Abstract
We describe the synthesis and fabrication of a graphene oxide (GO) and single-walled carbon nanotube (SWCNT) composite ink (GO–SWCNT ink) for electrochemically stable supercapacitors. Atomic force microscopy and scanning electron microscopy studies demonstrate that the obtained GO flakes are single layer with size distribution from 100 nm to 20 μm. SWCNTs are dispersed using a GO aqueous solution (2 mg/mL) with sonication support to achieve a SWCNT concentration of 12 mg/mL, the highest reported value so far without surfactant assistance. Raman spectroscopy studies indicate that the full-width at half-maximum of the G band increases with the mixing of SWCNT and GO indicating that electronic structure changes via π–π interactions of GO sheets and SWCNTs. Paper-based electrodes of supercapacitor were conveniently fabricated with GO–SWCNT composite ink via a dip casting method. By using different concentrations of SWCNT in the ink, the paper electrodes provide different capacitance values. The highest value of specific capacitance reaches 295 F/g at a current density of 0.5 A/g with a GO/SWCNT weight ratio of 1:5. The cycling stability for the GO–SWCNT paper electrode supercapacitors indicates capacitance retention of 85% over 60,000 cycles.
Similar content being viewed by others
References
Z.H. Zhong, D.L. Wang, Y. Cui, M.W. Bockrath, and C.M. Lieber: Nanowire crossbar arrays as address decoders for integrated nanosystems. Science 302, 1377 (2003).
J.A. Rogers: Electronic materials - making graphene for macroelectronics. Nat. Nanotechnol. 3, 254 (2008).
S. Guo, M. Ghazinejad, X. Qin, H. Sun, W. Wang, F. Zaera, M. Ozkan, and C.S. Ozkan: Tuning electron transport in graphene-based field-effect devices using block co-polymers. Small 8, 1073 (2012).
S-R. Guo, J. Lin, M. Penchev, E. Yengel, M. Ghazinejad, C.S. Ozkan, and M. Ozkan: Label free DNA detection using large area graphene based field effect transistor biosensors. J. Nanosci. Nanotechnol. 11, 5258 (2011).
M.K. Shukla, M. Dubey, and J. Leszczynski: Theoretical investigation of electronic structures and properties of C-60-gold nanocontacts. ACS Nano 2, 227 (2008).
T.O. Wehling, K.S. Novoselov, S.V. Morozov, E.E. Vdovin, M.I. Katsnelson, A.K. Geim, and A.I. Lichtenstein: Molecular doping of graphene. Nano Lett. 8, 173 (2008).
P.K. Ang, W. Chen, A.T.S. Wee, and K.P. Loh: Solution-gated epitaxial graphene as pH sensor. J. Am. Chem. Soc. 130, 14392 (2008).
J.B. Wu, M. Agrawal, H.A. Becerril, Z.N. Bao, Z.F. Liu, Y.S. Chen, and P. Peumans: Organic light-emitting diodes on solution-processed graphene transparent electrodes. ACS Nano 4, 43 (2010).
Y. Wang, X.H. Chen, Y.L. Zhong, F.R. Zhu, and K.P. Loh: Large area, continuous, few-layered graphene as anodes in organic photovoltaic devices. Appl. Phys. Lett. 95, 063302 (2009).
A.P. Alivisatos, I. Gur, N.A. Fromer, C.P. Chen, and A.G. Kanaras: Hybrid solar cells with prescribed nanoscale morphologies based on hyperbranched semiconductor nanocrystals. Nano Lett. 7, 409 (2007).
Y.W. Zhu, S. Murali, M.D. Stoller, K.J. Ganesh, W.W. Cai, P.J. Ferreira, A. Pirkle, R.M. Wallace, K.A. Cychosz, M. Thommes, D. Su, E.A. Stach, and R.S. Ruoff: Carbon-based supercapacitors produced by activation of graphene. Science 332, 1537 (2011).
L. Dai, D.W. Chang, J-B. Baek, and W. Lu: Carbon nanomaterials for advanced energy conversion and storage. Small 8, 1130 (2012).
Y.P. Zhai, Y.Q. Dou, D.Y. Zhao, P.F. Fulvio, R.T. Mayes, and S. Dai: Carbon materials for chemical capacitive energy storage. Adv. Mater. 23, 4828 (2011).
M.F. El-kady, V. Strong, S. Dubin, and R.B. Kaner: Laser scribing of high-performance and flexible graphene-based electrochemical capacitors. Science 335, 1326 (2012).
K.J. Ziegler, Z.N. Gu, H.Q. Peng, E.L. Flor, R.H. Hauge, R.E. Smalley: Controlled oxidative cutting of single-walled carbon nanotubes. J. Am. Chem. Soc. 127, 1541 (2005).
H. Sato and M. Sano: Characteristics of ultrasonic dispersion of carbon nanotubes aided by antifoam. Colloids Surf., A 322, 103 (2008).
X.H. Peng and S.S. Wong: Functional covalent chemistry of carbon nanotube surfaces. Adv. Mater. 21, 625 (2009).
G.D. Zhan, X.H. Du, D.M. King, L.F. Hakim, X.H. Liang, J.A. McCormick, and A.W. Weimer: Atomic layer deposition on bulk quantities of surfactant-modified single-walled carbon nanotubes. J. Am. Ceram. Soc. 91, 831 (2008).
J.F. Campbell, I. Tessmer, H.H. Thorp, and D.A. Erie: Atomic force microscopy studies of DNA-wrapped carbon nanotube structure and binding to quantum dots. J. Am. Chem. Soc. 130, 10648 (2008).
Y.Y. Ou and M.H. Huang: High-density assembly of gold nanoparticles on multiwalled carbon nanotubes using 1-pyrenemethylamine as interlinker. J. Phys. Chem. B 110, 2031 (2006).
J.Y. Luo, L.J. Cote, V.C. Tung, A.T.L. Tan, P.E. Goins, J.S. Wu, and J.X. Huang: Graphene oxide nanocolloids. J. Am. Chem. Soc. 132, 17667 (2010).
D.S. Yu and L.M. Dai: Self-assembled graphene/carbon nanotube hybrid films for supercapacitors. J. Phys. Chem. Lett. 1, 467 (2010).
J.M. Shen, A.D. Liu, Y. Tu, G.S. Foo, C.B. Yeo, M.B. Chan-Park, R.R. Jiang, and Y. Chen: How carboxylic groups improve the performance of single-walled carbon nanotube electrochemical capacitors? Energy Environ. Sci. 4, 4220 (2011).
B. Zhao, P. Liu, Y. Jiang, D.Y. Pan, H.H. Tao, J.S. Song, T. Fang, and W.W. Xu: Supercapacitor performances of thermally reduced graphene oxide. J. Power Sources 198, 423 (2012).
Y. Chen, X.O. Zhang, D.C. Zhang, P. Yu, and Y.W. Ma: High performance supercapacitors based on reduced graphene oxide in aqueous and ionic liquid electrolytes. Carbon 49, 573 (2011).
N. Jha, P. Ramesh, E. Bekyarova, M.E. Itkis, and R.C. Haddon: High energy density supercapacitor based on a hybrid carbon nanotube-reduced graphite oxide architecture. Adv. Energy Mater. 2, 438 (2012).
S.H. Aboutalebi, A.T. Chidembo, M. Salari, K. Konstantinov, D. Wexler, H.K. Liu, and S.X. Dou: Comparison of GO, GO/MWCNTs composite and MWCNTs as potential electrode materials for supercapacitors. Energy Environ. Sci. 4, 1855 (2011).
J. Jiang, J. Liu, W. Zhou, J. Zhu, X. Huang, X. Qi, H. Zhang, and T. Yu: CNT/Ni hybrid nanostructured arrays: Synthesis and application as high-performance electrode materials for pseudocapacitors. Energy Environ. Sci. 4, 5000–5007 (2011).
H. Li, C. Xu, N. Srivastava, and K. Banerjee: Carbon nanomaterials for next-generation interconnects and passives: Physics, status, and prospects. IEEE Trans. Electron Devices 56, 1799 (2009).
Y. Wang, Z.Q. Shi, Y. Huang, Y.F. Ma, C.Y. Wang, M.M. Chen, Y.S. Chen: Superp13103 (2009).
W. Wang, S. Guo, M. Penchev, I. Ruiz, K.N. Bozhilov, D. Yan, M. Ozkan, and C.S. Ozkan: Three dimensional few layer graphene and carbon nanotube foam architectures for high fidelity supercapacitors. Nano Energy.https://doi.org/10.1016/j.nanoen.2012.10.001.
M. Kaempgen, C.K. Chan, J. Ma, Y. Cui, and G. Gruner: Printable thin film supercapacitors using single-walled carbon nanotubes. Nano Lett. 9, 1872 (2009).
L.B. Hu, J.W. Choi, Y. Yang, S. Jeong, F. La Mantia, L.F. Cui, and Y. Cui: Highly conductive paper for energy-storage devices. Proc. Natl. Acad. Sci. U.S.A. 106, 21490 (2009).
J. Kim, L.J. Cote, F. Kim, W. Yuan, K.R. Shull, and J.X. Huang: Graphene oxide sheets at interfaces. J. Am. Chem. Soc. 132, 8180 (2010).
W.S. Hummers Jr and R.E. Offeman: Preparation of graphitic oxide. J. Am. Chem. Soc. 80, 1339 (1958).
F. Ali, N. Agarwal, P.K. Nayak, R. Das, and N. Periasamy: Chemical route to the formation of graphene. Curr. Sci. 97, 682 (2009).
D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z.Z. Sun, A. Slesarev, L.B. Alemany, W. Lu, and J.M. Tour: Improved synthesis of graphene oxide. ACS Nano 4, 4806 (2010).
D.R. Dreyer, S. Park, C.W. Bielawski, and R.S. Ruoff: The chemistry of graphene oxide. Chem. Soc. Rev. 39 228 (2010).
T. Szabo, O. Berkesi, and I. Dekany: DRIFT study of deuterium-exchanged graphite oxide. Carbon 43, 3186 (2005).
L. Qiu, X.W. Yang, X.L. Gou, W.R. Yang, Z.F. Ma, and G.G. Wallace, and D. Li: Dispersing carbon nanotubes with graphene oxide in water and synergistic effects between graphene derivatives. Chem. Eur. J. 16, 10653 (2010).
B. Das, R. Voggu, C.S. Rout, and C.N.R. Rao: Changes in the electronic structure and properties of graphene induced by molecular charge-transfer. Chem. Commun. 2008, 5155 (2008).
Z. Chen, V. Augustyn, J. Wen, Y.W. Zhang, M.Q. Shen, B. Dunn, and Y.F. Lu: High-performance supercapacitors based on intertwined CNT/V2O5 nanowire nanocomposites. Adv. Mater. 23, 791 (2011).
F. Yang, B. Luo, Y. Jia, X. Li, B. Wang, Q. Song, F. Kang, and L. Zhi: Renewing functionalized graphene as electrodes for high performance supercapacitors. Adv. Mater. 24, 6348–6355 (2012).
A. Al-zubaidi, T. Inoue, T. Matsushita, Y. Ishii, T. Hashimoto, and S. Kawasaki: Cyclic voltammogram profile of single-walled carbon nanotube electric double-layer capacitor electrode reveals dumbbell shape. J. Phys. Chem. C 116, 7681 (2012).
Y. Yamada, T. Tanaka, K. Machida, S. Suematsu, K. Tamamitsu, H. Kataura, and H. Hatori: Electrochemical behavior of metallic and semiconducting single-wall carbon nanotubes for electric double-layer capacitor. Carbon 50, 1422 (2012).
Carbon coated textiles for flexible energy storage. Energy Environ. Sci. 4, 5060–5067 (2011).
C.H. Chen, D.S. Tsai, W.H. Chung, K.Y. Lee, Y.M. Chen, and Y.S. Huang: Electrochemical capacitors of miniature size with patterned carbon nanotubes and cobalt hydroxide. J. Power Sources 205, 510 (2012).
S. Arepalli, H. Fireman, C. Huffman, P. Moloney, P. Nikolaev, L. Yowell, C.D. Higgins, K. Kim, P.A. Kohl, S.P. Turano, and W.J. Ready: Carbon-nanotube-based electrochemical double-layer capacitor technologies for spaceflight applications. JOM 57, 26 (2005).
Acknowledgments
We gratefully acknowledge financial support for this work by the Winston Chung Global Energy Center at UCR, The Riverside Public Utilities, the CMMI Division of the National Science Foundation (Award No. 0800680), the Materials Research Science and Engineering Center (NSF-MRSEC) on Polymers (Award No. 0213695), and the Nanoscale Science and Engineering Center (NSF-NSEC) on hierarchical manufacturing (CHM, Award No. 0531171).
Author information
Authors and Affiliations
Corresponding author
Supplementary Material
Supplementary Material
Supplementary material can be viewed in this issue of the Journal of Materials Research by visiting http://journals.cambridge.org/jmr.
Rights and permissions
About this article
Cite this article
Guo, S., Wang, W., Ozkan, C.S. et al. Assembled graphene oxide and single-walled carbon nanotube ink for stable supercapacitors. Journal of Materials Research 28, 918–926 (2013). https://doi.org/10.1557/jmr.2012.421
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1557/jmr.2012.421