skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4961904· OSTI ID:1340769
 [1]; ORCiD logo [2]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Univ. of Wisconsin - Parkside, Kenosha, WI (United States)
+ Show Author Affiliations

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.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1340769
Alternate ID(s):
OSTI ID: 1318756
Report Number(s):
PNNL-SA-118788; JCPSA6; KC0301050
Journal Information:
Journal of Chemical Physics, Vol. 145, Issue 9; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

References (26)

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
Li + Solvation in Pure, Binary, and Ternary Mixtures of Organic Carbonate Electrolytes journal February 2015
Li + –Oligoglyme Association in the Presence of Ionic Liquid Studied by Molecular Dynamics and Explicit or Implicit Solvent Model journal August 2015
Models of Ion Solvation Thermodynamics in Ethylene Carbonate and Propylene Carbonate journal August 2015
Dielectric Relaxation of Ethylene Carbonate and Propylene Carbonate from Molecular Dynamics Simulations journal November 2015
Electronic Structure Modeling of Electrochemical Reactions at Electrode/Electrolyte Interfaces in Lithium Ion Batteries journal December 2012
Solid–Electrolyte Interphase Formation and Electrolyte Reduction at Li-Ion Battery Graphite Anodes: Insights from First-Principles Molecular Dynamics journal November 2012
Molecular Dynamics Simulation of Li+BF4- in Ethylene Carbonate, Propylene Carbonate, and Dimethyl Carbonate Solvents journal January 1998
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
Coordination Number of Li + in Nonaqueous Electrolyte Solutions Determined by Molecular Rotational Measurements journal March 2014
Theoretical Studies of Lithium Perchlorate in Ethylene Carbonate, Propylene Carbonate, and Their Mixtures journal January 1999
CO[sub 2] Gas Evolution on Cathode Materials for Lithium-Ion Batteries journal January 2007
Gas Evolution in Operating Lithium-Ion Batteries Studied In Situ by Neutron Imaging journal October 2015
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
Lithium-Ion Conducting Electrolyte Salts for Lithium Batteries journal November 2011
Statistical mechanics of isomerization dynamics in liquids and the transition state approximation journal January 1978
The stable states picture of chemical reactions. II. Rate constants for condensed and gas phase reaction models journal September 1980
Hydration and mobility of ions in solution journal December 1983
Anion Effects on Interfacial Absorption of Gases in Ionic Liquids. A Molecular Dynamics Study journal June 2011
A smooth particle mesh Ewald method journal November 1995
Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes journal March 1977
Inorganic and Bioinorganic Solvent Exchange Mechanisms journal June 2005
Novel benzimidazole salts for lithium ion battery electrolytes: effects of substituents journal January 2015
Electrolyte Solvation and Ionic Association II. Acetonitrile-Lithium Salt Mixtures: Highly Dissociated Salts journal January 2012

Cited By (1)

Expanding the calculation of activation volumes: Self-diffusion in liquid water journal April 2018

Similar Records

Related Subjects

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