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Title: Rate theory of solvent exchange and kinetics of Li+ - BF4-/PF6- ion pairs in acetonitrile

Abstract

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li+(aq) and the kinetics of ion pairings in lithium-ion batteries (LIB). We report one of the first computer simulations of the exchange dynamics around hydrated Li+ in acetonitrile (ACN), which is common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li+-[BF4] and Li+-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li+(aq). We calculate exchange rates using transition state theory and weighted them with transmission coefficients determined by the reactive flux and Impey, Madden, and McDonald approaches and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li+-[BF4] and Li+-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. Here, these results will increase our understanding ofmore » the thermodynamic and kinetic properties of LIB systems.« less

Authors:
 [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Univ. of Wisconsin - Parkside, Kenosha, WI (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1340769
Alternate Identifier(s):
OSTI ID: 1318756
Report Number(s):
PNNL-SA-118788
Journal ID: ISSN 0021-9606; JCPSA6; KC0301050
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 9; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ions and properties; Batteries; Computer simulation; Ionic conductivity; Solvation; Chemical compounds; Free energy; Transition state theory; Polarizable force fields; Electrolytes

Citation Formats

Dang, Liem X., and Chang, Tsun-Mei. Rate theory of solvent exchange and kinetics of Li+ - BF4-/PF6- ion pairs in acetonitrile. United States: N. p., 2016. Web. doi:10.1063/1.4961904.
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Dang, Liem X., & Chang, Tsun-Mei. Rate theory of solvent exchange and kinetics of Li+ - BF4-/PF6- ion pairs in acetonitrile. United States. https://doi.org/10.1063/1.4961904
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Dang, Liem X., and Chang, Tsun-Mei. Fri . "Rate theory of solvent exchange and kinetics of Li+ - BF4-/PF6- ion pairs in acetonitrile". United States. https://doi.org/10.1063/1.4961904. https://www.osti.gov/servlets/purl/1340769.
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@article{osti_1340769,
title = {Rate theory of solvent exchange and kinetics of Li+ - BF4-/PF6- ion pairs in acetonitrile},
author = {Dang, Liem X. and Chang, Tsun-Mei},
abstractNote = {In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li+(aq) and the kinetics of ion pairings in lithium-ion batteries (LIB). We report one of the first computer simulations of the exchange dynamics around hydrated Li+ in acetonitrile (ACN), which is common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li+-[BF4] and Li+-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li+(aq). We calculate exchange rates using transition state theory and weighted them with transmission coefficients determined by the reactive flux and Impey, Madden, and McDonald approaches and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li+-[BF4] and Li+-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. Here, these results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.},
doi = {10.1063/1.4961904},
journal = {Journal of Chemical Physics},
number = 9,
volume = 145,
place = {United States},
year = {Fri Sep 02 00:00:00 EDT 2016},
month = {Fri Sep 02 00:00:00 EDT 2016}
}
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https://doi.org/10.1063/1.4961904
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Works referenced in this record:

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

Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics
journal, January 2015

  • Ong, Mitchell T.; Verners, Osvalds; Draeger, Erik W.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 4
  • DOI: 10.1021/jp508184f

Li + Solvation in Pure, Binary, and Ternary Mixtures of Organic Carbonate Electrolytes
journal, February 2015

  • Skarmoutsos, Ioannis; Ponnuchamy, Veerapandian; Vetere, Valentina
  • The Journal of Physical Chemistry C, Vol. 119, Issue 9
  • DOI: 10.1021/jp511132c

Li + –Oligoglyme Association in the Presence of Ionic Liquid Studied by Molecular Dynamics and Explicit or Implicit Solvent Model
journal, August 2015

  • Eilmes, Andrzej; Kubisiak, Piotr
  • The Journal of Physical Chemistry B, Vol. 119, Issue 35
  • DOI: 10.1021/acs.jpcb.5b05705

Models of Ion Solvation Thermodynamics in Ethylene Carbonate and Propylene Carbonate
journal, August 2015

  • Arslanargin, Ayse; Powers, August; Beck, Thomas L.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 8
  • DOI: 10.1021/acs.jpcb.5b06891

Dielectric Relaxation of Ethylene Carbonate and Propylene Carbonate from Molecular Dynamics Simulations
journal, November 2015

  • You, Xinli; Chaudhari, Mangesh I.; Rempe, Susan B.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 8
  • DOI: 10.1021/acs.jpcb.5b09561

Electronic Structure Modeling of Electrochemical Reactions at Electrode/Electrolyte Interfaces in Lithium Ion Batteries
journal, December 2012

  • Leung, Kevin
  • The Journal of Physical Chemistry C, Vol. 117, Issue 4
  • DOI: 10.1021/jp308929a

Solid–Electrolyte Interphase Formation and Electrolyte Reduction at Li-Ion Battery Graphite Anodes: Insights from First-Principles Molecular Dynamics
journal, November 2012

  • Ganesh, P.; Kent, P. R. C.; Jiang, De-en
  • The Journal of Physical Chemistry C, Vol. 116, Issue 46
  • DOI: 10.1021/jp3086304

Molecular Dynamics Simulation of Li+BF4- in Ethylene Carbonate, Propylene Carbonate, and Dimethyl Carbonate Solvents
journal, January 1998

  • Soetens, Jean-Christophe; Millot, Claude; Maigret, Bernard
  • The Journal of Physical Chemistry A, Vol. 102, Issue 7
  • DOI: 10.1021/jp972457+

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
journal, January 1998

  • Morita, Masayuki; Asai, Yoshiko; Yoshimoto, Nobuko
  • Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 23
  • DOI: 10.1039/a806278a

Coordination Number of Li + in Nonaqueous Electrolyte Solutions Determined by Molecular Rotational Measurements
journal, March 2014

  • Yuan, Kaijun; Bian, Hongtao; Shen, Yuneng
  • The Journal of Physical Chemistry B, Vol. 118, Issue 13
  • DOI: 10.1021/jp500877u

Theoretical Studies of Lithium Perchlorate in Ethylene Carbonate, Propylene Carbonate, and Their Mixtures
journal, January 1999

  • Li, Tao
  • Journal of The Electrochemical Society, Vol. 146, Issue 10
  • DOI: 10.1149/1.1392523

CO[sub 2] Gas Evolution on Cathode Materials for Lithium-Ion Batteries
journal, January 2007

  • Wuersig, Andreas; Scheifele, Werner; Novák, Petr
  • Journal of The Electrochemical Society, Vol. 154, Issue 5
  • DOI: 10.1149/1.2712138

Gas Evolution in Operating Lithium-Ion Batteries Studied In Situ by Neutron Imaging
journal, October 2015

  • Michalak, Barbara; Sommer, Heino; Mannes, David
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep15627

Gas generation mechanism due to electrolyte decomposition in commercial lithium-ion cell
journal, September 1999

Effect of Anions on Lithium Ion Conduction in Poly(ethylene carbonate)-based Polymer Electrolytes
journal, January 2015

  • Tominaga, Yoichi; Yamazaki, Kenta; Nanthana, Vannasa
  • Journal of The Electrochemical Society, Vol. 162, Issue 2
  • DOI: 10.1149/2.0211502jes

Lithium-Ion Conducting Electrolyte Salts for Lithium Batteries
journal, November 2011

  • Aravindan, Vanchiappan; Gnanaraj, Joe; Madhavi, Srinivasan
  • Chemistry - A European Journal, Vol. 17, Issue 51
  • DOI: 10.1002/chem.201101486

Statistical mechanics of isomerization dynamics in liquids and the transition state approximation
journal, January 1978

  • Chandler, David
  • The Journal of Chemical Physics, Vol. 68, Issue 6
  • DOI: 10.1063/1.436049

The stable states picture of chemical reactions. II. Rate constants for condensed and gas phase reaction models
journal, September 1980

  • Grote, Richard F.; Hynes, James T.
  • The Journal of Chemical Physics, Vol. 73, Issue 6
  • DOI: 10.1063/1.440485

Hydration and mobility of ions in solution
journal, December 1983

  • Impey, R. W.; Madden, P. A.; McDonald, I. R.
  • The Journal of Physical Chemistry, Vol. 87, Issue 25
  • DOI: 10.1021/j150643a008

Anion Effects on Interfacial Absorption of Gases in Ionic Liquids. A Molecular Dynamics Study
journal, June 2011

  • Dang, Liem X.; Wick, Collin D.
  • The Journal of Physical Chemistry B, Vol. 115, Issue 21
  • DOI: 10.1021/jp201113c

A smooth particle mesh Ewald method
journal, November 1995

  • Essmann, Ulrich; Perera, Lalith; Berkowitz, Max L.
  • The Journal of Chemical Physics, Vol. 103, Issue 19
  • DOI: 10.1063/1.470117

Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes
journal, March 1977

  • Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C.
  • Journal of Computational Physics, Vol. 23, Issue 3
  • DOI: 10.1016/0021-9991(77)90098-5

Inorganic and Bioinorganic Solvent Exchange Mechanisms
journal, June 2005

  • Helm, Lothar; Merbach, André E.
  • Chemical Reviews, Vol. 105, Issue 6
  • DOI: 10.1021/cr030726o

Novel benzimidazole salts for lithium ion battery electrolytes: effects of substituents
journal, January 2015

  • Sriana, T.; Leggesse, E. G.; Jiang, J. C.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 25
  • DOI: 10.1039/C5CP00982K

Electrolyte Solvation and Ionic Association II. Acetonitrile-Lithium Salt Mixtures: Highly Dissociated Salts
journal, January 2012

  • Seo, Daniel M.; Borodin, Oleg; Han, Sang-Don
  • Journal of The Electrochemical Society, Vol. 159, Issue 9
  • DOI: 10.1149/2.035209jes
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