Electric double layer capacitance for ionic liquids in nanoporous electrodes: Effects of pore size and ion composition
Abstract
The energy density of an electric double layer (EDL) capacitor, a type of supercapacitor, depends on the ion distribution within the micropores of electrodes that are typically made of amorphous carbon. By using coarse-grained models and the classical density functional theory, we investigate the distributions of ionic species among different idealized nanopores in contact with an asymmetric ionic liquid mixture and the effects of the bulk electrolyte composition on capacitive energy storage. We find that a charged pore is always small-ion selective, provided all ions have the same valence and similar non-electrostatic interactions. While small ions enhance both the EDL capacitance and the accessibility of micropores, an ionic mixture containing ions of different sizes may yield a capacitance higher than those corresponding to pure ionic liquids. Furthermore, the increased capacitance may be attributed to more efficient ion packing near the charged surface. At certain conditions, the improvement is on a par with the anomalous capacitance rise for pure ionic liquids in electrodes with ultranarrow pores.
- Authors:
-
[1];
[2];
- Univ. of California, Riverside, CA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Brigham Young Univ., Provo, UT (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1557520
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Molecular Liquids
- Additional Journal Information:
- Journal Volume: 270; Journal Issue: C; Journal ID: ISSN 0167-7322
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Porous electrodes; Capacitance; Ionic-liquid mixtures; EDL structure; Ion selectivity; Classical density functional theory
Citation Formats
Neal, Justin N., Wesolowski, David J., Henderson, Douglas, and Wu, Jianzhong. Electric double layer capacitance for ionic liquids in nanoporous electrodes: Effects of pore size and ion composition. United States: N. p., 2017.
Web. doi:10.1016/j.molliq.2017.10.128.
Neal, Justin N., Wesolowski, David J., Henderson, Douglas, & Wu, Jianzhong. Electric double layer capacitance for ionic liquids in nanoporous electrodes: Effects of pore size and ion composition. United States. https://doi.org/10.1016/j.molliq.2017.10.128
Neal, Justin N., Wesolowski, David J., Henderson, Douglas, and Wu, Jianzhong. Fri .
"Electric double layer capacitance for ionic liquids in nanoporous electrodes: Effects of pore size and ion composition". United States. https://doi.org/10.1016/j.molliq.2017.10.128. https://www.osti.gov/servlets/purl/1557520.
@article{osti_1557520,
title = {Electric double layer capacitance for ionic liquids in nanoporous electrodes: Effects of pore size and ion composition},
author = {Neal, Justin N. and Wesolowski, David J. and Henderson, Douglas and Wu, Jianzhong},
abstractNote = {The energy density of an electric double layer (EDL) capacitor, a type of supercapacitor, depends on the ion distribution within the micropores of electrodes that are typically made of amorphous carbon. By using coarse-grained models and the classical density functional theory, we investigate the distributions of ionic species among different idealized nanopores in contact with an asymmetric ionic liquid mixture and the effects of the bulk electrolyte composition on capacitive energy storage. We find that a charged pore is always small-ion selective, provided all ions have the same valence and similar non-electrostatic interactions. While small ions enhance both the EDL capacitance and the accessibility of micropores, an ionic mixture containing ions of different sizes may yield a capacitance higher than those corresponding to pure ionic liquids. Furthermore, the increased capacitance may be attributed to more efficient ion packing near the charged surface. At certain conditions, the improvement is on a par with the anomalous capacitance rise for pure ionic liquids in electrodes with ultranarrow pores.},
doi = {10.1016/j.molliq.2017.10.128},
journal = {Journal of Molecular Liquids},
number = C,
volume = 270,
place = {United States},
year = {2017},
month = {11}
}
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Works referenced in this record:
Mean spherical model for asymmetric electrolytes: I. Method of solution
journal, November 1975
- Blum, L.
- Molecular Physics, Vol. 30, Issue 5
Some exact results and the application of the mean spherical approximation to charged hard spheres near a charged hard wall
journal, December 1978
- Henderson, Douglas; Blum, Lesser
- The Journal of Chemical Physics, Vol. 69, Issue 12
Analytical solution of the mean spherical approximation for an arbitrary mixture of ions in a dipolar solvent
journal, July 1987
- Blum, L.; Wei, D. Q.
- The Journal of Chemical Physics, Vol. 87, Issue 1
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
Supercapacitors based on high-surface-area graphene
journal, January 2014
- Zhou, XiaoLin; Wang, Min; Lian, Jie
- Science China Technological Sciences, Vol. 57, Issue 2
Structure and Nanostructure in Ionic Liquids
journal, June 2015
- Hayes, Robert; Warr, Gregory G.; Atkin, Rob
- Chemical Reviews, Vol. 115, Issue 13
Materials for electrochemical capacitors
journal, November 2008
- Simon, Patrice; Gogotsi, Yury
- Nature Materials, Vol. 7, Issue 11
Ion distribution and selectivity of ionic liquids in microporous electrodes
journal, May 2017
- Neal, Justin N.; Wesolowski, David J.; Henderson, Douglas
- The Journal of Chemical Physics, Vol. 146, Issue 17
Enhanced ordering reduces electric susceptibility of liquids confined to graphene slit pores
journal, June 2016
- Terrones, Jeronimo; Kiley, Patrick J.; Elliott, James A.
- Scientific Reports, Vol. 6, Issue 1
Physics of Size Selectivity
journal, December 2005
- Roth, Roland; Gillespie, Dirk
- Physical Review Letters, Vol. 95, Issue 24
Structure and Dynamics of an Electrolyte Confined in Charged Nanopores
journal, March 2014
- Cazade, Pierre-Andre; Hartkamp, Remco; Coasne, Benoit
- The Journal of Physical Chemistry C, Vol. 118, Issue 10
In Situ Monitoring of Diffuse Double Layer Structure Changes of Electrochemically Addressable Self-Assembled Monolayers with an Atomic Force Microscope
journal, April 1999
- Hu, Kai; Chai, Zheng; Whitesell, James K.
- Langmuir, Vol. 15, Issue 9
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
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
Room-Temperature Ionic Liquids: Excluded Volume and Ion Polarizability Effects in the Electrical Double-Layer Structure and Capacitance
journal, September 2009
- Lauw, Y.; Horne, M. D.; Rodopoulos, T.
- Physical Review Letters, Vol. 103, Issue 11
Double Layer in Ionic Liquids: Overscreening versus Crowding
journal, January 2011
- Bazant, Martin Z.; Storey, Brian D.; Kornyshev, Alexei A.
- Physical Review Letters, Vol. 106, Issue 4
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
Selective adsorption of ions in charged slit-systems
journal, January 2013
- Valiskó,
- Condensed Matter Physics, Vol. 16, Issue 4
Theoretical interpretation of adsorption behavior of simple fluids in slit pores
journal, July 1993
- Balbuena, Perla B.; Gubbins, Keith E.
- Langmuir, Vol. 9, Issue 7
Ion Correlations in Nanofluidic Channels: Effects of Ion Size, Valence, and Concentration on Voltage- and Pressure-Driven Currents
journal, January 2013
- Hoffmann, Jordan; Gillespie, Dirk
- Langmuir, Vol. 29, Issue 4
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
Density functional theory for differential capacitance of planar electric double layers in ionic liquids
journal, March 2011
- Jiang, De-en; Meng, Dong; Wu, Jianzhong
- Chemical Physics Letters, Vol. 504, Issue 4-6
Oscillation of Capacitance inside Nanopores
journal, December 2011
- Jiang, De-en; Jin, Zhehui; Wu, Jianzhong
- Nano Letters, Vol. 11, Issue 12
Molecular Layering of Fluorinated Ionic Liquids at a Charged Sapphire (0001) Surface
journal, October 2008
- Mezger, M.; Schroder, H.; Reichert, H.
- Science, Vol. 322, Issue 5900
High capacitance of coarse-grained carbide derived carbon electrodes
journal, February 2016
- Dyatkin, Boris; Gogotsi, Oleksiy; Malinovskiy, Bohdan
- Journal of Power Sources, Vol. 306
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- Abbas, Qamar; Gollas, Bernhard; Presser, Volker
- Energy Technology, Vol. 7, Issue 9
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journal, January 2019
- Ali, Basant A.; Allam, Nageh K.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 32
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collection, January 2019
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