Electrolyte cation length influences electrosorption and dynamics in porous carbon supercapacitors
Abstract
We investigate the extent to which the alkyl chain on the cation of an imidazolium-based neat room-temperature ionic liquid influences mobility and electrochemical behavior in nanoporous supercapacitors. Changing the cation chain length from an ethyl (n=2) to a butyl (n=4) to a hexyl (n=6) group affects the electrolyte dynamics and their accumulation densities under dynamic charge-discharge processes. We relied on molecular dynamics (MD) computational simulations and classical density functional theory (cDFT) calculations of our system to reinforce the experimental results obtained from electrochemical measurements and quasi-elastic neutron scattering (QENS). We contrast the different dynamics of ionic liquids in bulk and confined states and demonstrate the effect of the cation dimension on resulting arrangements of positive and negative ions in pores. We correlate these fundamental properties with device performance metrics in an effort to properly tailor high-performance carbon supercapacitor electrodes with non-flammable and electrochemically stable electrolytes.
- Authors:
-
- Drexel Univ., Philadelphia, PA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of California, Riverside, CA (United States)
- Vanderbilt Univ., Nashville, TN (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:
- 1470860
- Alternate Identifier(s):
- OSTI ID: 1495268
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Electrochimica Acta
- Additional Journal Information:
- Journal Volume: 283; Journal Issue: C; Journal ID: ISSN 0013-4686
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Dyatkin, Boris, Osti, Naresh C., Gallegos, Alejandro, Zhang, Yu, Mamontov, Eugene, Cummings, Peter T., Wu, Jianzhong, and Gogotsi, Yury. Electrolyte cation length influences electrosorption and dynamics in porous carbon supercapacitors. United States: N. p., 2018.
Web. doi:10.1016/j.electacta.2018.06.200.
Dyatkin, Boris, Osti, Naresh C., Gallegos, Alejandro, Zhang, Yu, Mamontov, Eugene, Cummings, Peter T., Wu, Jianzhong, & Gogotsi, Yury. Electrolyte cation length influences electrosorption and dynamics in porous carbon supercapacitors. United States. https://doi.org/10.1016/j.electacta.2018.06.200
Dyatkin, Boris, Osti, Naresh C., Gallegos, Alejandro, Zhang, Yu, Mamontov, Eugene, Cummings, Peter T., Wu, Jianzhong, and Gogotsi, Yury. Thu .
"Electrolyte cation length influences electrosorption and dynamics in porous carbon supercapacitors". United States. https://doi.org/10.1016/j.electacta.2018.06.200. https://www.osti.gov/servlets/purl/1470860.
@article{osti_1470860,
title = {Electrolyte cation length influences electrosorption and dynamics in porous carbon supercapacitors},
author = {Dyatkin, Boris and Osti, Naresh C. and Gallegos, Alejandro and Zhang, Yu and Mamontov, Eugene and Cummings, Peter T. and Wu, Jianzhong and Gogotsi, Yury},
abstractNote = {We investigate the extent to which the alkyl chain on the cation of an imidazolium-based neat room-temperature ionic liquid influences mobility and electrochemical behavior in nanoporous supercapacitors. Changing the cation chain length from an ethyl (n=2) to a butyl (n=4) to a hexyl (n=6) group affects the electrolyte dynamics and their accumulation densities under dynamic charge-discharge processes. We relied on molecular dynamics (MD) computational simulations and classical density functional theory (cDFT) calculations of our system to reinforce the experimental results obtained from electrochemical measurements and quasi-elastic neutron scattering (QENS). We contrast the different dynamics of ionic liquids in bulk and confined states and demonstrate the effect of the cation dimension on resulting arrangements of positive and negative ions in pores. We correlate these fundamental properties with device performance metrics in an effort to properly tailor high-performance carbon supercapacitor electrodes with non-flammable and electrochemically stable electrolytes.},
doi = {10.1016/j.electacta.2018.06.200},
journal = {Electrochimica Acta},
number = C,
volume = 283,
place = {United States},
year = {Thu Jul 05 00:00:00 EDT 2018},
month = {Thu Jul 05 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011
- Dunn, B.; Kamath, H.; Tarascon, J. -M.
- Science, Vol. 334, Issue 6058
Capacitive Energy Storage in Nanostructured Carbon–Electrolyte Systems
journal, June 2012
- Simon, P.; Gogotsi, Y.
- Accounts of Chemical Research, Vol. 46, Issue 5
Where Do Batteries End and Supercapacitors Begin?
journal, March 2014
- Simon, P.; Gogotsi, Y.; Dunn, B.
- Science, Vol. 343, Issue 6176
Electrochemical double layer capacitors: What is next beyond the corner?
journal, December 2017
- Lin, Zifeng; Taberna, Pierre-Louis; Simon, Patrice
- Current Opinion in Electrochemistry, Vol. 6, Issue 1
Multidimensional materials and device architectures for future hybrid energy storage
journal, September 2016
- Lukatskaya, Maria R.; Dunn, Bruce; Gogotsi, Yury
- Nature Communications, Vol. 7, Issue 1
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
Efficient storage mechanisms for building better supercapacitors
journal, May 2016
- Salanne, M.; Rotenberg, B.; Naoi, K.
- Nature Energy, Vol. 1, Issue 6
Nanostructural Organization in Ionic Liquids
journal, February 2006
- Canongia Lopes, José N. A.; Pádua, Agílio A. H.
- The Journal of Physical Chemistry B, Vol. 110, Issue 7
Influence of solvation on the structural and capacitive properties of electrical double layer capacitors
journal, July 2013
- Merlet, Céline; Salanne, Mathieu; Rotenberg, Benjamin
- Electrochimica Acta, Vol. 101
Ionic liquids: perspectives for organic and catalytic reactions
journal, May 2002
- Olivier-Bourbigou, Hélène; Magna, Lionel
- Journal of Molecular Catalysis A: Chemical, Vol. 182-183, p. 419-437
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
Structure and Nanostructure in Ionic Liquids
journal, June 2015
- Hayes, Robert; Warr, Gregory G.; Atkin, Rob
- Chemical Reviews, Vol. 115, Issue 13
Nonaqueous Electrolytes for Electrochemical Capacitors: Imidazolium Cations and Inorganic Fluorides with Organic Carbonates
journal, April 1997
- McEwen, Alan B.; McDevitt, Stephen F.; Koch, Victor R.
- Journal of The Electrochemical Society, Vol. 144, Issue 4
Cycling stability of a hybrid activated carbon//poly(3-methylthiophene) supercapacitor with N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ionic liquid as electrolyte
journal, April 2005
- Balducci, Andrea; Henderson, Wesley A.; Mastragostino, Marina
- Electrochimica Acta, Vol. 50, Issue 11
Physical and Electrochemical Properties of N -Alkyl- N -methylpyrrolidinium Bis(fluorosulfonyl)imide Ionic Liquids: PY 13 FSI and PY 14 FSI
journal, October 2008
- Zhou, Qian; Henderson, Wesley A.; Appetecchi, Giovanni B.
- The Journal of Physical Chemistry B, Vol. 112, Issue 43
Physical properties of high Li-ion content N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide based ionic liquid electrolytes
journal, January 2015
- Yoon, Hyungook; Best, Adam S.; Forsyth, Maria
- Physical Chemistry Chemical Physics, Vol. 17, Issue 6
Electrochemical and thermal properties of graphite electrodes with imidazolium- and piperidinium-based ionic liquids
journal, July 2009
- Profatilova, Irina A.; Choi, Nam-Soon; Roh, Sae Weon
- Journal of Power Sources, Vol. 192, Issue 2
Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer
journal, September 2006
- Chmiola, J.
- Science, Vol. 313, Issue 5794
Highly confined ions store charge more efficiently in supercapacitors
journal, October 2013
- Merlet, C.; Péan, C.; Rotenberg, B.
- Nature Communications, Vol. 4, Issue 1
Ionic Liquid Electrolyte for Lithium Metal Batteries: Physical, Electrochemical, and Interfacial Studies of N -Methyl- N -butylmorpholinium Bis(fluorosulfonyl)imide
journal, November 2010
- Lane, George H.; Bayley, Paul M.; Clare, Bronya R.
- The Journal of Physical Chemistry C, Vol. 114, Issue 49
Quantum Chemistry Studies of the Oxidative Stability of Carbonate, Sulfone and Sulfonate-Based Electrolytes Doped with BF
conference, January 2011
- Borodin, Oleg; Jow, T. R.
- 218th ECS Meeting, ECS Transactions
Capacitive Energy Storage from −50 to 100 °C Using an Ionic Liquid Electrolyte
journal, September 2011
- Lin, Rongying; Taberna, Pierre-Louis; Fantini, Sébastien
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 19
Tuning Binary Ionic Liquid Mixtures: Linking Alkyl Chain Length to Phase Behavior and Ionic Conductivity
journal, February 2012
- Fox, Eric T.; Weaver, Joshua E. F.; Henderson, Wesley A.
- The Journal of Physical Chemistry C, Vol. 116, Issue 8
Selective Charging Behavior in an Ionic Mixture Electrolyte-Supercapacitor System for Higher Energy and Power
journal, December 2017
- Wang, Xuehang; Mehandzhiyski, Aleksandar Yordanov; Arstad, Bjørnar
- Journal of the American Chemical Society, Vol. 139, Issue 51
Outstanding performance of activated graphene based supercapacitors in ionic liquid electrolyte from −50 to 80°C
journal, May 2013
- Tsai, Wan-Yu; Lin, Rongying; Murali, Shanthi
- Nano Energy, Vol. 2, Issue 3
Geometrically confined favourable ion packing for high gravimetric capacitance in carbon–ionic liquid supercapacitors
journal, January 2016
- Wang, Xuehang; Zhou, Haitao; Sheridan, Edel
- Energy & Environmental Science, Vol. 9, Issue 1
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
Novel Electrochemical Studies of Ionic Liquids
journal, March 2002
- Quinn, Bernadette M.; Ding, Zhifeng; Moulton, Roger
- Langmuir, Vol. 18, Issue 5
Thermal stability of low temperature ionic liquids revisited
journal, March 2004
- Kosmulski, Marek; Gustafsson, Jan; Rosenholm, Jarl B.
- Thermochimica Acta, Vol. 412, Issue 1-2
Molecular-scale insights into the mechanisms of ionic liquids interactions with carbon nanotubes
journal, January 2012
- Frolov, Andrey I.; Kirchner, Kathleen; Kirchner, Tom
- Faraday Discuss., Vol. 154
Charging Dynamics and Optimization of Nanoporous Supercapacitors
journal, June 2013
- Kondrat, S.; Kornyshev, A.
- The Journal of Physical Chemistry C, Vol. 117, Issue 24
Dynamics of Ion Transport in Ionic Liquids
journal, September 2015
- Lee, Alpha A.; Kondrat, Svyatoslav; Vella, Dominic
- Physical Review Letters, Vol. 115, Issue 10
On the Influence of Surface Topography on the Electric Double Layer Structure and Differential Capacitance of Graphite/Ionic Liquid Interfaces
journal, August 2011
- Vatamanu, Jenel; Cao, Liulei; Borodin, Oleg
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 17
Computational insight into the capacitive performance of graphene edge planes
journal, May 2017
- Zhan, Cheng; Zhang, Yu; Cummings, Peter T.
- Carbon, Vol. 116
Influence of Surface Oxidation on Ion Dynamics and Capacitance in Porous and Nonporous Carbon Electrodes
journal, April 2016
- Dyatkin, Boris; Zhang, Yu; Mamontov, Eugene
- The Journal of Physical Chemistry C, Vol. 120, Issue 16
Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces
journal, April 2018
- Dyatkin, Boris; Osti, Naresh C.; Zhang, Yu
- Carbon, Vol. 129
Quantum Effects on the Capacitance of Graphene-Based Electrodes
journal, September 2015
- Zhan, Cheng; Neal, Justin; Wu, Jianzhong
- The Journal of Physical Chemistry C, Vol. 119, Issue 39
Enhancing graphene capacitance by nitrogen: effects of doping configuration and concentration
journal, January 2016
- Zhan, Cheng; Zhang, Yu; Cummings, Peter T.
- Physical Chemistry Chemical Physics, Vol. 18, Issue 6
High capacitance of coarse-grained carbide derived carbon electrodes
journal, February 2016
- Dyatkin, Boris; Gogotsi, Oleksiy; Malinovskiy, Bohdan
- Journal of Power Sources, Vol. 306
Ion Dynamics in Porous Carbon Electrodes in Supercapacitors Using in Situ Infrared Spectroelectrochemistry
journal, August 2013
- Richey, Francis W.; Dyatkin, Boris; Gogotsi, Yury
- Journal of the American Chemical Society, Vol. 135, Issue 34
Computer simulation studies of nanoporous carbon-based electrochemical capacitors
journal, June 2018
- Li, Zhujie; Mendez-Morales, Trinidad; Salanne, Mathieu
- Current Opinion in Electrochemistry, Vol. 9
Carbide-Derived Carbons - From Porous Networks to Nanotubes and Graphene
journal, February 2011
- Presser, Volker; Heon, Min; Gogotsi, Yury
- Advanced Functional Materials, Vol. 21, Issue 5
Structure and Electrochemical Performance of Carbide-Derived Carbon Nanopowders
journal, July 2012
- Pérez, Carlos R.; Yeon, Sun-Hwa; Ségalini, Julie
- Advanced Functional Materials, Vol. 23, Issue 8
Structural evolution of carbide-derived carbons upon vacuum annealing
journal, November 2012
- Osswald, Sebastian; Chmiola, John; Gogotsi, Yury
- Carbon, Vol. 50, Issue 13
Adsorption of Gases in Multimolecular Layers
journal, February 1938
- Brunauer, Stephen; Emmett, P. H.; Teller, Edward
- Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319
Quenched solid density functional theory method for characterization of mesoporous carbons by nitrogen adsorption
journal, April 2012
- Gor, Gennady Yu.; Thommes, Matthias; Cychosz, Katie A.
- Carbon, Vol. 50, Issue 4
Capacitance, charge dynamics, and electrolyte-surface interactions in functionalized carbide-derived carbon electrodes
journal, December 2015
- Dyatkin, Boris; Mamontov, Eugene; Cook, Kevin M.
- Progress in Natural Science: Materials International, Vol. 25, Issue 6
A time-of-flight backscattering spectrometer at the Spallation Neutron Source, BASIS
journal, August 2011
- Mamontov, E.; Herwig, K. W.
- Review of Scientific Instruments, Vol. 82, Issue 8
Mantid—Data analysis and visualization package for neutron scattering and SR experiments
journal, November 2014
- Arnold, O.; Bilheux, J. C.; Borreguero, J. M.
- Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764
DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009
- Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
- Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
Development of a Green Supercapacitor Composed Entirely of Environmentally Friendly Materials
journal, October 2013
- Dyatkin, Boris; Presser, Volker; Heon, Min
- ChemSusChem, Vol. 6, Issue 12
Influence of the structure of carbon onions on their electrochemical performance in supercapacitor electrodes
journal, August 2012
- McDonough, John K.; Frolov, Andrey I.; Presser, Volker
- Carbon, Vol. 50, Issue 9
Electrochemical Characteristics and Impedance Spectroscopy Studies of Carbon-Carbon Supercapacitors
journal, January 2003
- Taberna, P. L.; Simon, P.; Fauvarque, J. F.
- Journal of The Electrochemical Society, Vol. 150, Issue 3, p. A292-A300
Double layer in ionic liquids: The nature of the camel shape of capacitance
journal, February 2010
- Fedorov, M. V.; Georgi, N.; Kornyshev, A. A.
- Electrochemistry Communications, Vol. 12, Issue 2
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
Density-functional theory for the structures and thermodynamic properties of highly asymmetric electrolyte and neutral component mixtures
journal, September 2004
- Li, Zhidong; Wu, Jianzhong
- Physical Review E, Vol. 70, Issue 3
GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers
journal, September 2015
- Abraham, Mark James; Murtola, Teemu; Schulz, Roland
- SoftwareX, Vol. 1-2
Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985
- Hoover, William G.
- Physical Review A, Vol. 31, Issue 3
Improved Classical United-Atom Force Field for Imidazolium-Based Ionic Liquids: Tetrafluoroborate, Hexafluorophosphate, Methylsulfate, Trifluoromethylsulfonate, Acetate, Trifluoroacetate, and Bis(trifluoromethylsulfonyl)amide
journal, August 2011
- Zhong, Xiujuan; Liu, Zhiping; Cao, Dapeng
- The Journal of Physical Chemistry B, Vol. 115, Issue 33
A Second Generation Force Field for the Simulation of Proteins, Nucleic Acids, and Organic Molecules
journal, May 1995
- Cornell, Wendy D.; Cieplak, Piotr; Bayly, Christopher I.
- Journal of the American Chemical Society, Vol. 117, Issue 19
Carbide-Derived Carbons: A Comparative Study of Porosity Based on Small-Angle Scattering and Adsorption Isotherms
journal, October 2006
- Laudisio, Giovanna; Dash, Ranjan K.; Singer, Jonathan P.
- Langmuir, Vol. 22, Issue 21
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
Functional Groups and Pore Size Distribution Do Matter to Hierarchically Porous Carbons as High-Rate-Performance Supercapacitors
journal, January 2016
- Wei, Xianjun; Jiang, Xiaoqiang; Wei, Jishi
- Chemistry of Materials, Vol. 28, Issue 2
Characteristic features of water dynamics in restricted geometries investigated with quasi-elastic neutron scattering
journal, February 2016
- Osti, N. C.; Coté, A.; Mamontov, E.
- Chemical Physics, Vol. 465-466
Fast diffusion in a room temperature ionic liquid confined in mesoporous carbon
journal, March 2012
- Chathoth, S. M.; Mamontov, E.; Dai, S.
- EPL (Europhysics Letters), Vol. 97, Issue 6
Proton Dynamics in N , N , N ′, N ′-Tetramethylguanidinium Bis(perfluoroethylsulfonyl)imide Protic Ionic Liquid Probed by Quasielastic Neutron Scattering
journal, January 2009
- Mamontov, Eugene; Luo, Huimin; Dai, Sheng
- The Journal of Physical Chemistry B, Vol. 113, Issue 1
Microscopic Diffusion Dynamics of Silver Complex-Based Room-Temperature Ionic Liquids Probed by Quasielastic Neutron Scattering
journal, March 2011
- Mamontov, Eugene; Baker, Gary A.; Luo, Huimin
- ChemPhysChem, Vol. 12, Issue 5
Improving the Alkaline Stability of Imidazolium Cations by Substitution
journal, July 2014
- Dong, Huilong; Gu, Fenglou; Li, Min
- ChemPhysChem, Vol. 15, Issue 14
Effects of Alkyl Chain Length on Interfacial Structure and Differential Capacitance in Graphene Supercapacitors: A Molecular Dynamics Simulation Study
journal, September 2017
- Jo, Sungsik; Park, Sang-Won; Shim, Youngseon
- Electrochimica Acta, Vol. 247
Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging
journal, December 2015
- He, Yadong; Qiao, Rui; Vatamanu, Jenel
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 1
Ionic Liquids Confined in a Realistic Activated Carbon Model: A Molecular Simulation Study
journal, January 2014
- Rajput, Nav Nidhi; Monk, Joshua; Hung, Francisco R.
- The Journal of Physical Chemistry C, Vol. 118, Issue 3
On the Influence of Pore Size and Pore Loading on Structural and Dynamical Heterogeneities of an Ionic Liquid Confined in a Slit Nanopore
journal, February 2012
- Rajput, Nav Nidhi; Monk, Joshua; Singh, Ramesh
- The Journal of Physical Chemistry C, Vol. 116, Issue 8
Works referencing / citing this record:
Cation Molecular Structure Affects Mobility and Transport of Electrolytes in Porous Carbons
journal, January 2019
- Osti, Naresh C.; Dyatkin, Boris; Gallegos, Alejandro
- Journal of The Electrochemical Society, Vol. 166, Issue 4
Dynamics of ionic liquids in the presence of polymer-grafted nanoparticles
journal, January 2019
- Liu, Siqi; Liedel, Clemens; Tarakina, Nadezda V.
- Nanoscale, Vol. 11, Issue 42
Side-chain effects on the capacitive behaviour of ionic liquids in microporous electrodes
journal, August 2019
- Gallegos, Alejandro; Lian, Cheng; Dyatkin, Boris
- Molecular Physics, Vol. 117, Issue 23-24
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
Dynamic electrochemical impedance spectroscopy as a rapid screening tool for supercapacitor electrode materials
journal, December 2019
- Ramesh, T.; Vedarajan, R.; Rajalakshmi, N.
- Journal of Materials Science: Materials in Electronics, Vol. 31, Issue 2
Side-chain effects on the capacitive behaviour of ionic liquids in microporous electrodes
text, January 2019
- Gallegos, Alejandro; Lian, Cheng; Dyatkin, Boris
- Taylor & Francis