Li + solvation and kinetics of Li+–BF4-/PF 6 - ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

Chang, Tsun-Mei; Dang, Liem X.

doi:10.1063/1.4991565

Title: Li ⁺ solvation and kinetics of Li⁺–BF₄^-/PF ₆ ^- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

Journal Article · Sat Oct 28 00:00:00 EDT 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4991565· OSTI ID:1422313

^[1]; Dang, Liem X. ^[2]

Department of Chemistry, University of Wisconsin–Parkside, Kenosha, Wisconsin 53141, USA
Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 93352, USA

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+-[BF4] and Li+-[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux; Impey, Madden, and McDonald approaches; and Grote-Hynes theory. We found the residence times of EC around Li+ ions varied from 70 to 450 ps, depending on the correction method used. We found the relaxation times changed significantly from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influence the dissociation kinetics of ion pairing. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1422313

Report Number(s):: PNNL-SA-125713; KC0301050

Journal Information:: Journal of Chemical Physics, Vol. 147, Issue 16; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

References (36)

Hydration and mobility of ions in solution Impey, R. W.; Madden, P. A.; McDonald, I. R. The Journal of Physical Chemistry, Vol. 87, Issue 25 https://doi.org/10.1021/j150643a008	journal	December 1983
Statistical mechanics of isomerization dynamics in liquids and the transition state approximation Chandler, David The Journal of Chemical Physics, Vol. 68, Issue 6 https://doi.org/10.1063/1.436049	journal	January 1978
Molecular Dynamics Simulation of Li⁺BF₄^- in Ethylene Carbonate, Propylene Carbonate, and Dimethyl Carbonate Solvents Soetens, Jean-Christophe; Millot, Claude; Maigret, Bernard The Journal of Physical Chemistry A, Vol. 102, Issue 7 https://doi.org/10.1021/jp972457+	journal	January 1998
Current status of transition-state theory Truhlar, Donald G.; Hase, William L.; Hynes, James T. The Journal of Physical Chemistry, Vol. 87, Issue 15 https://doi.org/10.1021/j100238a003	journal	July 1983
Anion Effects on Interfacial Absorption of Gases in Ionic Liquids. A Molecular Dynamics Study Dang, Liem X.; Wick, Collin D. The Journal of Physical Chemistry B, Vol. 115, Issue 21 https://doi.org/10.1021/jp201113c	journal	June 2011
Coordination Number of Li ⁺ in Nonaqueous Electrolyte Solutions Determined by Molecular Rotational Measurements Yuan, Kaijun; Bian, Hongtao; Shen, Yuneng The Journal of Physical Chemistry B, Vol. 118, Issue 13 https://doi.org/10.1021/jp500877u	journal	March 2014
Gas Evolution in Operating Lithium-Ion Batteries Studied In Situ by Neutron Imaging Michalak, Barbara; Sommer, Heino; Mannes, David Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep15627	journal	October 2015
Development of Polarizable Models for Molecular Mechanical Calculations I: Parameterization of Atomic Polarizability Wang, Junmei; Cieplak, Piotr; Li, Jie The Journal of Physical Chemistry B, Vol. 115, Issue 12 https://doi.org/10.1021/jp112133g	journal	March 2011
CO[sub 2] Gas Evolution on Cathode Materials for Lithium-Ion Batteries Wuersig, Andreas; Scheifele, Werner; Novák, Petr Journal of The Electrochemical Society, Vol. 154, Issue 5 https://doi.org/10.1149/1.2712138	journal	January 2007
Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C. Journal of Computational Physics, Vol. 23, Issue 3 https://doi.org/10.1016/0021-9991(77)90098-5	journal	March 1977
Electronic Structure Modeling of Electrochemical Reactions at Electrode/Electrolyte Interfaces in Lithium Ion Batteries Leung, Kevin The Journal of Physical Chemistry C, Vol. 117, Issue 4 https://doi.org/10.1021/jp308929a	journal	December 2012
Temperature Dependence of Self-Diffusion Coefficients of Ions and Solvents in Ethylene Carbonate, Propylene Carbonate, and Diethyl Carbonate Single Solutions and Ethylene Carbonate + Diethyl Carbonate Binary Solutions of LiPF ₆ Studied by NMR Hayamizu, Kikuko Journal of Chemical & Engineering Data, Vol. 57, Issue 7 https://doi.org/10.1021/je3003089	journal	June 2012
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
Some thermodynamic properties of systems containing propylene carbonate and ethylene carbonate Hong, C. S.; Wakslak, R.; Finston, H. Journal of Chemical & Engineering Data, Vol. 27, Issue 2 https://doi.org/10.1021/je00028a012	journal	April 1982
Vapour pressure and enthalpy of vaporization of cyclic alkylene carbonates Verevkin, Sergey P.; Toktonov, Alexey V.; Chernyak, Yury Fluid Phase Equilibria, Vol. 268, Issue 1-2 https://doi.org/10.1016/j.fluid.2008.03.013	journal	June 2008
Structural and thermodynamic properties of liquid ethylene carbonate and propylene carbonate by Monte Carlo Simulations Silva, Luciene Borges; Freitas, Luiz Carlos Gomide Journal of Molecular Structure: THEOCHEM, Vol. 806, Issue 1-3 https://doi.org/10.1016/j.theochem.2006.10.014	journal	March 2007
Li ⁺ –Oligoglyme Association in the Presence of Ionic Liquid Studied by Molecular Dynamics and Explicit or Implicit Solvent Model Eilmes, Andrzej; Kubisiak, Piotr The Journal of Physical Chemistry B, Vol. 119, Issue 35 https://doi.org/10.1021/acs.jpcb.5b05705	journal	August 2015
Solid–Electrolyte Interphase Formation and Electrolyte Reduction at Li-Ion Battery Graphite Anodes: Insights from First-Principles Molecular Dynamics Ganesh, P.; Kent, P. R. C.; Jiang, De-en The Journal of Physical Chemistry C, Vol. 116, Issue 46 https://doi.org/10.1021/jp3086304	journal	November 2012
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
A smooth particle mesh Ewald method Essmann, Ulrich; Perera, Lalith; Berkowitz, Max L. The Journal of Chemical Physics, Vol. 103, Issue 19 https://doi.org/10.1063/1.470117	journal	November 1995
Raman intensity study of local structure in non-aqueous electrolyte solutions—I. Cation-solvent interaction in LiClO4/ethylene carbonate Hyodo, Shi-Aki; Okabayashi, Katsuaki Electrochimica Acta, Vol. 34, Issue 11 https://doi.org/10.1016/0013-4686(89)87040-9	journal	November 1989
The stable states picture of chemical reactions. II. Rate constants for condensed and gas phase reaction models Grote, Richard F.; Hynes, James T. The Journal of Chemical Physics, Vol. 73, Issue 6 https://doi.org/10.1063/1.440485	journal	September 1980
A Raman spectroscopic study of organic electrolyte solutions based on binary solvent systems of ethylene carbonate with low viscosity solvents which dissolve different lithium salts Morita, Masayuki; Asai, Yoshiko; Yoshimoto, Nobuko Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 23 https://doi.org/10.1039/a806278a	journal	January 1998
Li ⁺ Solvation in Pure, Binary, and Ternary Mixtures of Organic Carbonate Electrolytes Skarmoutsos, Ioannis; Ponnuchamy, Veerapandian; Vetere, Valentina The Journal of Physical Chemistry C, Vol. 119, Issue 9 https://doi.org/10.1021/jp511132c	journal	February 2015
Potential of mean force by constrained molecular dynamics: A sodium chloride ion-pair in water Guàrdia, E.; Rey, R.; Padró, J. A. Chemical Physics, Vol. 155, Issue 2 https://doi.org/10.1016/0301-0104(91)87019-r	journal	August 1991
Theoretical Studies of Lithium Perchlorate in Ethylene Carbonate, Propylene Carbonate, and Their Mixtures Li, Tao Journal of The Electrochemical Society, Vol. 146, Issue 10 https://doi.org/10.1149/1.1392523	journal	January 1999
Effect of Anions on Lithium Ion Conduction in Poly(ethylene carbonate)-based Polymer Electrolytes Tominaga, Yoichi; Yamazaki, Kenta; Nanthana, Vannasa Journal of The Electrochemical Society, Vol. 162, Issue 2 https://doi.org/10.1149/2.0211502jes	journal	January 2015
Lithium-Ion Conducting Electrolyte Salts for Lithium Batteries Aravindan, Vanchiappan; Gnanaraj, Joe; Madhavi, Srinivasan Chemistry - A European Journal, Vol. 17, Issue 51 https://doi.org/10.1002/chem.201101486	journal	November 2011
Models of Ion Solvation Thermodynamics in Ethylene Carbonate and Propylene Carbonate Arslanargin, Ayse; Powers, August; Beck, Thomas L. The Journal of Physical Chemistry B, Vol. 120, Issue 8 https://doi.org/10.1021/acs.jpcb.5b06891	journal	August 2015
Dielectric Relaxation of Ethylene Carbonate and Propylene Carbonate from Molecular Dynamics Simulations You, Xinli; Chaudhari, Mangesh I.; Rempe, Susan B. The Journal of Physical Chemistry B, Vol. 120, Issue 8 https://doi.org/10.1021/acs.jpcb.5b09561	journal	November 2015
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang ChemInform, Vol. 35, Issue 50 https://doi.org/10.1002/chin.200450271	journal	December 2004
Current Status of Transition-State Theory Truhlar, Donald G.; Garrett, Bruce C.; Klippenstein, Stephen J. The Journal of Physical Chemistry, Vol. 100, Issue 31 https://doi.org/10.1021/jp953748q	journal	January 1996
Effect of Anions on Lithium Ion Conduction in Poly(ethylene carbonate)-based Polymer Electrolytes Tominaga, Y.; Yamazaki, K.; Nanthana, V. ECS Transactions, Vol. 62, Issue 1 https://doi.org/10.1149/06201.0151ecst	journal	November 2014
Gas Evolution in Operating Lithium-Ion Batteries Studied in Situ by Neutron Imaging Michalak, B.; Sommer, H.; Mannes, D. Karlsruhe https://doi.org/10.5445/ir/1000050796	text	January 2015
Current status of transition-state theory Truhlar, Donald G.; Hase, William L.; Hynes, James T. The Journal of Physical Chemistry, Vol. 87, Issue 26 https://doi.org/10.1021/j150644a044	journal	December 1983
Electronic Structure Modeling of Electrochemical Reactions at Electrode/Electrolyte Interfaces in Lithium Ion Batteries Leung, Kevin arXiv https://doi.org/10.48550/arxiv.1304.5976	text	January 2013

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Title: Li ⁺ solvation and kinetics of Li⁺–BF₄^-/PF ₆ ^- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories