skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Influence of surface oxidation on ion dynamics and capacitance in porous and nonporous carbon electrodes

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [3];  [3];  [3];  [2];  [1]
  1. Drexel Univ., Philadelphia, PA (United States)
  2. Vanderbilt Univ., Nashville, TN (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Here, we investigate the influence of surface chemistry and ion confinement on capacitance and electrosorption dynamics of room-temperature ionic liquids (RTILs) in supercapacitors. Using air oxidation and vacuum annealing, we produced defunctionalized and oxygen-rich surfaces of carbide-derived carbons (CDCs) and graphene nanoplatelets (GNPs). While oxidized surfaces of porous CDCs improve capacitance and rate handling abilities of ions, defunctionalized nonporous GNPs improve charge storage densities on planar electrodes. Quasi-elastic neutron scattering (QENS) and inelastic neutron scattering (INS) probed the structure, dynamics, and orientation of RTIL ions confined in divergently functionalized pores. Oxidized, ionophilic surfaces draw ions closer to pore surfaces and enhance potential-driven ion transport during electrosorption. Molecular dynamics (MD) simulations corroborated experimental data and demonstrated the significance of surface functional groups on ion orientations, accumulation densities, and capacitance.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
DOE Contract Number:
AC05-00OR22725
OSTI ID:
1250416
Journal Information:
Journal of Physical Chemistry. C, Vol. 120, Issue 16; ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

References (65)

Capacitive Energy Storage in Nanostructured Carbon–Electrolyte Systems journal June 2012
Charge storage mechanism in nanoporous carbons and its consequence for electrical double layer capacitors
  • Simon, P.; Gogotsi, Y.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923, p. 3457-3467 https://doi.org/10.1098/rsta.2010.0109
journal June 2010
Is a Stern and diffuse layer model appropriate to ionic liquids at surfaces? journal October 2013
Double-Layer in Ionic Liquids:  Paradigm Change? journal May 2007
Graphene Oxide Supercapacitors: A Computer Simulation Study journal July 2014
Molecular Insights into Carbon Supercapacitors Based on Room-Temperature Ionic Liquids journal September 2013
Supercapacitor Capacitance Exhibits Oscillatory Behavior as a Function of Nanopore Size journal October 2011
Effect of pore size and surface area of carbide derived carbons on specific capacitance journal July 2006
A Universal Model for Nanoporous Carbon Supercapacitors Applicable to Diverse Pore Regimes, Carbon Materials, and Electrolytes journal July 2008
On the molecular origin of supercapacitance in nanoporous carbon electrodes journal March 2012
Highly confined ions store charge more efficiently in supercapacitors journal October 2013
Curvature Effect on the Capacitance of Electric Double Layers at Ionic Liquid/Onion-Like Carbon Interfaces journal February 2012
Accelerating charging dynamics in subnanometre pores journal March 2014
Effects of structural disorder and surface chemistry on electric conductivity and capacitance of porous carbon electrodes journal January 2014
First-Principles-Inspired Design Strategies for Graphene-Based Supercapacitor Electrodes journal December 2013
Electric double-layer capacitance between an ionic liquid and few-layer graphene journal April 2013
Quantum Effects on the Capacitance of Graphene-Based Electrodes journal September 2015
Effects of Oxygen-Containing Functional Groups on Supercapacitor Performance journal June 2014
Electrolytic Transport in Modified Carbon Nanotubes journal October 2003
pH-Tunable Ion Selectivity in Carbon Nanotube Pores journal September 2010
A superionic state in nano-porous double-layer capacitors: insights from Monte Carlo simulations journal January 2011
Confinement, Desolvation, And Electrosorption Effects on the Diffusion of Ions in Nanoporous Carbon Electrodes journal September 2015
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
Effects of Pore Size and Pore Loading on the Properties of Ionic Liquids Confined Inside Nanoporous CMK-3 Carbon Materials journal January 2011
Densification of Ionic Liquid Molecules within a Hierarchical Nanoporous Carbon Structure Revealed by Small-Angle Scattering and Molecular Dynamics Simulation journal December 2013
The influence of a hierarchical porous carbon network on the coherent dynamics of a nanoconfined room temperature ionic liquid: A neutron spin echo and atomistic simulation investigation journal November 2014
Single-File Charge Storage in Conducting Nanopores journal July 2014
Ionic Liquids at Electrified Interfaces journal March 2014
Surface Structure at the Ionic Liquid−Electrified Metal Interface journal March 2008
Molecular-scale insights into the mechanisms of ionic liquids interactions with carbon nanotubes journal January 2012
Unique Hydrogen-Bonded Structure of Water around Ca Ions Confined in Carbon Slit Pores journal June 2009
Ionic Liquid Dynamics in Nanoporous Carbon Nanofibers in Supercapacitors Measured with in Operando Infrared Spectroelectrochemistry journal September 2014
Nanostructural Organization in Ionic Liquids journal February 2006
Nanoporous carbide-derived carbon with tunable pore size journal August 2003
Carbide-Derived Carbons - From Porous Networks to Nanotubes and Graphene journal February 2011
Intact Pattern Transfer of Conductive Exfoliated Graphite Nanoplatelet Composite Films to Polyelectrolyte Multilayer Platforms journal May 2008
Structural evolution of carbide-derived carbons upon vacuum annealing journal November 2012
Monitoring oxidation of multiwalled carbon nanotubes by Raman spectroscopy journal January 2007
Development of a Green Supercapacitor Composed Entirely of Environmentally Friendly Materials journal October 2013
Capacitance, charge dynamics, and electrolyte-surface interactions in functionalized carbide-derived carbon electrodes journal December 2015
Adsorption of Gases in Multimolecular Layers journal February 1938
Quenched solid density functional theory method for characterization of mesoporous carbons by nitrogen adsorption journal April 2012
Understanding controls on interfacial wetting at epitaxial graphene: Experiment and theory journal January 2012
Best practice methods for determining an electrode material's performance for ultracapacitors journal January 2010
A time-of-flight backscattering spectrometer at the Spallation Neutron Source, BASIS journal August 2011
Quasielastic neutron scattering study of water confined in carbon nanopores journal July 2011
Resolution of VISION, a crystal-analyzer spectrometer
  • Seeger, Philip A.; Daemen, Luke L.; Larese, John Z.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 604, Issue 3 https://doi.org/10.1016/j.nima.2009.03.204
journal June 2009
GROMACS 4:  Algorithms for Highly Efficient, Load-Balanced, and Scalable Molecular Simulation journal February 2008
Molecular Force Field for Ionic Liquids Composed of Triflate or Bistriflylimide Anions journal October 2004
Modeling Ionic Liquids Using a Systematic All-Atom Force Field journal February 2004
A Second Generation Force Field for the Simulation of Proteins, Nucleic Acids, and Organic Molecules journal May 1995
Oxidation functional groups on graphene: Structural and electronic properties journal September 2010
Canonical dynamics: Equilibrium phase-space distributions journal March 1985
Ewald summation for systems with slab geometry journal August 1999
Particle mesh Ewald: An N ⋅log( N ) method for Ewald sums in large systems journal June 1993
Purification of carbon nanotubes by dynamic oxidation in air journal January 2009
The properties and applications of nanodiamonds journal December 2011
Scalable enhancement of graphene oxide properties by thermally driven phase transformation journal December 2013
Neutron scattering lengths and cross sections journal January 1992
Raman andab initio study of the conformational isomerism in the 1-ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide ionic liquid journal January 2007
Evidence of Conformational Equilibrium of 1-Ethyl-3-methylimidazolium in Its Ionic Liquid Salts:  Raman Spectroscopic Study and Quantum Chemical Calculations journal October 2005
Thermal stability of low temperature ionic liquids revisited journal March 2004
Vapor pressure and thermal stability of ionic liquid 1-butyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)amide journal December 2005
In situ chemical experiments in carbon nanotubes journal October 2002
Vertically Oriented Propylene Carbonate Molecules and Tetraethyl Ammonium Ions in Carbon Slit Pores journal March 2013

Cited By (4)

Revitalizing carbon supercapacitor electrodes with hierarchical porous structures journal January 2017
Structural and dynamic properties of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide/mica and graphite interfaces revealed by molecular dynamics simulation journal January 2018
Relationship between pore size and reversible and irreversible immobilization of ionic liquid electrolytes in porous carbon under applied electric potential journal October 2016
Microscopic dynamics in room-temperature ionic liquids confined in materials for supercapacitor applications journal January 2020

Similar Records

Influence of Surface Oxidation on Ion Dynamics and Capacitance in Porous and Nonporous Carbon Electrodes
Journal Article · Thu Apr 07 00:00:00 EDT 2016 · Journal of Physical Chemistry. C · OSTI ID:1250416

Ionic liquid structure, dynamics, and electrosorption in carbon electrodes with bimodal pores and heterogeneous surfaces
Journal Article · Tue Dec 05 00:00:00 EST 2017 · Carbon · OSTI ID:1250416

Cation Molecular Structure Affects Mobility and Transport of Electrolytes in Porous Carbons
Journal Article · Wed Feb 13 00:00:00 EST 2019 · Journal of the Electrochemical Society · OSTI ID:1250416