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:
-
- Univ. of California, Riverside, CA (United States)
- Univ. of California, Riverside, CA (United States); East China Univ. of Science and Technology, Shanghai (People's Republic of China)
- 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.
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
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.
@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 = {2016},
month = {12}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 5 works
Citation information provided by
Web of Science
Web of Science
Figures / Tables:
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 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
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
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
Anomalous or regular capacitance? The influence of pore size dispersity on double-layer formation
journal, September 2016
- Jäckel, N.; Rodner, M.; Schreiber, A.
- Journal of Power Sources, Vol. 326
The importance of ion size and electrode curvature on electrical double layers in ionic liquids
journal, January 2011
- Feng, Guang; Qiao, Rui; Huang, Jingsong
- Phys. Chem. Chem. Phys., Vol. 13, Issue 3
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
Applications of ionic liquids in the chemical industry
journal, January 2008
- Plechkova, Natalia V.; Seddon, Kenneth R.
- Chem. Soc. Rev., Vol. 37, Issue 1
Experimental measurement of the hygroscopic grade on eight imidazolium based ionic liquids
journal, April 2009
- Cuadrado-Prado, S.; Domínguez-Pérez, M.; Rilo, E.
- Fluid Phase Equilibria, Vol. 278, Issue 1-2
Microscopic density functional theory of wetting and drying of a solid substrate by an explicit solvent model of ionic solutions
journal, December 2009
- Oleksy, Anna; Hansen, Jean-Pierre
- Molecular Physics, Vol. 107, Issue 23-24
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
Ionic Liquids at Electrified Interfaces
journal, March 2014
- Fedorov, Maxim V.; Kornyshev, Alexei A.
- Chemical Reviews, Vol. 114, Issue 5
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
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
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
Interfacial ionic ‘liquids’: connecting static and dynamic structures
journal, December 2014
- Uysal, Ahmet; Zhou, Hua; Feng, Guang
- Journal of Physics: Condensed Matter, Vol. 27, Issue 3
Size Selectivity of Narrow Pores
journal, July 2000
- Goulding, David; Hansen, Jean-Pierre; Melchionna, Simone
- Physical Review Letters, Vol. 85, Issue 5
Ion distributions, exclusion coefficients, and separation factors of electrolytes in a charged cylindrical nanopore: A partially perturbative density functional theory study
journal, October 2009
- Peng, Bo; Yu, Yang-Xin
- The Journal of Chemical Physics, Vol. 131, Issue 13
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
Enhancing the Capacitive Performance of Electric Double-Layer Capacitors with Ionic Liquid Mixtures
journal, April 2016
- Lian, C.; Liu, K.; Van Aken, K. L.
- ACS Energy Letters, Vol. 1, Issue 1
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
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
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
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
Chemical and electrochemical ageing of carbon materials used in supercapacitor electrodes
journal, November 2008
- Zhu, M.; Weber, C. J.; Yang, Y.
- Carbon, Vol. 46, Issue 14
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
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
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
Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer
journal, September 2006
- Chmiola, J.
- Science, Vol. 313, Issue 5794
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
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
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
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
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
Oscillation of Capacitance inside Nanopores
journal, December 2011
- Jiang, De-en; Jin, Zhehui; Wu, Jianzhong
- Nano Letters, Vol. 11, Issue 12
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
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
Towards a microscopic theory of wetting by ionic solutions. I. Surface properties of the semi-primitive model
journal, September 2006
- Oleksy, Anna; Hansen, Jean-Pierre
- Molecular Physics, Vol. 104, Issue 18
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
Wetting and drying scenarios of ionic solutions
journal, March 2011
- Oleksy, Anna; Hansen, Jean-Pierre
- Molecular Physics, Vol. 109, Issue 7-10
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
Causes of supercapacitors ageing in organic electrolyte
journal, September 2007
- Azaïs, Philippe; Duclaux, Laurent; Florian, Pierre
- Journal of Power Sources, Vol. 171, Issue 2
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
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
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
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
Superionic state in double-layer capacitors with nanoporous electrodes
journal, December 2010
- Kondrat, S.; Kornyshev, A.
- Journal of Physics: Condensed Matter, Vol. 23, Issue 2
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
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
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
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
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
Interionic Interactions in Conducting Nanoconfinement
journal, December 2013
- Rochester, Christopher C.; Lee , Alpha A.; Pruessner, Gunnar
- ChemPhysChem, Vol. 14, Issue 18
Double-Layer in Ionic Liquids: Paradigm Change?
journal, May 2007
- Kornyshev, Alexei A.
- The Journal of Physical Chemistry B, Vol. 111, Issue 20
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
Applications of ionic liquids in the chemical industry
journal, January 2008
- Plechkova, Natalia V.; Seddon, Kenneth R.
- Chem. Soc. Rev., Vol. 37, Issue 1
Superionic state in double-layer capacitors with nanoporous electrodes
text, January 2010
- Kondrat, S.; Kornyshev, A.
- arXiv
Interfacial Ionic Liquids: Connecting Static and Dynamic Structures
text, January 2014
- Uysal, Ahmet; Zhou, Hua; Feng, Guang
- arXiv
On the theory of electric double layer with explicit account of a polarizable co-solvent
text, January 2016
- Budkov, Yu. A.; Kolesnikov, A. L.; Kiselev, M. G.
- arXiv
Charge neutrality breakdown in confined aqueous electrolytes: theory and simulation
text, January 2016
- Colla, Thiago; Girotto, Matheus; Santos, Alexandre P. dos
- arXiv
Works referencing / citing this record:
Computational Insights into Materials and Interfaces for Capacitive Energy Storage
journal, April 2017
- Zhan, Cheng; Lian, Cheng; Zhang, Yu
- Advanced Science, Vol. 4, Issue 7
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
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
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.