Materials Today  Volume 18, Number 9  November 2015 RESEARCH

RESEARCH: Review

Graphene fiber: a new trend in carbon

fibers
Zhen Xu and Chao Gao*
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, 38 Zheda Road,
Hangzhou 310027, PR China

New fibers with increased strength and rich functionalities have been untiringly pursued by materials
researchers. In recent years, graphene fiber has arisen as a new carbonaceous fiber with high expectations
in terms of mechanical and functional performance. In this review, we elucidated the concept of
sprouted graphene fibers, including strategies for their fabrication and their basic structural attributes.
We examine the rapid advances in the promotion of mechanical/functional properties of graphene
fibers, and summarize their versatile applications as multifunctional textiles. Finally, a tentative
prospect is presented. We hope this review will lead to further work on this new fiber species.

Introduction modulus (400 GPa) in the 1960s [7,8]. This almost purely carbo-
Human ingenuity in the discovery, creation and utilization of naceous fiber is usually prepared from natural cellulose, synthetic
fibers not only fulfills primary needs in clothing and shelter, but polyacrylonitrile (PAN) and pitch, by carbonization and/or graph-
also promotes important advances in technology and culture. itization at high temperatures to eliminate other chemical ele-
Before the 19th century, natural fiber species that mainly included ments and generate graphitic structures (Fig. 1) [5,6]. The first
animal, vegetable, and mineral products, were extensively used attractive merit of CFs are the extraordinary mechanical proper-
and dominated human life. It is such innovation and technical ties; that is, high tensile strength and elastic modulus, which,
advances in cotton workshops that reformed production and combined with their lightness in weight, mean they overwhelm
ushered in the First Industrial Revolution [1,2] After natural spe- steel in enforcement applications as structural components. Be-
cies, synthetic polymeric fibers were created from petrochemicals, yond their outstanding strength, CFs possess a wealth of function-
such as Nylon, to meet the rapidly increasing demand for fibers alities, such as good electrical and thermal conductivities,
and to complement the limited availability of natural products. favorable resistance to chemicals and harsh surroundings, and
Despite vast numbers of commercial fiber species having flooded stability at high temperatures. All of these merits render CFs an
both industry and daily life, the vigorous search for new ones with indispensable component of many high-tech uses such as aero-
better mechanical performance that can bear high stress and rich planes, vehicles, and cables, to mention but a few commercial
multifunctionalities for use in increasingly complicated tasks has products [3,4].
continued. For material researchers, CF does not represent the end of new
Carbon fiber (CF) is a species that permits the integration of fibers, but rather a promising beginning. The principal philosophy
high-performance and rich functionalities [3–6]. The creation of underlying all of their attractive merits is the interconnected
CF can be traced back to the pyrolysis of natural cellulose fibers for graphitic structure, which provides extraordinary combined me-
electrical-light bulbs by Sir Joseph Swan in 1883. CF became widely chanical, electrical, thermal properties. The ideal model counter-
attractive when teams at the Royal Aircraft Establishment and part of CF, graphite whiskers, has strengths of up to 20 GPa and
Rolls Royce, Ltd., promoted CF to the rank of a real high-perfor- electrical conductivity of 1.5  106 S/m [9], much higher than ever
mance fiber with high mechanical strength (1.7 GPa) and tensile obtained by CFs (5.9 GPa and 1.4  105 S/m, respectively.) The
polycrystalline nature of CFs and the presence of vast grain
*Corresponding author: Gao, C. ([email protected]) boundaries confine their properties compared with ideal graphite

1369-7021/ß 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). http://dx.doi.org/10.1016/
480 j.mattod.2015.06.009
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RESEARCH: Review
FIGURE 1
The precursor system of conventional carbon fibers and the new species including CNT and graphene fibers. Oxidization crosslinking and pyrolysis (and/or
graphitization) are employed to fabricate conventional CFs from cellulose, PAN and mesophase pitch precursors. The polycrystalline graphitic structure of
CFs is generated from these precursor macromolecules. By contrast, CNT fibers and graphene fibers are fabricated from individual carbon nanotubes and
graphene sheets, by a well-controlled macroscopic assembly method.

whiskers. This discrepancy is extremely hard to overcome because high expectations for the combined performances of their fibers to
all conventional CFs are fabricated by the pyrolysis of organic catch up and even exceed those of conventional CFs.
precursors, which inevitably generates polycrystalline graphitic CNT fibers can be fabricated by two methods; wet-spinning of
structures. In this context, great hope for new carbonaceous fibers CNT fluids or dry-spinning of CNT forests/cotton. Dry-spun CNT
that can surmount the limitations of conventional CFs has risen fibers generally have superior properties to wet-spun ones. To date,
from striking developments in the nanotechnology of carbon considerable efforts have yielded materials with combined prop-
allotropes, particularly from the discovery of carbon nanotubes erties comparable to those of CFs [15–18]. More impressive are
(CNT) in 1991 [10] and more recently graphene [11]. their rich functionalities, which already exceed conventional CFs.
CNT and graphene are one- and two-dimensional independent These advances have been summarized in many reviews that
carbon crystals, respectively, with long-range order up to the readers can refer to [15–17], so it is unnecessary to repeat them
millimeter scale. Because of the intrinsic covalent connection of further here.
sp2-hybridized carbon atoms, these two carbon crystals have ex- Since its initial development in 2011, graphene fiber (GF) has
tremely high mechanical strength, up to 130 GPa tensile strength become another promising carbonaceous fiber [19]. In this review,
and 1.1 TPa elastic modulus in the case of graphene, together with we mainly focus on newly sprouted GFs, describing their concept,
the valuable flexibility to accommodate deformation and tran- strategies of fabrication, structural attributes, mechanical proper-
scendental conductivity for electrical current and thermal flow ties and functionalities. A tentative prospect in the vicinity of GFs
[10–14]. Both CNT and graphene are possibly perfect building is also presented. We hope that this review provides a comprehen-
blocks for new carbonaceous fibers. By contrast to the regeneration sive introduction to GFs and, attracts more efforts to achieve
of the graphitic structure in the case of conventional CFs, the further progress in this new fiber species.
fabrication of new CNT and graphene fibers should rely on the
‘‘bottom-up assembly’’ concept to fashion individual building The new concept of GFs
blocks into an ordered state with atomic precision (Fig. 1). More In 2004, a significant experiment based on an extremely simple
importantly, the superior properties of CNT and graphene create principle, by Novelsov and Geim et al., announced the existence of

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graphene as the first freestanding 2D crystal [11]. Since then, engineered into macroscopic fibers, the extremely long-range
graphene has become one of the most important nanomaterials covalent crystalline nature is able to eliminate grain boundaries
and has attracted worldwide attention in fundamental condensed in the lateral direction to the utmost extent, which may bring
matter physics and materials extending from the nano to macro- about a breakthrough in the limitations of CFs.
scopic scale [12–14]. Graphene has extraordinary mechanical
properties, including a record tensile strength (130 GPa), elastic Strategies to fabricate GFs from graphite
modulus (1.1 TPa) and notable flexibility, and excellent electronic The building block of 2D topological graphene has extreme asym-
transport performances such as extremely high electric conduc- metry in its structure and properties, and its attractive mechanical
tivity (108 S/m), carrier mobility (200,000 cm2/V s) and ampacity and electronic attributes are in the planar direction (note that,
(1–2 GA/cm2). Other attractive properties of graphene encompass although we acknowledge the existence of graphene ribbons and
RESEARCH: Review

its high thermal conductivity (5000 W/m K), good stability against quantum dots, in this review, graphene means graphene sheets
chemicals and high temperatures, atomic thickness and valuable unless specifically stated otherwise). Making GFs from graphene
others. These recent advances have renovated the understanding building blocks is actually a process of regularly aligning graphene
of graphitic materials, together with their fabrication. For exam- sheets continuously in a uniaxial direction along which the asym-
ple, starting from solvated graphenes, graphene films/papers can metrical merits of graphene are translated into macroscopic prop-
be easily fabricated by many sophisticated solution-processing erties [23]. Because of the unmeltable nature of graphene, it is
methods and they exhibited many favorable properties in me- inconceivable to process graphene into neat fibers by the melt
chanics and electronics. Graphene papers are much stronger than spinning processes for some polymeric fibers such as nylon. In
commercial graphite die-cast foils [20,21]. Additionally, graphene addition, the lack of entanglement of 2D graphene also excludes
gave a fresh concept for the field of 3D frameworks. A typical the throwing method employed in ancient spinning for cotton
example is graphene aerogel, which is created by bridging these threads and dry-spinning used to make CNT fibers from CNT
thinnest building blocks and exhibits the extremely low density of aligned forests or cottons. Thus, the production of GF must utilize
a gas but in a solid state [22]. the strategy of solution assembly, which resembles the wet-spin-
As discussed above, the outstanding performances of conven- ning of polymeric fibers such as Kevlar and CNT fibers.
tional CFs are primarily because of the interior graphite crystallites To fabricate GF in a continuous manner and achieve sufficiently
consisting of turbostratically interconnected graphene. In their high quality further, there are three prerequisites that must be
established structural model, the size (width La and thickness Lc) fulfilled.
of graphite crystallites together with their alignment and interac- (i) Scalable synthesis of solution-processable graphene. Graphite,
tion play a key role in their performance (Fig. 2). However, further whether mineral or synthetic, is an abundant source of
improvement in their combined performance is confined by their graphene that can be commercially obtained in tons;
inherent polycrystalline nature of limited size and faulty align- different from chemically synthetic methods to produce
ment. Graphene sheets are actually 2D carbon monocrystals with a graphene in large area such as chemical vapor deposition
lateral size extending from dozens of microns, even to sub-milli- (CVD) which is especially suitable for electronic devices. The
meters, far larger than the size (smaller than 20 nm) of the gra- huge mass of graphene obtained from graphite is significant
phene substructure in the turbostratic graphite of CFs. Principally, to the scalability of graphene macroscopic materials, such as
the scaling of graphite crystallite size allows enhancement of composites, films, papers and certainly fibers [24]. To
the combined performance of fibers. Provided that graphene is circumvent the poor dispersibility of pristine graphene in

FIGURE 2
Lamellar crystalline structural model of graphitic materials. The whole structure encompasses a two-level hierarchy: (a) lamellar graphite crystal platelets at
the nano or sub-micro scale. The orientation degree and inter-connection among these crystals platelets are critical to the performance of macroscopic
materials, including fibers, films and bulks; (b) lamellar graphene sheets consist of graphite crystals at the atomic scale, with characteristic parameters of
lateral width (La) and perpendicular thickness (Lc).

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common solvents, chemical functionalization has been multifunctionalities has been developed. Importantly, many
proposed to introduce functional groups onto graphene attempts have been made to understand the basic relationship
and render the functionalized graphene with good disper- between structure and properties. We now summarize these
sibility and resultant processability by fluid assembly advances in detail and describe the deduction of a perspective
[24–29]. for these new carbonaceous fibers.
(ii) Continuous regular alignment of graphene. The task of aligning
dispersive graphene into its continuous solid form can be Graphene LCs
divided to two stages: pre-alignment in the fluid state and the LCs of asymmetrical colloids and macromolecules with ordered
subsequent phase transformation to regular alignment in the structures and the fluid attribute are key to their fluid assembly for
solid state. In the frame of traditional lyotropic liquid crystals ordered structures and materials, typically exemplified by CNT

RESEARCH: Review
(LCs) of asymmetrical colloids [30], the combination of high and liquid crystalline polymers. The 2D topology of graphene
asymmetry and engineered high enough dispersibility of undoubtedly satisfies the basic asymmetrical structural factor
graphene determines the spontaneous formation of LCs with for the formation of LCs, whereas, the remaining challenge lies
orientational or positional orders, that is, the pre-alignment in its limited dispersibility that originates from its barren surface
in the fluid state. Subsequently, starting from graphene- with poor interaction with solvents. This dilemma can be resolved
based LCs, the wet-spinning process may be an optimal by either finding good solvents to directly exfoliate graphite and
choice to make continuous GFs. Similarly, tuning critical stabilize the resultant graphene, or using chemical modifications
control factors of the wet-spinning process should generate to weaken the interlayer van der Waals attractions, enhancing
the optimal alignment of graphene in the solid fibers. interactions with solvents and its dispersibility.
(iii) Re-engineering of bonds among graphene building blocks. The Some common organic solvents with surface energy similar to
relatively weak van der Waals interactions between graphene that of pristine graphene (such as dimethylformamide and N-
sheets make graphite a popular lubricant and enable the methylpyrrolidinone) can exfoliate graphene from graphite with
exfoliation of graphene. Conversely, they become the weak the aid of sonication, but are only stable at very low concentrations
points that confine the enhancement of the performance of (typically far lower than 1 mg/mL) and only for small graphene
assembled graphene materials. Thus, beyond the simple with lateral sizes in the submicron range [31]. To date, chlorosul-
creation of GF, the re-engineering of the bonding among fonic acid, a good solvent for CNT, is the only reported good
graphene building blocks is necessary to optimize GF solvent that can directly solve graphite into graphene in a sponta-
performances, which is critical to push GF to a high level neous manner (Fig. 4A). This super acid strongly protonates
comparable to conventional CFs and CNT fibers. graphite and the resultant negatively charged graphene remains
To fabricate GF from graphite, the ‘‘graphene LC-wet-spinning’’ stable in it at high concentrations of up to 20 mg/mL. The obser-
system has been established in recent years and is becoming a vation of birefringence of graphite-chlorosulfonic acid dispersion
reliable method to obtain continuous GFs as monofilaments, tows indicated the formation of graphene LCs [32]. Deduced by a
and yarns (Fig. 3). A series of GFs with high performances and similar principle, graphene salts synthesized from alkali metal

FIGURE 3
The road from graphite to GFs. In the first step, graphite crystals (a) are exfoliated to individual graphene sheets, usually by chemical modification. The
modified graphene sheets form liquid crystals in solvents with orientational or positional order (b). In the second step, wet-spinning assembly is employed
to make continuous graphene fibers (c) from these graphene-based liquid crystals, which transform orders from the fluid state to orders in the solid state.

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FIGURE 4
Liquid crystalline system of graphene and modified graphenes. (a) Liquid crystal of pristine graphene in super acid. Graphite can simultaneously dissolve in
super acid, and is exfoliated into single layer graphenes that form nematic mesophase as the concentration increases. (b) GO liquid crystal. The rich
functional groups make GO dispersible in water and polar organic solvents. GO performed rich mesophases with structural orders (the middle panel)
depending on the concentration and size distribution of GO sheets, including nematic (optical texture in right panel), lamellar and chiral ones. (c) Modified
graphene liquid crystals, including linear, hyperbranched polymers and, ligand modified graphenes.

or halogen intercalated graphite could be another feasible protocol such as DMF and NMP. In principle, the remaining 2D topology of
to make pristine graphene LCs in more hazardous surroundings GO together with its excellent dispersibility renders the spontane-
than superacid [32–35]. ous formation of LCs. The question for GO LCs received affirma-
Alternatively, chemical functionalization can effectively en- tive answers sympathetically until 2011 [23,37–41]. The first
hance the stable dispersibility of graphene [24]. Graphene oxide several reports on GO LCs outlined their basic notion (Fig. 4b):
(GO), a single layer of graphite oxide crystal, has become one of the (1) The phase transition from isotropic to mesophases is depen-
most widely accessible chemical precursors to graphene and has dent on the dispersive concentration and the aspect ratio of GO,
been employed in many applications, especially those with have a approximately conforming to the classic Onsager’s LC theory,
high mass requirement [36]. Owing to the plentiful oxygen-con- more specifically, higher aspect ratio means lower critical concen-
taining functional groups on its surface, GO has versatile disper- tration at which LC forms. (2) GO LCs possess ordered structures
sibility not only in water but also in many polar organic solvents but with disclinations, including orientational order in the

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nematic phase, quasi-positional order in the lamellar phase, and incompatible with GO sheets, such as aqueous solutions with
twist-lamellar structure in chiral mesophase. acids, bases, diverse salts that screen the electrostatic repulsion
Aside from the utility of GO LCs in the fabrication of ordered of GO sheets [55], and some organic solvents such as ethyl acetate
structures, GO LCs also exhibited interesting optical responses. with a poor capability to disperse GO sheets [56–58] were chosen.
The GO chiral mesophase exhibited strong optical activity and After solvent exchange, GO liquid crystalline gel fibers formed
absorbed circularly polarized light with specific chirality [23]. Li with maintaining the structural integrity by hydrogen bonding
et al. reported that GO LCs behaved as photonic crystals and between GO sheets or ions crosslinking. During the drying section,
reflected light with a specific wavelength depending on their GO gel fibers underwent shrinkage in the radial direction. The
concentration [42]. Shen et al. found that dilute GO dispersions interior GO sheets folded in the same direction but remained
possessed the largest Kerr coefficient in molecular LCs, and the aligned along the fiber axis. In the last section, chemical or thermal

RESEARCH: Review
alignment can be controlled by a weak electric field, which may reduction was employed to transform GO fibers to GFs, which
makes GO LCs useful as electro-optical devices [43]. allowed the optimal expression of the outstanding mechanical,
The lability of GO suggests its preferred usage as a reliable electronic, and thermal merits of graphene in the macroscopic
chemical precursor of graphene. Generally, in real-world applica- performances and functionalities of GFs.
tions, GO should be converted into graphene by chemical and Recent efforts have provided qualitative understanding of the
thermal reductions to eliminate functional groups and restore its wet-spinning of GFs. Coagulation baths were chosen depending
conjugated structure [44,45]. To avoid irreversible precipitation, on the solvents of GO LC dopes, for example, ethanol/water
chemical modifications are employed to keep good dispersibility. mixture with Ca2+ ions was suitable for aqueous dopes [55] and
Through modifications, once graphene keeps stable when dis- ethyl acetate was used for DMF-based dopes [56–58]. The stretch-
persed in solvents at a high enough concentration, LCs should ing operation is believed to be important to achieve high align-
form. To date, macromolecules with linear and hyperbranched ment of GO sheets and to help the formation of compact structures
molecular architectures have been grafted onto reduced graphene, [57]. To obtain the highly compact structure of the final GFs,
and, these effectively modified graphenes with good dispersibility chemical reduction by hydriodic acid was found to be better than
exhibited rich liquid crystalline behaviors as in the case of GO other chemical reagents such as hydrazine hydrate and sodium
(Fig. 4c) [46–51]. Similarly, surfactant-wrapped chemically re- borohydride, which generate porosity and reduce mechanical
duced graphene was prone to form LCs as its dispersive concen- performances [59,60]. Based on these qualitative understandings,
tration increased [52]. forthcoming systematic investigations are needed to establish a
Graphene-based mesophases can be seemed as liquid crystalline sophisticated wet-spinning process for GFs with high enough
hosts of versatile guests from solvated nanoparticles such as CNT, quality. We should quantitatively connect the experimental pa-
metallic nanowires, and quantum dots, to polymers with linear or rameters (graphene size and distribution, dope concentrations,
hyperbranched molecular architectures [23]. As expected, these spinning rate, coagulation time, diffusion coefficient, stretching
multicomponent graphene-based LCs are useful to fabricate hy- ratio, collecting rate, and solidification temperatures, among
bridized graphene-based materials with ordered structure, just others) with the structural parameters (alignment degree, density,
resembling the significance of neat graphene LCs for neat gra- layered grain size, among others) to obtain the performance of
phene ordered materials. GFs.
Besides wet-spinning, there have emerged some alternative
Wet-spinning process for GFs methods for the fabrication of GFs from GO dispersions [61–74].
The transition from LCs to fibers is a familiar concept in polymer For example, Dong et al. proposed a dimensionally confined
science and technology. Even pitch-based CFs are melt-spun from hydrothermal strategy for GFs [66]. In their report, GO disper-
pitch mesophases. In this context, the discovery of graphene- sions in pipelines were subjected to a hydrothermal step and
based LCs points to the possibility of fabricating continuous were extruded to get GF followed by drying and further thermal
GFs by the wet-spinning method. Our first attempt in 2011 dem- annealing. Hu et al. developed a metal-wire templated assembly
onstrated the practicability of wet-spinning GF from GO LCs [19]. method to make graphene microtubes, and demonstrated the
The experiment outlined the following basic processes in obtain- possibility of designing a janus structure that consists of differ-
ing wet-spun GFs: (1) extruding LCs into coagulation baths with ent functionalizations on the inside and outside walls [67]. Jang
uniaxial flow; (2) phase transition by coagulation with solvents et al. used an electrophoretic self-assembly method to draw
exchange; (3) solidification by evaporating solvent; and (4) chem- fibers from dispersions of graphene nanoribbons [68]. Chemical
ical and/or thermal reduction. The whole process is depicted in reduction-induced self-assembly was also used to make GFs from
Fig. 5. GO hydrogel fibers [69,70]. Despite the different concrete opera-
In the first section, extrusion forces GO LC dopes through tions, these alternative methods have a similar principle to the
spinning pipes with uniaxial flow. Importantly, this common wet-spinning process, including the use of a relatively high
process unifies the random alignment of GO LCs in 3D space concentration of GO feed dispersions (that may imply the
along the flow direction and fashions GO sheets oriented along the formation of LCs) and continuous flow to ensure the continu-
resultant fiber axis [53,54]. SEM characterizations showed distinct ous alignment of graphene sheets along the fiber axis.
differences in GO LCs between the still and flowing states. The
flow-induced alignment of GO dispersions revealed their rheolog- Neat GF
ical attribute as typical shear flow. In the second section, coagula- With the aim of a new CF in mind, neat GF has been continuously
tion baths using solutions compatible with solvents of GO LCs but fabricated by wet-spinning together with chemical and/or thermal

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FIGURE 5
Liquid crystal-based wet-spinning for GF. (a) The schematic wet-spinning process from GO liquid crystals to fibers in a continuous manner. (b) The structural
evolution in the spinning process, which indicates the enhanced alignment process under uniaxial flow during the spinning (Section I), from the powder GO
LC with different orientation ordering to the regular alignment of the flowing GO LC dope, GO LC gel fibers (Section II) and final dried GO fibers (Section III).
The red arrows denote direct vectors.

reduction when employing neat GO LCs as raw materials radial direction (Fig. 6). Graphene sheets with a folding morphol-
[19,53,55–57,66]. The chemical composition of GF primarily con- ogy are well-aligned along the fiber axis, and their lateral size and
sists of carbon, oxygen and affiliated hydrogen elements. Depend- degree of alignment play key roles in the optimal expression of
ing on the reduction extent, the carbon content of neat GF ranges expected properties and, as a result, guide the improvement of the
from 80% to 99%. Chemical reduction by reagents such as hydra- performance. After the first GF was made of GO and corresponding
zine hydrate and hydriodic acid usually give around 80% carbon, graphene sheets with lateral sizes of several microns, the availabil-
and thermal annealing especially at high temperature above 8008C ity of GO with giant size (GGO) of up to one hundred microns has
raises the value up to 95%, approaching that of conventional CFs rendered the creation of GF from these giant materials, by wet-
[53,66]. spinning GGO LCs [39,41]. Several experiments in Refs. [55–58]
Neat GF consists of well-aligned graphene sheets only along the confirmed this trend: the enlargement of graphene lateral size
fiber axis. Its structural order involves two correlated aspects: the promoted the combined properties, not only in mechanical
alignment along the fiber axis and the layered attribute in the fiber strength but also in electronic functionalities. GFs made from

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FIGURE 6
Microstructural attributes of GF. Graphene sheets are well-aligned along the fiber axis, as demonstrated in the 2D XRD pattern (a, unpublished result). (b) On
the GF surface, wrinkles that originate from radial shrinkage during drying are well-aligned along the fiber axis. (c) Lamellar structure of graphene-assembled
bricks on the section. (d) Lamellar graphene sheets at atomic scale identified at the fracture tips.

GGO exhibited higher mechanical strength (0.5 GPa) and electri- highest bond energy are needed to bridge graphene sheets that will
cal conductivity (4.1  104 S/m), superior to those (140 MPa and enhance the properties of GFs. This extreme protocol does not
2.5  104 S/m) of GF spun from GO LC respectively. As to the mean the hard transformation of graphite into diamond; it can
alignment, the stretching operation in the whole wet-spinning actually be achieved by introducing multifunction binders that
process has been shown to be important and raised the elastic will couple graphene sheets together by virtue of versatile chemi-
modulus of GF up to 47 GPa [57]. cal reactions with basic units of graphene.
The thickness of graphite crystals that are re-assembled from
individual graphene sheets is essential as well (observed in the Graphene composite fibers and hybridized GFs
fracture tips), which is reflected in the compactness or density of In addition to fabricating neat GF, the fluid assembly of graphene
GF. Recent efforts have mainly been devoted to the control over into fibers provides the potential to tune components and struc-
the wet-spinning and the choice of reduction methods. Appropri- tures of GFs (also called graphene-based fibers) by wet-spinning
ate coagulation baths such as ethanol/water calcium ion solutions graphene-based LCs. In practical terms, GO LCs have been used as
and stretching were efficient to get compact structure of GFs, but an ordered matrix to host many guests ranging from macromole-
their density of lower than 1 g/cm3 is still much lower than that cules with either linear or hyperbranched topology to nanoparti-
(1.7–1.9 g/cm3) of conventional CFs, not to mention that (2.2 g/ cles such as 0D nanodots, 1D carbon nanotubes and nanowires
cm3) of ideal graphite crystals [55]. Possibly profiting from the (Fig. 7). The family of graphene-based fibers is growing, and mainly
sophisticated control system in wet-spinning industrial technolo- encompasses two categories: biomimetic graphene composite
gy and underlying theoretical understanding, the control system fibers and hybridized GFs.
of wet-spinning of GFs will be established in the near future.
During reduction, the elimination of oxygen functional groups Biomimetic graphene composite fibers
is prone to cause the exhaust of gas, which inevitably undermines As graphene has developed into an advanced carbon nanomaterial,
the integrated structure and results in GFs with pores, cracks and it is logical to add graphene to polymeric composites either in bulks
poor performance. For this reason, some reductants such as HI and or as fibers to enhance their performance and implement function-
vitamin A were testified more suitable for GF than other common alities. Example includes graphene-nylon fibers [29], graphene-
reductants for graphene powders such as N2H4 and NaBH4 [49,55]. CNT-PVA fibers [75] and graphene-cellulose fibers [76]. Biomimetic
In addition to these structural factors, the interlayer interaction graphene composite fibers are distinct from traditional composites;
among graphene sheets is essential at the atomic scale to dominate they possess extremely high graphene content, typically above 50%
the performance of neat GFs. For example, multi-valent Ca2+ ions even exceeding 90%, far more than that (usually below 1–5%) of
can bridge reduced graphene sheets by forming coordinate bonds traditional species. The overwhelming amount of 2D graphene in
with residual oxygen groups, and the introduction of these ions composite fibers creates their laminated structure that particularly
brought a remarkable enhancement by 65–100% in the mechan- resembles the ‘‘brick and mortar’’ layered attribute of nacre [77],
ical strength of GFs [55,56]. Ultimately, covalent links with the which is the origin of the ‘‘biomimetic’’ prefix. In these nacre-like

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FIGURE 7
Composite and hybridized GFs. Many guests, such as linear and hyperbranched polymers, nano clusters, nano wires/rods, 2D crystals and ions can be
introduced into GFs. The graphene composites polymer fibers have nacre-like layered structures and high mechanical strength.

fibers, 2D graphene behaves as bricks and the interlayer macromo- functions. From a mechanical perspective, the interlayer polymer-
lecules as mortar, and their mechanical behavior conforms to the ic ‘‘mortar’’ binds graphene sheets together by van der Waals
classical ‘‘tension-shear’’ model of nacre-like materials. interaction, hydrogen-bonding, or covalent links, which increase
Two strategies have been developed to fabricate biomimetic the mechanical strength. For example, the multifunctional groups
graphene fibers continuously based on the state of the guest of hyperbranched polymers allow the hydrogen-bond array to
components, as follows: (1) host–guest LC strategy in which guest tightly connect graphene sheets and the fibers exhibit strength
components are isolated and (2) building-block approach in which up to 650 MPa, although the mortar bulk alone is extremely weak
guests are attached on graphene to form independently hybridized in strength. The highest strength achieved has already exceeded
graphene building blocks. In the first strategy, polymeric guests that of natural nacre and previously fabricated biomimetic nacre-
were homogenously mixed with GO in water or other solvents to like materials. In terms of functionalities, biomimetic graphene
form GO-based composite LCs as dopes for the wet-spinning of the fibers possess good electrical conductivity of approximately
biomimetic fibers. The ever-reported polymeric guests included 5  103 S/m because of the high content of graphene, which is
linear polymers such as PVA and hyperbranched ones exemplified several orders of magnitude higher than that of conventional
by hyperbranched polyglycidol (HPG) [46,49]. In the second ap- graphene-based composites. In addition, the compact layered
proach, polymer guests were grafted onto graphene especially structure allows these fibers to resist chemical erosion by strong
through covalent bonds and rendered sufficient dispersibility to acids and bases.
form LCs for the wet-spinning of fibers. This approach has gener-
ated a rich family of biomimetic graphene fibers that combine Hybridized GFs
linear polymers such as PAN, PVA and hyperbranched ones Through two similar strategies for biomimetic graphene compos-
[47,48,50]. Importantly, the wet-spinning method for graphene ite fibers, hybridized GFs with other versatile nano-objects with
composite fibers actually yielded the continuous fabrication of rich functionalities have been fabricated as well [58,66,78–82].
biomimetic nacre-like materials, which was previously confined to These nano-guests have included 1D metallic nanowires and
a limited size of centimeters. CNTs, 0D quantum dots and nanoparticles, and extend to 2D
Merited from their ‘‘brick-mortar’’ structure, biomimetic gra- nano-platelets such as transition-metal dichalcogenides and 2D
phene composite fibers exhibited many favorable properties and crystals. The introduction of rich guests is able to enhance or add

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many functionalities in GFs. For example, the binary fiber of the alignment of graphene sheets, and raised the mechanical
graphene and 1D Ag nanowires greatly improved electrical con- performance, especially the ultimate strength of GF, up to
ductivity up to 9.3  104 S/m, promising for use as a lightweight 0.5 GPa. Stretching also promoted the compactness of graphene
conductor [58]. Incorporation of paramagnetic Fe3O4 nanoparti- laminates and therefore the elastic modulus to 47 GPa. The en-
cles imparted magnetism to GF that can be actuated by an external largement of the lateral size of graphene sheets has been confirmed
magnetic field [66,79]. GFs hosted with CNTs showed more favor- to effectively diminish defective grain boundaries. To enhance the
able uses in supercapacitors than neat GFs because of the syner- interlayer interaction on the atomic scale, Hu et al. introduced
gistic effect between graphene sheets and CNTs [80,81]. hyperbranched molecules with multifunctional groups into inter-
Alternatively, post-hybridization of neat GFs can improve their layer galleries, and their biomimetic fibers with hydrogen bonding
performances as well. For instance, the intercalation of electron arrays exhibit mechanical strength of 550 MPa, which was fur-

RESEARCH: Review
donors (alkali and rare earth metals) or acceptors (acids and metal ther increased to 650 MPa after chemical crosslinking [49]. Re-
halides) should substantially increase the electrical conductivity of cently, our lab has achieved a strength of 1.1–1.2 GPa by a
GF, similar to graphite intercalated compounds [83]. combination of methods to increase the alignment of graphene
sheets and the compactness of GFs (unpublished results). All of
Combined properties of GFs these rapid advances justify the thrilling prospect of GF as a new
Arising from the outstanding properties of graphene building high-performance carbonaceous fiber.
blocks, it is expected that GF should possess an outstanding
simultaneous combination of properties in mechanical, electronic Electronic performance
and thermal aspects, through a great deal of effort on GFs (Table 1). Another attractive merit of GFs is their excellent electronic prop-
Beyond its creation, the mission to enhance the intrinsic proper- erties, such as high electrical conductivity and current capacity. In
ties of GFs has advanced quickly in recent years. the preparative system of GO LC-spinning to produce GFs, post-
reduction has been designed to circumvent the deficit in electronic
Mechanical properties quality that is accompanied by good processability of GO. Jalili
The first GF only had a tensile strength of approximately 140 MPa et al. proposed a mild reduction in coagulation baths of strong
at 5.8% breakage elongation, but had good flexibility to make alkali base (NaOH) and achieved electrical conductivity of 250 S/m
tight knots [19]. The huge gap between the mechanical strengths [56]. More intensive reduction was obtained using HI or HBr,
of GFs and the constituent graphene sheets must be bridged. In the which enhanced the conductivity to 4.1  104 S/m [55]. Although
analysis of the structural characteristics of GFs, three strategies thermal annealing is more efficient than chemical reduction,
from atomic to macroscopic scales have been proposed to upgrade direct thermal annealing only yielded conductivity of
mechanical performance: (1) improving the alignment of gra- (1  103 S/m) [66], comparable to that by intense chemical re-
phene sheets along the fiber axis; (2) decreasing the structural duction. The underlying reasons may be that the carbon loss
defects that include sheets boundaries, voids and impurities; and during thermal annealing (the exhaust of carbon dioxide) can
(3) enhancing the interlayer interaction of the constituent gra- undermine the compactness of GFs. Thus, the combination of
phene sheets by either covalent or noncovalent bonds. chemical reduction and thermal annealing, even graphitization,
Guided by these ideas, the mechanical strength of GF has risen should improve the conductivity of GFs to the level (105–106 S/m)
to the GPa range in a stepwise fashion after only 3 years. Stretching that has been achieved in graphene films [84], already superior to
during the wet-spinning process has been employed to enhance that of conventional CFs.

TABLE 1
The mechanical properties of neat GFs and biomimetic graphene composite fibers.
Species Tensile strength (MPa) Young’s modulus (GPa) Failure elongation (%) Electrical conductivity (S/m) Ref.
GOF 102 5.4 6.8–10.1 – [19]
GF 140 7.7 5.8 2.5  104 [19]
GF-1 (CaCl2) 364.4 11.2 6.8 – [55]
412  30 20.1  2.1 3.2 – [56]
214  38 47  8.1 0.61  0.1 – [57]
GF-2 (CaCl2) 501.5 11.2 6.7 4.1  104 [55]
GF-Ag 300 9.5 5.5 9.3  104 [58]
Graphene-HPG fiber 555 15.9 3.5–5.6 5.2  103 [49]
Graphene-PAN fiber 452  24 8.31  0.56 4.5–5.4 – [50]
Graphene-PVA fiber 162 17.1 1.7–3.0 1.3  10 2 [46]
Graphene-PGMA fiber 500 18.8 3.0 186 [48]
CNT fibers Wet-spun 1000 120 1.4 2.9  105 [18]
Dry-spun 1300–8800 78–397 4–8 5  105 [17]
Carbon fibers PAN 3530–7000 230–290 1.5–2.4 5.8–7.1  104 [4]
Pitch 2740–4700 343–588 0.7–1.4 0.9–1.4  105
‘‘ ’’ No available data.

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As the restoration of the graphene structure improves, we are benchmark metals can be realized by wet-spinning GO-based
able to further improve the conductivity through molecular dop- LCs with nanoparticles of these metals, and this protocol has been
ing to increase carrier density or mixing with other benchmark used to fabricate Ag nanowire-hybridized GFs [57].
metals such as silver, copper and gold. Doping with Ag ions has
pushed the conductivity to 9.4  104 S/m, and other dopants Potential functional uses of GFs
(alkali metals, acids) may also possibly work well, as in the Because GFs possess many of the outstanding attributes of gra-
case of graphene transparent electrodes [85]. GFs mixed with phene, they should have many functionalities that can be used in a
RESEARCH: Review

FIGURE 8
Functional applications of GF. The high conductivity of GFs makes them good candidates for lightweight electrical conductors such as cables and flexible
wires. By tuning the structure of GF and introducing functional guests, GF can perform rich behaviors of actuation, such as rotation motor and remote
actuator. Additionally, GFs can be taken as wearable flexible textiles to be used in supercapacitors and solar cells.

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Materials Today  Volume 18, Number 9  November 2015 RESEARCH

wide variety of functional applications. Apart from the important whole GF to bend or curl reversibly [94]. For a torsional motor,
goal of upgrading the intrinsic properties of GF, considerable effort they rotated GO gel fibers in the radial direction during the drying
has been devoted to exploiting their functional uses in products, process and obtained GO fibers with helically twisted wrinkles on
such as electrical conductors, supercapacitors, actuators and solar the surface. The twisted GO fibers are able to reversibly respond to
cells, all of which indicated the rich functionalities of GFs that moisture by rotation, behaving like a typical rotational motor [95].
surpass those of conventional CFs (Fig. 8).
Comparison between graphene fibers and carbon fibers
Lightweight electrical conductors As a new member of carbonaceous fiber, graphene fibers (especially
Highly conductive lightweight GFs are good candidates for wires neat) are significantly different from conventional carbon fibers.
and cables to carry heavy current. Another advantage of GFs is First, in the aspect of precursor, GFs are prepared from graphite,

RESEARCH: Review
their valuable flexibility; they can be twisted into tight knots whereas, conventional CFs can be made from natural or synthetic
without breaking, which is not possible for conventional CFs. polymers and small pitch molecules. Second, in terms of fabrica-
As described in Ref. [52], chemical reduced GFs can be used as tion, GFs can be continuously fabricated by the wet-spinning of
conductors to connect prototype devices and batteries. In Ref. [57], solvated graphene derivatives, while a combination of spinning,
Ag-doping enhanced the electrical conductivity and only mini- oxidization and thermal pyrolysis is used in the case of conven-
mally affected the mechanical strength and flexibility of GFs. tional CFs. Third, the atomic to micro scale structure of GFs is
Through the ‘‘pre-stretching and buckling’’ strategy, flexible Ag- distinct from that of conventional CFs. GFs consist of well-aligned
doped GFs were employed to construct stretchable circuits on graphene sheets along the fiber axis, and basic units of CFs are
rubber substrate, and the resistance remained invariable during nano-graphite crystals that are interconnected. The lateral crystal
50 cycles of stretching-relaxation. The breakdown current density size of graphene sheets is much larger than that of CFs, by three
(ampacity) of this Ag-doped GF was 7.1  107 A/m2, which should orders of magnitude at the most, which can make some GF
be greatly improved by further thermal annealing and graphitiza- properties superior to those of CFs controlled by grain boundaries,
tion for practical uses. such as electrical conductivity and thermal conductivity.

Yarn supercapacitors and solar cells Conclusions and perspectives

In view of the prospect of using graphene-based films and frame- Graphene fiber is a new high performance carbonaceous fiber with
works as chemical supercapacitors for energy storage, graphene- rich functionalities. Its creation significantly demonstrates a novel
based fibers have been considered as having potential for becom- protocol to fabricate carbonaceous fibers just from mineral graph-
ing useful supercapacitor textiles that are flexible and can be ite. The preparative system of GF has been established in recent
knitted into wearable devices [78,85–93]. The capacitance of years, which encompasses reliable synthesis of solvated graphenes,
GFs was assessed at approximately 100 F/g, and the best result formation of liquid crystals and wet-spinning for neat or compos-
ever reported is 409 F/g because of the highly porous structure of ite GFs. A basic understanding of the structure and properties of
the spun fibers [83]. The introduction of CNTs, single or multi- GFs has been established preliminarily, and the critical control
walled, created extra hierarchical pores in GFs and enhanced their parameters have also been concluded, including, the lateral size of
capacitance from 100 F/cm3 to 300 F/cm3 in the case of single- graphene building blocks, the alignment thereof, and the interac-
walled CNTs [81]. Other ingredients such as oxides (MnO2 and tion between them. Guided by these concepts, the combined
Bi2O3) and conductive polymers (polypyrrole and polyaniline) properties of GFs have been rapidly promoted to a GPa level of
also supplemented their pseudo capacitance to the performance tensile strength and electrical conductivity comparable to conven-
of hybridized GFs [78,81–93]. Using a coaxial wet-spinning meth- tional CFs, promising a thrilling trend toward higher levels on par
od, polyelectrolyte-wrapped graphene/CNT core-sheath fibers with or even exceeding CFs.
were designed as safe electrode textiles for direct use in yarn GFs have demonstrated much more impressive rich functional
supercapacitors. In addition to their high capacitance (up to uses than conventional CFs. These potential applications involved
269 mF/cm2) and energy density (3.84 mWh/cm2), the yarn super- lightweight conductive cables and wires, knittable supercapacitors
capacitor fibers were flexible enough to be interwoven into wear- with high energy density, wearable solar cell textiles, environmen-
able cloth supercapacitors [90]. As for functional textiles that can tally responsive actuators, micro motors and so on. The functional
generate energy, GFs have been employed to construct photovol- application of GFs could become pioneering commercial products
taic wire devices that attained a high-energy conversion efficiency used in our daily lives, as a typical 1D delegate among forthcoming
of 8.45% [91] These energy flexible devices of GFs can be integrated batches of graphene macroscopic materials.
into conventional textile technology for many functional applica- The recent advances in GFs have urged us to address the central
tions. issue, that is, to upgrade its combined performance, mainly me-
chanical strength and electrical/thermal conductivities. In terms
Smart actuators of mechanics, more regular alignment and more compact micro-
Qu’s group established a series of smart actuators of GFs, such as structure can be achieved by the optimization of the spinning
self-driven GF tubes, moisture actuators, torsional motors and process parameters, such as stretching ratio, spinning velocity and
magnetic-driven springs, by virtue of the design of their structures so on. In the atomic aspect, the enhancement of interlayer action
[94–97]. They used lasers to reduce only one side of GO fibers and between graphene sheets should increase the mechanical strength
obtained GFs with asymmetrically hydrophilic attributes. The of GF, either by introducing external crosslinking reagents into the
remaining GO part was responsive to moisture and drove the interlayer gallery or by partly transforming graphene sheets into

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RESEARCH: Review

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