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Title: Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces

Abstract

In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysis shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architecturesmore » of supercapacitor electrodes.« less

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [2];  [2];  [4];  [4];  [3];  [4]; ORCiD logo [1]
+ Show Author Affiliations
  1. Drexel Univ., Philadelphia, PA (United States). A.J. Drexel Nanomaterials Inst. Dept. of Materials Science and Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
  3. Vanderbilt Univ., Nashville, TN (United States). Chemical and Biomolecular Engineering
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Drexel Univ., Philadelphia, PA (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:
1432166
Alternate Identifier(s):
OSTI ID: 1576053
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Carbon
Additional Journal Information:
Journal Volume: 129; Journal ID: ISSN 0008-6223
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; energy storage; carbide-derived carbon; ionic liquid; neutron scattering; self-diffusion; supercapacitor; pair distribution function; surface chemistry; molecular dynamics; interface

Citation Formats

Dyatkin, Boris, Osti, Naresh C., Zhang, Yu, Wang, Hsiu-Wen, Mamontov, Eugene, Heller, William T., Zhang, Pengfei, Rother, Gernot, Cummings, Peter T., Wesolowski, David J., and Gogotsi, Yury. Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces. United States: N. p., 2017. Web. doi:10.1016/j.carbon.2017.12.001.
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Dyatkin, Boris, Osti, Naresh C., Zhang, Yu, Wang, Hsiu-Wen, Mamontov, Eugene, Heller, William T., Zhang, Pengfei, Rother, Gernot, Cummings, Peter T., Wesolowski, David J., & Gogotsi, Yury. Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces. United States. https://doi.org/10.1016/j.carbon.2017.12.001
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Dyatkin, Boris, Osti, Naresh C., Zhang, Yu, Wang, Hsiu-Wen, Mamontov, Eugene, Heller, William T., Zhang, Pengfei, Rother, Gernot, Cummings, Peter T., Wesolowski, David J., and Gogotsi, Yury. Tue . "Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces". United States. https://doi.org/10.1016/j.carbon.2017.12.001. https://www.osti.gov/servlets/purl/1432166.
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@article{osti_1432166,
title = {Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces},
author = {Dyatkin, Boris and Osti, Naresh C. and Zhang, Yu and Wang, Hsiu-Wen and Mamontov, Eugene and Heller, William T. and Zhang, Pengfei and Rother, Gernot and Cummings, Peter T. and Wesolowski, David J. and Gogotsi, Yury},
abstractNote = {In this paper, we investigate the aggregation, diffusion, and resulting electrochemical behavior of ionic liquids inside carbon electrodes with complex pore architectures and surface chemistries. Carbide-derived carbons (CDCs) with bimodal porosities and defunctionalized or oxidized electrode surfaces served as model electrode materials. Our goal was to obtain a fundamental understanding of room-temperature ionic liquid ion orientation, mobility, and electrosorption behavior. Neat 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide confined in CDCs was studied using an integrated experimental and modeling approach, consisting of quasielastic neutron scattering, small-angle neutron scattering, X-ray pair distribution function analysis, and electrochemical measurements, which were combined with molecular dynamics simulations. Our analysis shows that surface oxygen groups increase the diffusion of confined electrolytes. Consequently, the ions become more than twice as mobile in oxygen-rich pores. Although greater self-diffusion of ions translates into higher electrochemical mobilities in oxidized pores, bulk-like behavior of ions dominates in the larger mesopores and increases the overall capacitance in defunctionalized pores. Experimental results highlight strong confinement and surface effects of carbon electrodes on electrolyte behavior, and molecular dynamics simulations yield insight into diffusion and capacitance differences in specific pore regions. Finally, we demonstrate the significance of surface defects on electrosorption dynamics of complex electrolytes in hierarchical pore architectures of supercapacitor electrodes.},
doi = {10.1016/j.carbon.2017.12.001},
journal = {Carbon},
number = ,
volume = 129,
place = {United States},
year = {Tue Dec 05 00:00:00 EST 2017},
month = {Tue Dec 05 00:00:00 EST 2017}
}
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Works referenced in this record:

Capacitive Energy Storage in Nanostructured Carbon–Electrolyte Systems
journal, June 2012

  • Simon, P.; Gogotsi, Y.
  • Accounts of Chemical Research, Vol. 46, Issue 5
  • DOI: 10.1021/ar200306b

Carbons and Electrolytes for Advanced Supercapacitors
journal, February 2014

  • Béguin, François; Presser, Volker; Balducci, Andrea
  • Advanced Materials, Vol. 26, Issue 14, p. 2219-2251
  • DOI: 10.1002/adma.201304137

Not just graphene: The wonderful world of carbon and related nanomaterials
journal, November 2015

Accelerating charging dynamics in subnanometre pores
journal, March 2014

  • Kondrat, Svyatoslav; Wu, Peng; Qiao, Rui
  • Nature Materials, Vol. 13, Issue 4
  • DOI: 10.1038/nmat3916

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

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

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
  • DOI: 10.1021/acs.jpcc.5b05930

First-Principles-Inspired Design Strategies for Graphene-Based Supercapacitor Electrodes
journal, December 2013

  • Wood, Brandon C.; Ogitsu, Tadashi; Otani, Minoru
  • The Journal of Physical Chemistry C, Vol. 118, Issue 1
  • DOI: 10.1021/jp4044013

Desolvation of Ions in Subnanometer Pores and Its Effect on Capacitance and Double-Layer Theory
journal, April 2008

  • Chmiola, John; Largeot, Celine; Taberna, Pierre-Louis
  • Angewandte Chemie, Vol. 120, Issue 18
  • DOI: 10.1002/ange.200704894

Carbon materials for the electrochemical storage of energy in capacitors
journal, May 2001

Ionic Liquids at Electrified Interfaces
journal, March 2014

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

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

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
  • DOI: 10.1021/jp056006y

Densification of Ionic Liquid Molecules within a Hierarchical Nanoporous Carbon Structure Revealed by Small-Angle Scattering and Molecular Dynamics Simulation
journal, December 2013

  • Bañuelos, José Leobardo; Feng, Guang; Fulvio, Pasquale F.
  • Chemistry of Materials, Vol. 26, Issue 2
  • DOI: 10.1021/cm4035159

Saturation of subnanometer pores in an electric double-layer capacitor
journal, March 2009

Activated Carbon, Carbon Blacks and Graphene Based Nanoplatelets as Active Materials for Electrochemical Double Layer Capacitors: A Comparative Study
journal, November 2014

  • Schütter, C.; Ramirez-Castro, C.; Oljaca, M.
  • Journal of The Electrochemical Society, Vol. 162, Issue 1
  • DOI: 10.1149/2.0381501jes

Titanium carbide derived nanoporous carbon for energy-related applications
journal, October 2006

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

Effect of cation on diffusion coefficient of ionic liquids at onion-like carbon electrodes
journal, June 2014

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
  • DOI: 10.1021/acs.jpcc.6b01204

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
  • DOI: 10.1016/j.pnsc.2015.11.007

Ordered mesoporous silicon carbide-derived carbon for high-power supercapacitors
journal, September 2013

3D Aperiodic Hierarchical Porous Graphitic Carbon Material for High-Rate Electrochemical Capacitive Energy Storage
journal, January 2008

  • Wang, Da-Wei; Li, Feng; Liu, Min
  • Angewandte Chemie International Edition, Vol. 47, Issue 2
  • DOI: 10.1002/anie.200702721

The electrochemistry of activated carbonaceous materials: past, present, and future
journal, May 2011

  • Noked, Malachi; Soffer, Abraham; Aurbach, Doron
  • Journal of Solid State Electrochemistry, Vol. 15, Issue 7-8
  • DOI: 10.1007/s10008-011-1411-y

Is a Stern and diffuse layer model appropriate to ionic liquids at surfaces?
journal, October 2013

  • Perkin, S.; Salanne, M.; Madden, P.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 44
  • DOI: 10.1073/pnas.1314188110

Modeling Ionic Liquids Using a Systematic All-Atom Force Field
journal, February 2004

  • Canongia Lopes, José N.; Deschamps, Johnny; Pádua, Agílio A. H.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 6
  • DOI: 10.1021/jp0362133

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
  • DOI: 10.1016/S1381-1169(01)00465-4

Nanoscale fine-tuning of porosity of carbide-derived carbon prepared from molybdenum carbide
journal, January 2009

Molybdenum carbide-derived carbon for hydrogen storage
journal, April 2009

Structural evolution of carbide-derived carbons upon vacuum annealing
journal, November 2012

Impact of synthesis conditions on surface chemistry and structure of carbide-derived carbons
journal, January 2010

  • Portet, Cristelle; Kazachkin, Dmitry; Osswald, Sebastian
  • Thermochimica Acta, Vol. 497, Issue 1-2
  • DOI: 10.1016/j.tca.2009.09.002

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
  • DOI: 10.1021/ja01269a023

Uncertainties in characterization of nanoporous carbons using density functional theory-based gas physisorption
journal, June 2014

Quenched solid density functional theory method for characterization of mesoporous carbons by nitrogen adsorption
journal, April 2012

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
  • DOI: 10.1063/1.3626214

Mantid—Data analysis and visualization package for neutron scattering and μ 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
  • DOI: 10.1016/j.nima.2014.07.029

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
  • DOI: 10.6028/jres.114.025

The extended Q -range small-angle neutron scattering diffractometer at the SNS
journal, July 2010

A simple model describes the PDF of a non-graphitizing carbon
journal, January 2004

Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408

PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data
journal, July 2004

  • Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L.
  • Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678
  • DOI: 10.1107/S0021889804011744

Rapid-acquisition pair distribution function (RA-PDF) analysis
journal, November 2003

  • Chupas, Peter J.; Qiu, Xiangyun; Hanson, Jonathan C.
  • Journal of Applied Crystallography, Vol. 36, Issue 6, p. 1342-1347
  • DOI: 10.1107/S0021889803017564

GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers
journal, September 2015

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

Development of a Green Supercapacitor Composed Entirely of Environmentally Friendly Materials
journal, October 2013

Knitted and screen printed carbon-fiber supercapacitors for applications in wearable electronics
journal, January 2013

  • Jost, Kristy; Stenger, Daniel; Perez, Carlos R.
  • Energy & Environmental Science, Vol. 6, Issue 9
  • DOI: 10.1039/c3ee40515j

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

Best practice methods for determining an electrode material's performance for ultracapacitors
journal, January 2010

  • Stoller, Meryl D.; Ruoff, Rodney S.
  • Energy & Environmental Science, Vol. 3, Issue 9
  • DOI: 10.1039/c0ee00074d

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
  • DOI: 10.1021/la060860e

Dispersion and Absorption in Dielectrics I. Alternating Current Characteristics
journal, April 1941

  • Cole, Kenneth S.; Cole, Robert H.
  • The Journal of Chemical Physics, Vol. 9, Issue 4
  • DOI: 10.1063/1.1750906

Fast diffusion in a room temperature ionic liquid confined in mesoporous carbon
journal, March 2012

Understanding inelastically scattered neutrons from water on a time-of-flight small-angle neutron scattering (SANS) instrument
journal, February 2014

  • Do, Changwoo; Heller, William T.; Stanley, Christopher
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 737
  • DOI: 10.1016/j.nima.2013.11.030

Scattering by an Inhomogeneous Solid. II. The Correlation Function and Its Application
journal, June 1957

  • Debye, P.; Anderson, H. R.; Brumberger, H.
  • Journal of Applied Physics, Vol. 28, Issue 6
  • DOI: 10.1063/1.1722830

Small-angle neutron scattering characterization of the structure of nanoporous carbons for energy-related applications
journal, February 2012

Local structure of nanoporous carbons
journal, October 1999

  • Petkov, V.; Difrancesco, R. G.; Billinge, S. J. L.
  • Philosophical Magazine B, Vol. 79, Issue 10
  • DOI: 10.1080/13642819908218319

New Insights into the Structure of Nanoporous Carbons from NMR, Raman, and Pair Distribution Function Analysis
journal, September 2015

Graphene Oxide Supercapacitors: A Computer Simulation Study
journal, July 2014

  • DeYoung, Andrew D.; Park, Sang-Won; Dhumal, Nilesh R.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 32
  • DOI: 10.1021/jp5072583

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

Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging
journal, December 2015

Dynamic Charge Storage in Ionic Liquids-Filled Nanopores: Insight from a Computational Cyclic Voltammetry Study
journal, December 2014

  • He, Yadong; Huang, Jingsong; Sumpter, Bobby G.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 1
  • DOI: 10.1021/jz5024306

Charging Rate Dependence of Ion Migration and Stagnation in Ionic-Liquid-Filled Carbon Nanopores
journal, October 2016

  • Pak, Alexander J.; Hwang, Gyeong S.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 43
  • DOI: 10.1021/acs.jpcc.6b06637

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
  • DOI: 10.1021/ja406120e

In Situ Small Angle Neutron Scattering Revealing Ion Sorption in Microporous Carbon Electrical Double Layer Capacitors
journal, February 2014

  • Boukhalfa, Sofiane; Gordon, Daniel; He, Lilin
  • ACS Nano, Vol. 8, Issue 3
  • DOI: 10.1021/nn406077n

An unusual slowdown of fast diffusion in a room temperature ionic liquid confined in mesoporous carbon
journal, April 2013

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