Anion Solvation in Carbonate Electrolytes

Zhang, Zhengcheng

doi:10.1021/acs.jpcc.5b08895

Anion Solvation in Carbonate Electrolytes

Journal Article · Mon Nov 16 04:00:00 EST 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b08895· OSTI ID:1244549

Zhang, Zhengcheng

With the correlation between Li+ solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. As of now, most studies are dedicated to the solvation of Li+, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. As a mirror effort to prior Li+ solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate, PF6–, and tetrafluoroborate, BF4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.

Research Organization:: Argonne National Laboratory (ANL)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1244549

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 49 Vol. 119; ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

References (48)

Li ⁺ -solvation/desolvation dictates interphasial processes on graphitic anode in Li ion cells Xu, Kang; von Wald Cresce, Arthur Journal of Materials Research, Vol. 27, Issue 18 https://doi.org/10.1557/jmr.2012.104	journal	August 2012
A Thermal Stabilizer for LiPF[sub 6]-Based Electrolytes of Li-Ion Cells Zhang, S. S.; Xu, K.; Jow, T. R. Electrochemical and Solid-State Letters, Vol. 5, Issue 9 https://doi.org/10.1149/1.1499669	journal	January 2002
Change of Conductivity with Salt Content, Solvent Composition, and Temperature for Electrolytes of LiPF[sub 6] in Ethylene Carbonate-Ethyl Methyl Carbonate Ding, M. S.; Xu, K.; Zhang, S. S. Journal of The Electrochemical Society, Vol. 148, Issue 10 https://doi.org/10.1149/1.1403730	journal	January 2001
Chemical Reactivity of PF[sub 5] and LiPF[sub 6] in Ethylene Carbonate/Dimethyl Carbonate Solutions Sloop, S. E.; Pugh, J. K.; Wang, S. Electrochemical and Solid-State Letters, Vol. 4, Issue 4 https://doi.org/10.1149/1.1353158	journal	January 2001
Effects of Solute–Solvent Hydrogen Bonding on Nonaqueous Electrolyte Structure Schroder, Kjell W.; Dylla, Anthony G.; Bishop, Logan D. C. The Journal of Physical Chemistry Letters, Vol. 6, Issue 15 https://doi.org/10.1021/acs.jpclett.5b01216	journal	July 2015
Role of Solution Structure in Solid Electrolyte Interphase Formation on Graphite with LiPF ₆ in Propylene Carbonate Nie, Mengyun; Abraham, Daniel P.; Seo, Daniel M. The Journal of Physical Chemistry C, Vol. 117, Issue 48 https://doi.org/10.1021/jp409765w	journal	November 2013
Quantum Chemistry Studies of the Oxidative Stability of Carbonate, Sulfone and Sulfonate-Based Electrolytes Doped with BF Borodin, Oleg; Jow, T. R. 218th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.3563092	conference	January 2011
Interfacing electrolytes with electrodes in Li ion batteries Xu, Kang; von Cresce, Arthur Journal of Materials Chemistry, Vol. 21, Issue 27 https://doi.org/10.1039/c0jm04309e	journal	January 2011
Kinetics of Lithium Ion Transfer at the Interface between Graphite and Liquid Electrolytes: Effects of Solvent and Surface Film Yamada, Yuki; Iriyama, Yasutoshi; Abe, Takeshi Langmuir, Vol. 25, Issue 21 https://doi.org/10.1021/la901829v	journal	November 2009
Measurement of the electrochemical oxidation of organic electrolytes used in lithium batteries by microelectrode Egashira, Minato; Takahashi, Hideki; Okada, Shigeto Journal of Power Sources, Vol. 92, Issue 1-2 https://doi.org/10.1016/S0378-7753(00)00553-X	journal	January 2001
Molecular Dynamics Simulation Studies of the Structure of a Mixed Carbonate/LiPF ₆ Electrolyte near Graphite Surface as a Function of Electrode Potential Vatamanu, Jenel; Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry C, Vol. 116, Issue 1 https://doi.org/10.1021/jp2101539	journal	December 2011
Electrolyte Solvation and Ionic Association Seo, Daniel M.; Borodin, Oleg; Han, Sang-Don Journal of The Electrochemical Society, Vol. 159, Issue 5 https://doi.org/10.1149/2.jes112264	journal	January 2012
Electrolyte Solvation and Ionic Association II. Acetonitrile-Lithium Salt Mixtures: Highly Dissociated Salts Seo, Daniel M.; Borodin, Oleg; Han, Sang-Don Journal of The Electrochemical Society, Vol. 159, Issue 9 https://doi.org/10.1149/2.035209jes	journal	January 2012
Unusual Stability of Acetonitrile-Based Superconcentrated Electrolytes for Fast-Charging Lithium-Ion Batteries Yamada, Yuki; Furukawa, Keizo; Sodeyama, Keitaro Journal of the American Chemical Society, Vol. 136, Issue 13, p. 5039-5046 https://doi.org/10.1021/ja412807w	journal	March 2014
Electrolyte Additive in Support of 5 V Li Ion Chemistry von Cresce, Arthur; Xu, Kang Journal of The Electrochemical Society, Vol. 158, Issue 3, p. A337-A342 https://doi.org/10.1149/1.3532047	journal	January 2011
Tris(pentafluorophenyl) Borane as an Additive to Improve the Power Capabilities of Lithium-Ion Batteries Chen, Zonghai; Amine, K. Journal of The Electrochemical Society, Vol. 153, Issue 6 https://doi.org/10.1149/1.2194633	journal	January 2006
Ligand Substitution and Interparticle Interactions in Solutions of Fluoroborate Complexes Plakhotnik, A. V.; Schmutzler, R.; Ernst, L. Russian Journal of Coordination Chemistry, Vol. 30, Issue 3 https://doi.org/10.1023/B:RUCO.0000022122.39508.5b	journal	March 2004
Preferential Solvation of Li+ Directs Formation of Interphase on Graphitic Anode von Cresce, Arthur; Xu, Kang Electrochemical and Solid-State Letters, Vol. 14, Issue 10 https://doi.org/10.1149/1.3615828	journal	January 2011
Nature of Tris(pentafluorophenyl)borane as a Functional Additive and Its Contribution to High Rate Performance in Lithium-Ion Secondary Battery Lee, Yong Min; Lee, Young-Gi; Kang, Yong-Mook Electrochemical and Solid-State Letters, Vol. 13, Issue 5 https://doi.org/10.1149/1.3329703	journal	January 2010
Molecular Modeling of Electrolytes Borodin, Oleg Modern Aspects of Electrochemistry https://doi.org/10.1007/978-1-4939-0302-3_8	book	January 2014
New electrolytes using Li2O or Li2O2 oxides and tris(pentafluorophenyl) borane as boron based anion receptor for lithium batteries Xie, B.; Lee, H. S.; Li, H. Electrochemistry Communications, Vol. 10, Issue 8 https://doi.org/10.1016/j.elecom.2008.05.043	journal	August 2008
Influence of the nature of the solvent on the chemical shift of the [BF4]− anion Plakhotnyk, Vladimir N.; Schmutzler, Reinhard; Ernst, Ludger Journal of Fluorine Chemistry, Vol. 116, Issue 1 https://doi.org/10.1016/S0022-1139(02)00072-6	journal	July 2002
Differentiating Contributions to “Ion Transfer” Barrier from Interphasial Resistance and Li ⁺ Desolvation at Electrolyte/Graphite Interface Xu, Kang; von Cresce, Arthur; Lee, Unchul Langmuir, Vol. 26, Issue 13 https://doi.org/10.1021/la1009994	journal	July 2010
Polarizable Force Field Development and Molecular Dynamics Simulations of Ionic Liquids Borodin, Oleg The Journal of Physical Chemistry B, Vol. 113, Issue 33 https://doi.org/10.1021/jp905220k	journal	August 2009
The Study of Electrolyte Solutions Based on Ethylene and Diethyl Carbonates for Rechargeable Li Batteries Aurbach, Doron Journal of The Electrochemical Society, Vol. 142, Issue 9 https://doi.org/10.1149/1.2048658	journal	January 1995
Dual-graphite chemistry enabled by a high voltage electrolyte Read, Jeffrey A.; Cresce, Arthur V.; Ervin, Matthew H. Energy Environ. Sci., Vol. 7, Issue 2 https://doi.org/10.1039/C3EE43333A	journal	January 2014
Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics Ong, Mitchell T.; Verners, Osvalds; Draeger, Erik W. The Journal of Physical Chemistry B, Vol. 119, Issue 4 https://doi.org/10.1021/jp508184f	journal	January 2015
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Carboranes: A New Class of Weakly Coordinating Anions for Strong Electrophiles, Oxidants, and Superacids Reed, Christopher A. Accounts of Chemical Research, Vol. 31, Issue 3 https://doi.org/10.1021/ar970230r	journal	March 1998
Structural Interactions within Lithium Salt Solvates: Acyclic Carbonates and Esters Afroz, Taliman; Seo, Daniel M.; Han, Sang-Don The Journal of Physical Chemistry C, Vol. 119, Issue 13 https://doi.org/10.1021/acs.jpcc.5b00309	journal	March 2015
Quantum Chemistry and Molecular Dynamics Simulation Study of Dimethyl Carbonate: Ethylene Carbonate Electrolytes Doped with LiPF ₆ Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry B, Vol. 113, Issue 6 https://doi.org/10.1021/jp809614h	journal	February 2009
Oxidative Stability and Initial Decomposition Reactions of Carbonate, Sulfone, and Alkyl Phosphate-Based Electrolytes Borodin, Oleg; Behl, Wishvender; Jow, T. Richard The Journal of Physical Chemistry C, Vol. 117, Issue 17 https://doi.org/10.1021/jp400527c	journal	April 2013
Solvation of the fluorine containing anions and their lithium salts in propylene carbonate and dimethoxyethane Chaban, Vitaly Journal of Molecular Modeling, Vol. 21, Issue 7 https://doi.org/10.1007/s00894-015-2717-y	journal	June 2015
Electrolyte Solvation and Ionic Association: VI. Acetonitrile-Lithium Salt Mixtures: Highly Associated Salts Revisited Borodin, Oleg; Han, Sang-Don; Daubert, James S. Journal of The Electrochemical Society, Vol. 162, Issue 4 https://doi.org/10.1149/2.0891503jes	journal	January 2015
Tris(hexafluoro-iso-propyl)phosphate as an SEI-Forming Additive on Improving the Electrochemical Performance of the Li[Li _0.2 Mn _0.56 Ni _0.16 Co _0.08 ]O ₂ Cathode Material Tan, Shi; Zhang, Zhongru; Li, Yixiao Journal of The Electrochemical Society, Vol. 160, Issue 2 https://doi.org/10.1149/2.066302jes	journal	December 2012
Preferential Adsorption of Solvents on the Cathode Surface of Lithium Ion Batteries Yu, Le; Liu, Huijin; Wang, Yan Angewandte Chemie, Vol. 125, Issue 22 https://doi.org/10.1002/ange.201209976	journal	April 2013
Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes Peled, E. Journal of The Electrochemical Society, Vol. 144, Issue 8 https://doi.org/10.1149/1.1837858	journal	January 1997
Insertion Electrode Materials for Rechargeable Lithium Batteries Winter, Martin; Besenhard, Jürgen O.; Spahr, Michael E. Advanced Materials, Vol. 10, Issue 10 https://doi.org/10.1002/(SICI)1521-4095(199807)10:10<725::AID-ADMA725>3.0.CO;2-Z	journal	July 1998
Understanding Li ⁺ –Solvent Interaction in Nonaqueous Carbonate Electrolytes with ¹⁷ O NMR Bogle, Xavier; Vazquez, Rafael; Greenbaum, Steven The Journal of Physical Chemistry Letters, Vol. 4, Issue 10 https://doi.org/10.1021/jz400661k	journal	May 2013
Toward Reliable Values of Electrochemical Stability Limits for Electrolytes Xu, Kang Journal of The Electrochemical Society, Vol. 146, Issue 11 https://doi.org/10.1149/1.1392609	journal	January 1999
Towards high throughput screening of electrochemical stability of battery electrolytes Borodin, Oleg; Olguin, Marco; Spear, Carrie E. Nanotechnology, Vol. 26, Issue 35 https://doi.org/10.1088/0957-4484/26/35/354003	journal	August 2015
Electrolyte solution for the improved cycling performance of LiCoPO4/C composite cathodes Sharabi, R.; Markevich, E.; Fridman, K. Electrochemistry Communications, Vol. 28 https://doi.org/10.1016/j.elecom.2012.12.001	journal	March 2013
Density Functional Theory Study of the Role of Anions on the Oxidative Decomposition Reaction of Propylene Carbonate Xing, Lidan; Borodin, Oleg; Smith, Grant D. The Journal of Physical Chemistry A, Vol. 115, Issue 47 https://doi.org/10.1021/jp206153n	journal	December 2011
Suppression of Convection Artifacts in Stimulated-Echo Diffusion Experiments. Double-Stimulated-Echo Experiments Jerschow, Alexej; Müller, Norbert Journal of Magnetic Resonance, Vol. 125, Issue 2 https://doi.org/10.1006/jmre.1997.1123	journal	April 1997
Interfacial reactions between graphite electrodes and propylene carbonate-based solutions: Electrolyte-concentration dependence of electrochemical lithium intercalation reaction Jeong, Soon-Ki; Inaba, Minoru; Iriyama, Yasutoshi Journal of Power Sources, Vol. 175, Issue 1 https://doi.org/10.1016/j.jpowsour.2007.08.065	journal	January 2008
Electrolytes and Interphases in Li-Ion Batteries and Beyond Xu, Kang Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500003w	journal	October 2014
Lithium transport within the solid electrolyte interphase Lu, Peng; Harris, Stephen J. Electrochemistry Communications, Vol. 13, Issue 10 https://doi.org/10.1016/j.elecom.2011.06.026	journal	October 2011
Structural Interactions within Lithium Salt Solvates: Cyclic Carbonates and Esters Seo, Daniel M.; Afroz, Taliman; Allen, Joshua L. The Journal of Physical Chemistry C, Vol. 118, Issue 45 https://doi.org/10.1021/jp5079168	journal	November 2014

Cited By (15)

“Water-in-Salt” Electrolyte Makes Aqueous Sodium-Ion Battery Safe, Green, and Long-Lasting Suo, Liumin; Borodin, Oleg; Wang, Yuesheng Advanced Energy Materials, Vol. 7, Issue 21 https://doi.org/10.1002/aenm.201701189	journal	July 2017
Exploring Classes of Co-Solvents for Fast-Charging Lithium-Ion Cells Hall, David S.; Eldesoky, Ahmed; Logan, E. R. Journal of The Electrochemical Society, Vol. 165, Issue 10 https://doi.org/10.1149/2.1351810jes	journal	January 2018
Dioxazolone and Nitrile Sulfite Electrolyte Additives for Lithium-Ion Cells Hall, David S.; Hynes, Toren; Dahn, J. R. Journal of The Electrochemical Society, Vol. 165, Issue 13 https://doi.org/10.1149/2.0341813jes	journal	January 2018
Intercalation Behavior of Hexafluorophosphate into Graphite Electrode from Propylene/Ethylmethyl Carbonates Fan, Hui; Qi, Li; Wang, Hongyu Journal of The Electrochemical Society, Vol. 164, Issue 9 https://doi.org/10.1149/2.0371712jes	journal	January 2017
Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy Zhang, Yirui; Katayama, Yu; Tatara, Ryoichi Energy & Environmental Science, Vol. 13, Issue 1 https://doi.org/10.1039/c9ee02543j	journal	January 2020
An ab initio molecular dynamics study of the solvation structure and ultrafast dynamics of lithium salts in organic carbonates: A comparison between linear and cyclic carbonates Zhang, Xiaoliu; Kuroda, Daniel G. The Journal of Chemical Physics, Vol. 150, Issue 18 https://doi.org/10.1063/1.5088820	journal	May 2019
The Solid-Electrolyte Interphase Formation Reactions of Ethylene Sulfate and Its Synergistic Chemistry with Prop-1-ene-1,3-Sultone in Lithium-Ion Cells Hall, David S.; Allen, J. P.; Glazier, Stephen L. Journal of The Electrochemical Society, Vol. 164, Issue 14 https://doi.org/10.1149/2.0181714jes	journal	January 2017
Progress in Aqueous Rechargeable Sodium-Ion Batteries Bin, Duan; Wang, Fei; Tamirat, Andebet Gedamu Advanced Energy Materials, Vol. 8, Issue 17 https://doi.org/10.1002/aenm.201703008	journal	March 2018
Converting detrimental HF in electrolytes into a highly fluorinated interphase on cathodes Ye, Changchun; Tu, Wenqiang; Yin, Limei Journal of Materials Chemistry A, Vol. 6, Issue 36 https://doi.org/10.1039/c8ta06150e	journal	January 2018
Properties of Ion Complexes and Their Impact on Charge Transport in Organic Solvent-Based Electrolyte Solutions for Lithium Batteries: Insights from a Theoretical Perspective Smiatek, Jens; Heuer, Andreas; Winter, Martin Batteries, Vol. 4, Issue 4 https://doi.org/10.3390/batteries4040062	journal	December 2018
Anion effects on the solvation structure and properties of imide lithium salt-based electrolytes Wang, Li; Luo, Zhen; Xu, Hong RSC Advances, Vol. 9, Issue 71 https://doi.org/10.1039/c9ra07824j	journal	January 2019
Stability of Li ₂ CO ₃ in cathode of lithium ion battery and its influence on electrochemical performance Bi, Yujing; Wang, Tao; Liu, Meng RSC Advances, Vol. 6, Issue 23 https://doi.org/10.1039/c6ra00648e	journal	January 2016
The nanoscale structure of the electrolyte–metal oxide interface Steinrück, Hans-Georg; Cao, Chuntian; Tsao, Yuchi Energy & Environmental Science, Vol. 11, Issue 3 https://doi.org/10.1039/c7ee02724a	journal	January 2018
Effect of standard light illumination on electrolyte’s stability of lithium-ion batteries based on ethylene and di-methyl carbonates Bouteau, Gaspard; Van-Nhien, Albert Nguyen; Sliwa, Michel Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-018-36836-9	journal	January 2019
Real-time mass spectrometric characterization of the solid–electrolyte interphase of a lithium-ion battery Zhou, Yufan; Su, Mao; Yu, Xiaofei Nature Nanotechnology, Vol. 15, Issue 3 https://doi.org/10.1038/s41565-019-0618-4	journal	January 2020

Similar Records

Anion Solvation in Carbonate-Based Electrolytes

Journal Article · Sun Nov 15 19:00:00 EST 2015 · Journal of Physical Chemistry. C · OSTI ID:1335377

Anion Effects on Interfacial Absorption of Gases in Ionic Liquids. A Molecular Dynamics Study

Journal Article · Thu Jun 02 00:00:00 EDT 2011 · Journal of Physical Chemistry B, 115(21):6964-6970 · OSTI ID:1015901

Solvate Structures and Computational/Spectroscopic Characterization of LiPF6 Electrolytes

Journal Article · Thu Apr 23 00:00:00 EDT 2015 · Journal of Physical Chemistry C, 119(16):8492-85 · OSTI ID:1221467

Anion Solvation in Carbonate Electrolytes

Citation Formats

References (48)

Cited By (15)

Similar Records

Related Subjects