Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Ion distribution and selectivity of ionic liquids in microporous electrodes [Ionic distribution and selectivity of ionic liquids in microporous electrodes]

Abstract

The energy density of an electric double layer capacitor, also known as supercapacitor, depends on ion distributions in the micropores of its electrodes. Herein we study ion selectivity and partitioning of symmetric, asymmetric, and mixed ionic liquids among different pores using the classical density functional theory. We find that a charged micropore in contact with mixed ions of the same valence is always selective to the smaller ions, and the ion selectivity, which is strongest when the pore size is comparable to the ion diameters, drastically falls as the pore size increases. Furthermore, the partitioning behavior in ionic liquids is fundamentally different from those corresponding to ion distributions in aqueous systems whereby the ion selectivity is dominated by the surface energy and entropic effects insensitive to the degree of confinement.

Authors:
 [1]; ORCiD logo [2];  [3];  [1]
+ Show Author Affiliations
  1. Univ. of California, Riverside, CA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Brigham Young Univ., Provo, UT (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1468250
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 17; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Neal, Justin N., Wesolowski, David J., Henderson, Douglas, and Wu, Jianzhong. Ion distribution and selectivity of ionic liquids in microporous electrodes [Ionic distribution and selectivity of ionic liquids in microporous electrodes]. United States: N. p., 2017. Web. doi:10.1063/1.4982351.
Copy to clipboard
Neal, Justin N., Wesolowski, David J., Henderson, Douglas, & Wu, Jianzhong. Ion distribution and selectivity of ionic liquids in microporous electrodes [Ionic distribution and selectivity of ionic liquids in microporous electrodes]. United States. https://doi.org/10.1063/1.4982351
Copy to clipboard
Neal, Justin N., Wesolowski, David J., Henderson, Douglas, and Wu, Jianzhong. Tue . "Ion distribution and selectivity of ionic liquids in microporous electrodes [Ionic distribution and selectivity of ionic liquids in microporous electrodes]". United States. https://doi.org/10.1063/1.4982351. https://www.osti.gov/servlets/purl/1468250.
Copy to clipboard
@article{osti_1468250,
title = {Ion distribution and selectivity of ionic liquids in microporous electrodes [Ionic distribution and selectivity of ionic liquids in microporous electrodes]},
author = {Neal, Justin N. and Wesolowski, David J. and Henderson, Douglas and Wu, Jianzhong},
abstractNote = {The energy density of an electric double layer capacitor, also known as supercapacitor, depends on ion distributions in the micropores of its electrodes. Herein we study ion selectivity and partitioning of symmetric, asymmetric, and mixed ionic liquids among different pores using the classical density functional theory. We find that a charged micropore in contact with mixed ions of the same valence is always selective to the smaller ions, and the ion selectivity, which is strongest when the pore size is comparable to the ion diameters, drastically falls as the pore size increases. Furthermore, the partitioning behavior in ionic liquids is fundamentally different from those corresponding to ion distributions in aqueous systems whereby the ion selectivity is dominated by the surface energy and entropic effects insensitive to the degree of confinement.},
doi = {10.1063/1.4982351},
journal = {Journal of Chemical Physics},
number = 17,
volume = 146,
place = {United States},
year = {Tue May 02 00:00:00 EDT 2017},
month = {Tue May 02 00:00:00 EDT 2017}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.4982351
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Formulation of Ionic-Liquid Electrolyte To Expand the Voltage Window of Supercapacitors
journal, March 2015

  • Van Aken, Katherine L.; Beidaghi, Majid; Gogotsi, Yury
  • Angewandte Chemie International Edition, Vol. 54, Issue 16
  • DOI: 10.1002/anie.201412257

Structures and correlation functions of multicomponent and polydisperse hard-sphere mixtures from a density functional theory
journal, July 2004

  • Yu, Yang-Xin; Wu, Jianzhong; Xin, Yu-Xuan
  • The Journal of Chemical Physics, Vol. 121, Issue 3
  • DOI: 10.1063/1.1763142

Nanoionics: ion transport and electrochemical storage in confined systems
journal, November 2005

  • Maier, J.
  • Nature Materials, Vol. 4, Issue 11, p. 805-815
  • DOI: 10.1038/nmat1513

Structure and capacitance of an electric double layer of an asymmetric valency dimer electrolyte: A comparison of the density functional theory with Monte Carlo simulations
journal, February 2017

  • Henderson, Douglas; Silvestre-Alcantara, Whasington; Kaja, Monika
  • Journal of Molecular Liquids, Vol. 228
  • DOI: 10.1016/j.molliq.2016.08.051

Revisiting density functionals for the primitive model of electric double layers
journal, January 2014

  • Jiang, Jian; Cao, Dapeng; Henderson, Douglas
  • The Journal of Chemical Physics, Vol. 140, Issue 4
  • DOI: 10.1063/1.4862990

Electrolyte pore/solution partitioning by expanded grand canonical ensemble Monte Carlo simulation
journal, March 2015

  • Moucka, Filip; Bratko, Dusan; Luzar, Alenka
  • The Journal of Chemical Physics, Vol. 142, Issue 12
  • DOI: 10.1063/1.4914461

Electrosorption selectivity of ions from mixtures of electrolytes inside nanopores
journal, December 2008

  • Hou, Chia-Hung; Taboada-Serrano, Patricia; Yiacoumi, Sotira
  • The Journal of Chemical Physics, Vol. 129, Issue 22
  • DOI: 10.1063/1.3033562

Physics of Size Selectivity
journal, December 2005

Real Ionic Solutions in the Mean Spherical Approximation. 1. Simple Salts in the Primitive Model
journal, January 1996

  • Simonin, Jean-Pierre; Blum, Lesser; Turq, Pierre
  • The Journal of Physical Chemistry, Vol. 100, Issue 18
  • DOI: 10.1021/jp953567o

Microscopic Insights into the Electrochemical Behavior of Nonaqueous Electrolytes in Electric Double-Layer Capacitors
journal, March 2013

  • Jiang, De-en; Wu, Jianzhong
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 8
  • DOI: 10.1021/jz4002967

A classical density functional theory for interfacial layering of ionic liquids
journal, January 2011

  • Wu, Jianzhong; Jiang, Tao; Jiang, De-en
  • Soft Matter, Vol. 7, Issue 23
  • DOI: 10.1039/c1sm06089a

Oscillation of Capacitance inside Nanopores
journal, December 2011

  • Jiang, De-en; Jin, Zhehui; Wu, Jianzhong
  • Nano Letters, Vol. 11, Issue 12
  • DOI: 10.1021/nl202952d

Materials for electrochemical capacitors
journal, November 2008

  • Simon, Patrice; Gogotsi, Yury
  • Nature Materials, Vol. 7, Issue 11
  • DOI: 10.1038/nmat2297

Charge Separation in Confined Charged Fluids
journal, November 1997

Mixtures of ionic liquids
journal, January 2012

  • Niedermeyer, Heiko; Hallett, Jason P.; Villar-Garcia, Ignacio J.
  • Chemical Society Reviews, Vol. 41, Issue 23
  • DOI: 10.1039/c2cs35177c

Monte Carlo Simulations of the Mechanism for Channel Selectivity:  The Competition between Volume Exclusion and Charge Neutrality
journal, September 2000

  • Boda, Dezsö; Busath, David D.; Henderson, Douglas
  • The Journal of Physical Chemistry B, Vol. 104, Issue 37
  • DOI: 10.1021/jp0019658

Nanotechnology and in Situ Remediation: A Review of the Benefits and Potential Risks
journal, December 2009

  • Karn, Barbara; Kuiken, Todd; Otto, Martha
  • Environmental Health Perspectives, Vol. 117, Issue 12
  • DOI: 10.1289/ehp.0900793

Room-Temperature Ionic Liquids: Excluded Volume and Ion Polarizability Effects in the Electrical Double-Layer Structure and Capacitance
journal, September 2009

Density Functional Theory for Planar Electric Double Layers:  Closing the Gap between Simple and Polyelectrolytes
journal, April 2006

  • Li, Zhidong; Wu, Jianzhong
  • The Journal of Physical Chemistry B, Vol. 110, Issue 14
  • DOI: 10.1021/jp060127w

Solvent Effect on the Pore-Size Dependence of an Organic Electrolyte Supercapacitor
journal, June 2012

  • Jiang, De-en; Jin, Zhehui; Henderson, Douglas
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 13
  • DOI: 10.1021/jz3004624

Enhancing the Capacitive Performance of Electric Double-Layer Capacitors with Ionic Liquid Mixtures
journal, April 2016

Monte Carlo simulations of ion selectivity in a biological Na channel: Charge–space competition
journal, January 2002

  • Boda, Dezső; Busath, David D.; Eisenberg, Bob
  • Phys. Chem. Chem. Phys., Vol. 4, Issue 20
  • DOI: 10.1039/b203686j

Structure and Nanostructure in Ionic Liquids
journal, June 2015

  • Hayes, Robert; Warr, Gregory G.; Atkin, Rob
  • Chemical Reviews, Vol. 115, Issue 13
  • DOI: 10.1021/cr500411q

Density functional theory for differential capacitance of planar electric double layers in ionic liquids
journal, March 2011

Confinement, Desolvation, And Electrosorption Effects on the Diffusion of Ions in Nanoporous Carbon Electrodes
journal, September 2015

  • Pean, Clarisse; Daffos, Barbara; Rotenberg, Benjamin
  • Journal of the American Chemical Society, Vol. 137, Issue 39
  • DOI: 10.1021/jacs.5b07416

Formulation of Ionic-Liquid Electrolyte To Expand the Voltage Window of Supercapacitors
journal, March 2015

  • Van Aken, Katherine L.; Beidaghi, Majid; Gogotsi, Yury
  • Angewandte Chemie, Vol. 127, Issue 16
  • DOI: 10.1002/ange.201412257

Nanotechnology and in situ remediation: a review of the benefits and potential risks
journal, January 2011

Double layer in ionic liquids: Overscreening vs. crowding
text, January 2010

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    A first-principles roadmap and limits to design efficient supercapacitor electrode materials
    journal, January 2019

    • Ali, Basant A.; Allam, Nageh K.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 32
    • DOI: 10.1039/c9cp02614b

    Microscopic dynamics in room-temperature ionic liquids confined in materials for supercapacitor applications
    journal, January 2020

    • Osti, Naresh C.; Mamontov, Eugene
    • Sustainable Energy & Fuels, Vol. 4, Issue 4
    • DOI: 10.1039/c9se00829b

    Side-chain effects on the capacitive behaviour of ionic liquids in microporous electrodes
    journal, August 2019

    Side-chain effects on the capacitive behaviour of ionic liquids in microporous electrodes
    text, January 2019

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: