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Reviews in Advanced Sciences and Engineering
Vol. 3, pp. 48–65, 2014
(www.aspbs.com/rase)

Electrical Conductivity of Graphene/Polymer

Nanocomposites
Jizhen Zhang, Jianguo Qiu, and Jingquan Liu∗
School of Chemistry, Chemical and Environmental Engineering; Laboratory of Fiber Materials and Modern Textile,
The Growing Base for State Key Laboratory, Qingdao University, Qingdao 266071, China

ABSTRACT
Graphene is a promising material for the preparation of graphene/polymer composites with enhanced electrical,
mechanical, thermal, and gas barrier properties at extremely low loading ratio due to its unique structure. Not
only do the properties of graphene and polymer complement each other, the new properties may also emerge
due to the synergistic effect. The conductivity of the graphene/polymer composites can be tuned from 10−17
to 102 S m−1 , which not only depends on the quality of graphene and but also the polymers utilized. This
review describes the recent developments that are related to conductive graphene/polymer nanocomposites.
Different strategies for the preparation of such nanocomposites are described, including physical processing,
covalent bonding and specific affinity. Advantages and disadvantages of each method are also addressed.
Moreover, potential applications in the fields of electronic and photonic devices, clean energy, and sensors are
also presented.
KEYWORDS: Graphene, Graphene Oxide, Conductivity, Graphene/Polymer Composite, Surface Modifications.

CONTENTS number of applications such as sensors,15 catalysis

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . .....
2. Preparation of Conductive Graphene/Polymer
Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Physical Mixing . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Covalent Bonding . . . . . . . . . . . . . . . . . . . . . . .
2.3. Specific Affinity . . . . . . . . . . . . . . . . . . . . . . . .
3. The Electrical Properties of Graphene/Polymer
Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . .....
3.1. Electrical Percolation Threshold and Conductivity
of Graphene/Polymer Composites . . . . . . . . . . . . .
3.2. Conductivity Influencing Factors . . . . . . . . . . . . . .
4. Application of Conductive Nanocomposites . . . . . . . . . .
5. Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . .
References and Notes . . . . . . . . . . . . . . . . . . . . . . . .
1. INTRODUCTION
Graphene, a one-atom-thick 2-dimensional carbon nano-
structure, has evoked enormous interest since its debut
in 2004.1–4 Graphene’s unique structure endows it with
remarkable characteristics such as the electric field
effect,4
5 superlative mechanical strength,6 large specific
surface area,7
8 high transparency,9–11 and excellent ther-
mal conductivity.12–14 Based on these extraordinary prop-
erties, graphene already has been utilized for a great
∗
Author to whom correspondence should be addressed.
Email: jliu@qdu.edu.cn
Received: 31 August 2013
Accepted: 27 October 2013
48 fields,16 energy-storage devices,17 environmental fields,18
capacitors,19 transparent conductive films,10 and high-
. . . 50
frequency transistors.20
. . . 50
. . . 52 Graphene possesses high current carrying capacity
. . . 55 (up to 109 A cm−2  and high thermal conductivity
(up to 5000 W m−1 K−1 .21 Graphene’s highly conju-
57 gated 2D structure contributes to its excellent electrical
properties.22–24 In addition to its superb charge carrier
. . . 57
. . . 58
behavior, graphene also possesses excellent mechanical
. . . 59 strength, the breaking strength is 42 N m−1 and the
. . . 62 Young’s modulus is 1.0 TPa, indicating graphene is one of
. . . 62 the strongest material ever found.6
25 Most of these record
. . . 62 properties refer to a pristine material under somewhat ide-
alized conditions. However, in its applications various fac-
tors might affect the conductivity, such as interaction with
the underlying substrate during the measurement, struc-
ture defect, surface charge traps,26 interfacial phonons27
and substrate ripples.28 In reality, graphene needs to adapt
to the complex conditions that are dictated by specific
applications.29
The exploration of polymer nanocomposites has greatly
broadened the areas of materials science research.30–32
Owing to their unique properties and low cost, polymer
nanocomposites have become the candidate for numer-
ous potential applications in the automotive, aerospace,
construction and electronic industries. Nowadays, polymer
composite materials play an important role in high-tech
fields. In traditional composites, a high concentration of

48 Rev. Adv. Sci. Eng. 2014, Vol. 3, No. 1 2157-9121/2014/3/048/018 doi:10.1166/rase.2014.1052

Zhang et al. Electrical Conductivity of Graphene/Polymer Nanocomposites

conventional filling modifiers is essential for an ideal
performance. In the last decades, new members of car-
bon family showed impressive properties and provided
new fillers for polymer composites.33–35 Among carbon
nanostructures, graphene oxide (GO) and graphene have
attracted the greatest attention of sciences and industries.
Until now, bottom-up and top-down approaches are
two popular methods of producing graphene. Chemical
vapor deposition (CVD),36
37 arc discharge,38 epitaxial
growth on SiC,39
40 chemical conversion,41 reduction of
CO,42 and unzipping carbon nanotubes43–45 are included
in bottom-up processes. The graphene sheets produced by
bottom-up process are much pure and more attractive for
fundamental studies and electronic applications. However,
bottom-up process can not meet the need, as preparation of
graphene-based nanocomposites requires a large amount
of graphene sheets preferably with modifiable surface
structure. In general, the top-down approaches including
mechanical exfoliation,4 thermal deposition, oxidation of
graphite46 and liquid-phase exfoliation of graphite25
47–51
are frequently used to synthesize graphene. The Hummers
method is one of the most developed methods in lit-
erature and much suitable for large scale production.
However, this method consumes large quantity of detri-
mental strong acids (e.g., H2 SO4 , HNO3 , oxidants (e.g.,
KMnO4 , K2 S2 O8 , H2 O2  and the carcinogenic reductant
(hydrazine). Furthermore, graphene sheets produced via
oxidation–reduction approach are usually small in size and
retain many defects due to the harsh oxidation conditions
used. In addition, the reduction process gives relatively
hydrophobic graphene sheets, which tends to aggregate
irreversibly, which greatly hinder their production, storage
and processing.
Theoretical and experimental studies have indicated
that the single-layered graphene has extremely high sur-
face area, good conductivity and outstanding mechanical
strength indicating that graphene has great potential for
improving the mechanical, electrical, thermal, and gas bar-
rier properties of polymers. Moreover, graphene and poly-
mer complement each other to improve the performance of
composites. It is well-known that the conductivity of poly-
mer matrix can be dramatically improved when conductive

Jizhen Zhang received his bachelor in applied chemistry at Qingdao University, China, in
2012. He is currently a Master candidate under the supervision of Professor Jingquan Liu.
His current research interests include the preparation of graphene oxide and graphene and
their composite with other materials for the applications in energy storage and electronic
applications.

Jianguo Qiu received his Bachelor’s degree from Shandong Normal University in 2001.
After graduation, he obtained a lecture position at Qingdao University. He earned Master
degree from Shandong University in 2007. He has published more than 20 papers and
participated in a number of research and management projects. His current research interest
focuses on the preparation of nanomaterials.

Jingquan Liu received his bachelor from Shandong University in 1989. His master and
Ph.D. were obtained from the University of New South Wales (UNSW) in 1999 and 2004
respectively, where his Ph.D. was undertaken under the guidance of Professor Justin Good-
ing. In 2004 he worked as a CSIRO-UTS post-doctoral fellow prior to returning to UNSW
with Professor Tom Davis as a Vice-Chancellor’s Research Fellow in 2006. In 2010 he
took up a professorship at Qingdao University. He has co-authored over 75 peer-reviewed
research papers with more 3000 citations. His research interests focus on the synthesis of
various bio- and nano-hybrids of versatile polymeric architectures.

Rev. Adv. Sci. Eng., 3, 48–65, 2014 49

Electrical Conductivity of Graphene/Polymer Nanocomposites
nanoparticles are introduced into system. In order to
enhance the conductivity of polymer, graphite,52
53 car-
bon nanotube.54
55 and graphene have been introduced into
polymer matrix. Previous studies indicated an association
between the conductivity of composites and the spatial
distribution of fillers in the polymer. If the dispersion of
graphene is too poor to form networks, the composites can
not exhibit a good conductivity. However, owing to the
irreversible aggregation of graphene, an overdispersion of
the fillers may be unfavorable to achieve a high conduc-
tivity neither.56
57
Three main methods used to prepare graphene/polymer
composites are solution blending,34
58
59 in-situ poly-
merization,60
61 and melt compounding.62
63 Most com-
posites are prepared via relatively weak non-specific
interaction forces between graphene and polymers. On
the other hand, covalent linkages and specific affinities
between graphene-based filler and the supporting polymer
gradually draw people’s attention. In this review we focus
particularly on the electrical conductive graphene/polymer
composites. The methods for preparing graphene/polymer
composites, their electrical properties and the relevant
applications are also discussed.
2. PREPARATION OF CONDUCTIVE
GRAPHENE/POLYMER
NANOCOMPOSITES
2.1. Physical Mixing
2.1.1. Non-Covalent In Situ Polymerization
Non-covalent in situ polymerization technique provides
a very straightforward way to prepare graphene/polymer
nanocomposites. This method generally involves mixing
of graphene in monomer or a solution of monomer, fol-
lowed by in situ polymerization. This is a good strategy
to fabricate graphene/polymer composites with strong
interaction between graphene and polymer matrix. For
example, graphene/polyaniline (PANI) can be prepared in
two steps: (i) homogenous composites of GO and polyani-
line nanofibers were prepared by in situ polymerization of
aniline in a suspension of GO in acidic solution; (ii) the
GO/polyaniline composites were reduced by hydrazine.64
(Fig. 1) However, the PANI in the composites can also
be reduced from the highly conductive halfly oxidized
emeraldine base (EB) state to the reduced neutral leu-
coemeraldine (LB) state during the reduction process, so
reoxidation and reprotonation are necessary to recover
the conductive PANI structure after the reduction of GO.
A very high capacitance of 480 F g−1 at a current density
of 0.1 A g−1 was achieved. The research revealed that
high specific capacitance and good cycling stability can be
achieved either by doping chemically modified graphene
sheets with PANI or by doping the bulky PANIs with
graphene/GO. This approach has been used to produce
a variety of other composites, such as graphene/PS,61
graphene/PANI,64–66 graphene/polyurethane (PU),67
68
50
Zhang et al.
Fig. 1. Illustration of the process for preparation of graphene/PANI
composites. Reprinted with permission from [64], K. Zhang, et al., Chem.
Mater. 22, 1392 (2010). © 2010, American Chemistry Society.
graphene/poly(ethylene) (PE),69 graphene/Poly(methyl
methacrylate) (PMMA),70
71 graphene/PS,72 graphene/
nylon-6,73 graphene/poly(pyrrole) (PP)74 and CRGO/poly
(3,4-ethylenedioxythiophene) (PEDOT).75 In situ polymer-
ization can also be an efficient way to produce composites
with covalent bonding between the matrix and filler,
the relevant examples will be given in the following
grafting-from sections.
2.1.2. Solution Blending
Solution blending is a simple way to fabricate homo-
geneous graphene/polymer composites.76
77 According to
the Hummers method,78 GO is a layer material gen-
erally produced by the oxidation of graphite. Different
from pristine graphite and graphene, GO sheets are heav-
ily oxygenated, bearing hydroxyl and epoxide functional
groups on their surface, and carbonyl and carboxyl groups
located at the sheet edges.79
80 The presence of these func-
tional groups endows GO with strongly hydrophilia, which
allows graphite oxide to readily swell and disperse in
water and highly polar organic solvents.81–83 As a result,
it is convenient for GO to mix with different kinds of
polymers in solution.84–86 The dispersion of hydrophobic
graphene sheets in water without the assistance of dispers-
ing agents has generally been considered to be an insur-
mountable challenge.87 An efficient method to improve the
dispersion of graphene is blending polymer with GO and
subsequently in situ reduce GO to graphene. For exam-
ple, Stankovich and co-workers first prepared graphene/PS
nanocomposites by dispersing phenyl isocyanate modi-
fied GO into PS solution.7 A plot of the electrical con-
ductivity of graphene/PS composites versus a function
of filler volume fraction was shown in Figure 2. The
Rev. Adv. Sci. Eng., 3, 48–65, 2014
Zhang et al.
Fig. 2. Electrical conductivity of the graphene/PS composites versus
filler volume fraction. Main figure, composite conductivity, c , plotted
against filler volume fraction, . Right inset, logc plotted against log(–
c , where c is the percolation threshold. Solid lines in both graphs
are calculated conductivities based on the fitting (inset, log–log plot) of
the experimental data to the effective conductivity equation described in
the text. Fitted parameters were: t = 274 ± 020, f = 10492±052 S m−1
and c = 01 vol.%. Left inset: top and middle diagrams illustrated the
four-probe setup for in-plane and transverse measurements, respectively;
bottom diagram, one of the computed distributions of the current density
(contour lines) with local directions and magnitude (shown by arrows) in
a specimen for the following conditions-the sample thickness was twice
the electrode width and the gap between them, and the in-plane resistivity
was 10 times lower than the transverse resistivity. Reprinted with per-
mission from [7], S. Stankovich, et al., Nature 442, 282 (2006). © 2006,
Nature Publishing Group.
composites exhibited a typical percolation behavior after
GO/PS composites being treated by chemical reduction,
and the introduction of graphene to PS increased the con-
ductivity to higher than 10 orders of magnitude. Percola-
tion in the composites occurs when the filler concentration
is near 0.1 vol.%. At only 1 vol.% loading of chemical
reduced graphene (CRGO), the composite has a conduc-
tivity of ∼ 0.1 S m−1 , indicating that highly conductive
graphene/polymer composites can be constructed using a
low loading of graphene.
This method was compared with directly mixed
graphene with polymer. It was found that this two-
step process can effectively prevent the aggregation of
graphene during reduction and composites exhibit high
electrical conductivity at a very low percolation threshold
(0.028 vol.%).88 Graphene/PVC composite was also fabri-
cated into thin film via solution blending, where PVC was
dissolved in DMF and graphene prepared through cationic
surfactant mediated exfoliation.89 Such a strategy has an
advantage in improving the dispersion of graphene sheets
due to the presence of surfactant. When graphene was
added into PVC as a filler the resulting composite exhib-
ited improved thermal stability, mechanical strength and
electrical conductivity. Consequently, the maximum con-
ductivity observed was 0.058 S/cm at 6.47 vol.% of the
Rev. Adv. Sci. Eng., 3, 48–65, 2014
Electrical Conductivity of Graphene/Polymer Nanocomposites
filler content which is 10 times higher than that of the
single walled CNT/PVC composites.90 However, it is dif-
ficult to remove the trace of residual solvents for solu-
tion blending91 and the loss of hydrophilicity can lead
to irreversible agglomeration process when the GO was
reduced into graphene. Moreover, reduction-extractive dis-
persion technology can effectively promote the dispersion
of graphene nanosheets and consequently an excellent con-
ductive network is formed in the matrix.92 The percolation
threshold of the composite is about 0.15 vol.%. When the
graphene nanosheet content is lower than 1.5 vol.%, the
conductivity of the composites is 3–5 orders of magni-
tude higher than that of composites filled with graphite
nanosheets.
Since solution blending is efficient, requires no expen-
sive instruments, and allows for a well dispersion of
graphene sheets in polymer solution. GO, functional-
ized graphene oxide (FGO), graphene and functionalized
graphene (FG) have been filled in different kinds of
polymer solution via solution blending, respectively.
For example, Kim et al.76 combined thermoplastic
polyurethane (TPU) with graphene and GO via three
methods and revealed that the solvent-based process were
more effective for obtaining well-distributed graphene
throughout the matrix than melting processing. Var-
ious polymer composites such as graphene/PVA,93
graphene/Poly(vinylidene fluoride) (PVDF),94 Graphene/
polyethylene (PE),95 graphene/PVDF/PMMA,96 graphene/
Polycarbonate (PC),97 graphene/PMMA,98 FG/Acryloni-
trile-butadiene-styrene (ABS)99 thermally reduced
graphene sheets (TRG)/poly[(-methylstyrene)-co-(acry-
lonitrile)]/PMMA,100 graphene/poly(styrene-co-butadiene-
co-styrene) (SBS)101 have been prepared using this
technique.
2.1.3. Melt Compounding
Melt compounding is another important processing for
high-yield production of polymer composites, which
involves the mixing of filler materials and polymer matri-
ces under high-shear forces at elevated temperatures.
Comparing with solution blending and in situ polymer-
ization, melt compounding is often considered as more
eco-friendly and allows for large-scale production. How-
ever, studies suggest that the drawbacks of this method
are low degree dispersion of graphene sheets in polymer
matrix, which leads to phase separation and compromised
mechanical and transport properties.76
102
103
Recently, polylactide (PLA)-exfoliated graphite com-
posites have been successfully prepared by mixing PLA
and exfoliated graphite in a mechanical mixer at 175–
200  C.104 Similar route was introduced to production
of graphene/polymer composites. Graphene/polyethylene
terephthalate (PET) composite was fabricated via feed-
ing thermal reduced GO into PET at 285  C and the
incorporation of graphene improved the electrical con-
ductivity of PET with a sharp transition from electrical
51
Electrical Conductivity of Graphene/Polymer Nanocomposites Zhang et al.

insulator to semiconductor at a low percolation thresh-

old of 0.47 vol.%, and a high electrical conductivity O F
of 2.11 S m−1 was achieved with only 3.0 vol.% of R CF3 R
F
graphene.105 In another research,106 polyethyleneoctene O
N N F N3
rubber grafted with maleic anhydride (POE-g-MA) was F

added by melt compounding to improve the electrical

Ca

ne
conductivity of graphene/polyamide 12 (PA12) nanocom-

ere
rbe

Ni t
posites with a low percolation threshold of 0.3 vol.%.

ne
O
A rapid increase in electrical conductivity from 2.8 × R R
Diels-Alder
GO R N N
or
10−14 S m−1 of PA12 to 6.7 × 10−2 S m−1 was achieved O OMe
reaction Graphene
Radical
OO
when ∼ 1.38 vol.% graphene was introduced. Graphene MeO O
OO

W a der
sheets were found to be homogeneously dispersed in PA12

Ar
als

yn
n
va
matrix. It is noteworthy that the electrical conductivity

of this composite is higher than those of many other
graphene-filled binary systems by melt compounding,76
and even comparable to some composites prepared by
in situ polymerization and solution blending. However,
owing to thermal instability of most chemically mod-
ified graphene, melt blending for graphene has so far
been limited to a few studies with the thermally stable
graphene oxide or exfoliated graphite. Additionally, the
use of high shear forces can sometimes damage the struc-
ture of filler materials, such as carbon nanotubes and
graphene sheets.107
2.2. Covalent Bonding
In a short period, there are numbers of literatures that
focused on preparing graphene/polymer nanocomposites
via covalent bonding emerged. As a matter of fact, because
graphene has a similar structure with fullerenes and carbon
nanotubes, the fabrication strategies of graphene/polymer
nanocomposites benefits a lot from their developments.
Though graphene sheets are chemical inert compared with
fullerenes and carbon nanotubes,108 it is noteworthy that
the GO and reduced graphene oxide (RGO) have sufficient
oxygen-containing functional groups so that the surface
of the GO sheets can be modified in a variety of ways,
such as covalent modification via the amidation of the car-
boxylic groups,109–115 nucleophilic substitution of epoxy
groups, diazonium salt coupling116
117 and other methods.
Covalent functionalization of pristine graphene typically
requires reactive species that can form covalent adducts
with the sp2 carbon structures in graphene. These reac-
tive species (such as reactive intermediates of radicals,
nitrenes, carbenes, and arynes) covalently modify graphene
through free radical addition, CH insertion, or cycloaddi-
tion reactions.108 (Fig. 3).
GO is heavily oxygenated and is regarded as insula-
tion. Moreover, the surface modification sometimes dam-
ages the plane structure and lead to a further decline
of conductivity. As a result, the insulating GO must
be reduced to graphene through chemical reduction or
thermal reduction118 to render the material electrically
conductive.24 In contrast, He and Gao119 reported that
covalent functionalization may keep the conjugation net-
work of graphene because only a small fraction of sp2
e
R R R1
TfO TMS
Fig. 3. Chemical modification of graphene or GO via different reaction
mechanisms.
bonds undergo the change into sp3 ones, and thus would
not impact the electrical properties of graphene consider-
ably. The conductive functionalized graphene is promising
in fabrication of novel electrical and electronic materials
and devices.
2.2.1. Grafting to Methodology
Covalent bonding for the preparation of graphene/polymer
composites involves the reaction between functional
molecules and groups on graphene sheets. To date, the
modification of graphene with polymers has been accom-
plished by two main methodologies: “grafting-from” and
“grafting-to.” The grafting-to approach provides a conve-
nient strategy to modify the surface of materials utiliz-
ing a terminal-functionalized polymer chain reacting with
an appropriately treated substrate. There are two possi-
ble routes to realize grafting-to modifications: one method
is to make functionalized GO (FGO) or graphene react
with specific polymer, another one is to functionalize poly-
mer first, followed by reacting with specific groups on
GO edge.113
120 In the first case, the properties of com-
posites not only depend on the molecular weight also
rely on the polydispersity of the polymer. Moreover, the
efficiency of coupling is related to the number of active
groups on GO or graphene surface. Esterification or ami-
dation reactions between carboxylic groups on GO surface
and hydroxyl or amine groups on the polymer chain have
been reported: A kind of bio-based polyester (PE) was syn-
thesized by polycondensation between plant-derived diols
and diacids. It was then grafted onto GO surface via the
easterification between hydroxyls of PE and carboxyls of
GO. Subsequently, the grafted GO was reduced by vita-
min C (Fig. 4). The prepared composite exhibits high elec-
trical and thermal conductivities. The uniform dispersion

52 Rev. Adv. Sci. Eng., 3, 48–65, 2014

Zhang et al.
Fig. 4. Schematic of synthesis of GO/PE and graphene/PE composite. Reprinted with permission from [121], Z. Tang, et al., Macromolecules 45,
3444 (2012). © 2012, American Chemical Society.
of graphene, strong interfacial covalent bonding between
graphene and PE and the network of graphene sheets
were responsible for concurrently improved electrical and
thermal conductivities.121 Another example of grafting-to
was via esterification between the carboxy groups in GO
and the hydroxyl groups in PVA.115 In addition, Mullen
et al.122 found that the hydrazine alone was not suffi-
cient to achieve maximum reduction, and the remaining
carbonyls allowed RGO to react with hydroxyl groups
on polymer via the esterification. Similarly, graphene
sheets were successfully modified with poly(vinyl alcohol)
(PVA) via the carbodiimide-activated esterification reac-
tion between the carboxylic acid moieties on the graphene
sheets and hydroxyl groups on PVA123 and alkoxyamine-
functionalized PMMA was grafted onto CRGO via radical
reaction.124 In addition,125 the surface functionalization of
GO can be achieved by grafting polymer chains to its sur-
face via direct use GO as the initiator for polymerization
of N -vinylpyrrolidone (NVP). This indicated that surface
properties of GO could be tailored by grafting different
polymer chains to meet the needs of various applications.
Composites prepared via grafting polymer to FGO were
also reported. FGO was synthesized and subsequently
incorporated into polyurethane acrylate (PUA) by UV cur-
ing technology.126 The results showed that FGO sheets
were uniformly dispersed into the PUA matrix and formed
strong interfacial adhesion with PUA owing to the for-
mation of the cross-linking networks between FGO and
PUA after UV curing. By contrast, untreated GO/PUA
nanocomposites exhibited relatively low thermal stabil-
ity and poor mechanical properties than its modified-
GO counterpart. Likewise, poly(arylene ethernitrile) (PEN)
was grafted to 4-aminophenoxyphthalonitrile functional-
ized GO127 and treelike hyperbranched poly(3-ethyl-3-
hydroxymethyloxetane) was efficiently synthesized and
grafted onto hydroxy-functional graphene nanosheets.128
In addition to the modification methods aforemen-
tioned, other approaches were also developed. Pris-
tine carbon nanostructures display a natural tendency
to undergo Diels–Alder (DA) reactions with a range
of functional dienes and dienophiles without the need
of a catalyst. This has sparked significant scientific
interest in exploiting the DA reaction as a powerful
Rev. Adv. Sci. Eng., 3, 48–65, 2014
Electrical Conductivity of Graphene/Polymer Nanocomposites
strategyfor functionalization of graphene surface.129
130
More precisely, in a recent work of Yuan et al.131 GO was
functionalized with cyclopentadienyl-capped poly(ethylene
glycol) monomethyl ether (mPEG-Cp) through a one-step
DA “click” reaction without any catalyst. Subsequently
chemical reduction at 80  C generated graphene/mPEG-Cp
nanocomposites. Similarly, cyclopentadienes (CPs) with
Raman and electrochemically active tags were patterned
covalently onto graphene surfaces using force-accelerated
DA reactions that were induced by an array of elastomeric
tips mounted onto the piezoelectric actuators of an atomic
force microscope.129 This force-accelerated cycloadditions
was a feasible route to locally alter the chemical compo-
sition of graphene defects and edge sites under ambient
atmosphere and temperature. After functionalization of the
graphene basal plane its conductivity was well maintained.
This method could find utility in sensors, electronics, and
optical devices.
The grafting efficiency via grafting-to is usually low
due to the difficulty in matching the unique surface chem-
istry of GO with the specific functionality on polymer
chains. More importantly, there are many active sites on
preprepared polymer and GO sheet, and the selectivity
of chemical reaction between these active sites is hardly
controlled; thus, the final structure of grafts is ill-defined.
For example, the multifunctionalized groups of the prepre-
pared polymer chains inevitably act as covalent cross-
linker between graphene sheets to form the interconnection
of graphene. In addition, the steric effect of polymer would
reduce the graft efficiency. Although the concept that the
well-defined structure and perfect dispersion of graphene
in host matrix is essential for the electrical and thermal
performances of the matrix is prevalent, it is believed that
the formation of graphene network in polymer host is the
origin for significantly improving the electrical property
and mechanical strength.
2.2.2. Grafting-from Methodology
In most cases, grafting-from process is necessary for sur-
face modification of graphene or GO. It appears that
the agglomeration can be mitigated and the dispersibility
can be ameliorated by functionalized graphene. In addi-
tion, graphene functionalization is available to improve the
53
Electrical Conductivity of Graphene/Polymer Nanocomposites
affinity of graphene in various solvents and reinforce the
interaction between compounds in nanocomposites. For
instance, graphene/polyimide (PI) nanocomposites pre-
pared via a two-stage process consisting of (a) surface
modification of graphene and (b) in situ polymerization.132
In the grafting-from approach, polymer chain grows from
the graphene surface. As a result, this method not only
minimizes the steric effect also offers template for growing
of desired polymers.133
Living/control radical polymerization is an efficient way
to precisely control the molecular weight and molec-
ular weight distributions, as well as gain functional-
ity terminated polymers. For example, Goncalves and
cooperators134 grafted poly(methyl methacrylate) (PMMA)
chains from the GO surface via atom transfer rad-
ical polymerization (ATRP), yielding a nanocompos-
ite which was soluble in chloroform. In addition, by
selective modification of graphene surface, grafting-
from method can be used to prepare special pat-
terned composites.135 Reversible addition-fragmentation
chain transfer (RAFT) polymerization136
137 is also widely
applied. For example, Jiang et al.138 used alkoxysilane-
functionalized RAFT agents modified GO, and sub-
sequently prepared GO/polymer nanocomposites with
exactly controlled molecular weight, relatively low poly-
dispersity and variable grafting density of grafted chains.
In this one-pot approach, simultaneous coupling reaction
and RAFT process using Z-group functionalized RAFT
agent seemed to afford grafted chains with shorter chain
length, narrower molecular weight distribution and lower
grafting density than R-group functionalized RAFT agent
mediated reaction, which could be attributed to differ-
ent grafting process and noticeable shielding effect. The
resultant composites were of exfoliated morphology and
enhanced solubility and dispersibility in a wide range of
Fig. 5. Fabrication of GO/PP nanocomposites by in situ Ziegler-Natta polymerization. Reprinted with permission from [140], B. Zhang, et al.,
Nanoscale. 4, 1742 (2012). © 2012, American Chemical Society.
54
Zhang et al.
solvents including hexane and water. The surface modifi-
cation offers an opportunity to alter GO morphologies and
makes it possible to prepare varied composites.
As shown in Figure 5, graphene oxide/polypropylene
(GO/PP) nanocomposites can also be prepared via in situ
Ziegler-Natta polymerization.139 A Mg/Ti catalyst species
was incorporated on GO via surface functional groups
including –OH and –COOH, giving a supported catalyst
system primarily structured by nanoscale, predominantly
single GO sheet. Subsequent propylene polymerization
led to the in situ formation of PP matrix, which was
accompanied by the nanoscale exfoliation of GO, as
well as its gradual dispersion. High electrical conductiv-
ity was discovered with thus prepared GO/PP nanocom-
posites; for example, at a GO loading of 4.9 wt%, c
was measured at 0.3 S m−1 . Besides changing the poly-
merization methods and polymer types, scientists also
attempted to change the initiation methods. Recently,
-ray irradiation-induced graft polymerization was suc-
cessfully used to decorate GO sheets with poly(vinyl
acetate) (PVAc).140 Otherwise, water-dispersible graphene
with temperature-responsive surfaces was synthesized
by grafting poly(N -isopropylacrylamide) (PNIPAM) from
graphene via surface-initiated ATRP.141
Comparing both methods through the examples
described above, it seems that grafting-to allows the
covalent attachment of a wider variety of polymers to
graphene. The polymers grafted from graphene are those
produced principally by some type of radical polymeriza-
tion. The drawback with grafting-from methodology is the
decrease of the polymerization rate at the later stage of
polymerization.142
143 In these cases, the immobilization
of the initiator on the graphene sheets is relatively easy.
In addition, the grafting-to and grafting-from methods
create new linkages between graphene and the attached
Rev. Adv. Sci. Eng., 3, 48–65, 2014
Zhang et al. Electrical Conductivity of Graphene/Polymer Nanocomposites

polymer, which might cause additional defects on the
graphene sheet and weaken the intrinsic properties of
graphene correspondingly. However, it has also proved
that the polymerization took place at the graphene defects
and its conjugated structure has not been damaged. There-
fore, the electrical properties of graphene is maximally
protected.144
2.3. Specific Affinity
It is difficult to efficiently modify pure graphene through
covalent bonding because the ideal graphene lacks active
groups on its surface. In order to address this problem,
non-covalent interaction such as hydrogen bonding, elec-
trostatic interaction and – interaction are introduced
into modification of GO and graphene.53
135
145–148
2.3.1. Hydrogen Bonding
In contrast to the block graphene/polymer composites that
the graphene fillers are randomly distributed in the poly-
mer matrices, the layered graphene derivatives in polymer
matrix can be fabricated for specific applications, such
as the directional load-bearing membranes, and thin films
for photovoltaic applications.149 Recent increasing inter-
ests focus on the construction of nanoscale layer-by-layer
(LBL) assembled materials. Hydrogen bonding opened
a new opportunity for the LBL technique. For example
ultrathin multilayer (GO/PVA)n films were fabricated by
bottom-up layer-by-layer assembly of poly(vinyl alcohol)
and exfoliated GO via hydrogen bond, in which exfoli-
ated GO nanosheets were used as the building blocks.150
(Fig. 6) Also, PVA can form hydrogen bonds with sul-
fonated RGO in water. A well dispersion of sulfonated
graphene was achieved and showed a percolation threshold
at a sulfonated RGO concentration of 0.37 wt.%.151
2.3.2. Electrostatic Interaction
It is well-known that the GO and RGO sheets are highly
negatively charged when dispersed in an aqueous solu-
tion, especially in an alkaline solution, due to the ion-
ization of the phenolic hydroxyl and carboxylic acid
groups.87 According to this property, the self-assembly
of negatively charged RGO with positively charged poly-
mer has been performed to fabricate graphene/polymer
composites.152
153 Pham and coworkers153 carried out
an approach for the preparation of highly conductive
CRGO/PMMA composites by self-assembly of positive-
charged PMMA latex particles with negative-charged
GO sheets through electrostatic interactions, followed by
hydrazine reduction. The PMMA latex was prepared by
surfactant-free emulsion polymerization, where cationic
free radical initiators provided the positive charges on
the surface of the PMMA particle. (Fig. 7) The obtained
RGO/PMMA exhibited excellent electrical properties with

Fig. 6. (a) Schematic of the composite film deposition process using glass substrate. The basic buildup sequence for the simplest film architecture
A/Bn includes four steps: (1) and (3) represent the adsorption of PVA and GO nanosheets, respectively, and (2) and (4) refer to wash steps. The cycle
could be repeated as necessary to obtain the desired number of bilayers (GO/PVA)n . (b) Simply schematic representation of the assembling process
(left) with an interaction of GO surface and PVA macromolecular chains and the internal architecture of the GO/PVA ultrathin film (right). Reprinted
with permission from [152], S. A. Ju et al., ACS Appl. Mater. Interfaces 3, 2904 (2011). © 2011, American Chemical Society.

Rev. Adv. Sci. Eng., 3, 48–65, 2014 55

Electrical Conductivity of Graphene/Polymer Nanocomposites
Fig. 7. (a) Schematic illustration of self-assembly of PMMA latex and GO, followed by hydrazine reduction of GO and (b) photographs of PMMA
latex, GO dispersion, GO/PMMA, and RGO/PMMA suspensions. Reprinted with permission from [153], V. H. Pham, et al., ACS Appl. Mater. Interfaces
4, 2630 (2012). © 2012, American Chemical Society.
a percolation threshold as low as 0.16 vol.% and an electri-
cal conductivity of 64 S m−1 at only 2.7 vol.%. Moreover,
the mechanical properties of RGO/PMMA were also sig-
nificantly improved. The storage modulus of RGO/PMMA
increased by about 30% at 4.0 wt.% RGO at room
temperature while the glass transition temperature of
RGO/PMMA increased 15  C at only 0.5 wt.% RGO.
Similarly, LBL assembly via the Langmuir–Blodgett
(LB) technique has been used to deposit GO sheets onto
films of polyelectrolyte poly(allylamine hydrochloride)
(PAH) and poly(sodium 4-styrene sulfonate) (PSS).154 The
resulting composite membrane showed enhanced direc-
tional elastic modulus by an order of magnitude, i.e.,
from 1.5 to 20 GPa with 8 vol% loading of the GO.
Electrostatic interaction can be conveniently used to pre-
pare graphene suspension. Graphite can be directly exfo-
liated into FG nanosheets with the assistance of an ionic
liquid.155 These graphene nanosheets are individuated and
homogeneously distributed into polar aprotic solvents.
Different types of ionic liquids and different ratios of
the ionic liquid to water can influence the properties of
the graphene nanosheets. Graphene/PS composites synthe-
sized by a solution blend route exhibited a percolation
threshold of 0.1 vol.% and a conductivity of 13.84 S m−1
at only 4.19 vol.%. Electrostatic interactions were also
used for synthesis of other graphene/polymer composites
such as CRGO/PMMA,156 FGN/water-borne polyurethane
(WPU)157 and graphene/PS.158
2.3.3. – Interactions
As a non-covalent approach to modify graphene, – stack-
ing interactions can be comparable to covalent attachment
56
Zhang et al.
in strength and hence provide more stable alternatives to
the relatively weaker hydrogen bonding, electrostatic bond-
ing and coordination bonding strategies as discussed above.
Furthermore, – stacking modification does not disrupt
the conjugation of the graphene sheets, and hence pre-
serves the electronic properties of graphene. Therefore, –
 stacking interactions have been used to enhance the
interaction between polymer and graphene.159 Pyrene is
a -orbital rich group that can easily form strong –
 stacking interactions with other polyaromatic materials
such as fullerene, carbon nanotubes and graphene. Pyrene-
tethered precursors have been successfully prepared160–162
and attached onto GO109 and graphene.163 A number
of small -orbital rich aromatic molecules have also
been attached previously onto graphene surface using
the – stacking approach.164–170 For instance, positively
charged imidazolium groups of imidazolium ionic liq-
uids (Imi-ILs) underwent ion-exchange with negatively
charged GO sheets and Imi-ILs were non-covalently
attached onto the large surfaces of graphene through –
and/or cation-stacking interactions,171 followed by in situ
copolymerization of the vinyl-benzyl reactive sites with
methyl methacrylate to fabricate graphene/PMMA com-
posites. More importantly, vinyl-benzyl groups in imida-
zolium ionic liquids acted as cross-linking reactive sites
to copolymerize with MMA to fabricate graphene/polymer
composites. As expected, graphene sheets were uniformly
dispersed in PMMA, and the resultant graphene/PMMA
composites exhibited excellent electrical properties with
a low percolation threshold. In addition, the combination
between the PMMA matrix and graphene contributed greatly
to mechanical and thermal properties of the final composites.
Rev. Adv. Sci. Eng., 3, 48–65, 2014
Zhang et al.
Fig. 8. A schematic of the direct exfoliation of graphene from graphite using amphiphilic block copolymers with multi-pyrene pendent groups, which
were synthesized using the RAFT mechanism. Reprinted with permission from [51], Z. Liu, et al., Carbon 51, 148 (2013). © 2013 Elsevier.
As pyrene-tethered polymers are steadily absorbed onto
graphene or GO via – stacking interactions, they can
effectively stabilize single- and few-layer graphene flakes
in aqueous dispersions.148
172 – stacking interaction is
a convenient strategy to graft polymer onto graphene sur-
face. Liu et al.51 prepared graphene/polymer composites by
direct exfoliation of graphene from micro-sized graphite
 − c / 1 − c t for  > c
using a pyrene-functionalised amphiphilic block copoly-
mer, poly(pyrenemethyl acrylate)-b-poly[(polyethylene
glycol) acrylate] (polyPA-b-polyPEG-A) prepared via
RAFT polymerization (Fig. 8). The one-step prepared
graphene/polymer composites can not only be employed
to prepare composite films with increased tensile strength
and tunable conductivity, but can also be good precursors
for the generation of pure graphene sheets.
3. THE ELECTRICAL PROPERTIES OF
GRAPHENE/POLYMER
NANOCOMPOSITES
3.1. Electrical Percolation Threshold and Conductivity
of Graphene/Polymer Composites
Recent theoretical173 and experimental174
175 studies have
demonstrated that graphene-filled composites exhibit lower
percolation thresholds and higher conductivities than those
filled by CNTs. A conductive network of graphene sheets
is not available at a low loading until the loading reach the
percolation threshold, a connected network created a route
Rev. Adv. Sci. Eng., 3, 48–65, 2014
Electrical Conductivity of Graphene/Polymer Nanocomposites
for electronic transport, and the insulator turned into a
semiconductor. A classical percolation model is frequently
used for carbon based polymer composites to describe
the relationship between composite conductivity (c  and
filler volume fraction () above the percolation threshold
(c .7
171 That is,
c = f
where f and t are the conductivity of filler and critical
exponents, respectively. Although f is not a real conduc-
tivity, it is positively related to the intrinsic conductivity
of the pristine filler. These parameters can be determined
by the least squares fitting of the experimental data. For
example, as applied to Figure 2 we can obtain fitted param-
eters are: t = 274 ± 020, f = 10492±052 S m−1 and c =
01 vol.%.7
In Table I, the highest electrical conductivity and c
of graphene/polymer composites from the literatures are
summarized. It can be observed that graphene/polymer
composites can have an electrical conductivity rang-
ing from 10−17 to 102 S m−1 and a c ranging from
0.02 vol.% for graphene/P(St-co-MMA) composites to
7.5 wt.% for TRGO/polyamide6 (PA6) composites. It can
be seen that most of graphene/polymer composites with
high electrical conductivity are prepared with TRGO or
CRGO as fillers, because of the lower production cost
of RGO than that of graphene prepared by other meth-
ods such as graphene prepared by CVD (CVDG). Wang
57
Electrical Conductivity of Graphene/Polymer Nanocomposites Zhang et al.

Table I. Electrical percolation threshold (c  and the max conductivity (c  of varied graphene/polymer composites.

Polymer Adulterant Method c c (S m−1 ) Ref.

−2
PA6 TRGO Melt extrusion 7.5 wt.% 0.71 × 10 at 12 wt.% [179]
PA12 Graphene Melt copulating 0.3 vol.% 0.067 at 1.38 vol.% [106]
PMMA FG Solution blending 0.16 vol.% 64 at 2.7 vol.% [153]
PMMA CRGO Solution blending 0.05 wt.% 0.037 at 2.0 wt.% [98]
PMMA Non-covalent FG Solution blending 0.25 vol.% 13.37 at 2.08 vol.% [171]
PMMA TRGO Solution blending 0.6 vol.% 3.11 at 1.8 vol.% [180]
Epoxy CRGO Solution blending 0.52 vol.% [181]
WPU CRGO Solution blending 5.1 at 5 vol.% [157]
PS Graphene In situ polymerization 0.1 vol.% 13.84 at 4.19 vol.% [155]
PS CRGO Solute blending 0.19 vol.% 72.18 at 2.45 vol.% [182]
PS Graphene Solute blending 0.8 wt.% 15 at 1.2 wt.% [183]
PS FGO Solute blending and 0.1 vol.% 1 at 2.5 vol.% [7]
chemical reduction
PS FG Solute blending 2.7 wt.% 10−4 at 5 wt.% [184]
PS TRGO Solution mixing 0.075–0.33 vol.% 3.49 at 1.1 vol.% [185]
PS Graphene In situ emulsion polymerization 0.029 at 2.0 wt.% [61]
PS GO Solution blending and two 22.68 at 4 wt.% [186]
steps reduction
PS/PMMA FG Solution blending 0.5 wt.% [187]
PS/PMMA FGO In situ polymerization and 0.35 vol.% [188]
chemical reduction
P(St-co-MMA) GO Solution blending and 0.02 vol.% [188]
chemical reduction
PC FG Solution blending 0.38 vol.% 22.6 at 2.2 vol.% [97]
PVA GO Solution blending and 1 wt.% 10 at 7.5 wt.% [189]
chemical reduction
PVA FG Solution blending 0.37 wt.% [151]
PVC CRGO Solution blending 0.6 vol.% 5.8 at 6.47 vol.% [89]
PEI TRGO Solution blending 0.21 vol.% 0.0022 at 1.38 vol.% [190]
PP FGO In situ polymerization 0.3 at 4.9 wt.% [139]
PU FG Solution blending 2 wt.% 0.0275 at 6 wt.% [191]
PU FG Solution blending 2 wt.% 0.0492 at 7 wt.% [68]
PU TRGO Solution blending 2 wt.% 0.191 at 4 wt.% [192]
PVDF FG Solution blending 0.5 wt.% 10.16 at 2 wt.% [193]
PE Graphene Solution blending 1 vol.% 0.01 at 3.8 vol.% [175]
PET TRGO Melt extrusion 0.47 vol.% 2.11 at 3 vol.% [105]
Vinyl chloride/vinyl CRGO Solution blending 0.15 vol.% 1 at 3.5 vol.% [92]
acetate copolymer
Poly(styrene-co-butadiene- CRGO Solution blending 0.25 vol.% 13 at 4.5 vol.% [101]
co-styrene) (SBS)

et al.176 reported the preparation and dielectric proper-
ties of CRGO/PP composites with an ultra low per-
colation threshold as low as 0.033 vol%. This value
is the lowest among those that have been reported in
graphene-filled composites. However, the electrical prop-
erties of both CRGO/polymer and TRGO/polymer com-
posites are much lower than those of the CVDG/polymer
composites. For example, Chen et al.177 directly syn-
thesized three-dimensional graphene sheets via template-
directed CVD. Even with a graphene loading as low
as 0.5 wt%, the graphene/poly(dimethyl siloxane) com-
posite showed a very high electrical conductivity of
∼ 1000 S m−1 , which was much higher than CRGO and
TRGO/polymer composites. In addition, neat CRGO fibers
were reported to have much higher electrical conduc-
tivity (about 2.5 × 104 S m−1  178 than CVDG/polymer
and the other RGO/polymer composites reported because
of compact stacking and low contact resistance between
CRGO sheets.
3.2. Conductivity Influencing Factors
The conductivity of composites is related to the both prop-
erties of basis materials and adulterants. It is well known
that polymer can be recognized as conductive polymer
and insulated polymer, and the former showed an impres-
sive high conductivity than that of the latter. For example,
PS is one traditional industry material with conductiv-
ity approximately 1.0 × 10−10 S m−1 . The conductivity
of PS rocketed to a high conductivity after mixing with
graphene sheets7 (Table I). In addition, mixing different
kinds of polymers together may lead to double perco-
lated structure. Mao et al.187 fabricated PS/PMMA blends
filled with octadecylamine-FG conductive composites, and
found that the electrical conductivity of the composites can

58 Rev. Adv. Sci. Eng., 3, 48–65, 2014

Zhang et al.
Fig. 9. Left: SEM images of PS/PMMA blends filled with 1.0 wt.%
GE-ODA: (a) 70 w/30 w, (b) 50 w/50 w, (c) 30 w/70 w. (a) and
(b) PMMA phase was etched by formic acid. (c) PS phase was etched
by cyclohexane. Right: Conductivity (at 1 Hz) versus PMMA content
in PS/PMMA blends. The measurements were performed at room tem-
perature. The total weight concentration of GE-ODA incorporated in the
entire polymer blends is fixed at 1.0 wt.%. Reprinted with permission
from [187], C. Mao, et al., ACS Appl. Mater. Interfaces 4, 5281 (2012).
© 2012, American Chemical Society.
be optimal when PS and PMMA phases form a cocon-
tinuous structure and octadecylamine-FG nanosheets were
selectively located and percolated in the PS phase. When
the PS/PMMA ratio was 50 w/50 w, the formation of
a perfect double percolated structure contributed to an
extremely low electrical percolation threshold 0.5 wt.%
(Fig. 9).
Further research found that graphene/polymer
composites of different polymers with the same polymer-
ization degree exhibited similar conductivity.194 However,
when the polymer chain was designed as random copoly-
mer the conductivity was significantly decreased. It was
also observed that the longer the grafted polymer chains
the lower the conductivity.194 Also, the manipulation
of the conductivity of graphene papers was realized
at the molecular level, via either covalent bonding or
– stacking interactions using either monofunctional
or bifunctional molecules. The graphene papers can be
tailored with controllable conductivity from around 10−3
to below 102 S m−1 195 (Fig. 10).
Graphene sheets can provide electron transfer percolated
pathways to improve electrically conductivity. The mor-
phology of adulterant plays an important role in determin-
ing the percolation threshold. It was found that planar-like
graphene is much more readily for percolate at lower load-
ing than fiber-like carbon nanotube.76
185 All these experi-
mental results indicate that rapid transition from insulation
polymer to high conductivity composite depends on the
formation of an interconnected conductivity graphene net-
work. This means the superior conductivity arises from
the high reduction degree of GO and its high dispersion
and the formation of a network structure in the poly-
mer matrix. At the same time, the mechanical and elec-
trical properties of paper materials prepared by filtration
are related to the concentration of CRGO. Park196 pro-
posed that the electrical conductivity of composite films
Rev. Adv. Sci. Eng., 3, 48–65, 2014
Electrical Conductivity of Graphene/Polymer Nanocomposites
increased with the increasing concentration of graphene.
An interesting result showed that a concentrated suspen-
sion will lead to agglomeration of reduced GO sheets, and
the composite paper sample produced by the agglomerated
mixture showed a significantly higher modulus and electri-
cal conductivity than those generated from homogeneous
colloidal suspensions. This will be helpful in prepara-
tion of graphene/polymer composites with low percolation
threshold.197
The concentration of graphene can be controlled by
phase separation in order to achieve low percolation
threshold190 (Fig. 11). With the phase separation continued,
the nuclei grew up. After removing the solvent from the
cells, graphene/polyetherimide (PEI) nanocomposite foams
were obtained. It was observed that the concentration of
graphene was increased when the nuclei grew up. This
action decreased the c from 0.21 vol.% of graphene/PEI
nanocomposite to 0.18 vol.% of graphene/PEI foam.
Furthermore, the foaming process significantly increased
the specific electromagnetic interference (EMI) shielding
effectiveness from 17 to 44 dB cm3 g−1 .
In fact, the conductivity of composite sample not only
related to the concentration of graphene also related to
the degree of reduction of graphene. GO with hydroxyl
and epoxide functional groups on their basal planes was
deemed as insulation, the conductivity of GO can be
adjusted by alter the C/O ratio.118 Zhang et al.198 stud-
ied the influence of surface chemistry of graphene on
rheological and electrical properties of graphene/PMMA
nanocomposites. Owing to the favorable interfacial inter-
actions arising from polarity matching, the graphene with
a C/O ratio of 13.2 showed a better dispersion in PMMA
than those with lower C/O ratios, and thus this composites
showed a dramatic increase in electrical conductivity of
over 12 orders of magnitude, from 3.33×10−14 S m−1 with
0.4 vol.% of graphene to 2.38×10−2 S m−1 with 0.8 vol.%
of graphene. The conductivity reaches up to 10 S m−1 at
2.67 vol.% and 20 S m−1 at 4.23 vol.%. It was believed
that the residual oxygen functional groups contribute to
the interaction between RGO and PMMA matrix, result-
ing in enhancement on the thermal properties of PMMA.98
It can be concluded that many factors including intrinsic
electrical conductivity, aspect ratio, dispersion state, and
contact resistance between graphene might affect the elec-
trical properties of graphene/polymer composites.32
54
4. APPLICATION OF CONDUCTIVE
NANOCOMPOSITES
With significantly enhanced conductivity and mechani-
cal properties, graphene/polymer composites usually have
potential applications as antistatic coatings, electromag-
netic interferences (EMI) shielding materials,180
190
199
200
electrode materials.9
29
64
201–206 etc. The EMI shielding
is defined as the logarithmic ratio of incoming (Pi ) to
outgoing power (Po ) of radiation. In general, efficiency
59
Electrical Conductivity of Graphene/Polymer Nanocomposites Zhang et al.

Fig. 10. Schematic illustrating the modification of graphene sheets with (a) monoaryl diazonium salt, (b) biaryl diazonium salt, and (c) bipyrene-
terminated molecular wire. (d) Model proposed to illustrate the in-sheet and inter-sheet charge transfer. (1) The in-sheet charge transfer, (2) the electron
hopping from one sheet to another, and (3) the charge transfer through the inter-sheet molecular conduits. Reprinted with permission from [195], J. Liu,
et al., J. Phys. Chem. C 116, 17939 (2012). © 2012 American Chemical Society.

Fig. 11. (a) Schematic of preparation of PEI/graphene nanocomposite foam. (b) Electrical conductivity for graphene/PEI nanocomposites and micro-
cellular foams as the function of graphene content. Reprinted with permission from [190], J. Ling, et al., ACS Appl. Mater. Interfaces 5, 2677 (2013).
© 2013, American Chemical Society.

60 Rev. Adv. Sci. Eng., 3, 48–65, 2014

Zhang et al.
of any shielding material is expressed in decibels (dB).
Higher the decibel level of EMI shielding, less energy
is transmitted through shielding material. EMI may be
induced as electromagnetic radiation emitted by electric
circuits under current operation. The EMI signal is unde-
sirable because it not only impedes the good functional-
ity of electronic devices but is also harmful to humans.
Compared with conventional metal-based EMI shield-
ing materials, conductive polymer composites and poly-
mer composites with discontinuous conducting fillers are
attractive for the development of effective EMI shielding
applications because of their own superiorities, including
being lightweight, anti-corrosive, flexible, and having pro-
cessing advantages. Graphene/PMMA180 nanocomposites
were prepared by solution blending and melt compound-
ing. This novel graphene-PMMA nanocomposite micro-
cellular foams with a low graphene loading of 1.8 vol%
exhibited not only a high conductivity of 3.11 S m−1 ,
but also a good EMI shielding efficiency of 13–19 dB
at the frequencies from 8 to 12 GHz. According to their
research, EMI shielding efficiency is mainly attributed to
the absorption rather than the reflection in the investi-
gated frequency range and the presence of microcellular
cells greatly improves the ductility and tensile toughness
of the brittle graphene-PMMA nanocomposites. PS/carbon
nanofiller composite foams was also prepared using a
chemical blowing agent.207 The specific shielding effec-
tiveness of this lightweight composite was as high as
64.4 dB cm3 g−1 . In addition to PS and PMMA, other
polymer systems such as epoxy,181 PVDF,193 WPU157 and
PDMS199 have also been used for the fabrication of EMI
shielding materials. However, the general properties of
these polymers, such as low heat-resistance, poor flame
retardancy, and high smoke generation, restrict their use as
Fig. 12. Schematic illustration of the fabrication procedure of RGO/PW multilayer films, which involves the LBL assembly of GO nanosheets and
PW clusters using cationic polyelectrolytes PEI and PAH as electrostatic linkers, and a subsequent in situ photoreduction to convert GO to RGO.
Reprinted with permission from [201], H. Li, et al., J. Am. Chem. Soc. 133, 9423 (2011). © 2011, American Chemical Society.
Rev. Adv. Sci. Eng., 3, 48–65, 2014
Electrical Conductivity of Graphene/Polymer Nanocomposites
the EMI shielding materials in aerospace and other special
fields.
Electrode material is another significant application for
graphene/polymer composites owing to their specific elec-
trical property. For example, Lee et al.208 developed a
new method to simultaneously transfer and dope chemi-
cal vapor deposition grown graphene onto a target sub-
strate using a fluoropolymer as both the supporting and
doping layer. This method was used to fabricate a flexi-
ble and transparent graphene electrode on a plastic sub-
strate. Furthermore, Song and coworkers209 developed
nanocomposites combining graphene with two promising
polymer cathode materials, poly(anthraquinonyl sulfide)
and polyimide, to improve their high-rate performance.
The graphene/polymer nanocomposites were synthesized
through a simple grafting-from polymerization in the pres-
ence of graphene sheets. The highly dispersed graphene
sheets in the nanocomposite drastically enhanced the elec-
tronic conductivity and allowed the electrochemical activ-
ity of the polymer cathode to be efficiently utilized.
This allows for ultrafast charging and discharging; the
composite can deliver more than 100 mA h g−1 within just
a few seconds.
Graphene/polymer composites can also be served as
electrical devices. A GO/polyoxometalate composite film
has been prepared as follows201 GO and a Keggin-type
polyoxometalate cluster H3 PW12 O40 (PW) are alterna-
tively deposited on a substrate via electrostatic adsorp-
tion (Fig. 12). The PW cluster acts as a photocatalyst
and reduces GO (RGO), yielding a product with good
conductivity. Furthermore, photomasks were used to pro-
duce conductive patterns of RGO domains on the films,
which served as efficient microelectrodes for photodetec-
tor devices. Supercapacitor devices based on conductive
61
Electrical Conductivity of Graphene/Polymer Nanocomposites
flexible CRGO/PANI composite film exhibited large
electrochemical capacitance (210 F g−1  at a discharge rate
of 0.3 A g−1 . The greatly improved electrochemical stabil-
ity and rate performances were also observed.86
5. SUMMARY AND OUTLOOK
Graphene is a promising material for the preparation of
graphene/polymer composites with improved electrical,
mechanical, thermal properties at extremely low loading.
Different synthetic strategies for the preparation of such
nanocomposites are described, including not only physical
processing, but also covalent bonding and specific affinity.
The advantages and disadvantages of each method are also
addressed. Moreover, potential applications in the fields of
electronic and photonic devices, clean energy, and sensors
are also presented.
Several challenges need to be addressed for these
nanocomposites to reach their full potential, such as
homogeneous dispersion of materials with minimal aggre-
gation, effective modification of graphene surface and
well-controlled interfacial structure in composites. One
of the most promising aspects of graphene/polymer
composite is their potential for use in device and other
electronics applications, owing to their high electrical
conductivity. Further property improvements in graphene-
based composites will be influenced by improved morpho-
logical control. Defects and wrinkles in platelets are likely
to influence their reinforcing capabilities, and so exfoli-
ation and/or dispersion techniques that promote a more
elongated morphology could conceivably further improve
mechanical properties of these composites. In addition,
increased control over alignment and spatial organization
of graphene-based fillers could be beneficial to the prop-
erties of almost all types of composites.
Acknowledgments: Jingquan Liu acknowledges the
fund from NSFC (51173087), NSF of Shandong
(ZR2011EMM001), NSF of Qingdao (12-1-4-2-2-jc) and
the Taishan Scholar Program of Shandong Provence for
financial support.
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