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

Title: Impurity effects on ionic-liquid-based supercapacitors

Abstract

Small amounts of an impurity may affect the key properties of an ionic liquid and such effects can be dramatically amplified when the electrolyte is under confinement. Here the classical density functional theory is employed to investigate the impurity effects on the microscopic structure and the performance of ionic-liquid-based electrical double-layer capacitors, also known as supercapacitors. Using a primitive model for ionic species, we study the effects of an impurity on the double layer structure and the integral capacitance of a room temperature ionic liquid in model electrode pores and find that an impurity strongly binding to the surface of a porous electrode can significantly alter the electric double layer structure and dampen the oscillatory dependence of the capacitance with the pore size of the electrode. Meanwhile, a strong affinity of the impurity with the ionic species affects the dependence of the integral capacitance on the pore size. Up to 30% increase in the integral capacitance can be achieved even at a very low impurity bulk concentration. By comparing with an ionic liquid mixture containing modified ionic species, we find that the cooperative effect of the bounded impurities is mainly responsible for the significant enhancement of the supercapacitor performance.

Authors:
 [1];  [2];  [3];  [1]
+ Show Author Affiliations
  1. Univ. of California, Riverside, CA (United States)
  2. Univ. of California, Riverside, CA (United States); East China Univ. of Science and Technology, Shanghai (People's Republic of China)
  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:
1399241
Alternate Identifier(s):
OSTI ID: 1388372
Grant/Contract Number:  
AC05-00OR22725; ERKCC61
Resource Type:
Accepted Manuscript
Journal Name:
Molecular Physics
Additional Journal Information:
Journal Volume: 115; Journal Issue: 4; Journal ID: ISSN 0026-8976
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; electrical double layer; energy storage; classical density functional theory; catalysis (heterogeneous), solar (fuels), energy storage (including batteries and capacitors), hydrogen and fuel cells, electrodes - solar, mechanical behavior, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Liu, Kun, Lian, Cheng, Henderson, Douglas, and Wu, Jianzhong. Impurity effects on ionic-liquid-based supercapacitors. United States: N. p., 2016. Web. doi:10.1080/00268976.2016.1271154.
Copy to clipboard
Liu, Kun, Lian, Cheng, Henderson, Douglas, & Wu, Jianzhong. Impurity effects on ionic-liquid-based supercapacitors. United States. https://doi.org/10.1080/00268976.2016.1271154
Copy to clipboard
Liu, Kun, Lian, Cheng, Henderson, Douglas, and Wu, Jianzhong. Tue . "Impurity effects on ionic-liquid-based supercapacitors". United States. https://doi.org/10.1080/00268976.2016.1271154. https://www.osti.gov/servlets/purl/1399241.
Copy to clipboard
@article{osti_1399241,
title = {Impurity effects on ionic-liquid-based supercapacitors},
author = {Liu, Kun and Lian, Cheng and Henderson, Douglas and Wu, Jianzhong},
abstractNote = {Small amounts of an impurity may affect the key properties of an ionic liquid and such effects can be dramatically amplified when the electrolyte is under confinement. Here the classical density functional theory is employed to investigate the impurity effects on the microscopic structure and the performance of ionic-liquid-based electrical double-layer capacitors, also known as supercapacitors. Using a primitive model for ionic species, we study the effects of an impurity on the double layer structure and the integral capacitance of a room temperature ionic liquid in model electrode pores and find that an impurity strongly binding to the surface of a porous electrode can significantly alter the electric double layer structure and dampen the oscillatory dependence of the capacitance with the pore size of the electrode. Meanwhile, a strong affinity of the impurity with the ionic species affects the dependence of the integral capacitance on the pore size. Up to 30% increase in the integral capacitance can be achieved even at a very low impurity bulk concentration. By comparing with an ionic liquid mixture containing modified ionic species, we find that the cooperative effect of the bounded impurities is mainly responsible for the significant enhancement of the supercapacitor performance.},
doi = {10.1080/00268976.2016.1271154},
journal = {Molecular Physics},
number = 4,
volume = 115,
place = {United States},
year = {Tue Dec 27 00:00:00 EST 2016},
month = {Tue Dec 27 00:00:00 EST 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1080/00268976.2016.1271154
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1. Figure 1.: The restricted primitive model of an ionic liquid (charged spheres) and an impurity (neutral spheres) inside a slit pore. The impurity molecules may accumulate inside the pore due to strong surface affinity.
All figures and tables (9 total)
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:

Ionic-liquid materials for the electrochemical challenges of the future
journal, July 2009

  • Armand, Michel; Endres, Frank; MacFarlane, Douglas R.
  • Nature Materials, Vol. 8, Issue 8, p. 621-629
  • DOI: 10.1038/nmat2448

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

Water in Ionic Liquids at Electrified Interfaces: The Anatomy of Electrosorption
journal, October 2014

  • Feng, Guang; Jiang, Xikai; Qiao, Rui
  • ACS Nano, Vol. 8, Issue 11
  • DOI: 10.1021/nn505017c

Anomalous or regular capacitance? The influence of pore size dispersity on double-layer formation
journal, September 2016

Ion Partitioning between Charged Micropores and Bulk Electrolyte Solution. Mixtures of Mono- and Divalent Counterions and Monovalent Co-Ions
journal, August 1995

  • Jamnik, B.; Vlachy, V.
  • Journal of the American Chemical Society, Vol. 117, Issue 30
  • DOI: 10.1021/ja00135a020

Applications of ionic liquids in the chemical industry
journal, January 2008

  • Plechkova, Natalia V.; Seddon, Kenneth R.
  • Chem. Soc. Rev., Vol. 37, Issue 1
  • DOI: 10.1039/b006677j

Experimental measurement of the hygroscopic grade on eight imidazolium based ionic liquids
journal, April 2009

Microscopic density functional theory of wetting and drying of a solid substrate by an explicit solvent model of ionic solutions
journal, December 2009

A Generic Model for Electric Double Layers in Porous Electrodes
journal, April 2016

  • Lian, Cheng; Jiang, De-en; Liu, Honglai
  • The Journal of Physical Chemistry C, Vol. 120, Issue 16
  • DOI: 10.1021/acs.jpcc.6b00964

Ionic Liquids at Electrified Interfaces
journal, March 2014

  • Fedorov, Maxim V.; Kornyshev, Alexei A.
  • Chemical Reviews, Vol. 114, Issue 5
  • DOI: 10.1021/cr400374x

Charging Ultrananoporous Electrodes with Size-Asymmetric Ions Assisted by Apolar Solvent
journal, May 2016

  • Rochester, Christopher C.; Kondrat, Svyatoslav; Pruessner, Gunnar
  • The Journal of Physical Chemistry C, Vol. 120, Issue 29
  • DOI: 10.1021/acs.jpcc.5b12730

Capacitance in carbon pores of 0.7 to 15 nm: a regular pattern
journal, January 2011

  • Centeno, Teresa A.; Sereda, Olha; Stoeckli, Fritz
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 27
  • DOI: 10.1039/c1cp20748b

Influence of chloride, water, and organic solvents on the physical properties of ionic liquids
journal, January 2000

  • Seddon, Kenneth R.; Stark, Annegret; Torres, María-José
  • Pure and Applied Chemistry, Vol. 72, Issue 12
  • DOI: 10.1351/pac200072122275

Interfacial ionic ‘liquids’: connecting static and dynamic structures
journal, December 2014

Size Selectivity of Narrow Pores
journal, July 2000

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

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

Mobility and solvation of ions in channels
journal, November 1996

  • Lynden‐Bell, R. M.; Rasaiah, Jayendran C.
  • The Journal of Chemical Physics, Vol. 105, Issue 20
  • DOI: 10.1063/1.472757

Relation between the Ion Size and Pore Size for an Electric Double-Layer Capacitor
journal, March 2008

  • Largeot, Celine; Portet, Cristelle; Chmiola, John
  • Journal of the American Chemical Society, Vol. 130, Issue 9
  • DOI: 10.1021/ja7106178

The interface ionic liquid(s)/electrode(s): In situSTM and AFM measurements
journal, January 2012

  • Endres, Frank; Borisenko, Natalia; El Abedin, Sherif Zein
  • Faraday Discuss., Vol. 154
  • DOI: 10.1039/C1FD00050K

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

Chemical and electrochemical ageing of carbon materials used in supercapacitor electrodes
journal, November 2008

A superionic state in nano-porous double-layer capacitors: insights from Monte Carlo simulations
journal, January 2011

  • Kondrat, S.; Georgi, N.; Fedorov, M. V.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 23
  • DOI: 10.1039/c1cp20798a

Nanowindow-Regulated Specific Capacitance of Supercapacitor Electrodes of Single-Wall Carbon Nanohorns
journal, January 2007

  • Yang, Cheol-Min; Kim, Yong-Jung; Endo, Morinobu
  • Journal of the American Chemical Society, Vol. 129, Issue 1
  • DOI: 10.1021/ja065501k

Monte Carlo and Poisson-Boltzmann study of electrolyte exclusion from charged cylindrical micropores
journal, January 1993

  • Jamnik, B.; Vlachy, V.
  • Journal of the American Chemical Society, Vol. 115, Issue 2
  • DOI: 10.1021/ja00055a040

Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer
journal, September 2006

The large scale synthesis of pure imidazolium and pyrrolidinium ionic liquids
journal, January 2007

  • Burrell, Anthony K.; Sesto, Rico E. Del; Baker, Sheila N.
  • Green Chemistry, Vol. 9, Issue 5
  • DOI: 10.1039/b615950h

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

Microstructure and Capacitance of the Electrical Double Layers at the Interface of Ionic Liquids and Planar Electrodes
journal, February 2009

  • Feng, G.; Zhang, J. S.; Qiao, R.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 11
  • DOI: 10.1021/jp809900w

A perturbative density functional theory for square-well fluids
journal, May 2011

  • Jin, Zhehui; Tang, Yiping; Wu, Jianzhong
  • The Journal of Chemical Physics, Vol. 134, Issue 17
  • DOI: 10.1063/1.3585677

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

Monte Carlo Simulation for the Double Layer Structure of an Ionic Liquid Using a Dimer Model: A Comparison with the Density Functional Theory
journal, August 2012

  • Bhuiyan, Lutful Bari; Lamperski, Stanisław; Wu, Jianzhong
  • The Journal of Physical Chemistry B, Vol. 116, Issue 34
  • DOI: 10.1021/jp304362y

Charge neutrality breakdown in confined aqueous electrolytes: Theory and simulation
journal, September 2016

  • Colla, Thiago; Girotto, Matheus; dos Santos, Alexandre P.
  • The Journal of Chemical Physics, Vol. 145, Issue 9
  • DOI: 10.1063/1.4962198

Towards a microscopic theory of wetting by ionic solutions. I. Surface properties of the semi-primitive model
journal, September 2006

Structures of hard-sphere fluids from a modified fundamental-measure theory
journal, December 2002

  • Yu, Yang-Xin; Wu, Jianzhong
  • The Journal of Chemical Physics, Vol. 117, Issue 22
  • DOI: 10.1063/1.1520530

Wetting and drying scenarios of ionic solutions
journal, March 2011

Structure and dynamics of electrical double layers in organic electrolytes
journal, January 2010

  • Feng, Guang; Huang, Jingsong; Sumpter, Bobby G.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 20
  • DOI: 10.1039/c000451k

Causes of supercapacitors ageing in organic electrolyte
journal, September 2007

Effect of dissolved LiCl on the ionic liquid–Au(111) electrical double layer structure
journal, January 2012

  • Hayes, Robert; Borisenko, Natalia; Corr, Brendan
  • Chemical Communications, Vol. 48, Issue 82
  • DOI: 10.1039/c2cc35737b

On the theoretical description of weakly charged surfaces
journal, March 2015

  • Wang, Rui; Wang, Zhen-Gang
  • The Journal of Chemical Physics, Vol. 142, Issue 10
  • DOI: 10.1063/1.4914170

Purification or contamination? The effect of sorbents on ionic liquids
journal, January 2008

  • Clare, Bronya R.; Bayley, Paul M.; Best, Adam S.
  • Chemical Communications, Issue 23
  • DOI: 10.1039/b802488j

A review of electrolyte materials and compositions for electrochemical supercapacitors
journal, January 2015

  • Zhong, Cheng; Deng, Yida; Hu, Wenbin
  • Chemical Society Reviews, Vol. 44, Issue 21
  • DOI: 10.1039/C5CS00303B

Superionic state in double-layer capacitors with nanoporous electrodes
journal, December 2010

X-Ray reflectometry studies on the effect of water on the surface structure of [C4mpyr][NTf2] ionic liquid
journal, January 2009

  • Lauw, Y.; Horne, M. D.; Rodopoulos, T.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 48
  • DOI: 10.1039/b916046a

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

Wetting of a solid substrate by a “civilized” model of ionic solutions
journal, May 2010

  • Oleksy, Anna; Hansen, Jean-Pierre
  • The Journal of Chemical Physics, Vol. 132, Issue 20
  • DOI: 10.1063/1.3428704

Supercapacitor Capacitance Exhibits Oscillatory Behavior as a Function of Nanopore Size
journal, October 2011

  • Feng, Guang; Cummings, Peter T.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 22
  • DOI: 10.1021/jz201312e

Non-Haloaluminate Room-Temperature Ionic Liquids in Electrochemistry—A Review
journal, August 2004

  • Buzzeo, Marisa C.; Evans, Russell G.; Compton, Richard G.
  • ChemPhysChem, Vol. 5, Issue 8
  • DOI: 10.1002/cphc.200301017

Interionic Interactions in Conducting Nanoconfinement
journal, December 2013

  • Rochester, Christopher C.; Lee , Alpha A.; Pruessner, Gunnar
  • ChemPhysChem, Vol. 14, Issue 18
  • DOI: 10.1002/cphc.201300834

Double-Layer in Ionic Liquids:  Paradigm Change?
journal, May 2007

  • Kornyshev, Alexei A.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 20
  • DOI: 10.1021/jp067857o

On the theory of electric double layer with explicit account of a polarizable co-solvent
journal, May 2016

  • Budkov, Yu. A.; Kolesnikov, A. L.; Kiselev, M. G.
  • The Journal of Chemical Physics, Vol. 144, Issue 18
  • DOI: 10.1063/1.4948634

Interfacial Ionic Liquids: Connecting Static and Dynamic Structures
text, January 2014

On the theory of electric double layer with explicit account of a polarizable co-solvent
text, January 2016

Charge neutrality breakdown in confined aqueous electrolytes: theory and simulation
text, January 2016

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Computational Insights into Materials and Interfaces for Capacitive Energy Storage
    journal, April 2017

    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

    Wettability of ultra-small pores of carbon electrodes by size-asymmetric ionic fluids
    journal, February 2020

    • Liu, Kun; Wu, Jianzhong
    • The Journal of Chemical Physics, Vol. 152, Issue 5
    • DOI: 10.1063/1.5131450
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Figure 1. (p. 3)figure
      Figure 2. (p. 7)figure
      Figure 3. (p. 9)figure
      Figure 4. (p. 10)figure
      Figure 5. (p. 11)figure
      Figure 6. (p. 12)figure
      Figure 7. (p. 13)figure
      Figure 8. (p. 15)figure
      Figure 9. (p. 16)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections:

        Other research related to this record: