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Procedia IUTAM 21 (2017) 94 – 101

2016 IUTAM Symposium on Nanoscale Physical Mechanics

Graphene and Carbon Nanotube Hybrid Structure: A Review

Kang Xia, Haifei Zhan, and Yuantong Gu *
School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology (QUT), Brisbane QLD 4001, Australia

Abstract

Graphene has been reported with record-breaking properties which have opened up huge potential applications. Considerable
amount of researches have been devoted to manipulating or modify the properties of graphene to target a more smart nanoscale
device. Graphene and carbon nanotube hybrid structure (GNHS) is one of the promising graphene derivate. The synthesis process
and the mechanical properties are essential for the GNHS based devices. Therefore, this review will summarise the recent progress
of the highly ordered GNHS synthesis/assembly, and discuss the mechanical properties of GNHS under various conditions as
obtained from molecular dynamics simulations.
©2017
© 2017The
TheAuthors.
Authors. Published
Published by Elsevier
by Elsevier B.V.B.V.
This is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of organizing committee of Institute of the 2016 IUTAM Symposium on Nanoscale Physical
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Mechanics.under responsibility of organizing committee of Institute of the 2016 IUTAM Symposium on Nanoscale Physical Mechanics
Peer-review

Keywords: Graphene, nanotube, mechanical behaviour, molecular dynamics simulation, Chemical vapor deposition –keep uniform format

1. Introduction

After the discovery of graphene and carbon nanotube hybrid structure1, extensive researches have been conducted on
this structure. To enhance interface thermal conductivity of the ‘building blocks’ for future nanoscale mechanical and
electrical device and bring solution to quick energy dissipation, nanotube-graphene structure is suggested by Vikas et
al.2. In the electricity perspective, Frederico et al.3 and Yu et al.4 also indicated such ‘pillared-graphene’ system would
extend the excellent electrical conductivity of graphene and nanotube to three dimensions. In addition, recently,
graphene has been applied as the electrode of supercapacitors because of its significant specific capacitance (135
Fg  1 ). According to Fan et al.5, due to the double layer configuration of carbon nanotube (CNT) and graphene hybrid,

* Corresponding author. Tel.: +61731381009

E-mail address: [email protected]

2210-9838 © 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of organizing committee of Institute of the 2016 IUTAM Symposium on Nanoscale Physical Mechanics
doi:10.1016/j.piutam.2017.03.042
 Kang Xia et al. / Procedia IUTAM 21 (2017) 94 – 101 95

the structure is expected to have better electrochemical performance, which indicates that the hybrid structure is
suitable to be used as electrode in supercapacitors. What’s more, CNT-graphene hybrid structure also shows huge
1
potential in hydrogen storage (hydrogen storage capacity can be as high as 41 gL ), due to its extremely large surface
area6. This review is aim to briefly summarize the latest progress in ordered GNHS synthesis, and also the
investigations of the mechanical behaviours of GNHSs under various loading, which will shed lights on the design
and engineering applications of GNHS.

2. Synthesis and assemblies of GNHS

Early researches on GNNH family compounds are focused on the assembly of GNHS into order structure for a specific
application. The synthesis/fabrication of GNHSs generally can be categorized into four different approaches, including
solution processing/casting7-12, layer-by-layer deposition13-15, vacuum filtration16,17 and chemical vapour deposition
(CVD)5,18-31. Among all the GNHS synthesis method reported, CVD approaches is shown to build hierarchical
nanostructures with reasonable structure stability and mechanical strength18,32.
In 2012, Yu et al disclosed an approach to synthesise seamless, covalently bonded three-dimensional graphene and
carbon nanotube hybrid material with the aid of a floating buffer layer in chemical vapour deposition environment4,
as illustrated in Fig. 1. In detail, graphene is synthesised on the copper foil first, then iron catalyst and alumina buffer
layer are deposited on top of graphene respectively using electron evaporation. In the growth stage the buffer is lifted
up and CNT carpet grow directly out of the graphene. The density of CNTs forest can be well controlled by the
thickness of the iron catalyst layer and the growth rate can be as high as 120 ȝm in 10 mins. The STEM reveal that
the graphene and CNT junction region are well covalent bonded and are suggested to be utilized in the high
performance supercapacitor and energy storages.

Fig. 1. Scheme for the synthesis of CNT carpets directly from graphene. (a) Copper foil substrate. (b) Graphene is formed on the copper foil by
CVD or solid carbon-source growth. (c) Iron and alumina are deposited on the graphene-covered copper foil by using e-beam evaporation. (d) A
CNT carpet is directly grown from graphene surface. The iron catalyst and alumina protective layer are lifted up by the CNT carpet as it grows.
Reprinted by permission from Macmillan Publisher Ltd: Nature Communications4, copyright 2016.

To facilitate the application of GNHS in the field of energy storage, Cheng et al.18 developed a two-step CVD growth
method (see Fig. 2). First of all, FeMo/vermiculite composed of exfoliated vermiculite (EV) embedded with FeMo
nanoparticles in the interlayer space serves as the bifunctional catalyst to help the synthesis of CNT/Graphene in a
low temperature CVD environment of 650 °C. Subsequently, a higher temperature of 950 °C CVD was conducted for
uniform graphene layer deposition. To obtain the high carbon purity GNHS, facile acid treatments are applied to
remove the FeMo/ vermiculite catalysts. The GNHS which produced via this approach demonstrates outstanding
compression and recovery performance which shows the potential in the energy storage industry.
96 Kang Xia et al. / Procedia IUTAM 21 (2017) 94 – 101

Fig. 2. Schematic illustration for the synthesis of aligned GNHS on bifunctional catalysts. (a) Metal NPs nucleated on the surface of EV flakes;
(b) aligned CNT grown on EV flakes by a low temperature CVD; (c) graphene sheets deposited on EV flake by high temperature CVD for
aligned GNHS formation. Reprinted with permission from18. Copyright 2016 Elsevier.

3. Mechanical behaviours of GNHS

A comprehensive understanding of the mechanical properties of GNHS is a crucial prerequisite for its engineering
applications, which relies heavily on the experimental tests and numerical simulations. In 2014, Cheng et al.18
performed compression tests on a freestanding block of aligned GNHS with the size of 4 mm and a CNT length of ~
10 ȝm was repeatedly tested at strain range from 10 to 95%. It is found that the roots of aligned which anchored on
the graphene sheets provides excellent loading transfer between graphene and CNTs at high stress loading and the
compressive modulus can reach as high as 2.3 GPa before the collapse of the structure. The GNHS shows excellent
structure stability and energy density of 237.1 kJ/kg at 95% strain and exhibits superiority over other conventional
material like steel which is shown in the Fig. 3.
In terms of numerical simulations, several works have been reported on GNHS, focusing on different size scales.
Based on structural molecular mechanics approach Sangwook et al.33 conducted a finite element analysis to predict
the effective mechanical stiffness properties of GNHSs. This parametric study suggests that the pillar length and inter-
pillar distance significantly impact on the Young’s modulus. That is, GNHSs with shorter CNTs yield higher planar
Young’s and shear moduli, while those with smaller inter pillar distance yield higher through-thickness moduli.
Negative in-plane Poisson’s ratios are observed for all sets of GNHSs and are believed to be associated with curvature
at the junction. Xu et al.34 performed a thorough investigation on GNHSs using MD approach, Young’s moduli
obtained from a tensile loading test along the armchair direction of the graphene is found to be around 0.9 TPa, and
the corresponding tensile strength and strain are ~ 65-72 GPa and 0.09, respectively. These properties are significantly
smaller compared with that of the pristine graphene. Similar trends are also observed in our recent work35,36. Generally,
the GNHS exhibit a brittle behaviour and the stretched carbon bonds are observed around the connecting regions
between graphene and CNT during the elastic deformation period. Affluent formations of monoatomic chains and
rings are found at the fracture vicinity (Fig. 4).
 Kang Xia et al. / Procedia IUTAM 21 (2017) 94 – 101 97

Fig. 3. Energy density of various mechanical energy storage materials. Reprinted with permission from [18]. Copyright 2016 Elsevier.

Fig. 4. GNHS with multi-walled CNTs at different strain of: (a) 9.4%, inset shows a multi-walled CNT-graphene junction; (b) 10.1%, inset shows
the deformation around the multi-walled CNT-graphene junctions; (c) 10.15%, inset shows the fracture of the outer CNTs. Reprinted with
permission from35.

To meet different application purposes of the material, physical or chemical modification is frequently applied. Doping
is one of the effective approach that allows for the intrinsic modification to the electrical and chemical properties of
nanomaterials, such as graphene37. In this regard, our recent work has assessed how the dopants would affect the
mechanical properties of GNHS38 through large-scale molecular dynamics simulations. It is found that with the
presence of dopants, the hybrid structures usually exhibit lower yield strength, Young’s modulus, and earlier yielding
comparing with that of a pristine hybrid structure. Particularly, increase the dopant density (below 2.5%), significant
degradation in Young’s modulus or yield strength is not observed (Fig. 5).
98 Kang Xia et al. / Procedia IUTAM 21 (2017) 94 – 101

Fig. 5. Yielding strain (YP) and Young’s modulus (E) as a function of the density of N-, B-, and NB-dopant. Reprinted with permission from [38].
Copyright 2016 Beilstein Journal of Nanotechnology

Similar as obtained from the pristine GNHS, the failure of the doped GNHS is found to initiate at the region where
the nanotube and graphene sheets are connected. After failure, monatomic chains are normally observed around the
failure region. Dangling graphene layers without the separation of a residual CNT wall are found to adhere to each
other after failure with a distance of about 3.4 Å. Such deformation mechanisms are uniformly observed from the
boron, nitrogen, or both-doped GNHS.
In order to fully understand mechanical properties and deformation pattern under more complex loading condition,
MD based nanoindentation test is carried Wang et al39. For the samples studied, a strong correlation is found between
CNT dimeter and mechanical strength. For instance, vary the dimeter of CNT, a maximum increase in hardness of
approximately 40% is observed, also, the reduced modulus increases with increasing CNT diameter during the
indentation process. In addition, the maximum load which observed before the collapse of the GHNS decrease with
temperature, when the temperature is 700 the GNHS bears the smallest load which is ~3.0nN (Fig. 7), this observation
probably due to the increase in the atomic mobility at higher temperatures. The loading and unloading does not match
perfectly with each other which shows viscoelastic property.
 Kang Xia et al. / Procedia IUTAM 21 (2017) 94 – 101 99

Fig. 6. Atomic configurations of GNHS-0.75%B0.75%N at different strain of: (a) 0.097; (b) 0.101 (c) @ 0.102; (d) 0.115. Atomic configurations
of GNHS-1.5%B1.5%N at the strain of: (e) 0.097; (f) 0.101; (g) 0.102; (h) 0.103. Reprinted with permission from38. Copyright 2016 Beilstein
Journal of Nanotechnology

Fig. 7. Variation of load force of zigzag 3D-pillared graphene with tip displacement at 400, 500, 600, and 700K (in dentation depth was set at 1.0
nm). Reprinted with permission from39. Copyright 2016 Cambridge University Press and Copyright Clearance Center
100 Kang Xia et al. / Procedia IUTAM 21 (2017) 94 – 101

4. Summary

The development on graphene and graphene based structure is currently in a fast line with enormous research
achievement on the daily basis. Graphene and carbon nanotube hybrid structure is one of the promising graphene
derivatives and material scientists have devoted tremendous effort in realizing their potential applications in areas
such as energy storage, supercapacitor and building blocks composite. Experimental works have shown that nicely
aligned hybrid structures between graphene and carbon nanotube are achievable. Their highly tailorable structures
endow them with highly tunable mechanical properties.
It is worth mentioning that other properties of the graphene and CNT hybrid structures are also of great interest, such
as chemical properties and thermal transport properties. In this regard, Varshney et al.2 find that the thermal transport
is governed by the minimum interpillar distance and the CNT length. Additionally, plenty of works have also been
reported on other carbon nanoarchitectures, such as CNT based hexagonal structure40 or super-tube structure41. The
large variety of hybrid structures as constructed from low dimensional carbon materials (graphene/CNT), signifying
their promising and wide applications in engineering sectors.

Acknowledgement

Support from the ARC Discovery Project (DP150100828) is gratefully acknowledged.

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