietsch, Patrick; Westhoff, Daniel; Feinauer, Julian
- Nature Communications, Vol. 7, Issue 1
Failure mechanisms of nano-silicon anodes upon cycling: an electrode porosity evolution model
journal, January 2014
- Radvanyi, Etienne; Porcher, Willy; De Vito, Eric
- Phys. Chem. Chem. Phys., Vol. 16, Issue 32
An Introduction to Surface Analysis by XPS and AES
book, March 2003
- Watts, John F.; Wolstenholme, John
- Wiley
Investigation of silica nanoparticles by Auger electron spectroscopy (AES): Characterization of nanoparticles by Auger electron spectroscopy
journal, January 2014
- Rades, S.; Wirth, T.; Unger, W.
- Surface and Interface Analysis, Vol. 46, Issue 10-11
Electrochemically lithiated graphite characterised by photoelectron spectroscopy
journal, June 2003
- Andersson, A. M.; Henningson, A.; Siegbahn, H.
- Journal of Power Sources, Vol. 119-121
Smoothing and Differentiation of Data by Simplified Least Squares Procedures.
journal, July 1964
- Savitzky, Abraham.; Golay, M. J. E.
- Analytical Chemistry, Vol. 36, Issue 8
Chemical Shifts of Auger Electron Lines and Electron Binding Energies in Free Molecules. Silicon Compounds
journal, January 1980
- Kelfve, P.; Blomster, B.; Siegbahn, H.
- Physica Scripta, Vol. 21, Issue 1
Auger Si LVV, O KLL and N KLL lineshapes at air-exposed silicon nitride surfaces: Pattern recognition analysis
journal, November 1994
- Zemek, J.; Vystrcil, T.; Lesiak-Orlowska, B.
- Surface and Interface Analysis, Vol. 21, Issue 11
Experimental determination of attenuation lengths of photo- and augerelectrons in silicon dioxide and in silicon nitride in the energy range 500 eV < Ekin < 3100 eV
journal, July 1994
- Ebel, M. F.; Ebel, H.; Hofmann, A.
- Surface and Interface Analysis, Vol. 22, Issue 1-12
Sputter depth profiling: past, present, and future: Sputter depth profiling: past, present, and future
journal, April 2014
- Hofmann, S.
- Surface and Interface Analysis, Vol. 46, Issue 10-11
Sputtering of nanoparticles: Molecular dynamics study of Au impact on 20nm sized Au nanoparticles
journal, April 2008
- Zimmermann, Steffen; Urbassek, Herbert M.
- International Journal of Mass Spectrometry, Vol. 272, Issue 1
Sputtering of Si nanospheres
journal, July 2014
- Nietiadi, Maureen L.; Sandoval, Luis; Urbassek, Herbert M.
- Physical Review B, Vol. 90, Issue 4
Sputtering of freestanding metal nanocrystals
journal, February 2012
- Järvi, T. T.; Nordlund, K.
- Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 272
Depth Profiling and Melting of Nanoparticles in Secondary Ion Mass Spectrometry (SIMS)
journal, July 2013
- Yang, Li; Seah, Martin P.; Gilmore, Ian S.
- The Journal of Physical Chemistry C, Vol. 117, Issue 31
Angular dependence of sputtering yield of amorphous and polycrystalline materials
journal, August 2008
- Wei, Qiangmin; Li, Kun-Dar; Lian, Jie
- Journal of Physics D: Applied Physics, Vol. 41, Issue 17
Topography effects and monatomic ion sputtering of undulating surfaces, particles and large nanoparticles: Sputtering yields, effective sputter rates and topography evolution
journal, June 2011
- Seah, M. P.
- Surface and Interface Analysis, Vol. 44, Issue 2
Reduction of Carbonate Electrolytes and the Formation of Solid-Electrolyte Interface (SEI) in Lithium-Ion Batteries. 2. Radiolytically Induced Polymerization of Ethylene Carbonate
journal, September 2013
- Shkrob, Ilya A.; Zhu, Ye; Marin, Timothy W.
- The Journal of Physical Chemistry C, Vol. 117, Issue 38, p. 19270-19279
Reduction of Carbonate Electrolytes and the Formation of Solid-Electrolyte Interface (SEI) in Lithium-Ion Batteries. 1. Spectroscopic Observations of Radical Intermediates Generated in One-Electron Reduction of Carbonates
journal, September 2013
- Shkrob, Ilya A.; Zhu, Ye; Marin, Timothy W.
- The Journal of Physical Chemistry C, Vol. 117, Issue 38, p. 19255-19269
Failure and Stabilization Mechanisms of Graphite Electrodes
journal, March 1997
- Aurbach, Doron; Levi, Mikhail D.; Levi, Elena
- The Journal of Physical Chemistry B, Vol. 101, Issue 12
Identification of Surface Films Formed on Lithium in Propylene Carbonate Solutions
journal, January 1987
- Aurbach, D.
- Journal of The Electrochemical Society, Vol. 134, Issue 7
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
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004
- Xu, Kang
- Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418
Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014
- Xu, Kang
- Chemical Reviews, Vol. 114, Issue 23
Silicon Solid Electrolyte Interphase (SEI) of Lithium Ion Battery Characterized by Microscopy and Spectroscopy
journal, June 2013
- Nie, Mengyun; Abraham, Daniel P.; Chen, Yanjing
- The Journal of Physical Chemistry C, Vol. 117, Issue 26
Characterization of maximally random jammed sphere packings: Voronoi correlation functions
journal, November 2014
- Klatt, Michael A.; Torquato, Salvatore
- Physical Review E, Vol. 90, Issue 5
The structure of a hard-sphere fluid in contact with a soft repulsive wall
journal, January 1977
- Abraham, Farid F.; Singh, Y.
- The Journal of Chemical Physics, Vol. 67, Issue 5
On the interface between a fluid and a planar wall: Theory and simulations of a hard sphere fluid at a hard wall
journal, March 1984
- Henderson, J. R.; van Swol, Frank
- Molecular Physics, Vol. 51, Issue 4
Monte Carlo study of a hard‐sphere fluid near a hard wall
journal, March 1978
- Snook, Ian K.; Henderson, Douglas
- The Journal of Chemical Physics, Vol. 68, Issue 5
Exceptional Electrochemical Performance of Si-Nanowires in 1,3-Dioxolane Solutions: A Surface Chemical Investigation
journal, March 2012
- Etacheri, Vinodkumar; Geiger, Uzi; Gofer, Yossi
- Langmuir, Vol. 28, Issue 14
Works referencing / citing this record:
Designing superior solid electrolyte interfaces on silicon anodes for high-performance lithium-ion batteries
journal, January 2019
- Zhang, Yaguang; Du, Ning; Yang, Deren
- Nanoscale, Vol. 11, Issue 41
Rapid coating of asphalt to prepare carbon-encapsulated composites of nano-silicon and graphite for lithium battery anodes
journal, December 2019
- Liu, Wenping; Xu, Huarui; Qin, Haiqing
- Journal of Materials Science, Vol. 55, Issue 10