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Graphene fiber: A new material platform for unique applications

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 NPG Asia Materials (2014) 6, e113; doi:10.1038/am.2014.48
OPEN & 2014 Nature Publishing Group All rights reserved 1884-4057/14
www.nature.com/am

REVIEW

Graphene fiber: a new material platform for unique

applications
Huhu Cheng, Chuangang Hu, Yang Zhao and Liangti Qu

Graphene fiber (GF) is of practical importance because it integrates the remarkable properties of individual graphene sheets
into useful, macroscopic ensembles that possess the common characteristics of fibers, such as mechanical flexibility for
textiles, while maintaining the unique advantages over conventional carbon fibers, such as low cost, light weight, shapeability
and ease of functionalization in an in situ or post-synthetic manner for various applications. In this review, we judiciously
summarize the significant advances in GFs achieved by our group and others in recent years, including the tunable and
controllable preparation of GFs with functionality and their remarkable applications for unconventional devices, such as flexible
fiber-type actuators, robots, motors, photovoltaic cells and supercapacitors.
NPG Asia Materials (2014) 6, e113; doi:10.1038/am.2014.48; published online 18 July 2014

INTRODUCTION result of the irregular size and shape of chemically derived graphenes
Carbon fibers are widely used in daily life because of their light and the movable layer-by-layer stacking of graphenes in contrast to
weight, high mechanical strength and environmental stability. As one the highly tangled CNT assemblies, which could seriously obstruct the
of the carbon-based fibers, the emergence of carbon nanotube (CNT) formation of GFs and impair their macroscopic mechanical
fibers/yarns has attracted tremendous attention as a result of the properties. Nevertheless, the recent success in assembling graphenes
integration of such properties as high strength and high electrical and into macroscopic fibers has inspired extensive interest in these
thermal conductivities of the individual nanotubes into useful, materials because of the lower cost of GFs compared with CNTs
macroscopic ensembles beyond those of common carbon fibers.1–8 and commercial carbon fibers, and their practical importance for
However, the limitations that result from the high cost of producing specific applications (http://efie.net/a-new-way-to-make-carbon-fiber/).
the initial superaligned CNT arrays5,7,8 and the extremely rigorous In addition to the useful complementarity of 2D films and 3D bulk
conditions, such as high temperature (41000 1C)6 and caustic media graphenes, 1D GFs are especially important for textile-enabled
(for example, fuming sulfuric acid2 and chlorosulfonic acid4), used in materials and devices, and can also act as the building blocks for
their production must be overcome for CNT technology to become forming 2D and 3D macroscopic structures for practical applications.
widely used. To date, great advances have been made from laboratory studies to
Graphene, a two-dimensional (2D) monolayer of carbon atoms the potential industrial applications of GFs. However, a comprehen-
packed into a honeycomb lattice, is the basic building block for sive review that presents the current status and the perspective of GF
carbon materials of all other dimensionalities.9 This material gains research is absent in the literature. In this feature article, we focus our
immense recognition because of its fascinating properties, such as discussion on the tunable and controllable preparation of GFs with
high electron mobility,10–12 high thermal conductivity,13 and functionality and their unique applications for unconventional
extraordinary elasticity and stiffness.14 Therefore, the development devices, such as flexible fiber-type actuators, robots, motors, photo-
of an effective strategy for well-controlled assembly is crucial for voltaic cells and supercapacitors.
integration of the remarkable properties of individual graphenes
into advanced, macroscopic and functional structures for practical PREPARATION OF GFS
applications. The assembly of nanoscale graphene sheets into Wet spinning of graphene oxide (GO) liquid crystal phases
macroscopic 2D film is generally achieved by simple solution The finding that soluble, chemically oxidized graphene or GO sheets
filtration, whereas 3D bulk graphene can be obtained through can form liquid crystals (LCs) in a twist-grain-boundary phase-like
hydrothermal treatment.15 In contrast, it appears to be an model with simultaneous lamellar ordering and long-range helical
extraordinary challenge to directly assemble 2D microscopic frustrations has led to the opportunity for continuous spinning of
graphene sheets into macroscopic fibers. This observation may be a this material into macroscopic GO fibers.16 GO LCs with lamellar

Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry, Beijing
Institute of Technology, Beijing, P.R. China
Correspondence: Professor L Qu, Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion
Materials, School of Chemistry, Beijing Institute of Technology, 5 South Zhongguancun Street, Haidian District, Beijing 100081, P.R. China.
E-mail: [email protected]
Received 22 February 2014; revised 4 May 2014; accepted 8 May 2014
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structures allow for the dispersion of GO at high enough concentrations (7 wt%) of viscous dope coupled with an
concentrations suitable for efficient alignment and effective appropriate selection of the coagulation solvent, the obtained fibers
coagulation. Gao et al.16 have fabricated neat GO fibers (Figures spun from large flake GO showed high flexibility with an
1a–c) by loading the GO dispersions into glass syringes and injecting unconventional 100% knot efficiency (Figure 1d), which has never
them into a coagulation bath of a 5 wt% NaOH/methanol solution. before been attained for polymer-based fibers.
Subsequently, the GFs were collected by chemical reduction of GO By modifying the wet-spinning process, our group developed a
fibers in hydroiodic acid. This approach of wet-spinning GO LCs coaxial two-capillary spinning strategy for continuously engineered
opens the pathway to large-scale production of flexible GFs, although production of morphology-controlled graphene-based hollow fibers.22
their mechanical strength needs further enhancement. Later, the same Figure 2a shows a schematic illustration of the setup for the direct
group prepared porous GFs by spinning the liquid crystalline GO gels spinning of hollow GO fibers in a coagulation bath of methanol
into liquid nitrogen.17 The porosity gives the graphene aerogel fibers a solution (Figure 2b). The concentrated GO suspension has a high
high surface area, affording a simple and effective way to prepare viscosity, allowing it to be directly bubbled, thus providing the chance
multifunctional fibers. to elaborately tune the morphologic character of the resultant GO
Other researchers found that the formulation of LC GO ‘inks’ fibers. Once replacing the inner fluid with compressed air, the
enabling the spinning of continuously conducting and robust fibers obtained hollow GO fibers display a necklace-like structure where
could have a concentration as low as 0.075 wt%, eliminating the need each of the hollow microspheres is connected by the fiber (Figure 2c).
for relatively concentrated spinning dope dispersions.18 Dilute LC GO To further control the fiber structure for tailored properties and
dispersions have proven to be suitable for fiber spinning using a new applications, Cao et al.23 introduced shear stress during wet
number of coagulation strategies, including non-solvent precipitation, spinning to produce macroscopic ribbon-like GFs with high
dispersion destabilization, ionic cross-linking and polyelectrolyte flexibility. The graphene ribbons showed high performance in many
complexation. This low concentration enables a wide range of applications, such as elastic strain sensors, flexible counter electrodes
possibilities, including new formulations of LC GO with different for fiber solar cells and fabric electrodes for supercapacitors.
materials (CNTs, metallic-based particles, polymers, etc.) that are not
accessible in the case of concentrated dispersions because of their Dimension-confined hydrothermal strategy
viscosity limitations. Hydrothermal treatment of GO will induced spontaneous assembly of
Notably, Yu et al.19 subsequently demonstrated that neat and graphene sheets in the graphene network via the strong interlayer p–p
macroscopic GFs can be fluidly spun from common GO suspensions stacking between graphenes.15 Our group24 developed a one-step
followed by chemical reduction. The curliness-fold formation dimension-confined hydrothermal strategy to fabricate neat GFs from
mechanism of GO fibers has been proposed. This wet-spinning aqueous GO suspensions. A glass pipeline of 0.4 mm in inner
technique facilitates the multifunctionalization of graphene-based diameter was used as the reactor. An aqueous GO suspension of
fibers with various organic or inorganic components. Other wet- 8 mg ml–1 was injected into the glass pipeline, and subsequently baked
spinning techniques for GO suspensions can be found in reference at 230 1C for 2 h after sealing the two ends of the pipeline. Finally, a
Chen et al.20 GF matching the pipe geometry was produced. Only 1 ml of GO
Wet-spun GO fibers generally have a relatively low tensile modulus, suspension (8 mg ml–1) will generate a GF 46-m long. The fiber
which is directly related to the intrinsic alignment of the GO layers diameter (typically 5–200 mm) and length (typically several meters)
along the fiber. To solve this problem, Tour and co-workers21 further can be easily controlled by either using a pipeline with a predesigned
utilized large flake GO (22 mm average diameter) as the building length and inner diameter or adjusting the initial GO concentration.
blocks to assemble fibers by the wet-spinning method. The resulting As a result of the dense stacking of graphene layers induced by the
fibers exhibited a one order of magnitude higher modulus than hydrothermal process, the assembled GFs have a relatively high
that of previously reported fibers. Upon spinning from high strength of up to 180 MPa.

Figure 1 Macroscopic neat graphene oxide (GO) fibers. (a) Four-meter-long GO fiber wound on a Teflon drum (diameter, 2 cm). (b) Scanning electron
microscope (SEM) image of graphene fiber (GF) and (c) the tightened knot. Scale bars, 50 mm. Reproduced with permission. Copyright 2011 from
reference. (http://efie.net/a-new-way-to-make-carbon-fiber/). (d) A tied large flake GO (LFGO) fiber with continuous pull until it breaks at a point far from the
knot. Reproduced with permission. Copyright 2013 from Xiang et al.21

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Figure 2 (a) Schematic illustration of the setup using a dual-capillary spinneret to directly spin hollow graphene oxide fibers (hGOFs). (b) Photos of the
spun hGOFs in methanol solution and (c) photos of the typical necklace-like hGOFs. Reproduced with permission. Copyright 2013 from Zhao et al.22

Based on the hydrothermal method, a dually geometric confine-

ment approach for preparing meter-long hollow GFs (hGFs) with
tunable diameters has been further developed.25 For example, one
removable wire-type template (for example, Cu wire) was placed
within the glass pipeline, which was thermally treated to induce the
aggregation of hydrothermally RGO along the wire. Finally, meters of
hGFs with diameters depending on the supporting wire template were
collected. Interestingly, two-, three- and four-channel hGFs can be
readily fabricated by utilizing two-, three- and four-ply Cu wires,
respectively.

Chemical vapor deposition (CVD)-assisted process

Zhu and co-workers26 developed a direct drawing approach to
fabricate GFs from CVD grown graphene films. Graphene films
were first transferred from the growth substrate to an organic solvent
(for example, ethanol) and were then drawn out from the solvent
using tweezers to form a fiber-like structure upon the evaporation of
the ethanol. The surface tension and the evaporation rate of the
solvent have important roles in the formation of porous GF
structures. Although the formed fibers have high electrical Figure 3 (a) Substrate-assisted reduction and assembly of graphene oxide
conductivity (B1000 S m–1), this method struggles to continuously (SARA-GO) process on active metal substrates. The active metal substrates
(Sub0) are oxidized to Subn þ ions with the loss of an electron (e ),
produce uniform GFs with desired lengths and strength on a large
whereas the GO is reduced by accepting an electron. (b, c) Photograph and
scale. scanning electron microscope (SEM) image of the hollow graphene fiber
The same group utilized atmospheric CVD to directly grow (hGF) produced by SARA-GO on a Cu wire. Scale bars: b, 1 cm; c, 50 mm.
graphene onto Cu meshes, a network of Cu wires.27 After removing Reproduced with permission. Copyright 2013 from Hu et al.28
the Cu wires with an FeCl3/HCl aqueous solution, a network
configuration of the hGFs was achieved, which is called graphene- oxidized to metal ions with the loss of electrons, while the GO is
based woven fabric (GWF). Graphene-based woven fabrics could be reduced by accepting electrons. The electron transport through the
further transferred onto polydimethylsiloxane (PDMS) substrates to metal to the GO allows for the 3D assembly of reduced GO (RGO).
produce graphene-based woven fabric/PDMS hybrid films for various This method also allows for the reduction of GO and its well-
applications. organized assembly on arbitrary conductive surfaces, such as active
metals Zn, Fe and Cu; inert metals Ag, Pt and Au; semiconducting Si
Spontaneous reduction and assembly of GO wafers; nonmetallic carbon-based films; and even indium-tin oxide
As we have discussed, hGFs can be prepared by CVD growth of glass, without any additional reducing agents. In the case of Cu wire
graphene along Cu wires or meshes. In fact, even without the CVD as the active substrate, the hGFs can be produced by substrate-assisted
process, hGFs can be spontaneously formed on Cu wires based on a reduction and assembly of GO as presented in Figures 3b and c. This
facile and efficient substrate-assisted reduction and assembly of GO method is favorable for the formation of the structure-defined
method (Figure 3a).28 In this approach, the active metal substrates are assembly of graphenes.

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From aligned CNT sheets to graphene yarn As an example of post-synthetic functionalization, TiO2 nanopar-
Graphene nanoribbons can be derived from CNTs29–31 that already ticles have been intercalated into the framework of graphene sheets by
possess the high aspect ratio. Based on this concept, Baughman soaking the wet as-prepared GFs in a commercial TiO2 aqueous
et al.32 fabricated graphene nanoribbon yarns by chemically unzipping suspension with slight stirring.24 After drying and annealing, the
sheets of highly aligned CNTs and densifying them during the drying TiO2-GFs exhibit a fast photocurrent response with good repeatability
process. In this case, the original multiwalled CNT sheets were first (Figure 4b). The strong photocurrent response indicates a direct
layered onto a polytetrafluoroethylene frame that allowed for the electron/hole injection between the TiO2 particles and graphene
unzipped GO nanoribbon (GONR) sheet to collapse onto a GONR sheets through photoexcitation of TiO2, suggesting the significant
yarn when removed from the liquid-phase solution. Specifically, applications in optoelectronic systems, such as photodetectors,
multiwalled CNT layers wrapped vertically around a polytetra- photocatalysts and photovoltaic cells. However, selective functionali-
fluoroethylene framework immersed in solution (first an oxidizing zation can be achieved in a site-specific outer-wall, inner-wall,
bath, followed by a rinsing solution) render GONR sheets. After outer/inner-wall and within-wall fashion on hGFs.25
drying at room temperature, the GONR yarn shrinks from B1 mm to To improve the electrical conductivity of GFs, Gao et al.38 prepared
B25 mm in diameter. A combination of different reduction graphene-metal hybrid fibers by wet spinning of GO LCs mixed
treatments can tune the presence/absence of superficial chemical with commercial Ag nanowires, followed by chemical reduction
groups useful for improving their mechanical, electrical and (Figure 4c). The Ag-doped GFs exhibited a record high electrical
electrochemical properties. In fact, GONRs and chemically reduced conductivity up to 9.3  104 S m–1 and a high current capacity of
graphene nanoribbons can also be dispersed at high concentrations 7.1  103 A cm–2. The combination of high conductivity and high
in chlorosulfonic acid to form anisotropic LC phases for wet spinning mechanical strength and flexibility of doped GFs renders them ideal
of GFs.33 stretchable conductors to be applied in soft circuits.
Aside from their high electrical conductivity, excellent mechanical
Other methods properties are also highly desired for GFs. Generally, a large aspect
Although the aforementioned methods provide a considerable ratio of the building blocks and better alignment in the fiber axis are
number of options to controllably prepare different types of GFs the main factors. It was also found that the introduction of divalent
for diverse purposes, other methods have been reported. Kim and ionic cross-linking between graphene sheets could further enhance
co-workers reported an electrophoretic assembly method for the their mechanical strength.39 As an example, a record tensile strength
fabrication of reduced GONR fibers.34 A graphitic tip as a positive of up to 0.5 GPa has been achieved among neat graphene materials
electrode was immersed into the chemically reduced GONR colloidal (Figure 4d).
solution in which the counter electrode was embedded. A constant To achieve strong GFs, Gao et al.40 further produced bio-mimic
voltage ranging from 1 to 2 V was applied between the electrodes continuous fibers with ‘brick-and-mortar’ structures of alternating
during the withdrawal process for the graphitic tip (0.1 mm min 1). graphene sheets and hyperbranched polyglycerol binders via wet-
Similar to the direct drawing method mentioned above, this approach spinning assembly technology. The formation of strong and adaptive
also has relatively low production efficiency unsuitable for large-scale hydrogen bonding networks between GO and hyperbranched
processes. Alternatively, Xu et al.35 reported a facile solution self- polyglycerol contributes to their super properties. The optimized
assembly strategy to fabricate neat GO fibers from aqueous GO results41 showed that the biomimetic composites achieved record high
suspensions at the liquid/air interface based on repulsive electrostatic tensile strength (0.65 GPa) and toughness (18 MJ m 3) among nacre
forces, attractive van der Waals forces and p p stacking. During the mimics. In addition, the composites exhibited high electrical
assembly process and ultrasonic cleaning, the morphology conductivity (5261 S m 1) comparable to that of neat graphene
interestingly varied from the source graphite powder to GO sheets, papers. Meanwhile, it was discovered that polymer-grafted GO
then to GO fibers and finally to neat GO fiber films. This method fibers show remarkable chemical resistance, even to 98% sulfuric
provides a simple approach toward the scalable preparation of acid, because of their compact layered structures and strong interlayer
random GFs with a small diameter of 1 2 mm and a length of interactions.42 As a result of the covalent and uniform immobilization
approximately hundreds of micrometers, although the formation of polymer chains on the surface of individual GO sheets, local
mechanism may need further study. phase separation is fundamentally avoided and strong interfacial
Thus, various methods are available for the fabrication of different interactions are simultaneously introduced. Polymer chains were
types of GFs with specific features (Table 1), which provides abundant then covalently bonded to the nanoplatelets through in situ free
material platforms that are unique for different applications, as radical polymerization of vinyl monomers (for example, glycidyl
further demonstrated below. methacrylate).

FUNCTIONAL COMPOSITES All-carbon composites

Intercalation of functional components Graphenes are typical 2D nanostructures with unique properties,
Integration of functional components into GFs will facilitate impor- whereas CNTs are important 1D nanomaterials. Thus, the hybrid of
tant applications, such as stimulus-responsive and electronic textiles. these two materials could possess interesting properties. Li et al.43
The GFs provide a platform for in situ and post-synthetic incorpora- achieved CNT and graphene hybrid multiple-thread yarns, consisting
tion of various materials with unique properties into the fiber bodies of tens or hundreds of single-thread CNTs, from a chemical vapor gas
for weavable, multifunctional applications.36,37 For example, magnetic flowing reaction followed by post-treatment processing. A thick CNT
GFs have been fabricated by in situ introduction of Fe3O4 stick-like assembly was first fabricated by CVD processing with a
nanoparticles into the fibers.24 The Fe3O4-incorporated GFs with horizontal reactor. CNT and graphene hybrid multiple-thread yarns
good mechanical flexibility exhibit a sensitive magnetic response. As were then drawn from the stretched, thick stick-like CNT assembly.
demonstrated in Figure 4a, the magnetized GFs can iteratively bend to The as-obtained CNT and graphene hybrid multiple-thread yarns can
the magnet from its initial upright position. be twisted to form one fiber. The mechanical measurement of the

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Table 1 Brief summary of the typical features of GFs fabricated by different methods

Diameter Young’s modulus Conductivity

Preparation method of GFs Flexibility (mm) Strength (MPa) (GPa) (S cm 1) Remarks Ref.

Spinning of GO High 50–100 140 5.4 B250a Scalable Xu and Gao16

25–120 145 for GO fiber; 4.2 for GO fiber; 35a Scalable Cong et al.19
182 for GF 8.7 for GF
40–150 85 to 192 2.8 to 9.8 68–230a Scalable Chen et al.20
o100 442±18 22.6±1.9 28.44b Scalable Jalili et al.18
Spinning of GONRs High 29–80 33.2; 383b 3.2; 39.9 b 285b Scalable Xiang et al.33
Hydrothermal strategy High 10–100 140 B10 Scalable Xu et al.15
CVD assistant process Low 20–50 B10 Li et al.26
Spontaneous reduction and Low 15–100 B10 Morphology predefined Hu et al.28
assembly of GO
Aligned CNT sheets to High B100 Up to 100 S cm2 g 1 after Carretero-Gonzalez
graphene yarn annealing et al.32
Electrophoretic self-assembly 20–40 Jang et al.34
Self-assembled graphene oxide High 1 2 1.1±0.031 B15b Hundreds of micrometers in Tian et al.35
fibers length

Abbreviations: CNT, carbon nanotube; CVD, chemical vapor deposition; GF, graphene fiber; GO, graphene oxide; GONR, GO nanoribbon.
aAfter chemical reduction.
bAfter annealing at high temperature.

Figure 4 (a) Magnetic Fe3O4/graphene fiber (GF) attracted to the magnet. (b) A typical photocurrent response for a TiO2 immobilized GF upon exposure to
on/off light at room temperature. The inset shows an enlarged view for a small portion of the photocurrent response curve. Reproduced with permission.
Copyright 2012 from Dong et al.24 (c) Possible complex mechanism by Ag nanowires with graphene sheets. Reproduced with permission. Copyright 2013
from Xu et al.38 (d) Mechanical measurements under tension for GFs cross-linked by different divalent ions. Reproduced with permission. Copyright 2013
from Xu et al.39

twisted yarn resulted in a strength of 300 MPa and the electrical has been prepared and used as an electrode for the construction of
conductivity was found to be 105 S m 1. flexible supercapacitors.
Another method is to directly grow the CNTs from the GF. Cheng In contrast to the graphene/CNT fibers, a unique all-graphene
et al.44 prepared GFs with intercalated Fe3O4 nanoparticles by a core-sheath fiber has been fabricated in which a core of GF is covered
hydrothermal process, which were then treated through the CVD with a sheath of 3D porous network-like graphene framework,45
process for growth of CNTs along the GFs. Although the hybrid fibers named GF@3D-G. 3D graphene structures exhibit notable features,
have relatively low mechanical strength, a flexible textile of CNT/GFs including highly exposed surface areas, high electrical conductivity

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Figure 5 Preparation and structure of polymer composite fibers. (a) Schematic diagram showing the formation of the oriented interconnected network of
reduced graphene oxide (RGO) flakes (curved rectangles) and single-walled carbon nanotube (SWNT) bundles (grey lines) as a result of sonication and
subsequent wet-spinning. (b) Scanning electron microscope (SEM) image of the cross-sectional area of a RGO/SWNT/poly(vinyl alcohol) (PVA) fiber, which
clearly shows the co-assembly of RGO flakes and SWNTs. Scale bar, 100 nm. (c) Schematic illustration of the structural evolution between coagulation-spun
RGO gel (left), polymer composite (middle) and polymer-free fibers (right). Yellow lines and blue curved rectangles represent PVA chains and RGO flakes,
respectively. (d) SEM image of the cross-sectional area of a polymer-free RGO fiber, which clearly shows the wrinkled RGO flakes. Scale bar, 500 nm.
Reproduced with permission. Copyright 2012 from Shin et al.46

and good chemical stability. Herein, the high electronic conduction of provide good integration with a polymer matrix because of its planar
the core GF and the highly exposed surface area of the 3D graphene structure with large interfacial area for p p stacking with the
network are combined within the GF@3D-G, thus offering the great polymer matrix. In addition, the carboxyl and hydroxyl functional
advantages as flexible electrodes for efficient fiber-based devices. groups on the basal planes and edges of the starting GO nanosheets
may act as linkers between the graphene and the polymer. For
example, the graphene nanoribbon/carbon composite nanofiber yarns
Polymer composites
were prepared by electrospinning from poly(acrylonitrile) containing
Previous work has shown that the toughness of the CNT-reinforced
GONRs, followed by successive twisting and carbonization.47 The
polymer fibers exceeds that of previously known materials.1 Kim
electrospinning process can exert directional shear force coupling with
et al.46 showed further increased toughness results from the
the external electric field to the flow of the spinning solution. During
combination of CNTs with RGO flakes in solution-spun polymer
electrospinning, the well-dispersed GONRs were highly oriented
fibers. The process for fabricating hybrid fibers based on RGO flakes
along the fiber axis in an electrified thin liquid jet. The addition of
and single-walled carbon nanotubes (SWNTs) is shown in Figure 5a.
GONRs at a low weight fraction significantly improved the
Uniform dispersions of various relative amounts of RGOs and SWNTs
mechanical properties of the composite nanofiber yarns. Typical
in aqueous solutions of sodium dodecyl benzene sulfonate were
graphene–polymer nanofibers fabricated by the electrospinning
prepared. The dispersions were then injected into the flow stream of
method have been reported on the basis of PVA,48,49 poly(vinyl
an aqueous solution of 5 wt% poly(vinyl alcohol) (PVA) dissolved in
acetate)50 and poly-acrylic acid.51
deionized water, which resulted in coagulation and formation of
RGO/SWNT/PVA hybrid fibers. After washing in deionized water,
drying and subsequently treating with methanol to increase PVA UNIQUE APPLICATIONS
crystallinity, mechanically robust hybrid fibers consisting of RGO/ New type of functional fibers
SWNT imbedded in a PVA matrix were obtained (Figure 5b). The pliability of GFs facilitates their weaving into a variety of
Figure 5c schematically illustrates the transformation of as-spun gel macroscopic objects. For example, a textile structure of GFs with
fibers into solid RGO/PVA fibers and then polymer-free fibers of self-supported stability can be achieved (Figure 6a),24 which displays
wrinkled RGO flakes. The polymer-free fibers were mechanically great potential for electronic textile applications in view of the good
stable, indicating the formation of an interconnected network of RGO conductivity of GFs. The flexible and mechanically stable GFs can also
flakes (Figure 5d). The polymer composite fibers have a gravimetric be shaped into specific geometries on demand, as exemplified in
toughness of 1000 J g 1, far exceeding that of spider dragline silk Figure 6b for a GF spring with stretchable and compressible
(165 J g 1) and Kevlar (78 J g 1). This toughness enhancement is character.24 In addition, the GFs can be expediently integrated into
consistent with the observed formation of an interconnected network flexible, transparent, conductive composite films. Figure 6c shows a
of partially aligned RGO flakes and CNTs during solution spinning, GF network embedded into a PDMS matrix with tolerance to
which act to deflect cracks and allow energy-consuming polymer deformation.24 Similarly, the GF can also be knitted in cotton
deformation. The hybrid fibers were sewable and weavable, and could textiles (Figure 6d).16 Others, such as the specifically defined
be shaped into high-modulus helical springs. configurations of four-way pipe (Figures 6e and f)28 with tunable
In fact, graphene as a filler has been widely studied for polymer length and diameter, can also be readily prepared.
composites. The addition of a low fraction of graphene nanosheets Ag-doped GFs have high electrical conductivity with high flexibility
could result in a significant improvement in the mechanical strength that makes them attractive for flexible conductors. Gao et al.38
and electrical properties of the composites. Graphene nanosheets prepared a stretchable array of graphene–Ag fibers (Figure 7a) on

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Figure 7 (a) The stretchable array constructed by Ag-graphene fibers (GFs)

in the stretched (top) and relaxed state (bottom). The inserted images are
magnified photos of the Ag-GFs in the respective areas indicated by the
rectangles. (b) The working states of Ag-GF-based stretchable circuit in the
stretched (top) and relaxed state (bottom). Reproduced with permission.
Copyright 2013 from Xu et al.38

These remarkable features provide graphene with prominent

advantages for the development of unconventional, flexible, stimu-
lus-responsive structures, especially in fiber form. A novel electro-
chemical fiber actuator based on GF/polypyrrole bilayer structures has
been recently demonstrated.62 The fiber actuator was found to have a
high actuation activity and durability comparable to other graphene-
based actuators. Multi-armed tweezers and net actuators have been
fabricated, which exhibit great promise in different fields including
biological studies and microfabrication.
Our group63 rationally designed and fabricated graphene/GO (G/
GO) asymmetric fibers as a result of the positioned laser reduction of
freshly spun GO fibers (Figures 8a and b). Remarkably, the G/GO
fibers display complex, well-confined and predetermined motion and
Figure 6 (a) Photographs of the hand-knitted textile of graphene fibers deformation once exposed to moisture. The excellent humidity-
(GFs). (b) The spring of the GF. (c) Photograph of a GF network embedded responsive bending/unbending ability of the G/GO fibers enabled a
in a polydimethylsiloxane (PDMS) matrix. Reproduced with permission. new type of microfiber walking device. The G/GO fiber walker can
Copyright 2012 from Dong et al.24 (d) A GF pattern knitted in the cotton travel in a narrow slit. As shown in Figure 8c, the G/GO fiber walker
network (white) using two GFs (black). Scale bars, 2 mm. Reproduced with
was placed between two glass slides with a gap of approximately
permission. Copyright 2011 from Xu et al.16 (e) Photograph of a four-way
tube with the corresponding SEM images of the nozzles, and (f) the 1 mm, which is also supported by a ratchet substrate. Initially, the G/
corresponding schematic diagram. Scale bars: e, 1 cm; e inset, 100 mm. GO fiber walker stands under ambient conditions (Figure 8d). Once
Reproduced with permission. Copyright 2013 from Hu et al.28 the relative humidity increases, its back end shifts because of the
increased bending (Figure 8e). During the stretching process induced
PDMS substrates. The Ag–GFs were fixed to Al foils by silver glue on by the removal of moisture, the front end of the G/GO fiber walker
the 150% prestrained PDMS substrate. Under compression in the slides forward, while the back tip is fixed by the indentations on the
fiber axis during the strain relaxation, the Ag–GFs buckled to become rough surface of the substrate (Figure 8f). With the alternation of the
relative humidity, the device walks unidirectionally step-by-step with
curved threads without breakage because of their good flexibility
(Figure 7a). The stretchable conductors can be safely stretched below a moving rate of 4 mm per cycle. In principle, the moving speed and
150% strain under electrical loading. As shown in Figure 7b, the motion of this proof-of-concept prototype for the walking robot
could be readily improved by regulating the frequency of the
constructed circuit kept working after 150% stretching, as indicated
by the light emitting diode chips. humidity alternation and also the device length.

GF motors
GF actuators GFs typically possess in-line assembled graphene sheets that are
Smart materials and structures with fast, reversible and controllable induced during the fiber formation process. By reconstructing the
shape changes in response to environmental stimuli have attracted intrinsic configuration of graphenes within the fiber body, a new type
tremendous attention because of their remarkable potential in of moisture-driven rotational motors64 can be achieved by rotary
applications ranging from robots and sensors to memory chips. processing of the freshly spun GO fiber hydrogel (Figures 9a–c). As a
Graphene-based structures exhibit many exciting properties that result of the oxygen-rich functional groups of GO, the relatively fast
could benefit such actuation systems,52–57 for example, and reversible expansion/contraction of GO layers will take place
electrochemical actuators based on unimorph and bilayer graphene through the adsorption and desorption of water molecules. Therefore,
films and 3D graphene skeletons.58–61 GFs possess the mechanical the formed helical geometry of GO fibers will enable the reversible
flexibility required for textiles, yet are unique in that they are light- torsional rotation under the alternation of humidity (Figure 9d). The
weight and easy to functionalize in comparison with conventional maximum torsional rotation rate can reach 5190 rotations min 1
carbon fibers. (543 rad s 1) and the entire rotation process contains 327 full turns.

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Figure 8 (a) Representation of positioned laser reduction on one side of a graphene oxide (GO) fiber. The black region corresponds to the laser-induced G
region along the brown GO fiber. (b) Photomicrograph of the top surface of the asymmetric graphene/GO (G/GO) fiber. Scale bar, 50 mm. (c) Photograph of
the G/GO fiber walker within the narrow slit between two glass slides on the ratchet paper. (d) The initial state of the G/GO fiber walker, which is manually
bent slightly in advance to provide a standing pose. (e, f) A series of photographs of the G/GO fiber walker crawling on the ratchet paper in response to the
‘on’ and ‘off’ states of applied moisture. The G side of G/GO fiber is placed downward. Relative humidity (RH; ‘on’ state) ¼ 80%, RH (‘off’ state) ¼ 25%.
Scale bars in (c, d), 1 cm. Reproduced with permission. Copyright 2013 from Cheng et al.63

The torsional rotation of twisted GF (TGF) enabled the fabrication H2O2 aqueous solution is recorded in Figures 10b–h. As seen in the
of a new type of humidity switch. As shown in Figure 9e, when the figure, a large number of gas bubbles are jetted out from the hGF tail,
environment humidity increases, the TGF will drive the paddle which pushes the hGF a distance of approximately 24 cm within 6 s.
rotation, which triggers the switch and turns on the light emitting This proof-of-concept hGF motor demonstrated the potential of site-
diode (Figure 9e, inset). Upon removal of the moisture, the TGF will specific modification of hGFs for advanced self-powered micromotors
pull the paddle to its original position and release the press on the for various applications.
aluminum pad, hence switching off the light.
These unique TGFs that are sensitive in response to moisture also Dye-sensitized photovoltaic wires
provide the opportunity to develop a humidity-triggered electric The combined remarkable mechanical and electrical properties of GFs
generator, which will produce power using mechanical work induced ensure them to be a promising new family of electrode materials. Peng
by the variation of ambient moisture. As shown in Figure 9f, when the et al.68 developed novel wire-shaped photovoltaic devices based on
entire device was exposed to an environment with varying humidity, graphene/Pt composite fibers as counter electrodes, and Ti wire
the TGF could drive the magnet in a reversible rotation, thus leading impregnated with TiO2 nanotubes as working electrodes (Figure 11).
to the generation of electricity in the Cu coils. This generator The high flexibility, mechanical strength and electrical conductivity of
produced an open-circuit voltage of up to 1 mV (Figure 9g), and a GFs resulted in a certified maximum energy conversion efficiency of
short-circuit current of up to 40 mA (Figure 9h) despite the absence of 8.45%, which is much higher than that of other wire-shaped
device optimization. photovoltaic devices. These photovoltaic wires have the potential to
Micro-motors propelled by self-generated forces have gained be easily woven into clothes, packages and other portable devices
substantial interest in the scientific community. The ability of the to serve as self-powered electric generators by conventional textile
transport and delivery of cargo in various environments is of great technology.
importance.65–67 Based on the site-specific functionalized hGF, a self-
powered graphene micromachine can be designed that will move in GF-based supercapacitors
aqueous medium.25 As illustrated in Figure 10a, the inner-wall Graphene materials are also attractive for applications in electro-
modified hGF with Pt nanoparticles is ideal as a transporting chemical capacitors.69,70 Conventional supercapacitors are heavy and
motor. Similar to the tubular microjet, the O2 bubbles from H2O2 bulky, targeted for applications in electric or hybrid vehicles and
decomposition were thrust out at one open end, causing a fast and auxiliary power sources. However, the development of high-efficiency
directional movement, whereas the Pt nanoparticles were the catalyst miniaturized supercapacitor devices that are compatible with flexible
for the decomposition of H2O2 to produce O2. Once sealed in one and wearable electronics is lacking. Combining the high electrical
end of the hGF, the ejected O2 bubbles from the other end will drive conductivity of GFs with the highly exposed surface area of 3D
the hGF in the opposite direction. The fast motion of an hGF graphene networks (Figures 12a and b), the core–sheath GF@3D-G
micromotor (6 mm in length and 100 mm in diameter) in 20 wt% offers great advantages as flexible electrodes for efficient fiber-based

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Figure 9 (a) Scheme of the twisted graphene fiber (TGF) fabrication. (b, c) Scanning electron microscope (SEM) images of the directly dried graphene oxide
(GO) fiber and TGF formed with an applied 5000 turns per meter, respectively. Scale bars, 50 mm. (d) Schematic rotation of a TGF with a paddle at low
(left) and high (right) humidity. When the moisture increases (right), the TGF can drive the paddle rotating fast; then the paddle can reverse to the initial
state when the moisture decreases (left). (e, f) Scheme of the designed humidity switch and the alternating current generator based on the humidity-
responsive TGFs. In the switch (e), TGF in response to moisture (for example, RH ¼ 85%) can rotate a paddle to press on the metal plate, as indicated by
the arrow, so that the electric circle powered by the battery will turn on the light emitting diode, as shown in the inset photo. The generator (f) contains four
Cu coils around the TGF with a magnet. When the environment humidity changes, the TGF can reversibly rotate the magnet within the surrounding Cu coils
to generate electricity. (g, h) Open-circuit voltage and short-circuit current of the generator tested under humidity changes between 20 and 85%.
Reproduced with permission. Copyright 2014 from Cheng et al.64

electrochemical supercapacitor.45 Fiber supercapacitors consist of two applications, such as catalysis, separation and adsorption, can be
intertwined electrodes, both of which are solidified in H2SO4-PVA gel envisioned for the graphene-CNT hybrid fibers. Other examples of
electrolyte for formation of an all solid-state fiber supercapacitor. The flexible all solid-state supercapacitors based on GFs and assembled
assembled fiber supercapacitor of GF@3D-G is highly flexible, which graphenes on fibers can be found in references.72–74
can be manipulated to a spring shape with highly compressible and
stretchable properties, and can also be conveniently woven into Solid-phase microextraction (SPME) sorbents
textiles for wearable electronics (Figures 12c and d). SPME has been widely used in the analysis of trace organic
A novel hybrid fiber of MnO2-modified graphene sheets on GF has contaminants75 because of its simple operation and easy coupling
also been fabricated by direct deposition of MnO2 onto the graphene to separation techniques, such as gas chromatography (GC),
network surrounding the GF (MnO2/G/GF).71 By combining the liquid chromatography, capillary electrophoresis and ion
electric double layer capacitance of the graphene network with the chromatography.76–78 When coupled with GC, SPME integrates
pseudocapacitance of the MnO2 nanostructures, the all solid- sampling, isolation, enrichment and injection steps, making the
state fiber supercapacitor shows greatly enhanced electrochemical analysis much more convenient. To date, several coating fibers are
capacitive behavior with robust tolerance to mechanical deformation. commercially available for SPME, including PDMS, polyacrylate,
However, the graphene-CNT hybrid fibers can be further woven into divinylbenzene, carboxen, carbowax and their copolymers.75,76
textile electrodes for the construction of flexible supercapacitors These commercial fibers generally exhibit some drawbacks, such as
with a high tolerance to repeated bending cycles.44 Various other high cost, thermal, mechanical and/or chemical instability, insufficient

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Figure 10 The hollow graphene fiber (hGF) micromotor. (a) Scheme of a moving micromotor. A one-end sealed hGF inner-wall modified with Pt
nanoparticles propelled in an aqueous H2O2 solution. (b–h) Snapshots of the track for a moving hGF micromotor in a 20 wt% H2O2 solution. Reproduced
with permission. Copyright 2012 from Hu et al.25

selectivity, fragility of the fused-silica substrate, and limited range of

polarity and reuse times, which largely restrict the application of
SPME.
Graphene was first used as an SPME coating for extraction of
pyrethroid pesticides from environmental water samples by Chen
et al.79 Compared with commercial fibers, these graphene-based fibers
show not only higher extraction efficiencies toward the targeted
analytes but also far superior thermal and mechanical stabilities.
Feng et al.80 used a hydrothermally synthesized GF for SPME, the
performance of which was investigated through the analysis of five
organochlorine pesticides using GC/electron capture detector (GC/
ECD). The results indicated that the GFs not only exhibited higher
enrichment factors toward organochlorine pesticides compared with
PDMS fibers but also possessed higher thermal stability and longer
service life compared with commercial fibers. Finally, a headspace
SPME (HS-SPME) technique for the determination of organochlorine
pesticides in water samples was developed using GF as the sorbent
coupled to GC/ECD (HS-SPME-GC/ECD). Similarly, the monolithic
GFs coupled to capillary GC in a direct-immersion mode achieved
higher extraction efficiencies for aromatics than those for n-alkanes,
especially for polycyclic aromatic hydrocarbons as a result of p–p
stacking interactions and hydrophobic effects.81 In addition, the fibers
exhibited excellent durability and can be repetitively used 4160 times
without significant loss of extraction performance.

Other applications
Aside from the applications mentioned above, graphene-based fibers
Figure 11 Dye-sensitized photovoltaic wire prepared by using a graphene/Pt could also be used in other interesting fields. For example, the
composite fiber as the counter electrode and a Ti wire impregnated with electrospinning process can incorporate graphene sheets into a
TiO2 nanotubes as the working electrode. (a) Schematic illustration.
(b) Scanning electron microscope (SEM) image. (c, d) Photographs of
continuous nanoscale composite fiber, which could be applied as an
photovoltaic wires sealed in a capillary glass tube and flexible fluorinated optical element in fiber lasers. Loh et al.50 presented that electrospun
ethylene propylene tube, respectively. Reproduced with permission. graphene nanocomposites are promising candidates as saturable
Copyright 2013 from Yang et al.68 absorbers with wideband absorption, which could be used as

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Figure 12 (a) Scanning electron microscope (SEM) images of a GF@3D-G and (b) cross-sectional view of a GF@3D-G showing the core graphene fiber (GF)
surrounded by standing graphene sheets. Scale bars: 100 mm. (c, d) Photos of the textile embedded with two GF@3D-G fiber supercapacitors (each
approximately 2 cm in length) in the flat and bending state, respectively. Reproduced with permission. Copyright 2013 from Meng et al.45

practical and efficient photonic materials for the generation of ultra introduction of cross-linkers or metal nanowires into GFs for new
short pulses in fiber lasers, attaining a larger modulation depth and hybrids38,46 may be one method for solving this challenge.
smaller nonsaturable loss than SWNTs. By using graphene–polymer Furthermore, control over the preparation process of GFs requires
composites, it is possible to realize full waveband ultrafast lasers. deep study. GFs are mainly assembled from graphene or GO
nanosheets with uncertain sizes, defects, shapes and chemical
compositions. These factors strongly affect the assembly process and
SUMMARY AND OUTLOOK thus determine all the aspects of GF properties. For example, large
The active research in GFs during recent years has revealed numerous and small graphene sizes can produce GFs with much different
interesting findings and breakthroughs on the fabrication and mechanical properties.21 However, most of the current studies mainly
applications of these fascinating materials. In particular, the integra- focus on the establishment of new strategies for GF fabrication, and
tion of graphene nanosheets into macroscopic fibers provides a new the systematic consideration of all the factors for the final
material platform for developing unconventional smart systems and performance is generally absent. The precise modulation and
devices. Various preparation methods have been developed thus far control of the assembly of graphene sheets for GFs also remains a
for large scale production of GFs, which have paved the way for challenge. Although the production of GFs has been achieved through
diverse applications of GFs in the future. Accordingly, many of the the continuous process of the wet-spinning method, the generation of
in situ and post-synthetic functional approaches and the available practical products based on these unique GFs requires the
composites provide GFs with new functions and properties. Impress- cooperation of more researchers from various fields.
ive examples for various applications include fiber-type actuators, In summary, the macroscopic assembly of graphene into GFs has
robots, motors, photovoltaic cells and supercapacitors. rendered new opportunities for the development of new materials and
Compared with the long-term development of common carbon devices over common fibers. With the progress on the understanding
fibers, research on GFs is still in its early stages and there is no and control of the assembly of graphene, high-performance GFs will
systematic theory established thus far to support this specific field. be achieved in the near future and new applications will also be
Many challenges still remain to be solved. For example, more effort revealed beyond smart electronic textiles.
needs to be continuously devoted to the high mechanical strength and
electric conductivity of GFs. The highest strength achieved thus far is
only 0.65 GPa for biomimetic GFs.41 As a new type of fiber, GFs are CONFLICT OF INTEREST
still inferior to metal wires and high-performance carbon fibers in The authors declare no conflict of interest.
both mechanical and electrical properties, which mainly results from
the relatively loosely stacked structure of graphene nanosheets within ACKNOWLEDGEMENTS
the fiber bodies. For high-strength fiber applications, the mechanical The authors thank the 973 program (2011CB013000) of China and NSFC
properties of GFs need further enhancement to reach values (21325415, 21174019 and 51161120361), the Fok Ying Tong Education
comparable to that of high quality carbon fibers. As a light-weight Foundation (no. 131043) and the 111 Project 807012 for their financial
conductive wire, the electric conductivity of GFs is still low. The support.

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Huhu Cheng is currently a PhD candidate under the supervision of Professor Liangti Qu at the School of Chemistry in Beijing Institute
of Technology. His research focuses on assembly of graphene-based materials for smart devices.

Chuangang Hu is currently a PhD student in the research group of functional nanostructures supervised by Professor Liangti Qu at
Beijing Institute of Technology. His research focus is the functionalization of graphenes for energy conversion and storage applications.

Yang Zhao is currently a PhD student under the supervision of Professor Liangti Qu at the School of Chemistry in Beijing Institute of
Technology. Her research interests lie in the development of new methods and strategies for fabrication of carbon-based functional
materials for various applications.

Liangti Qu received a PhD in chemistry from Tsinghua University (Beijing, China) in 2004. He becomes a professor of chemistry at
Beijing Institute of Technology in 2009 after working at University of Dayton in Ohio, USA for 5 years. As Xu-Teli Distinguished
Professor, he now leads the Nanocarbon research group with interest in material chemistry mainly focusing on the synthesis,
functionalization and application of nanomaterials with carbon–carbon conjugated structures including graphenes, carbon nanotubes
and conducting polymers. So far, Dr Qu has published 4110 scientific papers in the prestigious journals.

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