Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy
Abstract
Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by sum frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.
- Authors:
-
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); National Inst. of Metrology, Quality and Technology, Rio de Janiero (Brazil)
- Honda Research Inst., Inc., Columbus, OH (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Honda Research Inst., Inc., Columbus, OH (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES); Honda Research Inst. (United States)
- OSTI Identifier:
- 1379649
- Alternate Identifier(s):
- OSTI ID: 1378806
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Advanced Energy Materials
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 17; Journal ID: ISSN 1614-6832
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; fluorinated electrolytes; lithium-ion batteries; solid-electrolyte interface; sum frequency vibrational spectroscopy
Citation Formats
Horowitz, Yonatan, Han, Hui-Ling, Ralston, Walter T., de Araujo, Joyce Rodrigues, Kreidler, Eric, Brooks, Chris, and Somorjai, Gabor A. Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy. United States: N. p., 2017.
Web. doi:10.1002/aenm.201602060.
Horowitz, Yonatan, Han, Hui-Ling, Ralston, Walter T., de Araujo, Joyce Rodrigues, Kreidler, Eric, Brooks, Chris, & Somorjai, Gabor A. Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy. United States. https://doi.org/10.1002/aenm.201602060
Horowitz, Yonatan, Han, Hui-Ling, Ralston, Walter T., de Araujo, Joyce Rodrigues, Kreidler, Eric, Brooks, Chris, and Somorjai, Gabor A. 2017.
"Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy". United States. https://doi.org/10.1002/aenm.201602060. https://www.osti.gov/servlets/purl/1379649.
@article{osti_1379649,
title = {Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy},
author = {Horowitz, Yonatan and Han, Hui-Ling and Ralston, Walter T. and de Araujo, Joyce Rodrigues and Kreidler, Eric and Brooks, Chris and Somorjai, Gabor A.},
abstractNote = {Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by sum frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.},
doi = {10.1002/aenm.201602060},
url = {https://www.osti.gov/biblio/1379649},
journal = {Advanced Energy Materials},
issn = {1614-6832},
number = 17,
volume = 7,
place = {United States},
year = {Fri May 12 00:00:00 EDT 2017},
month = {Fri May 12 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Physical and Electrolytic Properties of Partially Fluorinated Organic Solvents and Its Application to Secondary Lithium Batteries: Partially Fluorinated Dialkoxyethanes
conference, January 2009
- Sasaki, Yukio; Shimazaki, Gengo; Nanbu, Noritoshi
- 214th ECS Meeting, ECS Transactions
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
Prospects for Dendrite-Free Cycling of Li Metal Batteries
journal, January 2015
- Chen, Qing; Geng, Ke; Sieradzki, K.
- Journal of The Electrochemical Society, Vol. 162, Issue 10
A Catalytic Path for Electrolyte Reduction in Lithium-Ion Cells Revealed by in Situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy
journal, February 2015
- Shi, Feifei; Ross, Philip N.; Zhao, Hui
- Journal of the American Chemical Society, Vol. 137, Issue 9
Progression of Solid Electrolyte Interphase Formation on Hydrogenated Amorphous Silicon Anodes for Lithium-Ion Batteries
journal, April 2012
- Arreaga-Salas, David E.; Sra, Amandeep K.; Roodenko, Katy
- The Journal of Physical Chemistry C, Vol. 116, Issue 16
Dendrite-Free Lithium Deposition with Self-Aligned Nanorod Structure
journal, November 2014
- Zhang, Yaohui; Qian, Jiangfeng; Xu, Wu
- Nano Letters, Vol. 14, Issue 12
In Situ Potentiodynamic Analysis of the Electrolyte/Silicon Electrodes Interface Reactions - A Sum Frequency Generation Vibrational Spectroscopy Study
journal, January 2016
- Horowitz, Yonatan; Han, Hui-Ling; Ross, Philip N.
- Journal of the American Chemical Society, Vol. 138, Issue 3
Polymer Adsorption on Graphite and CVD Graphene Surfaces Studied by Surface-Specific Vibrational Spectroscopy
journal, September 2015
- Su, Yudan; Han, Hui-Ling; Cai, Qun
- Nano Letters, Vol. 15, Issue 10
Investigation of the Chemical Purity of Silicon Surfaces Reacted with Liquid Methanol
journal, July 2008
- Michalak, David J.; Amy, Sandrine Rivillon; Estève, A.
- The Journal of Physical Chemistry C, Vol. 112, Issue 31
In Situ Probing of Solid-Electrolyte Interfaces with Nonlinear Coherent Vibrational Spectroscopy
journal, January 2012
- Mukherjee, Prabuddha; Lagutchev, Alexei; Dlott, Dana D.
- Journal of The Electrochemical Society, Vol. 159, Issue 3
Adsorption of dialkylethers of ethylene glycol (dialkoxyethane)at the free surface of water and at the Hg-water interface
journal, December 1988
- Daghetti, A.; Trasatti, S.; Zagorska, I.
- Electrochimica Acta, Vol. 33, Issue 12
Prototype systems for rechargeable magnesium batteries
journal, October 2000
- Aurbach, D.; Lu, Z.; Schechter, A.
- Nature, Vol. 407, Issue 6805, p. 724-727
Performance Enhancing Electrolyte Additives for Lithium Ion Batteries with Silicon Anodes
journal, January 2012
- Dalavi, Swapnil; Guduru, Pradeep; Lucht, Brett L.
- Journal of The Electrochemical Society, Vol. 159, Issue 5
Direct Determination of Solid-Electrolyte Interphase Thickness and Composition as a Function of State of Charge on a Silicon Anode
journal, August 2015
- Veith, Gabriel M.; Doucet, Mathieu; Baldwin, J. Kevin
- The Journal of Physical Chemistry C, Vol. 119, Issue 35
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004
- Xu, Kang
- Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418
Infrared Spectroscopy: Fundamentals and Applications
book, June 2004
- Stuart, Barbara H.
- Analytical Techniques in the Sciences
Progress in quantitative surface analysis by X-ray photoelectron spectroscopy: Current status and perspectives
journal, May 2010
- Powell, C. J.; Jablonski, A.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 178-179
Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014
- Xu, Kang
- Chemical Reviews, Vol. 114, Issue 23
Identification of Surface Films Formed on Lithium in Dimethoxyethane and Tetrahydrofuran Solutions
journal, January 1988
- Aurbach, D.
- Journal of The Electrochemical Society, Vol. 135, Issue 8
Poly(vinylidene fluoride)-graft-poly(2-hydroxyethyl methacrylate): a novel material for high energy density capacitors
journal, January 2011
- Thakur, Vijay Kumar; Tan, Eu Jin; Lin, Meng-Fang
- Journal of Materials Chemistry, Vol. 21, Issue 11
Confession of a Magnesium Battery
journal, August 2015
- Bucur, Claudiu B.; Gregory, Thomas; Oliver, Allen G.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 18
In Situ XRD and Electrochemical Study of the Reaction of Lithium with Amorphous Silicon
journal, January 2004
- Hatchard, T. D.; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 151, Issue 6
Dominant Decomposition Pathways for Ethereal Solvents in Li–O 2 Batteries
journal, April 2015
- García, Jeannette M.; Horn, Hans W.; Rice, Julia E.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 10
Electric Potential Gradient at the Buried Interface between Lithium-Ion Battery Electrodes and the SEI Observed Using Photoelectron Spectroscopy
journal, April 2016
- Maibach, Julia; Lindgren, Fredrik; Eriksson, Henrik
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 10
Structures and adsorption energetics for chemisorbed fluorine atoms on Si(100)-2×1
journal, April 1992
- Wu, Christine J.; Carter, Emily A.
- Physical Review B, Vol. 45, Issue 16
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
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
Superoxide (Electro)Chemistry on Well-Defined Surfaces in Organic Environments
journal, February 2016
- Genorio, Bostjan; Staszak-Jirkovský, Jakub; Assary, Rajeev S.
- The Journal of Physical Chemistry C, Vol. 120, Issue 29
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
Colossal Reversible Volume Changes in Lithium Alloys
journal, January 2001
- Beaulieu, L. Y.; Eberman, K. W.; Turner, R. L.
- Electrochemical and Solid-State Letters, Vol. 4, Issue 9
Vapor Phase Self-Assembly of Fluorinated Monolayers on Silicon and Germanium Oxide
journal, April 1997
- Hoffmann, Patrick W.; Stelzle, Martin; Rabolt, John F.
- Langmuir, Vol. 13, Issue 7
Preferential Adsorption of Solvents on the Cathode Surface of Lithium Ion Batteries
journal, April 2013
- Yu, Le; Liu, Huijin; Wang, Yan
- Angewandte Chemie International Edition, Vol. 52, Issue 22
Interfacial Processes of a Model Lithium Ion Battery Anode Observed, in Situ, with Vibrational Sum-Frequency Generation Spectroscopy
journal, May 2015
- Nicolau, Bruno G.; Garcı́a-Rey, Natalia; Dryzhakov, Bogdan
- The Journal of Physical Chemistry C, Vol. 119, Issue 19
Spectroscopic Insight into Li-Ion Batteries during Operation: An Alternative Infrared Approach
journal, November 2015
- Alves Dalla Corte, Daniel; Caillon, Georges; Jordy, Christian
- Advanced Energy Materials, Vol. 6, Issue 2
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
Role of Surface Oxides in the Formation of Solid–Electrolyte Interphases at Silicon Electrodes for Lithium-Ion Batteries
journal, November 2014
- Schroder, Kjell W.; Dylla, Anthony G.; Harris, Stephen J.
- ACS Applied Materials & Interfaces, Vol. 6, Issue 23
Microscopic properties of lithium, sodium, and magnesium battery anode materials related to possible dendrite growth
journal, November 2014
- Jäckle, Markus; Groß, Axel
- The Journal of Chemical Physics, Vol. 141, Issue 17
Nanopatterning Si(111) surfaces as a selective surface-chemistry route
journal, January 2010
- Michalak, David J.; Amy, Sandrine Rivillon; Aureau, Damien
- Nature Materials, Vol. 9, Issue 3
Adsorption of Propylene Carbonate (PC) on the LiCoO 2 Surface Investigated by Nonlinear Vibrational Spectroscopy
journal, November 2009
- Liu, Huijin; Tong, Yujin; Kuwata, Naoaki
- The Journal of Physical Chemistry C, Vol. 113, Issue 48
In-Situ Spectro-electrochemical Insight Revealing Distinctive Silicon Anode Solid Electrolyte Interphase Formation in a Lithium-ion Battery
journal, March 2016
- Yang , Junfeng; Solomatin, Nickolay; Kraytsberg, Alexander
- ChemistrySelect, Vol. 1, Issue 3
Role of Surface Functionality in the Electrochemical Performance of Silicon Nanowire Anodes for Rechargeable Lithium Batteries
journal, April 2014
- Zhou, Hui; Nanda, Jagjit; Martha, Surendra K.
- ACS Applied Materials & Interfaces, Vol. 6, Issue 10
Sum-frequency vibrational spectroscopy of the solid/liquid interface
journal, January 1995
- Bain, Colin D.
- Journal of the Chemical Society, Faraday Transactions, Vol. 91, Issue 9
High damage tolerance of electrochemically lithiated silicon
journal, September 2015
- Wang, Xueju; Fan, Feifei; Wang, Jiangwei
- Nature Communications, Vol. 6, Issue 1
Effect of electrolyte composition on initial cycling and impedance characteristics of lithium-ion cells
journal, May 2008
- Abraham, D. P.; Furczon, M. M.; Kang, S. -H.
- Journal of Power Sources, Vol. 180, Issue 1
High voltage stable liquid electrolytes for Li1+xMn2O4/carbon rocking-chair lithium batteries
journal, March 1995
- Guyomard, D.; Tarascon, J. M.
- Journal of Power Sources, Vol. 54, Issue 1
Dendrite Growth in Lithium/Polymer Systems
journal, January 2003
- Monroe, Charles; Newman, John
- Journal of The Electrochemical Society, Vol. 150, Issue 10
Surface properties probed by second-harmonic and sum-frequency generation
journal, February 1989
- Shen, Y. R.
- Nature, Vol. 337, Issue 6207
Structure of the Submonolayer of Ethanol Adsorption on a Vapor/Fused Silica Interface Studied with Sum Frequency Vibrational Spectroscopy
journal, November 2014
- Xu, Huijie; Zhang, Donghua; Hu, Jun
- The Journal of Physical Chemistry A, Vol. 119, Issue 19
Catalysis and Interfacial Chemistry in Lithium Batteries: A Surface Science Approach
journal, June 2014
- Ross, Philip N.
- Catalysis Letters, Vol. 144, Issue 8
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
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
Stable lithium electrodeposition in liquid and nanoporous solid electrolytes
journal, August 2014
- Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A.
- Nature Materials, Vol. 13, Issue 10
Works referencing / citing this record:
Fluor und Lithium: Ideale Partner für Elektrolyte in wiederaufladbaren Hochleistungsbatterien
journal, July 2019
- Aspern, N.; Röschenthaler, G. ‐V.; Winter, M.
- Angewandte Chemie, Vol. 131, Issue 45
Fluorine and Lithium: Ideal Partners for High‐Performance Rechargeable Battery Electrolytes
journal, November 2019
- Aspern, N.; Röschenthaler, G. ‐V.; Winter, M.
- Angewandte Chemie International Edition, Vol. 58, Issue 45