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Title: The Interplay between Salt Association and the Dielectric Properties of Low Permittivity Electrolytes: The Case of LiPF6 and LiAsF6 in Dimethyl Carbonate

Journal Article · · Journal of Physical Chemistry. C
ORCiD logo [1];  [2]; ORCiD logo [3];  [4]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area; Univ. of California, Berkeley, CA (United States). Dept. of Applied Science and Technology
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area
  4. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering, and Dept. of Applied Science and Technology; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area
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Here, we present evidence that the dielectric constant of an electrolyte solution can be effectively used to infer the association regime of the salt species from computational methods. As case studies, we consider the low dielectric constant solvent dimethyl carbonate with LiAsF6 and LiPF6 salts at low concentrations. Using both quantum “ab initio” methods as well classical molecular dynamics simulations, we elucidate the salt’s contribution to the dielectric constant as well as the dipolar relaxation times, which act as quantitative signatures. By comparing to previously published measurements, we provide strong evidence for the presence of contact-ion pairs at these low concentrations. Interestingly, these ion pairs increase the dielectric constant of the solution, allowing for significantly improved ionic conductivity as a function of salt concentrations. We also discuss the role of multimeric equilibrium species as contributors to the functional properties of designer electrolytes, such as dielectric properties of the solution and ionic conductivity.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; AC02-05CH11231
OSTI ID:
1483679
Journal Information:
Journal of Physical Chemistry. C, Vol. 122, Issue 4; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 39 works
Citation information provided by
Web of Science

References (32)

Ion Pairing journal November 2006
Electrolyte Solvation and Ionic Association II. Acetonitrile-Lithium Salt Mixtures: Highly Dissociated Salts journal January 2012
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal October 2004
Dielectric Relaxation of Ethylene Carbonate and Propylene Carbonate from Molecular Dynamics Simulations journal November 2015
Simulation studies of ionic liquids: Orientational correlations and static dielectric properties journal December 2006
Simulation studies of the protein-water interface. I. Properties at the molecular resolution journal June 2006
Dissecting ion-specific dielectric spectra of sodium-halide solutions into solvation water and ionic contributions journal December 2014
A study of the Li/Li+ couple in DMC and PC solvents journal March 1999
Ionic conductivity and microwave dielectric relaxation of lithium hexafluoroarsenate (LiAsF6) and lithium perchlorate (LiClO4) in dimethyl carbonate journal November 1985
Electrolytic characteristics of fluoromethyl methyl carbonate for lithium rechargeable batteries journal January 2009
Effect of Concentration Changes on Permittivity of Electrolyte Solutions journal February 1968
Evaluation and Reparametrization of the OPLS-AA Force Field for Proteins via Comparison with Accurate Quantum Chemical Calculations on Peptides † journal July 2001
Molecular Dynamics Simulation of Li+BF4- in Ethylene Carbonate, Propylene Carbonate, and Dimethyl Carbonate Solvents journal January 1998
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics journal August 1997
Comment on “Reaction field treatment of charge penetration” [J. Chem. Phys. 112, 5558 (2000)] journal January 2001
Quantum Mechanical Continuum Solvation Models journal August 2005
Dielectric Constants for Quantum Chemistry and Li-Ion Batteries: Solvent Blends of Ethylene Carbonate and Ethyl Methyl Carbonate journal September 2015
GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers journal September 2015
The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics journal February 2015
PACKMOL: A package for building initial configurations for molecular dynamics simulations journal October 2009
Molecular Force Field for Ionic Liquids Composed of Triflate or Bistriflylimide Anions journal October 2004
Atom Substitution Effects of [XF 6 ] − in Ionic Liquids. 2. Theoretical Study journal July 2009
Broadband Dielectric Spectroscopy book January 2003
MDAnalysis: A toolkit for the analysis of molecular dynamics simulations journal April 2011
Toward Accurate Modeling of the Effect of Ion-Pair Formation on Solute Redox Potential journal August 2016
The Cluster−Continuum Model for the Calculation of the Solvation Free Energy of Ionic Species journal August 2001
Dramatic Effects of Low Salt Concentrations on Li-Ion Cells Containing EC-Free Electrolytes journal January 2017
A Guide to Ethylene Carbonate-Free Electrolyte Making for Li-Ion Cells journal November 2016
Superconcentrated electrolytes for a high-voltage lithium-ion battery journal June 2016
High Concentration Dinitrile, 3-Alkoxypropionitrile, and Linear Carbonate Electrolytes Enabled by Vinylene and Monofluoroethylene Carbonate Additives journal January 2012

Cited By (6)

Cation−Solvent, Cation−Anion, and Solvent−Solvent Interactions with Electrolyte Solvation in Lithium Batteries journal January 2019
A Critical Evaluation of the Advanced Electrolyte Model journal January 2018
Higher Energy Barrier for Interfacial Li-Ion Transfer from EC/LiPF 6 Electrolyte into (010) LiFePO 4 Cathode Surface than Bulk Li-Ion Diffusion within Both Cathode and Electrolyte journal January 2019
Ion Association Constants for Lithium Ion Battery Electrolytes from First-Principles Quantum Chemistry journal January 2019
Exploring Classes of Co-Solvents for Fast-Charging Lithium-Ion Cells journal January 2018
Cation−Solvent, Cation−Anion, and Solvent−Solvent Interactions with Electrolyte Solvation in Lithium batteries journal January 2019

Figures / Tables (5)

Figure 1(p. 5)figure Figure 1
Figure 2(p. 8)figure Figure 2
Figure 3(p. 9)figure Figure 3
Table 1(p. 11)table Table 1
Table 2(p. 12)table Table 2

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