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Title: 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:
 [1];  [2];  [1];  [3];  [4];  [4];  [5]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); National Inst. of Metrology, Quality and Technology, Rio de Janiero (Brazil)
  4. Honda Research Inst., Inc., Columbus, OH (United States)
  5. 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 Lab. (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) (SC-22); Honda Research Inst. (United States)
OSTI Identifier:
1379649
Alternate Identifier(s):
OSTI ID: 1378806
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
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. doi:10.1002/aenm.201602060.
Horowitz, Yonatan, Han, Hui-Ling, Ralston, Walter T., de Araujo, Joyce Rodrigues, Kreidler, Eric, Brooks, Chris, and Somorjai, Gabor A. Fri . "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. doi: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},
journal = {Advanced Energy Materials},
number = 17,
volume = 7,
place = {United States},
year = {2017},
month = {5}
}

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Works referenced in this record:

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
  • DOI: 10.1021/jacs.6b02882

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
  • DOI: 10.1149/2.0261510jes

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
  • DOI: 10.1021/ja5128456

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
  • DOI: 10.1021/jp300787p

Dendrite-Free Lithium Deposition with Self-Aligned Nanorod Structure
journal, November 2014

  • Zhang, Yaohui; Qian, Jiangfeng; Xu, Wu
  • Nano Letters, Vol. 14, Issue 12
  • DOI: 10.1021/nl5039117

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
  • DOI: 10.1021/jacs.5b10333

Polymer Adsorption on Graphite and CVD Graphene Surfaces Studied by Surface-Specific Vibrational Spectroscopy
journal, September 2015


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
  • DOI: 10.1021/jp8030539

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
  • DOI: 10.1149/2.022203jes

Adsorption of dialkylethers of ethylene glycol (dialkoxyethane)at the free surface of water and at the Hg-water interface
journal, December 1988


Prototype systems for rechargeable magnesium batteries
journal, October 2000

  • Aurbach, D.; Lu, Z.; Schechter, A.
  • Nature, Vol. 407, Issue 6805, p. 724-727
  • DOI: 10.1038/35037553

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
  • DOI: 10.1149/2.076205jes

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
  • DOI: 10.1021/acs.jpcc.5b06817

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004


Progress in quantitative surface analysis by X-ray photoelectron spectroscopy: Current status and perspectives
journal, May 2010


Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014


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
  • DOI: 10.1149/1.2096170

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
  • DOI: 10.1039/c0jm02408b

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
  • DOI: 10.1021/acs.jpclett.5b01219

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
  • DOI: 10.1149/1.1739217

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
  • DOI: 10.1021/acs.jpclett.5b00529

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
  • DOI: 10.1021/acs.jpclett.6b00391

Structures and adsorption energetics for chemisorbed fluorine atoms on Si(100)-2×1
journal, April 1992


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
  • DOI: 10.1039/c0jm04353b

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
  • DOI: 10.1021/jp307372m

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
  • DOI: 10.1021/acs.jpcc.5b12230

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
  • DOI: 10.1149/2.004203jes

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
  • DOI: 10.1149/1.1388178

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
  • DOI: 10.1002/anie.201209976

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
  • DOI: 10.1021/acs.jpcc.5b01290

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
  • DOI: 10.1002/aenm.201501768

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
  • DOI: 10.1021/acs.jpcc.5b03591

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
  • DOI: 10.1021/am506517j

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
  • DOI: 10.1063/1.4901055

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
  • DOI: 10.1021/jp907146n

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
  • DOI: 10.1002/slct.201600119

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
  • DOI: 10.1021/am500855a

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
  • DOI: 10.1039/ft9959101281

High damage tolerance of electrochemically lithiated silicon
journal, September 2015

  • Wang, Xueju; Fan, Feifei; Wang, Jiangwei
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9417

Effect of electrolyte composition on initial cycling and impedance characteristics of lithium-ion cells
journal, May 2008


High voltage stable liquid electrolytes for Li1+xMn2O4/carbon rocking-chair lithium batteries
journal, March 1995


Dendrite Growth in Lithium/Polymer Systems
journal, January 2003

  • Monroe, Charles; Newman, John
  • Journal of The Electrochemical Society, Vol. 150, Issue 10
  • DOI: 10.1149/1.1606686

Surface properties probed by second-harmonic and sum-frequency generation
journal, February 1989


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
  • DOI: 10.1021/jp510706u

Catalysis and Interfacial Chemistry in Lithium Batteries: A Surface Science Approach
journal, June 2014


A Review of Solid Electrolyte Interphases on Lithium Metal Anode
journal, November 2015


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
  • DOI: 10.1038/nmat4041

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
  • DOI: 10.1038/nmat2611

    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
    • DOI: 10.1002/ange.201901381

    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
    • DOI: 10.1002/ange.201901381