Capacity Fade and Its Mitigation in Li-Ion Cells with Silicon-Graphite Electrodes
Abstract
Silicon-graphite (Si-Gr) electrodes typically contain lithiated carboxylates as polymer binders that are introduced through aqueous processing. Li-ion cells with such electrodes show significantly faster capacity fade than cells with graphite (Gr) electrodes. Here we examine the causes for capacity loss in Si-Gr cells containing LiPF6-based electrolytes. The presence of SiOxFy in the Si-Gr electrode, fluorophosphate species in the electrolyte, and silica on the positive electrode indicates the crucial role of the hydrolytic cycle. In particular, HF acid that is generated through LiPF6 hydrolysis corrodes Si particles. As it reacts, the released water re-enters the cycle. We trace the moisture initiating this detrimental cycle to the hydration water in the lithiated binders that cannot be fully removed by thermal treatment. The rate of HF corrosion can be reduced through the use of electrolyte additives. For the fluoroethylene carbonate (FEC) additive, the improved performance arises from changes to the solid electrolyte interphase (SEI) that serves as a barrier against HF attack. Here, we propose that the greater extent of polymer cross-linking, that gives FEC-derived SEI elastomer properties, slows down HF percolation through this SEI membrane and inhibits the formation of deep cracks through which HF can access and degrade the Si surface.
- Authors:
-
[1];
[1];
[1]
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Div.
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Div.; KTH Royal Institute of Technology, Stockholm (Sweden)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
- OSTI Identifier:
- 1405319
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 38; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 25 ENERGY STORAGE; NMR; XPS; electrochemistry; hydrolysis; lithium ion battery; polymer binder; silicon electrode
Citation Formats
Bareno, Javier, Shkrob, Ilya A., Gilbert, James A., Klett, Matilda, and Abraham, Daniel P. Capacity Fade and Its Mitigation in Li-Ion Cells with Silicon-Graphite Electrodes. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.7b06118.
Bareno, Javier, Shkrob, Ilya A., Gilbert, James A., Klett, Matilda, & Abraham, Daniel P. Capacity Fade and Its Mitigation in Li-Ion Cells with Silicon-Graphite Electrodes. United States. https://doi.org/10.1021/acs.jpcc.7b06118
Bareno, Javier, Shkrob, Ilya A., Gilbert, James A., Klett, Matilda, and Abraham, Daniel P. Wed .
"Capacity Fade and Its Mitigation in Li-Ion Cells with Silicon-Graphite Electrodes". United States. https://doi.org/10.1021/acs.jpcc.7b06118. https://www.osti.gov/servlets/purl/1405319.
@article{osti_1405319,
title = {Capacity Fade and Its Mitigation in Li-Ion Cells with Silicon-Graphite Electrodes},
author = {Bareno, Javier and Shkrob, Ilya A. and Gilbert, James A. and Klett, Matilda and Abraham, Daniel P.},
abstractNote = {Silicon-graphite (Si-Gr) electrodes typically contain lithiated carboxylates as polymer binders that are introduced through aqueous processing. Li-ion cells with such electrodes show significantly faster capacity fade than cells with graphite (Gr) electrodes. Here we examine the causes for capacity loss in Si-Gr cells containing LiPF6-based electrolytes. The presence of SiOxFy in the Si-Gr electrode, fluorophosphate species in the electrolyte, and silica on the positive electrode indicates the crucial role of the hydrolytic cycle. In particular, HF acid that is generated through LiPF6 hydrolysis corrodes Si particles. As it reacts, the released water re-enters the cycle. We trace the moisture initiating this detrimental cycle to the hydration water in the lithiated binders that cannot be fully removed by thermal treatment. The rate of HF corrosion can be reduced through the use of electrolyte additives. For the fluoroethylene carbonate (FEC) additive, the improved performance arises from changes to the solid electrolyte interphase (SEI) that serves as a barrier against HF attack. Here, we propose that the greater extent of polymer cross-linking, that gives FEC-derived SEI elastomer properties, slows down HF percolation through this SEI membrane and inhibits the formation of deep cracks through which HF can access and degrade the Si surface.},
doi = {10.1021/acs.jpcc.7b06118},
journal = {Journal of Physical Chemistry. C},
number = 38,
volume = 121,
place = {United States},
year = {2017},
month = {9}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 10 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
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
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
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
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
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
Hydrolysis in the system LiPF6—propylene carbonate—dimethyl carbonate—H2O
journal, January 2005
- Plakhotnyk, Andriy V.; Ernst, Ludger; Schmutzler, Reinhard
- Journal of Fluorine Chemistry, Vol. 126, Issue 1
Decomposition of LiPF 6 in High Energy Lithium-Ion Batteries Studied with Online Electrochemical Mass Spectrometry
journal, January 2016
- Guéguen, Aurélie; Streich, Daniel; He, Minglong
- Journal of The Electrochemical Society, Vol. 163, Issue 6
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
Thermal Decomposition of LiPF[sub 6]-Based Electrolytes for Lithium-Ion Batteries
journal, January 2005
- Campion, Christopher L.; Li, Wentao; Lucht, Brett L.
- Journal of The Electrochemical Society, Vol. 152, Issue 12
Additives for Stabilizing LiPF[sub 6]-Based Electrolytes Against Thermal Decomposition
journal, January 2005
- Li, Wentao; Campion, Christopher; Lucht, Brett L.
- Journal of The Electrochemical Society, Vol. 152, Issue 7
The Impact of Intentionally Added Water to the Electrolyte of Li-ion Cells: I. Cells with Graphite Negative Electrodes
journal, January 2013
- Burns, J. C.; Sinha, N. N.; Jain, Gaurav
- Journal of The Electrochemical Society, Vol. 160, Issue 11
Adsorbed Water on Nano-Silicon Powder and Its Effects on Charge and Discharge Characteristics as Anode in Lithium-Ion Batteries
journal, October 2016
- Yoshida, Shuhei; Masuo, Yuta; Shibata, Daisuke
- Journal of The Electrochemical Society, Vol. 164, Issue 1
Toward Efficient Binders for Li-Ion Battery Si-Based Anodes: Polyacrylic Acid
journal, October 2010
- Magasinski, Alexandre; Zdyrko, Bogdan; Kovalenko, Igor
- ACS Applied Materials & Interfaces, Vol. 2, Issue 11
Electrochemical lithiation performance and characterization of silicon–graphite composites with lithium, sodium, potassium, and ammonium polyacrylate binders
journal, January 2015
- Han, Zhen-Ji; Yamagiwa, Kiyofumi; Yabuuchi, Naoaki
- Physical Chemistry Chemical Physics, Vol. 17, Issue 5
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
Fluoroethylene Carbonate as an Important Component for the Formation of an Effective Solid Electrolyte Interphase on Anodes and Cathodes for Advanced Li-Ion Batteries
journal, May 2017
- Markevich, Elena; Salitra, Gregory; Aurbach, Doron
- ACS Energy Letters, Vol. 2, Issue 6
Hard X-ray Photoelectron Spectroscopy (HAXPES) Investigation of the Silicon Solid Electrolyte Interphase (SEI) in Lithium-Ion Batteries
journal, August 2015
- Young, Benjamin T.; Heskett, David R.; Nguyen, Cao Cuong
- ACS Applied Materials & Interfaces, Vol. 7, Issue 36
Fluoroethylene Carbonate and Vinylene Carbonate Reduction: Understanding Lithium-Ion Battery Electrolyte Additives and Solid Electrolyte Interphase Formation
journal, November 2016
- Michan, Alison L.; Parimalam, Bharathy. S.; Leskes, Michal
- Chemistry of Materials, Vol. 28, Issue 22
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
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
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
Poly(acrylic acid) (PAA) XPS Reference Core Level and Energy Loss Spectra
journal, December 2005
- Louette, Pierre; Bodino, Frederic; Pireaux, Jean-Jacques
- Surface Science Spectra, Vol. 12, Issue 1
Syntheses and Characterization of Lithium Alkyl Mono- and Dicarbonates as Components of Surface Films in Li-Ion Batteries
journal, March 2006
- Xu, Kang; Zhuang, Guorong V.; Allen, Jan L.
- The Journal of Physical Chemistry B, Vol. 110, Issue 15
Lithium Ethylene Dicarbonate Identified as the Primary Product of Chemical and Electrochemical Reduction of EC in 1.2 M LiPF 6 /EC:EMC Electrolyte
journal, September 2005
- Zhuang, Guorong V.; Xu, Kang; Yang, Hui
- The Journal of Physical Chemistry B, Vol. 109, Issue 37
Impact of Selected LiPF 6 Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells
journal, November 2016
- Wagner, Ralf; Korth, Martin; Streipert, Benjamin
- ACS Applied Materials & Interfaces, Vol. 8, Issue 45
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
Cycling Behavior of NCM523/Graphite Lithium-Ion Cells in the 3–4.4 V Range: Diagnostic Studies of Full Cells and Harvested Electrodes
journal, September 2016
- Gilbert, James A.; Bareño, Javier; Spila, Timothy
- Journal of The Electrochemical Society, Vol. 164, Issue 1
Hydration of poly(acrylic acid) lithium salts
journal, January 1980
- Hiraoka, Kyoko; Yokoyama, Tetsuo
- Polymer Bulletin, Vol. 3, Issue 4
Hydration of poly(acrylic acid) sodium salts
journal, February 1980
- Hiraoka, Kyoko; Yokoyama, Tetsuo
- Polymer Bulletin, Vol. 2, Issue 3
Hydration of poly(acrylic acid) potassium salts
journal, May 1980
- Hiraoka, Kyoko; Gotanda, Masatoshi; Yokoyama, Tetsuo
- Polymer Bulletin, Vol. 2, Issue 9
Thermal stability and degradation mechanisms of poly(acrylic acid) and its salts: Part 2—Sodium and potassium salts
journal, January 1990
- McNeill, I. C.; Sadeghi, S. M. T.
- Polymer Degradation and Stability, Vol. 30, Issue 2
Thermal properties of polyacrylic acid
journal, January 1975
- Kabanov, V. P.; Dubnitskaya, V. A.; Khar'kov, S. N.
- Polymer Science U.S.S.R., Vol. 17, Issue 7
Thermal stability and degradation mechanisms of poly(acrylic acid) and its salts: Part 1—Poly(acrylic acid)
journal, January 1990
- McNeill, I. C.; Sadeghi, S. M. T.
- Polymer Degradation and Stability, Vol. 29, Issue 2
Long-Term Lithium-Ion Battery Performance Improvement via Ultraviolet Light Treatment of the Graphite Anode
journal, January 2016
- An, Seong Jin; Li, Jianlin; Sheng, Yangping
- Journal of The Electrochemical Society, Vol. 163, Issue 14
A Novel Fluoride Process for Producing TiO2 from Titaniferous Ore
journal, January 1995
- Pong, Teresa K.; Besida, John; O'Donnell, Thomas A.
- Industrial & Engineering Chemistry Research, Vol. 34, Issue 1
Lithium-Ion Batteries Working at 85°C: Aging Phenomena and Electrode/Electrolyte Interfaces Studied by XPS
journal, January 2012
- Bodenes, Lucille; Dedryvère, Rémi; Martinez, Hervé
- Journal of The Electrochemical Society, Vol. 159, Issue 10
A High Precision Coulometry Study of the SEI Growth in Li/Graphite Cells
journal, January 2011
- Smith, A. J.; Burns, J. C.; Zhao, Xuemei
- Journal of The Electrochemical Society, Vol. 158, Issue 5
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
Aging mechanism in Li ion cells and calendar life predictions
journal, July 2001
- Broussely, M.; Herreyre, S.; Biensan, P.
- Journal of Power Sources, Vol. 97-98
Solvent Diffusion Model for Aging of Lithium-Ion Battery Cells
journal, January 2004
- Ploehn, Harry J.; Ramadass, Premanand; White, Ralph E.
- Journal of The Electrochemical Society, Vol. 151, Issue 3
What Makes Fluoroethylene Carbonate Different?
journal, June 2015
- Shkrob, Ilya A.; Wishart, James F.; Abraham, Daniel P.
- The Journal of Physical Chemistry C, Vol. 119, Issue 27
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
Allotropic Control: How Certain Fluorinated Carbonate Electrolytes Protect Aluminum Current Collectors by Promoting the Formation of Insoluble Coordination Polymers
journal, August 2016
- Shkrob, Ilya A.; Pupek, Krzysztof Z.; Abraham, Daniel P.
- The Journal of Physical Chemistry C, Vol. 120, Issue 33
On the Electrochemical Behavior of Aluminum Electrodes in Nonaqueous Electrolyte Solutions of Lithium Salts
journal, January 2010
- Markovsky, Boris; Amalraj, Francis; Gottlieb, Hugo E.
- Journal of The Electrochemical Society, Vol. 157, Issue 4
Aluminum Corrosion in Lithium Batteries An Investigation Using the Electrochemical Quartz Crystal Microbalance
journal, January 2000
- Yang, Haesik; Kwon, Kyungjung; Devine, Thomas M.
- Journal of The Electrochemical Society, Vol. 147, Issue 12
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004
- Xu, Kang
- Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418
Works referencing / citing this record:
Lithium ion car batteries: Present analysis and future predictions
journal, February 2019
- Arambarri, James; Hayden, James; Elkurdy, Mostafa
- Environmental Engineering Research, Vol. 24, Issue 4
Integration of Graphite and Silicon Anodes for the Commercialization of High‐Energy Lithium‐Ion Batteries
journal, January 2020
- Chae, Sujong; Choi, Seong‐Hyeon; Kim, Namhyung
- Angewandte Chemie International Edition, Vol. 59, Issue 1
Resistance Growth in Lithium-Ion Pouch Cells with LiNi 0.80 Co 0.15 Al 0.05 O 2 Positive Electrodes and Proposed Mechanism for Voltage Dependent Charge-Transfer Resistance
journal, January 2019
- Weber, Rochelle; Louli, A. J.; Plucknett, K. P.
- Journal of The Electrochemical Society, Vol. 166, Issue 10
Graphit‐ und‐Silicium‐Anoden für Lithiumionen‐ Hochenergiebatterien
journal, October 2019
- Chae, Sujong; Choi, Seong‐Hyeon; Kim, Namhyung
- Angewandte Chemie, Vol. 132, Issue 1
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
Dopamine-grafted heparin as an additive to the commercialized carboxymethyl cellulose/styrene-butadiene rubber binder for practical use of SiOx/graphite composite anode
journal, July 2018
- Lee, Kukjoo; Lim, Sanghyun; Go, Nakgyu
- Scientific Reports, Vol. 8, Issue 1
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