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Title: Structure and dynamics of electrical double layers in organic electrolytes

Abstract

The organic electrolyte of tetraethylammonium tetrafluoroborate (TEABF{sub 4}) in the aprotic solvent of acetonitrile (ACN) is widely used in electrochemical systems such as electrochemical capacitors. In this paper, we examine the solvation of TEA{sup +} and BF{sub 4}{sup -} in ACN, and the structure, capacitance, and dynamics of the electrical double layers (EDLs) in the TEABF{sub 4}-ACN electrolyte using molecular dynamics simulations complemented with quantum density functional theory calculations. The solvation of TEA+ and BF4- ions is found to be much weaker than that of small inorganic ions in aqueous solutions, and the ACN molecules in the solvation shell of both types of ions show only weak packing and orientational ordering. These solvation characteristics are caused by the large size, charge delocalization, and irregular shape (in the case of TEA+ cation) of the ions. Near neutral electrodes, the double-layer structure in the organic electrolyte exhibits a rich organization: the solvent shows strong layering and orientational ordering, ions are significantly contact-adsorbed on the electrode, and alternating layers of cations/anions penetrate ca. 1.1 nm into the bulk electrolyte. The significant contact adsorption of ions and the alternating layering of cation/anion are new features found for EDLs in organic electrolytes. These features essentiallymore » originate from the fact that van der Waals interactions between organic ions and the electrode are strong and the partial desolvation of these ions occurs easily, as a result of the large size of the organic ions. Near charged electrodes, distinct counter-ion concentration peaks form, and the ion distribution cannot be described by the Helmholtz model or the Helmholtz + Poisson-Boltzmann model. This is because the number of counter-ions adsorbed on the electrode exceeds the number of electrons on the electrode, and the electrode is over-screened in parts of the EDL. The computed capacitances of the EDLs are in good agreement with that inferred from experimental measurements. Both the rotations (ACN only) and translations of interfacial ACN and ions are found to slow down as the electrode is electrified. We also observe an asymmetrical dependence of these motions on the sign of the electrode charge. The rotation/diffusion of ACN and the diffusion of ions in the region beyond the first ACN or ion layer differ only weakly from those in the bulk« less

Authors:
 [1];  [1];  [1];  [1];  [2]
+ Show Author Affiliations
  1. ORNL
  2. Clemson University
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Center for Computational Sciences
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
980722
DOE Contract Number:
DE-AC05-00OR22725
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Chemistry Chemical Physics; Journal Volume: 12; Journal Issue: 20
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETONITRILE; ADSORPTION; AQUEOUS SOLUTIONS; BEVERAGES; CAPACITANCE; CAPACITORS; DENSITY; DIFFUSION; DISTRIBUTION; DYNAMICS; ELECTRODES; ELECTROLYTES; ELECTRONS; FUNCTIONALS; INTERACTIONS; IONS; LAYERS; MOLECULES; PEAKS; SHAPE; SHELLS; SOLVATION; SOLVENTS; STOWING

Citation Formats

Huang, Jingsong, Sumpter, Bobby G, Meunier, Vincent, Qiao, Rui, and Feng, Guang. Structure and dynamics of electrical double layers in organic electrolytes. United States: N. p., 2010. Web.
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Huang, Jingsong, Sumpter, Bobby G, Meunier, Vincent, Qiao, Rui, & Feng, Guang. Structure and dynamics of electrical double layers in organic electrolytes. United States.
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Huang, Jingsong, Sumpter, Bobby G, Meunier, Vincent, Qiao, Rui, and Feng, Guang. Fri . "Structure and dynamics of electrical double layers in organic electrolytes". United States. doi:.
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@article{osti_980722,
title = {Structure and dynamics of electrical double layers in organic electrolytes},
author = {Huang, Jingsong and Sumpter, Bobby G and Meunier, Vincent and Qiao, Rui and Feng, Guang},
abstractNote = {The organic electrolyte of tetraethylammonium tetrafluoroborate (TEABF{sub 4}) in the aprotic solvent of acetonitrile (ACN) is widely used in electrochemical systems such as electrochemical capacitors. In this paper, we examine the solvation of TEA{sup +} and BF{sub 4}{sup -} in ACN, and the structure, capacitance, and dynamics of the electrical double layers (EDLs) in the TEABF{sub 4}-ACN electrolyte using molecular dynamics simulations complemented with quantum density functional theory calculations. The solvation of TEA+ and BF4- ions is found to be much weaker than that of small inorganic ions in aqueous solutions, and the ACN molecules in the solvation shell of both types of ions show only weak packing and orientational ordering. These solvation characteristics are caused by the large size, charge delocalization, and irregular shape (in the case of TEA+ cation) of the ions. Near neutral electrodes, the double-layer structure in the organic electrolyte exhibits a rich organization: the solvent shows strong layering and orientational ordering, ions are significantly contact-adsorbed on the electrode, and alternating layers of cations/anions penetrate ca. 1.1 nm into the bulk electrolyte. The significant contact adsorption of ions and the alternating layering of cation/anion are new features found for EDLs in organic electrolytes. These features essentially originate from the fact that van der Waals interactions between organic ions and the electrode are strong and the partial desolvation of these ions occurs easily, as a result of the large size of the organic ions. Near charged electrodes, distinct counter-ion concentration peaks form, and the ion distribution cannot be described by the Helmholtz model or the Helmholtz + Poisson-Boltzmann model. This is because the number of counter-ions adsorbed on the electrode exceeds the number of electrons on the electrode, and the electrode is over-screened in parts of the EDL. The computed capacitances of the EDLs are in good agreement with that inferred from experimental measurements. Both the rotations (ACN only) and translations of interfacial ACN and ions are found to slow down as the electrode is electrified. We also observe an asymmetrical dependence of these motions on the sign of the electrode charge. The rotation/diffusion of ACN and the diffusion of ions in the region beyond the first ACN or ion layer differ only weakly from those in the bulk},
doi = {},
journal = {Physical Chemistry Chemical Physics},
number = 20,
volume = 12,
place = {United States},
year = {Fri Jan 01 00:00:00 EST 2010},
month = {Fri Jan 01 00:00:00 EST 2010}
}
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