Origins and Implications of Interfacial Capacitance Enhancements in C60-Modified Graphene Supercapacitors
Abstract
Understanding and controlling the electrical response at a complex electrode–electrolyte interface is key to the development of next-generation supercapacitors and other electrochemical devices. In this work, we apply a theoretical framework based on the effective screening medium and reference interaction site model to explore the role of electrical double-layer (EDL) formation and its interplay with quantum capacitance in graphene-based supercapacitors. In addition to pristine graphene, we investigate a novel C60-modified graphene supercapacitor material, which promises higher charge-storage capacity. Beyond the expected enhancement in the quantum capacitance, we find that the introduction of C60 molecules significantly alters the EDL response. These changes in EDL are traced to the interplay between surface morphology and charge localization character and ultimately dominate the overall capacitive improvement in the hybrid system. Our study highlights a complex interplay among surface morphology, electronic structure, and interfacial capacitance, suggesting general improvement strategies for optimizing carbon-based supercapacitor materials.
- Authors:
-
[2];
[4];
[2];
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of California, Riverside, CA (United States). Dept. of Chemistry
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
- Univ. of California, Riverside, CA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1512603
- Report Number(s):
- LLNL-JRNL-754189
Journal ID: ISSN 1944-8244; 940742
- Grant/Contract Number:
- AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 43; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; electric double layer; energy storage; first-principles simulations; quantum capacitance; supercapacitor
Citation Formats
Zhan, Cheng, Pham, Tuan Anh, Cerón, Maira R., Campbell, Patrick G., Vedharathinam, Vedasri, Otani, Minoru, Jiang, De-en, Biener, Juergen, Wood, Brandon C., and Biener, Monika. Origins and Implications of Interfacial Capacitance Enhancements in C60-Modified Graphene Supercapacitors. United States: N. p., 2018.
Web. doi:10.1021/acsami.8b10349.
Zhan, Cheng, Pham, Tuan Anh, Cerón, Maira R., Campbell, Patrick G., Vedharathinam, Vedasri, Otani, Minoru, Jiang, De-en, Biener, Juergen, Wood, Brandon C., & Biener, Monika. Origins and Implications of Interfacial Capacitance Enhancements in C60-Modified Graphene Supercapacitors. United States. https://doi.org/10.1021/acsami.8b10349
Zhan, Cheng, Pham, Tuan Anh, Cerón, Maira R., Campbell, Patrick G., Vedharathinam, Vedasri, Otani, Minoru, Jiang, De-en, Biener, Juergen, Wood, Brandon C., and Biener, Monika. Mon .
"Origins and Implications of Interfacial Capacitance Enhancements in C60-Modified Graphene Supercapacitors". United States. https://doi.org/10.1021/acsami.8b10349. https://www.osti.gov/servlets/purl/1512603.
@article{osti_1512603,
title = {Origins and Implications of Interfacial Capacitance Enhancements in C60-Modified Graphene Supercapacitors},
author = {Zhan, Cheng and Pham, Tuan Anh and Cerón, Maira R. and Campbell, Patrick G. and Vedharathinam, Vedasri and Otani, Minoru and Jiang, De-en and Biener, Juergen and Wood, Brandon C. and Biener, Monika},
abstractNote = {Understanding and controlling the electrical response at a complex electrode–electrolyte interface is key to the development of next-generation supercapacitors and other electrochemical devices. In this work, we apply a theoretical framework based on the effective screening medium and reference interaction site model to explore the role of electrical double-layer (EDL) formation and its interplay with quantum capacitance in graphene-based supercapacitors. In addition to pristine graphene, we investigate a novel C60-modified graphene supercapacitor material, which promises higher charge-storage capacity. Beyond the expected enhancement in the quantum capacitance, we find that the introduction of C60 molecules significantly alters the EDL response. These changes in EDL are traced to the interplay between surface morphology and charge localization character and ultimately dominate the overall capacitive improvement in the hybrid system. Our study highlights a complex interplay among surface morphology, electronic structure, and interfacial capacitance, suggesting general improvement strategies for optimizing carbon-based supercapacitor materials.},
doi = {10.1021/acsami.8b10349},
journal = {ACS Applied Materials and Interfaces},
number = 43,
volume = 10,
place = {United States},
year = {Mon Oct 08 00:00:00 EDT 2018},
month = {Mon Oct 08 00:00:00 EDT 2018}
}
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Figures / Tables:
Figure 1: Comparison of the charging behavior of (a) graphene/C60 and (b) pristine graphene electrodes within a voltage window determined by an excess charge of $q$ = [−1 : 1]×|$e$|. The charge-voltage potential ($CV$ ) dependencies of the systems are represented by black lines. The $CV$ associated with quantum andmore »
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Works referenced in this record:
MATERIALS SCIENCE: Electrochemical Capacitors for Energy Management
journal, August 2008
- Miller, J. R.; Simon, P.
- Science, Vol. 321, Issue 5889
Materials for electrochemical capacitors
journal, November 2008
- Simon, Patrice; Gogotsi, Yury
- Nature Materials, Vol. 7, Issue 11
Where Do Batteries End and Supercapacitors Begin?
journal, March 2014
- Simon, P.; Gogotsi, Y.; Dunn, B.
- Science, Vol. 343, Issue 6176
Nanoporous carbide-derived carbon with tunable pore size
journal, August 2003
- Gogotsi, Yury; Nikitin, Alexei; Ye, Haihui
- Nature Materials, Vol. 2, Issue 9
Carbon-based materials as supercapacitor electrodes
journal, January 2009
- Zhang, Li Li; Zhao, X. S.
- Chemical Society Reviews, Vol. 38, Issue 9
Carbon Materials for Chemical Capacitive Energy Storage
journal, September 2011
- Zhai, Yunpu; Dou, Yuqian; Zhao, Dongyuan
- Advanced Materials, Vol. 23, Issue 42
Interfacial capacitance of single layer graphene
journal, January 2011
- Stoller, Meryl D.; Magnuson, Carl W.; Zhu, Yanwu
- Energy & Environmental Science, Vol. 4, Issue 11
A Computational Study of the Interfacial Structure and Capacitance of Graphene in [BMIM][PF 6 ] Ionic Liquid
journal, November 2012
- Paek, Eunsu; Pak, Alexander J.; Hwang, Gyeong S.
- Journal of The Electrochemical Society, Vol. 160, Issue 1
Capacitance of carbon-based electrical double-layer capacitors
journal, February 2014
- Ji, Hengxing; Zhao, Xin; Qiao, Zhenhua
- Nature Communications, Vol. 5, Issue 1
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
An interpretation of the double layer capacity of graphite electrodes in relation to the density of states at the Fermi level
journal, September 1985
- Gerischer, H.
- The Journal of Physical Chemistry, Vol. 89, Issue 20
Nitrogen doping of graphene and its effect on quantum capacitance, and a new insight on the enhanced capacitance of N-doped carbon
journal, January 2012
- Zhang, Li Li; Zhao, Xin; Ji, Hengxing
- Energy & Environmental Science, Vol. 5, Issue 11, p. 9618-9625
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
Quinone-Decorated Onion-Like Carbon/Carbon Fiber Hybrid Electrodes for High-Rate Supercapacitor Applications
journal, May 2015
- Zeiger, Marco; Weingarth, Daniel; Presser, Volker
- ChemElectroChem, Vol. 2, Issue 8
Towards High-Energy-Density Pseudocapacitive Flowable Electrodes by the Incorporation of Hydroquinone
journal, January 2015
- Boota, M.; Hatzell, K. B.; Kumbur, E. C.
- ChemSusChem, Vol. 8, Issue 5, p. 835-843
Pseudocapacitance and excellent cyclability of 2,5-dimethoxy-1,4-benzoquinone on graphene
journal, January 2016
- Boota, Muhammad; Chen, Chi; Bécuwe, Matthieu
- Energy & Environmental Science, Vol. 9, Issue 8
Carbons and Electrolytes for Advanced Supercapacitors
journal, February 2014
- Béguin, François; Presser, Volker; Balducci, Andrea
- Advanced Materials, Vol. 26, Issue 14, p. 2219-2251
Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer
journal, September 2006
- Chmiola, J.
- Science, Vol. 313, Issue 5794
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
Oscillation of Capacitance inside Nanopores
journal, December 2011
- Jiang, De-en; Jin, Zhehui; Wu, Jianzhong
- Nano Letters, Vol. 11, Issue 12
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
Van der Waals Density Functional for General Geometries
journal, June 2004
- Dion, M.; Rydberg, H.; Schröder, E.
- Physical Review Letters, Vol. 92, Issue 24
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009
- Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
- Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
Optimized pseudopotentials
journal, January 1990
- Rappe, Andrew M.; Rabe, Karin M.; Kaxiras, Efthimios
- Physical Review B, Vol. 41, Issue 2
First-principles calculations of charged surfaces and interfaces: A plane-wave nonrepeated slab approach
journal, March 2006
- Otani, M.; Sugino, O.
- Physical Review B, Vol. 73, Issue 11
Contribution of Dielectric Screening to the Total Capacitance of Few-Layer Graphene Electrodes
journal, February 2016
- Zhan, Cheng; Jiang, De-en
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 5
On the Origin of the Enhanced Supercapacitor Performance of Nitrogen-Doped Graphene
journal, March 2013
- Paek, Eunsu; Pak, Alexander J.; Kweon, Kyoung E.
- The Journal of Physical Chemistry C, Vol. 117, Issue 11
Impact of Graphene Edges on Enhancing the Performance of Electrochemical Double Layer Capacitors
journal, September 2014
- Pak, Alexander J.; Paek, Eunsu; Hwang, Gyeong S.
- The Journal of Physical Chemistry C, Vol. 118, Issue 38
On the influence of polarization effects in predicting the interfacial structure and capacitance of graphene-like electrodes in ionic liquids
journal, January 2015
- Paek, Eunsu; Pak, Alexander J.; Hwang, Gyeong S.
- The Journal of Chemical Physics, Vol. 142, Issue 2
Theoretical characterization of the “ridge” in the supercritical region in the fluid phase diagram of water
journal, March 2014
- Matsugami, Masaru; Yoshida, Norio; Hirata, Fumio
- The Journal of Chemical Physics, Vol. 140, Issue 10
Computer simulations of NaCl association in polarizable water
journal, March 1994
- Smith, David E.; Dang, Liem X.
- The Journal of Chemical Physics, Vol. 100, Issue 5
UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
journal, December 1992
- Rappe, A. K.; Casewit, C. J.; Colwell, K. S.
- Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035
Self-consistent description of a metal–water interface by the Kohn–Sham density functional theory and the three-dimensional reference interaction site model
journal, May 1999
- Kovalenko, Andriy; Hirata, Fumio
- The Journal of Chemical Physics, Vol. 110, Issue 20
Measurement of the quantum capacitance of graphene
journal, July 2009
- Xia, Jilin; Chen, Fang; Li, Jinghong
- Nature Nanotechnology, Vol. 4, Issue 8, p. 505-509
VMD: Visual molecular dynamics
journal, February 1996
- Humphrey, William; Dalke, Andrew; Schulten, Klaus
- Journal of Molecular Graphics, Vol. 14, Issue 1
Curvature Effect on the Capacitance of Electric Double Layers at Ionic Liquid/Onion-Like Carbon Interfaces
journal, February 2012
- Feng, Guang; Jiang, De-en; Cummings, Peter T.
- Journal of Chemical Theory and Computation, Vol. 8, Issue 3
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
All Pseudocapacitive MXene-RuO 2 Asymmetric Supercapacitors
journal, January 2018
- Jiang, Qiu; Kurra, Narendra; Alhabeb, Mohamed
- Advanced Energy Materials, Vol. 8, Issue 13
Works referencing / citing this record:
Specific ion effects at graphitic interfaces
journal, October 2019
- Zhan, Cheng; Cerón, Maira R.; Hawks, Steven A.
- Nature Communications, Vol. 10, Issue 1
Investigating the asymmetry in the EDL response of C 60 /graphene supercapacitors
journal, January 2019
- Fileti, Eudes Eterno; Colherinhas, Guilherme
- Physical Chemistry Chemical Physics, Vol. 21, Issue 28
Progress in supercapacitors: roles of two dimensional nanotubular materials
journal, January 2020
- Panda, Pritam Kumar; Grigoriev, Anton; Mishra, Yogendra Kumar
- Nanoscale Advances, Vol. 2, Issue 1
A first-principles roadmap and limits to design efficient supercapacitor electrode materials
journal, January 2019
- Ali, Basant A.; Allam, Nageh K.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 32
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.