DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Paradoxical roles of hydrogen in electrochemical performance of graphene: High rate capacity and atomistic origins

Abstract

Atomic hydrogen exists ubiquitously in graphene materials made by chemical methods. Yet determining the effect of hydrogen on the electrochemical performance of graphene remains a significant challenge. Here we report the experimental observations of high rate capacity in hydrogen-treated 3-dimensional (3D) graphene nanofoam electrodes for lithium ion batteries. Structural and electronic characterization suggests that defect sites and hydrogen play synergistic roles in disrupting sp2 graphene to facilitate fast lithium transport and reversible surface binding, as evidenced by the fast charge-transfer kinetics and increased capacitive contribution in hydrogen-treated 3D graphene. In concert with experiments, multiscale calculations reveal that defect complexes in graphene are prerequisite for low-temperature hydrogenation, and that the hydrogenation of defective or functionalized sites at strained domain boundaries plays a beneficial role in improving rate capacity by opening gaps to facilitate easier Li penetration. Additional reversible capacity is provided by enhanced lithium binding near hydrogen-terminated edge sites. Furthermore, these findings provide qualitative insights in helping the design of graphene-based materials for high-power electrodes.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1251039
Report Number(s):
LLNL-JRNL-670804
Journal ID: ISSN 2045-2322
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 5; Journal Issue: C; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; graphene; hydrogen; electrochemical performance; first principles; pseudocapacitance

Citation Formats

Ye, Jianchao C., Ong, Mitchell T., Heo, Tae Wook, Campbell, Patrick G., Worsley, Marcus A., Liu, Yuanyue Y., Charnvanichborikarn, Supakit, Matthews, Manyalibo J., Bagge-Hansen, Michael, Lee, Jonathan R. I., Wood, Brandon C., Wang, Y. Morris, and Shin, Swanee J.. Paradoxical roles of hydrogen in electrochemical performance of graphene: High rate capacity and atomistic origins. United States: N. p., 2015. Web. doi:10.1038/srep16190.
Ye, Jianchao C., Ong, Mitchell T., Heo, Tae Wook, Campbell, Patrick G., Worsley, Marcus A., Liu, Yuanyue Y., Charnvanichborikarn, Supakit, Matthews, Manyalibo J., Bagge-Hansen, Michael, Lee, Jonathan R. I., Wood, Brandon C., Wang, Y. Morris, & Shin, Swanee J.. Paradoxical roles of hydrogen in electrochemical performance of graphene: High rate capacity and atomistic origins. United States. https://doi.org/10.1038/srep16190
Ye, Jianchao C., Ong, Mitchell T., Heo, Tae Wook, Campbell, Patrick G., Worsley, Marcus A., Liu, Yuanyue Y., Charnvanichborikarn, Supakit, Matthews, Manyalibo J., Bagge-Hansen, Michael, Lee, Jonathan R. I., Wood, Brandon C., Wang, Y. Morris, and Shin, Swanee J.. Thu . "Paradoxical roles of hydrogen in electrochemical performance of graphene: High rate capacity and atomistic origins". United States. https://doi.org/10.1038/srep16190. https://www.osti.gov/servlets/purl/1251039.
@article{osti_1251039,
title = {Paradoxical roles of hydrogen in electrochemical performance of graphene: High rate capacity and atomistic origins},
author = {Ye, Jianchao C. and Ong, Mitchell T. and Heo, Tae Wook and Campbell, Patrick G. and Worsley, Marcus A. and Liu, Yuanyue Y. and Charnvanichborikarn, Supakit and Matthews, Manyalibo J. and Bagge-Hansen, Michael and Lee, Jonathan R. I. and Wood, Brandon C. and Wang, Y. Morris and Shin, Swanee J.},
abstractNote = {Atomic hydrogen exists ubiquitously in graphene materials made by chemical methods. Yet determining the effect of hydrogen on the electrochemical performance of graphene remains a significant challenge. Here we report the experimental observations of high rate capacity in hydrogen-treated 3-dimensional (3D) graphene nanofoam electrodes for lithium ion batteries. Structural and electronic characterization suggests that defect sites and hydrogen play synergistic roles in disrupting sp2 graphene to facilitate fast lithium transport and reversible surface binding, as evidenced by the fast charge-transfer kinetics and increased capacitive contribution in hydrogen-treated 3D graphene. In concert with experiments, multiscale calculations reveal that defect complexes in graphene are prerequisite for low-temperature hydrogenation, and that the hydrogenation of defective or functionalized sites at strained domain boundaries plays a beneficial role in improving rate capacity by opening gaps to facilitate easier Li penetration. Additional reversible capacity is provided by enhanced lithium binding near hydrogen-terminated edge sites. Furthermore, these findings provide qualitative insights in helping the design of graphene-based materials for high-power electrodes.},
doi = {10.1038/srep16190},
journal = {Scientific Reports},
number = C,
volume = 5,
place = {United States},
year = {Thu Nov 05 00:00:00 EST 2015},
month = {Thu Nov 05 00:00:00 EST 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage
journal, January 2015


Holey graphene frameworks for highly efficient capacitive energy storage
journal, August 2014

  • Xu, Yuxi; Lin, Zhaoyang; Zhong, Xing
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5554

Liquid-Mediated Dense Integration of Graphene Materials for Compact Capacitive Energy Storage
journal, August 2013


Carbon-Based Supercapacitors Produced by Activation of Graphene
journal, May 2011


Flexible graphene-based lithium ion batteries with ultrafast charge and discharge rates
journal, October 2012

  • Li, N.; Chen, Z.; Ren, W.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 43
  • DOI: 10.1073/pnas.1210072109

Titelbild: Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte upon Reversible Li + /H + Exchange in Aqueous Solutions (Angew. Chem. 1/2015)
journal, December 2014

  • Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu
  • Angewandte Chemie, Vol. 127, Issue 1
  • DOI: 10.1002/ange.201410930

Chemical methods for the production of graphenes
journal, March 2009

  • Park, Sungjin; Ruoff, Rodney S.
  • Nature Nanotechnology, Vol. 4, Issue 4, p. 217-224
  • DOI: 10.1038/nnano.2009.58

High-yield production of graphene by liquid-phase exfoliation of graphite
journal, August 2008

  • Hernandez, Yenny; Nicolosi, Valeria; Lotya, Mustafa
  • Nature Nanotechnology, Vol. 3, Issue 9, p. 563-568
  • DOI: 10.1038/nnano.2008.215

Effect of airborne contaminants on the wettability of supported graphene and graphite
journal, July 2013

  • Li, Zhiting; Wang, Yongjin; Kozbial, Andrew
  • Nature Materials, Vol. 12, Issue 10
  • DOI: 10.1038/nmat3709

Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane
journal, January 2009


Reversible Basal Plane Hydrogenation of Graphene
journal, December 2008

  • Ryu, Sunmin; Han, Melinda Y.; Maultzsch, Janina
  • Nano Letters, Vol. 8, Issue 12
  • DOI: 10.1021/nl802940s

Bandgap opening in graphene induced by patterned hydrogen adsorption
journal, March 2010

  • Balog, Richard; Jørgensen, Bjarke; Nilsson, Louis
  • Nature Materials, Vol. 9, Issue 4
  • DOI: 10.1038/nmat2710

Mechanisms for Lithium Insertion in Carbonaceous Materials
journal, October 1995


Enhancement of hydrogen physisorption on graphene and carbon nanotubes by Li doping
journal, November 2005

  • Cabria, I.; López, M. J.; Alonso, J. A.
  • The Journal of Chemical Physics, Vol. 123, Issue 20
  • DOI: 10.1063/1.2125727

Pillared Graphene A New 3-D Network Nanostructure for Enhanced Hydrogen Storage
journal, October 2008

  • Dimitrakakis, Georgios K.; Tylianakis, Emmanuel; Froudakis, George E.
  • Nano Letters, Vol. 8, Issue 10, p. 3166-3170
  • DOI: 10.1021/nl801417w

Can the performance of graphene nanosheets for lithium storage in Li-ion batteries be predicted?
journal, January 2012

  • Vargas C., Oscar A.; Caballero, Álvaro; Morales, Julián
  • Nanoscale, Vol. 4, Issue 6
  • DOI: 10.1039/c2nr11936f

Enhanced electrochemical performance of ion-beam-treated 3D graphene aerogels for lithium ion batteries
journal, April 2015


Li Absorption and Intercalation in Single Layer Graphene and Few Layer Graphene by First Principles
journal, January 2012

  • Lee, Eunseok; Persson, Kristin A.
  • Nano Letters, Vol. 12, Issue 9
  • DOI: 10.1021/nl3019164

Feasibility of Lithium Storage on Graphene and Its Derivatives
journal, May 2013

  • Liu, Yuanyue; Artyukhov, Vasilii I.; Liu, Mingjie
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 10
  • DOI: 10.1021/jz400491b

Synthesis and Characterization of Highly Crystalline Graphene Aerogels
journal, October 2014

  • Worsley, Marcus A.; Pham, Thang T.; Yan, Aiming
  • ACS Nano, Vol. 8, Issue 10, p. 11013-11022
  • DOI: 10.1021/nn505335u

Double resonant Raman spectra in graphene and graphite: A two-dimensional explanation of the Raman amplitude
journal, October 2008


Origin of dispersive effects of the Raman D band in carbon materials
journal, March 1999


Probing the Nature of Defects in Graphene by Raman Spectroscopy
journal, July 2012

  • Eckmann, Axel; Felten, Alexandre; Mishchenko, Artem
  • Nano Letters, Vol. 12, Issue 8
  • DOI: 10.1021/nl300901a

Effect of defects on the intrinsic strength and stiffness of graphene
journal, January 2014

  • Zandiatashbar, Ardavan; Lee, Gwan-Hyoung; An, Sung Joo
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4186

Near‐edge x‐ray absorption of carbon materials for determining bond hybridization in mixed sp 2/ sp 3 bonded materials
journal, July 1996

  • Coffman, F. L.; Cao, R.; Pianetta, P. A.
  • Applied Physics Letters, Vol. 69, Issue 4
  • DOI: 10.1063/1.117789

Doped Graphene Sheets As Anode Materials with Superhigh Rate and Large Capacity for Lithium Ion Batteries
journal, June 2011

  • Wu, Zhong-Shuai; Ren, Wencai; Xu, Li
  • ACS Nano, Vol. 5, Issue 7
  • DOI: 10.1021/nn2006249

Challenges for Rechargeable Li Batteries
journal, February 2010

  • Goodenough, John B.; Kim, Youngsik
  • Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
  • DOI: 10.1021/cm901452z

High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance
journal, April 2013

  • Augustyn, Veronica; Come, Jérémy; Lowe, Michael A.
  • Nature Materials, Vol. 12, Issue 6
  • DOI: 10.1038/nmat3601

Pseudocapacitive oxide materials for high-rate electrochemical energy storage
journal, January 2014

  • Augustyn, Veronica; Simon, Patrice; Dunn, Bruce
  • Energy & Environmental Science, Vol. 7, Issue 5
  • DOI: 10.1039/c3ee44164d

Graphene hydrogenation by molecular hydrogen in the process of graphene oxide thermal reduction
journal, February 2013

  • Mikoushkin, V. M.; Nikonov, S. Yu.; Dideykin, A. T.
  • Applied Physics Letters, Vol. 102, Issue 7
  • DOI: 10.1063/1.4793484

N-type graphene induced by dissociative H2 adsorption at room temperature
journal, September 2012

  • Kim, Byung Hoon; Hong, Sung Ju; Baek, Seung Jae
  • Scientific Reports, Vol. 2, Issue 1
  • DOI: 10.1038/srep00690

Physical origins of weak H 2 binding on carbon nanostructures: Insight from ab initio studies of chemically functionalized graphene nanoribbons
journal, May 2014

  • Ulman, Kanchan; Bhaumik, Debarati; Wood, Brandon C.
  • The Journal of Chemical Physics, Vol. 140, Issue 17
  • DOI: 10.1063/1.4873435

Enhanced Gas Adsorption on Graphitic Substrates via Defects and Local Curvature: A Density Functional Theory Study
journal, April 2014

  • Dutta, Debosruti; Wood, Brandon C.; Bhide, Shreyas Y.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 15
  • DOI: 10.1021/jp411338a

The Role of Intercalated Water in Multilayered Graphene Oxide
journal, October 2010

  • Acik, Muge; Mattevi, Cecilia; Gong, Cheng
  • ACS Nano, Vol. 4, Issue 10
  • DOI: 10.1021/nn101844t

Carbon 1s near-edge-absorption fine structure in graphite
journal, July 1993


Algorithms for the rapid simulation of Rutherford backscattering spectra
journal, June 1985

  • Doolittle, Lawrence R.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 9, Issue 3
  • DOI: 10.1016/0168-583X(85)90762-1

Absolute cross section for hydrogen forward scattering
journal, February 1992

  • Baglin, J. E. E.; Kellock, A. J.; Crockett, M. A.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 64, Issue 1-4
  • DOI: 10.1016/0168-583X(92)95518-V

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Projector augmented-wave method
journal, December 1994


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Enhanced electrochemical performance of ion-beam-treated 3D graphene aerogels for lithium ion batteries
journal, April 2015


Enhanced Electrochemical Lithium Storage by Graphene Nanoribbons
journal, September 2010

  • Bhardwaj, Tarun; Antic, Aleks; Pavan, Barbara
  • Journal of the American Chemical Society, Vol. 132, Issue 36
  • DOI: 10.1021/ja106162f

Enhanced Gas Adsorption on Graphitic Substrates via Defects and Local Curvature: A Density Functional Theory Study
journal, April 2014

  • Dutta, Debosruti; Wood, Brandon C.; Bhide, Shreyas Y.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 15
  • DOI: 10.1021/jp411338a

Feasibility of Lithium Storage on Graphene and Its Derivatives
journal, May 2013

  • Liu, Yuanyue; Artyukhov, Vasilii I.; Liu, Mingjie
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 10
  • DOI: 10.1021/jz400491b

Li Absorption and Intercalation in Single Layer Graphene and Few Layer Graphene by First Principles
journal, January 2012

  • Lee, Eunseok; Persson, Kristin A.
  • Nano Letters, Vol. 12, Issue 9
  • DOI: 10.1021/nl3019164

Pillared Graphene A New 3-D Network Nanostructure for Enhanced Hydrogen Storage
journal, October 2008

  • Dimitrakakis, Georgios K.; Tylianakis, Emmanuel; Froudakis, George E.
  • Nano Letters, Vol. 8, Issue 10, p. 3166-3170
  • DOI: 10.1021/nl801417w

Doped Graphene Sheets As Anode Materials with Superhigh Rate and Large Capacity for Lithium Ion Batteries
journal, June 2011

  • Wu, Zhong-Shuai; Ren, Wencai; Xu, Li
  • ACS Nano, Vol. 5, Issue 7
  • DOI: 10.1021/nn2006249

Synthesis and Characterization of Highly Crystalline Graphene Aerogels
journal, October 2014

  • Worsley, Marcus A.; Pham, Thang T.; Yan, Aiming
  • ACS Nano, Vol. 8, Issue 10, p. 11013-11022
  • DOI: 10.1021/nn505335u

Effect of defects on the intrinsic strength and stiffness of graphene
journal, January 2014

  • Zandiatashbar, Ardavan; Lee, Gwan-Hyoung; An, Sung Joo
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4186

Bandgap opening in graphene induced by patterned hydrogen adsorption
journal, March 2010

  • Balog, Richard; Jørgensen, Bjarke; Nilsson, Louis
  • Nature Materials, Vol. 9, Issue 4
  • DOI: 10.1038/nmat2710

High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance
journal, April 2013

  • Augustyn, Veronica; Come, Jérémy; Lowe, Michael A.
  • Nature Materials, Vol. 12, Issue 6
  • DOI: 10.1038/nmat3601

Effect of airborne contaminants on the wettability of supported graphene and graphite
journal, July 2013

  • Li, Zhiting; Wang, Yongjin; Kozbial, Andrew
  • Nature Materials, Vol. 12, Issue 10
  • DOI: 10.1038/nmat3709

High-yield production of graphene by liquid-phase exfoliation of graphite
journal, August 2008

  • Hernandez, Yenny; Nicolosi, Valeria; Lotya, Mustafa
  • Nature Nanotechnology, Vol. 3, Issue 9, p. 563-568
  • DOI: 10.1038/nnano.2008.215

Chemical methods for the production of graphenes
journal, March 2009

  • Park, Sungjin; Ruoff, Rodney S.
  • Nature Nanotechnology, Vol. 4, Issue 4, p. 217-224
  • DOI: 10.1038/nnano.2009.58

N-type graphene induced by dissociative H2 adsorption at room temperature
journal, September 2012

  • Kim, Byung Hoon; Hong, Sung Ju; Baek, Seung Jae
  • Scientific Reports, Vol. 2, Issue 1
  • DOI: 10.1038/srep00690

Can the performance of graphene nanosheets for lithium storage in Li-ion batteries be predicted?
journal, January 2012

  • Vargas C., Oscar A.; Caballero, Álvaro; Morales, Julián
  • Nanoscale, Vol. 4, Issue 6
  • DOI: 10.1039/c2nr11936f

Pseudocapacitive oxide materials for high-rate electrochemical energy storage
journal, January 2014

  • Augustyn, Veronica; Simon, Patrice; Dunn, Bruce
  • Energy & Environmental Science, Vol. 7, Issue 5
  • DOI: 10.1039/c3ee44164d

Near‐edge x‐ray absorption of carbon materials for determining bond hybridization in mixed sp 2/ sp 3 bonded materials
journal, July 1996

  • Coffman, F. L.; Cao, R.; Pianetta, P. A.
  • Applied Physics Letters, Vol. 69, Issue 4
  • DOI: 10.1063/1.117789

Enhancement of hydrogen physisorption on graphene and carbon nanotubes by Li doping
journal, November 2005

  • Cabria, I.; López, M. J.; Alonso, J. A.
  • The Journal of Chemical Physics, Vol. 123, Issue 20
  • DOI: 10.1063/1.2125727

Graphene hydrogenation by molecular hydrogen in the process of graphene oxide thermal reduction
journal, February 2013

  • Mikoushkin, V. M.; Nikonov, S. Yu.; Dideykin, A. T.
  • Applied Physics Letters, Vol. 102, Issue 7
  • DOI: 10.1063/1.4793484

Physical origins of weak H 2 binding on carbon nanostructures: Insight from ab initio studies of chemically functionalized graphene nanoribbons
journal, May 2014

  • Ulman, Kanchan; Bhaumik, Debarati; Wood, Brandon C.
  • The Journal of Chemical Physics, Vol. 140, Issue 17
  • DOI: 10.1063/1.4873435

Assessing Carbon-Based Anodes for Lithium-Ion Batteries: A Universal Description of Charge-Transfer Binding
journal, July 2014


Core excitons and vibronic coupling in diamond and graphite
journal, November 1993


Raman Spectrum of Graphene and Graphene Layers
journal, October 2006


Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane
journal, January 2009


Carbon-Based Supercapacitors Produced by Activation of Graphene
journal, May 2011


Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage
journal, January 2015


Mechanisms for Lithium Insertion in Carbonaceous Materials
journal, October 1995


Reversible Basal Plane Hydrogenation of Graphene
text, January 2008


Probing the Nature of Defects in Graphene by Raman Spectroscopy
text, January 2012


Works referencing / citing this record:

The applications of carbon nanotubes and graphene in advanced rechargeable lithium batteries
journal, January 2016

  • Yuan, Wenyu; Zhang, Yani; Cheng, Laifei
  • Journal of Materials Chemistry A, Vol. 4, Issue 23
  • DOI: 10.1039/c6ta01546h