Electrochemical Dilatometry of Si-Bearing Electrodes: Dimensional Changes and Experiment Design
Abstract
The severe volumetric changes in Si particles during the Li (de)alloying process cause expansion and contraction of the electrodes, which along with excessive electrolyte reduction and solid electrolyte interphase formation brings about rapid decay in cell capacity. In this work, we use operando electrochemical dilatometry to quantify the (de)lithiation-induced expansion/contraction of Si-based and graphite-rich electrodes during electrochemical cycling. We evaluate the relationship between electrode capacity and dilation and observe that by increasing the Si contribution to the electrode capacity, the swelling is aggravated upon lithiation. For silicon-rich anodes, the electrode dilation can be higher than 300%, and the expansion profile consists of a combination of slow swelling at low lithiation followed by an accelerated increase at higher lithium contents. We investigate how electrode properties, such as porosity, affect the dilation profile and quantify the irreversible expansion of the electrodes. Finally, we discuss some of the challenges associated with the dilatometry technique and suggest experimental approaches for obtaining consistent and reliable data.
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1755253
- Alternate Identifier(s):
- OSTI ID: 1777164
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society Journal Volume: 167 Journal Issue: 16; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; LiFSI; electrode polarization; electrode porosity; graphite; silicon
Citation Formats
Prado, Andressa Y. R., Rodrigues, Marco-Tulio F., Trask, Stephen E., Shaw, Leon, and Abraham, Daniel P. Electrochemical Dilatometry of Si-Bearing Electrodes: Dimensional Changes and Experiment Design. United States: N. p., 2020.
Web. doi:10.1149/1945-7111/abd465.
Prado, Andressa Y. R., Rodrigues, Marco-Tulio F., Trask, Stephen E., Shaw, Leon, & Abraham, Daniel P. Electrochemical Dilatometry of Si-Bearing Electrodes: Dimensional Changes and Experiment Design. United States. https://doi.org/10.1149/1945-7111/abd465
Prado, Andressa Y. R., Rodrigues, Marco-Tulio F., Trask, Stephen E., Shaw, Leon, and Abraham, Daniel P. Tue .
"Electrochemical Dilatometry of Si-Bearing Electrodes: Dimensional Changes and Experiment Design". United States. https://doi.org/10.1149/1945-7111/abd465.
@article{osti_1755253,
title = {Electrochemical Dilatometry of Si-Bearing Electrodes: Dimensional Changes and Experiment Design},
author = {Prado, Andressa Y. R. and Rodrigues, Marco-Tulio F. and Trask, Stephen E. and Shaw, Leon and Abraham, Daniel P.},
abstractNote = {The severe volumetric changes in Si particles during the Li (de)alloying process cause expansion and contraction of the electrodes, which along with excessive electrolyte reduction and solid electrolyte interphase formation brings about rapid decay in cell capacity. In this work, we use operando electrochemical dilatometry to quantify the (de)lithiation-induced expansion/contraction of Si-based and graphite-rich electrodes during electrochemical cycling. We evaluate the relationship between electrode capacity and dilation and observe that by increasing the Si contribution to the electrode capacity, the swelling is aggravated upon lithiation. For silicon-rich anodes, the electrode dilation can be higher than 300%, and the expansion profile consists of a combination of slow swelling at low lithiation followed by an accelerated increase at higher lithium contents. We investigate how electrode properties, such as porosity, affect the dilation profile and quantify the irreversible expansion of the electrodes. Finally, we discuss some of the challenges associated with the dilatometry technique and suggest experimental approaches for obtaining consistent and reliable data.},
doi = {10.1149/1945-7111/abd465},
journal = {Journal of the Electrochemical Society},
number = 16,
volume = 167,
place = {United States},
year = {Tue Dec 29 00:00:00 EST 2020},
month = {Tue Dec 29 00:00:00 EST 2020}
}
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Works referenced in this record:
Negative ion reactions with PF 5 and the electron affinity of PF 5
journal, May 1994
- Miller, Thomas M.; Stevens Miller, Amy E.; Viggiano, A. A.
- The Journal of Chemical Physics, Vol. 100, Issue 10
Volume Changes of Graphite Anodes Revisited: A Combined Operando X-ray Diffraction and In Situ Pressure Analysis Study
journal, April 2018
- Schweidler, Simon; de Biasi, Lea; Schiele, Alexander
- The Journal of Physical Chemistry C, Vol. 122, Issue 16
The compression behavior, microstructure evolution and properties variation of three kinds of commercial battery separators under compression load
journal, March 2020
- Ding, Lei; Zhang, Chao; Wu, Tong
- Journal of Power Sources, Vol. 451
Regulated Breathing Effect of Silicon Negative Electrode for Dramatically Enhanced Performance of Li-Ion Battery
journal, January 2015
- Xiao, Xingcheng; Zhou, Weidong; Kim, Youngnam
- Advanced Functional Materials, Vol. 25, Issue 9
Nanosized Si/cellulose fiber/carbon composites as high capacity anodes for lithium-ion batteries: A galvanostatic and dilatometric study
journal, November 2009
- Gómez Cámer, J. L.; Morales, J.; Sánchez, L.
- Electrochimica Acta, Vol. 54, Issue 26
Impact of the Slurry pH on the Expansion/Contraction Behavior of Silicon/Carbon/Carboxymethylcellulose Electrodes for Li-Ion Batteries
journal, January 2016
- Tranchot, A.; Idrissi, H.; Thivel, P. X.
- Journal of The Electrochemical Society, Vol. 163, Issue 6
An In Situ X-Ray Diffraction Study of the Reaction of Li with Crystalline Si
journal, January 2007
- Li, Jing; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 154, Issue 3
Protective coatings on silicon particles and their effect on energy density and specific energy in lithium ion battery cells: A model study
journal, June 2020
- Casino, Simone; Niehoff, Philip; Börner, Markus
- Journal of Energy Storage, Vol. 29
Operando Quantification of (De)Lithiation Behavior of Silicon-Graphite Blended Electrodes for Lithium-Ion Batteries
journal, January 2019
- Yao, Koffi P. C.; Okasinski, John S.; Kalaga, Kaushik
- Advanced Energy Materials, Vol. 9, Issue 8
On the correlation between electrode expansion and cycling stability of graphite/Si electrodes for Li-ion batteries
journal, August 2016
- Gómez-Cámer, Juan Luis; Bünzli, Christa; Hantel, Moritz M.
- Carbon, Vol. 105
Towards better estimability of electrode-specific state of health: Decoding the cell expansion
journal, July 2019
- Mohtat, Peyman; Lee, Suhak; Siegel, Jason B.
- Journal of Power Sources, Vol. 427
Multi-scale investigation of thickness changes in a commercial pouch type lithium-ion battery
journal, May 2016
- Rieger, B.; Schlueter, S.; Erhard, S. V.
- Journal of Energy Storage, Vol. 6
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
Dilatometric Investigations of Graphite Electrodes in Nonaqueous Lithium Battery Electrolytes
journal, January 2000
- Winter, Martin; Wrodnigg, Gerhard H.; Besenhard, Jürgen O.
- Journal of The Electrochemical Society, Vol. 147, Issue 7, p. 2427-2431
Ion transport restriction in mechanically strained separator membranes
journal, March 2013
- Cannarella, John; Arnold, Craig B.
- Journal of Power Sources, Vol. 226
Carbon-coated silicon as anode material for lithium ion batteries: advantages and limitations
journal, May 2003
- Dimov, Nikolay; Kugino, Satoshi; Yoshio, Masaki
- Electrochimica Acta, Vol. 48, Issue 11
Fast Charging of Li-Ion Cells: Part I. Using Li/Cu Reference Electrodes to Probe Individual Electrode Potentials
journal, January 2019
- Rodrigues, Marco-Tulio F.; Kalaga, Kaushik; Trask, Stephen E.
- Journal of The Electrochemical Society, Vol. 166, Issue 6
In situ X-ray spatial profiling reveals uneven compression of electrode assemblies and steep lateral gradients in lithium-ion coin cells
journal, January 2020
- Okasinski, John S.; Shkrob, Ilya A.; Chuang, Andrew
- Physical Chemistry Chemical Physics, Vol. 22, Issue 38
A continuum model of deformation, transport and irreversible changes in atomic structure in amorphous lithium–silicon electrodes
journal, October 2015
- Bower, Allan F.; Chason, Eric; Guduru, Pradeep R.
- Acta Materialia, Vol. 98
A Dilatometric Study of Lithium Intercalation into Powder-Type Graphite Electrodes
journal, January 2008
- Hahn, M.; Buqa, H.; Ruch, P. W.
- Electrochemical and Solid-State Letters, Vol. 11, Issue 9
Solid-State NMR and Electrochemical Dilatometry Study on Li[sup +] Uptake/Extraction Mechanism in SiO Electrode
journal, January 2007
- Kim, Taeahn; Park, Sangjin; Oh, Seung M.
- Journal of The Electrochemical Society, Vol. 154, Issue 12
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
Synthesis and Characterization of Nanoporous NiSi-Si Composite Anode for Lithium-Ion Batteries
journal, January 2007
- Liu, Wei-Ren; Wu, Nae-Lih; Shieh, Deng-Tswen
- Journal of The Electrochemical Society, Vol. 154, Issue 2
Facile fabrication of a nanoporous silicon electrode with superior stability for lithium ion batteries
journal, January 2011
- Du, Chunyu; Gao, Cuihua; Yin, Geping
- Energy & Environmental Science, Vol. 4, Issue 3
Structure and Properties of Li−Si Alloys: A First-Principles Study
journal, December 2010
- Kim, Hyunwoo; Chou, Chia-Yun; Ekerdt, John G.
- The Journal of Physical Chemistry C, Vol. 115, Issue 5
Stabilizing dimensional changes in Si-based composite electrodes by controlling the electrode porosity: An in situ electrochemical dilatometric study
journal, May 2011
- Jeong, Goojin; Lee, Sang Min; Choi, Nam Soon
- Electrochimica Acta, Vol. 56, Issue 14
Confronting Issues of the Practical Implementation of Si Anode in High-Energy Lithium-Ion Batteries
journal, September 2017
- Chae, Sujong; Ko, Minseong; Kim, Kyungho
- Joule, Vol. 1, Issue 1
Irreversible dilation of graphite composite anodes influenced by vinylene carbonate
journal, May 2020
- Ivanov, Svetlozar; Sauerteig, Daniel; Dimitrova, Anna
- Journal of Power Sources, Vol. 457
Si powders and electrodes for high-energy lithium-ion cells
journal, June 2020
- Haasch, Richard T.; Trask, Stephen E.; Rodrigues, Marco-T. F.
- Surface Science Spectra, Vol. 27, Issue 1
The mechanism of HF formation in LiPF6 based organic carbonate electrolytes
journal, January 2012
- Lux, S. F.; Lucas, I. T.; Pollak, E.
- Electrochemistry Communications, Vol. 14, Issue 1
Morphological Changes of Silicon Nanoparticles and the Influence of Cutoff Potentials in Silicon-Graphite Electrodes
journal, January 2018
- Wetjen, Morten; Solchenbach, Sophie; Pritzl, Daniel
- Journal of The Electrochemical Society, Vol. 165, Issue 7
Dynamics of Electrochemical Lithiation/Delithiation of Graphene-Encapsulated Silicon Nanoparticles Studied by In-situ TEM
journal, January 2014
- Luo, Langli; Wu, Jinsong; Luo, Jiayan
- Scientific Reports, Vol. 4, Issue 1
Si-Encapsulating Hollow Carbon Electrodes via Electroless Etching for Lithium-Ion Batteries
journal, September 2012
- Park, Yuwon; Choi, Nam-Soon; Park, Sangjin
- Advanced Energy Materials, Vol. 3, Issue 2
The effect of external compressive loads on the cycle lifetime of lithium-ion pouch cells
journal, October 2017
- Barai, Anup; Tangirala, Ravichandra; Uddin, Kotub
- Journal of Energy Storage, Vol. 13
Si-based materials for lithium-ion batteries I: Surface-modified Si/C powder
journal, June 2020
- Haasch, Richard T.; Abraham, Daniel P.
- Surface Science Spectra, Vol. 27, Issue 1
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
Extreme Fast Charge Challenges for Lithium-Ion Battery: Variability and Positive Electrode Issues
journal, January 2019
- Tanim, Tanvir R.; Dufek, Eric J.; Evans, Michael
- Journal of The Electrochemical Society, Vol. 166, Issue 10
Fast charging of an electric vehicle lithium-ion battery at the limit of the lithium deposition process
journal, July 2019
- Sieg, Johannes; Bandlow, Jochen; Mitsch, Tim
- Journal of Power Sources, Vol. 427
A step towards understanding the beneficial influence of a LIPON-based artificial SEI on silicon thin film anodes in lithium-ion batteries
journal, January 2018
- Reyes Jiménez, A.; Nölle, R.; Wagner, R.
- Nanoscale, Vol. 10, Issue 4
Studying the Kinetics of Crystalline Silicon Nanoparticle Lithiation with In Situ Transmission Electron Microscopy
journal, September 2012
- McDowell, Matthew T.; Ryu, Ill; Lee, Seok Woo
- Advanced Materials, Vol. 24, Issue 45
All-Solid Lithium Electrodes with Mixed-Conductor Matrix
journal, January 1981
- Boukamp, B. A.
- Journal of The Electrochemical Society, Vol. 128, Issue 4
30 Years of Lithium-Ion Batteries
journal, June 2018
- Li, Matthew; Lu, Jun; Chen, Zhongwei
- Advanced Materials, Vol. 30, Issue 33
Reaction of Li with Alloy Thin Films Studied by In Situ AFM
journal, January 2003
- Beaulieu, L. Y.; Hatchard, T. D.; Bonakdarpour, A.
- Journal of The Electrochemical Society, Vol. 150, Issue 11
Influence of the Si particle size on the mechanical stability of Si-based electrodes evaluated by in-operando dilatometry and acoustic emission
journal, October 2016
- Tranchot, A.; Idrissi, H.; Thivel, P. -X.
- Journal of Power Sources, Vol. 330
Reversible and irreversible dilation of lithium-ion battery electrodes investigated by in-situ dilatometry
journal, February 2017
- Sauerteig, Daniel; Ivanov, Svetlozar; Reinshagen, Holger
- Journal of Power Sources, Vol. 342
Modulating electrode utilization in lithium-ion cells with silicon-bearing anodes
journal, November 2020
- Rodrigues, Marco-Tulio F.; Prado, Andressa Y. R.; Trask, Stephen E.
- Journal of Power Sources, Vol. 477
Electrochemical Dilatometry Study on Si-Embedded Carbon Nanotube Powder Electrodes
journal, January 2007
- Park, Sangjin; Kim, Taeahn; Oh, Seung M.
- Electrochemical and Solid-State Letters, Vol. 10, Issue 6
Lithium bis(fluorosulfonyl)imide (LiFSI) as conducting salt for nonaqueous liquid electrolytes for lithium-ion batteries: Physicochemical and electrochemical properties
journal, April 2011
- Han, Hong-Bo; Zhou, Si-Si; Zhang, Dai-Jun
- Journal of Power Sources, Vol. 196, Issue 7
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
Pragmatic Approach to Design Silicon Alloy Anode by the Equilibrium Method
journal, February 2020
- Umirov, Nurzhan; Seo, Deok-Ho; Kim, Hyang-Yeon
- ACS Applied Materials & Interfaces, Vol. 12, Issue 15
Size-Dependent Fracture of Silicon Nanoparticles During Lithiation
journal, January 2012
- Liu, Xiao Hua; Zhong, Li; Huang, Shan
- ACS Nano, Vol. 6, Issue 2
Differentiating the Degradation Phenomena in Silicon-Graphite Electrodes for Lithium-Ion Batteries
journal, January 2017
- Wetjen, Morten; Pritzl, Daniel; Jung, Roland
- Journal of The Electrochemical Society, Vol. 164, Issue 12
Stable high-capacity and high-rate silicon-based lithium battery anodes upon two-dimensional covalent encapsulation
journal, July 2020
- Zhang, Xinghao; Wang, Denghui; Qiu, Xiongying
- Nature Communications, Vol. 11, Issue 1
Designing Polyolefin Separators to Minimize the Impact of Local Compressive Stresses on Lithium Ion Battery Performance
journal, January 2018
- Lagadec, Marie Francine; Zahn, Raphael; Wood, Vanessa
- Journal of The Electrochemical Society, Vol. 165, Issue 9
Intrinsic Chemical Reactivity of Silicon Electrode Materials: Gas Evolution
journal, March 2020
- Seitzinger, Claire L.; Sacci, Robert L.; Coyle, Jaclyn E.
- Chemistry of Materials, Vol. 32, Issue 7
Nano silicon for lithium-ion batteries
journal, November 2006
- Holzapfel, Michael; Buqa, Hilmi; Hardwick, Laurence J.
- Electrochimica Acta, Vol. 52, Issue 3
Calendar Aging and Gas Generation in Commercial Graphite/NMC-LMO Lithium-Ion Pouch Cell
journal, January 2017
- Mao, Z.; Farkhondeh, M.; Pritzker, M.
- Journal of The Electrochemical Society, Vol. 164, Issue 14
The role of mechanically induced separator creep in lithium-ion battery capacity fade
journal, October 2011
- Peabody, Christina; Arnold, Craig B.
- Journal of Power Sources, Vol. 196, Issue 19, p. 8147-8153
Structural Changes in Silicon Anodes during Lithium Insertion/Extraction
journal, January 2004
- Obrovac, M. N.; Christensen, Leif
- Electrochemical and Solid-State Letters, Vol. 7, Issue 5
Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte
journal, August 2010
- Luo, Jia-Yan; Cui, Wang-Jun; He, Ping
- Nature Chemistry, Vol. 2, Issue 9
Alloy Design for Lithium-Ion Battery Anodes
journal, January 2007
- Obrovac, M. N.; Christensen, Leif; Le, Dinh Ba
- Journal of The Electrochemical Society, Vol. 154, Issue 9, p. A849-A855