Materials Science & Engineering R 142 (2020) 100577

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Materials Science & Engineering R

journal homepage: www.elsevier.com/locate/mser

Thermal conductivity of graphene-based polymer nanocomposites T

a, b a c d a,
Xingyi Huang *, Chunyi Zhi , Ying Lin , Hua Bao , Guangning Wu , Pingkai Jiang *,
Yiu-Wing Maie,*
a
Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai
200240 China
b
Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, China
c
University of Michigan - Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University, Shanghai 200240, China
d
School of Electrical Engineering, Southwest Jiaotong University, Chengdu, China
e
Centre for Advanced Materials Technology (CAMT), School of Aerospace, Mechanical and Mechatronic Engineering J07, The University of Sydney, Sydney, NSW 2006,
Australia

ARTICLE INFO ABSTRACT

Keywords: As a material possessing extremely high thermal conductivity, graphene has been considered as the ultimate
Graphene filler for fabrication of highly thermally conductive polymer composites. In the past decade, graphene and its
Polymer composites derivatives were demonstrated in many studies to be very effective in enhancing the thermal conductivity of
Thermal conductivity various polymers. This paper reviews current progress in the development of graphene/polymer composites with
Surface modification
high thermal conductivity. We began with the effects of isotopes, defects/doping, edges and substrate, poly­
crystallinity, functionalization, size and layer number, and folding/twisting on the thermal conductivity of
graphene. We then modelled the thermal conductivity of graphene/polymer composites and, through molecular
dynamics (MD) simulations, demonstrated its dependence on interfacial thermal conductance as well as size,
dispersion and volume fraction of graphene. After a critique of recent studies on thermally conductive graphene/
polymer composites and their potential applications, we identified several outstanding issues, new challenges
and opportunities for future endeavours.

1. Introduction new findings of heat-flow physics which potentially lead to novel

Thermally conductive polymer composites are attracting consider­
able attention especially in recent years because increasingly more
powerful electronics are being developed. This class of materials can be
comprehensively used as electronic packaging materials, thermal in­
terface materials (TIMs) and base materials for printed circuit broads,
etc. [1]. These thermally conductive polymer composites consist of a
polymer matrix and thermally conductive fillers. Their final thermal
conductivities are determined by the processing techniques and ther­
mally conductive fillers which can be metal powder, ceramic powder
(mainly for thermally conductive but electrically insulating composites)
and carbon materials [2,3]. Among these, carbon materials are the most
used and intensively studied fillers with excellent thermal con­
ductivities, different morphologies, low densities and inexpensive costs.
These carbon-based fillers incorporated in polymers include graphite
platelets, carbon nanotubes (CNTs) and graphene [4–6].
The unusual thermal properties of graphene originate from its un­
ique two-dimensional (2D) nature, giving a solid platform for different
thermal management applications. Graphene with a perfect structure
has almost the highest thermal conductivity (TC) among all known
materials (> 5000 W/m·K that is on par with diamond materials) [7,8].
Also, its 2D morphology and super-high aspect ratio make it suitable as
a filler for polymers to achieve superbly high TC [9–12].
However, when applying graphene as a filler in polymer matrices,
many scientific and technological issues appear and the advantages of
graphene as a highly thermally conductive filler cannot be realized.
Indeed, in some situations, it is found that thick graphite sheets or
platelets can deliver even better TC results than graphene [13].
There are two issues of highly thermally conductive graphene/
polymer composites. One issue is due to the graphene itself. Super-high
TC can only be achieved if there is a perfect graphene structure; the
presence of any edges, defects, doping and modifications gives dramatic
drops in the intrinsic TC [7,14]. The other issue arises from the fabri­
cation of polymer composites, which includes poor dispersion of gra­
phene due to its 2D morphology and high aspect ratio, interfacial and
contact thermal resistances, difficulties of constructing 3D structures,

⁎
Corresponding authors.
E-mail addresses: xyhuang@sjtu.edu.cn (X. Huang), pkjiang@sjtu.edu.cn (P. Jiang), yiu-wing.mai@sydney.edu.au (Y.-W. Mai).

https://doi.org/10.1016/j.mser.2020.100577
Received 18 May 2020; Received in revised form 29 June 2020; Accepted 3 July 2020
Available online 22 September 2020
0927-796X/ © 2020 Elsevier B.V. All rights reserved.
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

Nomenclature NMP N-methyl-2-pyrrolidone

NR natural rubber
1D one-dimensional PA polyamide
2D two-dimensional PA6 polyamide 6
3D three-dimensional PAN polyacrylonitrile
ABS acrylonitrile-butadiene-styrene PBT polybutylene terephthalate
ATRP atom transfer radical polymerization PC polycarbonate
BN boron nitride PCC phase change composite
CB carbon black PCF pitch-based carbon fiber
CNT carbon nanotube PCM phase change material
CNF carbon nanofiber PDMS polydimethylsiloxane
CPU central processing unit PE polyethylene
CVD chemical vapour deposition PEG polyethylene-glycol
DMF N, N-dimethylformamide PEI polyether imide
DP degree of polymerization phr per hundred parts of resin
E-51 bisphenol-A epoxy PGMA poly(glycidyl methacrylate)
GRMs graphene-materials PI polyimide
EG expanded graphite PMMA polymethyl methacrylate
EMD equilibrium molecular dynamics POSS polyhedral oligomeric silsesquioxane
EP epoxy resin PP polypropylene
EVA ethylene-vinyl acetate copolymer PPS polyphenylene sulphide
f-GF functionalized graphene flake PS polystyrene
f-GO functionalized graphene oxide PTFE polytetrafluoroethylene
FLG few-layered graphene PU polyurethane
f-RGO functionalized reduced graphene oxide Py pyrene
GF graphene flake PVA poly(vinyl alcohol)
GMP graphite microparticle PVDF poly(vinylidene fluoride)
GNP, GnP graphene nanoplatelet RGO, rGO reduced graphene oxide
GNR graphene nanoribbon SCA silane coupling agents
GO graphene oxide SCF supercritical fluid
GrO graphite oxide SLG single-layered graphene
GS graphene sheet SWCNT single-walled carbon nanotube
HDPE high density polyethylene TC thermal conductivity
KH-560 γ-(2,3-epoxypropoxy)propytrimethoxysilane TCA titanate coupling agents
LLDPE linear low-density polyethylene TCE thermal conductivity enhancement
MD molecular dynamics THF tetrahydrofuran
MLG multi-layered graphene TIM thermal interface material
MSA methanesulfonic acid VDOS vibrational density of states
MWCNT multi-walled carbon nanotube VPS vibration power spectrum
NEMD non-equilibrium molecular dynamics XRD X-ray diffraction
NFG natural flake graphite

etc. as illustrated in Fig. 1.
This paper is a critical review on thermally conductive polymer
composites with graphene materials as fillers. Herein, graphene mate­
rials (GRMs) are defined as 2D, flake- or sheet-like carbon forms, which
include few-layer graphene (FLG), graphene flake (GF), graphene na­
noflake (GNF), graphene nanoplatelet (GNP, GnP), graphene oxide
(GO), graphene nanoribbon (GNR), multi-layered graphene (MLG), re­
duced graphene oxide (rGO, RGO) and single-layered graphene (SLG)
[15] as well as three-dimensional (3D) forms (e.g., aerogels and foams)
of these 2D carbon materials. Other 2D carbon materials such as ex­
panded graphite (EG), exfoliated graphite (ExG), graphite micro-par­
ticle (GMP) and natural flake graphite (NFG) are not considered as
graphene materials. However, their composites will be reviewed, as
appropriate, for comparative studies. All potential factors which affect
the TC of fabricated polymer composites, and their current and emer­
ging applications will be discussed (Fig. 1). In Section 2, we first
summarize recent progress on the intrinsic TC of graphene materials
and the main factors which reduce their TC. Section 3 is focused on
theoretical studies and molecular dynamics (MD) simulations on TC of
graphene/polymer composites. The effects of interfacial thermal re­
sistance due to graphene functionalization, size, volume fraction and
dispersion are included. Then, in Sections 4 and 5, we discuss the
experimental results and advances obtained on the TC of polymer
composites filled with graphene materials and graphene-based hybrids.
Here, graphene-based hybrids are defined as one graphene material
plus another filler, and in some cases, graphene-based hybrids also
mean two different graphene materials. Issues on the fabrication tech­
niques are highlighted. While the practical applications of these highly
thermally conductive graphene/polymer composites are not mature
enough yet, Section 6 shows three potential applications as graphene-
enabled TIMs, phase change materials (PCMs) and separators for ef­
fective thermal management of electronic devices and lithium batteries.
Finally, in Section 7, we summarize the current progress made in the
field and identify some unsolved problems, pointing to future research
directions.
2. TC of graphene
Graphene has an extremely high in-plane TC, probably the highest
in comparison with any currently known material. Fig. 2 shows a brief
summary of experimental TCs of some typical carbon structures and
metals. Although the values reported in the literature are quite di­
versified, the figure clearly shows extremely high TCs of carbon-based
materials. Experimentally, at room temperature, a free-standing

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X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

Fig. 1. Factors which affect the fabrication of thermally conductive graphene/polymer composites to maximize their thermal conductivity (TC) and TC enhancement
(TCE) and their prospective applications. The flowchart also shows the framework of this review article.

graphene sheet exhibits an in-plane TC of up to 1500−5400 W/m·K

Fig. 2. Summary of room-temperature experimental TC values of diamond
[25,26], graphite (in-plane) [16,17,23,27], CNT [5], suspended graphene
[16,19] and some metal materials.
[16–24], which is even higher than that of diamond materials (∼
2000 W/m·K) [25,26]. It should be noted that the highest in-plane TC of
graphene claimed is achieved in isotopically purified samples with large
grains; whereas defects, small grains and edges will dramatically reduce
the TC values [16,17].
Graphene is both thermally and electrically conductive. Thus, both
electrons and phonons contribute to its high TC. However, instead of
electrons, phonon behaviours dominate the thermal transport of gra­
phene [28,29]. The mechanism of the ultrahigh TC value of graphene
has been discussed in detail in the published literature. In short, its high
TC is mainly attributed to two mechanisms. First, the sp2 orbital hy­
bridization and light carbon atoms provide a very high phonon group
velocity and extremely harmonic lattice. Second, the 2D lattice allows
through-plane flexural (Z) phonon vibrations and these modes have
small scattering rates owing to the reflectional symmetry of the gra­
phene lattice [30,31]. These two features yield an extremely high TC of
graphene, which is also very sensitive to any phonon scattering.
The very high TC of graphene makes it very suitable for fabrication
of thermally conductive polymer composites. Except interface issues
which are commonly considered for polymer composites, factors

Fig. 3. TC of graphene as a function of its iso­

topic composition. (a) TC of graphene with 13C
isotope concentrations of 0.01 %, 1.1 % (nat­
ural abundance), 50 % and 99.2 % measured by
the micro-Raman method. (b) Average value of
measured TC as a function of 13C concentration
at ∼380 K. MD simulation results for TC are
shown as yellow squares for comparison
(Reproduced with permission from Ref. [17]).
(For interpretation of the references to colour in
this figure legend, the reader is referred to the
web version of this article.)

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X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

affecting the TC of graphene itself are also important. External per­ of defect types (substitutional N and Si, structurally different pyridinic
turbations are known to have strong effects on the intrinsic TC of low- N, pure structural single vacancy and Stone–Wales defects as shown in
dimensional materials [32]. Below, we will concisely examine and Fig. 5) on TC of 2D graphene [48]. The structural defects give com­
discuss major results of previous studies on the TC of graphene-based parable reductions in TC because their scattering effects are sig­
materials and their applications in polymer composites. Interested nificantly weakened by the 2D feature of graphene. By contrast, the
readers may refer to published reviews on this topic [7,33]. substitutional Si defect yields a larger reduction of TC. Unlike the effect
of substitutional N defect, pyridinic N leads to a higher reduction of TC
2.1. Isotope effects compared to single vacancy defects.
The effect of single and multiple defects/doping (single vacancy,
Carbon has many isotopes with 12C and 13C as most typical. CH3 functional group and N-doping) on the TC of MLG was investigated
Different mass of carbon isotopes results in different phonon feature through equilibrium MD (EMD) simulation [49] at 300, 700 and 1500
and scattering process, which affect the TC of graphene as it is domi­ K. When only one single type of defect/doping is present, the single
nated by lattice vibrations instead of electrons as mentioned earlier. vacancy defect gives the largest effect on TC reduction at 300, 700 and
Most studies on isotope effects regarding TC of graphene were 1500 K; however, the effect of N-doping is the least. When the graphene
performed by theoretical calculations. In a typical MD simulation study, sheets contain three types of defects/doping, the single vacancy defect
it was found that the TC of graphene with 5 % 13C is 12 % lower than produces a most significant effect on TC reduction at 300 and 700 K,
that of pure 12C graphene caused by the so-called phonon localization while the CH3 functional group dominates TC reduction at 1500 K.
[34]. In another MD simulation work [35], it is confirmed that isotope Besides, compared to the effect of a single type of defects/doping, the
mixing can reduce TC of graphene and super-lattice distribution gives presence of multiple defects/doping can further reduce the lattice TC at
higher reduction than random distribution. 300 and 700 K.
Chen et al. conducted experiments to evaluate the isotope effects on
TC of graphene [17]. Graphene with different percentage of 13C was
2.3. Effects of edges and substrate
fabricated on a copper foil by chemical vapour deposition (CVD) and
their thermal conductivities were determined by the optothermal
GNRs with smooth edges possess higher TC than those with rough
Raman technique. It was revealed that isotopically pure 12C (0.01 %
13 edges. Rough edges can induce more diffusive phonon boundary scat­
C) graphene has a TC value up to > 4000 W/m·K at ∼320 K, which is
tering and hence hinder more effectively phonon transport [50–52].
more than two times that in graphene comprising a 50:50 mixture of
12 Because graphene has small intrinsic phonon scattering, the edge
C and 13C (see Fig. 3a). These results agree with those obtained by MD
roughness can effectively lower the TC of graphene, especially for GNRs
simulations (see Fig. 3b). Natural graphite has 12C:13C of roughly 99:1.
with small widths [28,50,53]. As shown in Fig. 6, a rough edge can
According to this study [17], natural graphene has a TC ∼2700 W/m·K
reduce TC of GNR by one order of magnitude. This is because for GNRs
at 300 K, which is high enough for fabrication of thermally conductive
with rough edges, only the phonon modes with wavelengths compar­
polymer composites.
able to the ribbon width can contribute to heat transport, and a ma­
jority of oscillatory eigen-modes are localized and do not contribute to
2.2. Effect of defects/doping
the TC. Concerning the two typical edges (i.e., zigzag and armchair),
MD simulations show that TC of graphene depends on the edge chirality
All theoretical studies have revealed that defects and doping can
and GNRs with zigzag edges possess 20–50 % higher TC than that of
yield remarkable reductions of TC of graphene, which is attributed to
armchair edges induced by different phonon scattering rate. Though the
phonon scattering that greatly shortens the phonon mean free path
edge effect is relatively strong in extremely narrow GNRs where phonon
[36–39]. Yeo et al. [40] confirmed the presence of Stone-Wales defects
boundary scattering dominates, this effect is expected to be much less
(pairs of opposing 5-membered or 7-membered rings formed by just
prominent for wider GNRs.
rotating a pair of carbon atoms) or double vacancy defects would de­
The interaction between graphene and substrate may markedly af­
crease TC of graphene by over 80 % as the defect densities were in­
fect its TC. Yu and Zhang reported that if a graphene is suspended
creased to 10 % coverage for both zigzag- and armchair-structured
between two metal blocks (substrates), the heat flux can only be 40 %
GNRs. In zigzag-structured GNRs, double vacancies in a nanoribbon led
that of ideally suspended graphene (no contact to anything, i.e., no
to more significant reductions in TC than Stone-Wales defects. These
substrate) [54]. Guo et al. revealed that a SiC substrate has strong
trends are obvious in the temperature range 100−600 K. Other studies
also reported similar results [28,41–43]. For example, Ng et al. [44]
showed that Stone-Wales defects could decrease TC of graphene by over
50 %, with much higher reductions in zigzag than armchair GNRs for all
defect densities. Malekpour et al. [45] also found that TC of graphene
decreased [∼(1.8 ± 0.2)×103 to ∼(4.0 ± 0.2)×102 W/m·K] with in­
creasing defect density near ambient temperature at relatively low
densities (2.0 × 1010 to 1.8 × 1011/cm2). However, with higher defect
densities, the TC of graphene showed a weak dependence on defect
density at a relatively high value of ∼400 W/m·K.
Similar to defects, doping can greatly enhance phonon scattering,
resulting in a lower TC. N-doping has been intensively studied for
graphene by theory. Substituting only 1 % of N atoms in the graphene
lattice may lead to more than 50 % reduction of TC [46] (Fig. 4). It is
interesting that N-doped graphene can decrease dramatically the TC
dependence on chirality due to the scattering of phonons caused by the
high loading of N atoms concealing the chirality effect. In another
study, it has been found that N-doped GNRs exhibit higher TC than
GNRs with defects alone; but the TC of both are much lower than the Fig. 4. Effect of nitrogen atom (N) concentration on the normalized TC of SLG
pristine defect-free graphene [47]. along the armchair and zigzag chirality directions. NB: This figure is redrawn
Using non-equilibrium (NE) MD simulation, Lee compared the role based on the original data. (Reproduced with permission from Ref. [46]).

4
X. Huang, et al.
Fig. 5. (a) Defect-free graphene andgraphene sheets with (b) quaternary N, (c) pyridinic N, (d) single vacancy (SV) and (e) Stone-Wales (SW) defects. (NB: This figure
is redrawn based on the original [48]). TC values of MLG with single kind of defect including (f) 1-4 % N atoms, (g) 2-8 % methyl group, and (h) 1-4 % single vacancy
at 300, 700 and 1500 K. (Reproduced with permission from Ref [49].).
interaction with SLG during thermal transport, which greatly reduces
the TC. However, high TC can be obtained for the second layer of a
suspended double-layered graphene due to the weak van der Waals
force between the two layers [55]. Hence, weak interactions between
graphene and substrate is critical to maintaining the high TC of gra­
phene. Also, the interaction of graphene with substrate effectively re­
duces the length dependence of TC, that is, the TC of graphene on
substrate is no longer sensitive to its length [56].
No systematic experimental studies on substrate/edge effects on TC
of graphene have been reported to date. It is impossible to draw a
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Materials Science & Engineering R 142 (2020) 100577
definitive conclusion from existing data published in different papers.
For example, the TC of graphene on SiO2 substrate was measured to be
∼ 1800−2200 W/m·K [57], but experiments showed that suspended
graphene had a TC of only ∼ 100−1000 W/m·K [58]. It is believed that
the quality of graphene, measurement method and associated large
errors may have overwhelmed the substrate/edge effects although they
are theoretically predicted to be significant.
Fig. 6. (A) Examples of hydrogen-terminated
zigzag nanoribbons with rough edges for the
density of edge layers where: (a) d = 0, (b) d
= 0.1, (c) d = 0.5, (d) d = 0.9 and (e) d = 1.
Here, “d” is defined as the ratio of the number
of atoms in the edge layers to four times the
dimensionless length of the nanoribbon
(number of longitudinal cells). (B) Dependence
of TC of a finite nanoribbon with rough edges
on density d. TC is calculated from temporal
evolution during 3 ns. (Reproduced with per­
mission from Ref. [53]).
X. Huang, et al.
2.4. Effect of polycrystallinity
CVD is by far the most powerful technique to prepare industry-scale
graphene sheets, which have a polycrystalline rather than mono­
crystalline structure [59]. Polycrystalline graphene sheets contain in­
evitably grain boundaries, grain misorientation and other structures,
which can cause severe phonon scattering than that of single crystalline
graphene sheets [60–62]. Many studies have illustrated that the TC of
polycrystalline graphene depends primarily on its grain size. Lee et al.
reported the in-plane thermal conductivities of polycrystalline gra­
phene on Si3N4 substrate at 320∼510 K as 2600∼1230, 1890∼1020
and 680∼340 W/m·K for average grain size of 4.1, 2.2 and 0.5 μm,
respectively, which are much lower than the best fitted values
(5500∼1980 W/m·K obtained by the simple linear chain model in the
same temperature range) of single crystalline graphene [63]. Fig. 7a
shows that, as grain size decreases from infinity to 0.5 μm, significant
TC reductions are observed. This result is mainly caused by the in­
creased grain boundaries and higher defect concentration as the grain
size is decreased (see Fig. 7b).
Lee et al. [64] studied the effect of grain misorientation angle on in-
plane TC of polycrystalline graphene. Their results showed that thermal
conduction in graphene also depends mainly on grain size. A slight
misorientation (< 4°) between two adjacent grains would cause a large
decrease in the TC of bi-crystalline graphene. Since phonon scattering
in polycrystalline graphene is determined by the grain boundaries and
corresponding defects, the TC of graphene can be tailored by control­
ling the nucleation densities by adjusting the CVD process parameters,
such as operating temperature and partial pressure.
2.5. Effect of functionalization of graphene
Functionalization of graphene is very important to improving its
dispersion in composite materials and its affinity with polymer ma­
trices, which may finally impart an effectively enhanced performance
[65]. However, functionalization is a double-edged sword because the
functional groups attached on the graphene surface are found to reduce
remarkably its inherently high TC [66]. This is expected since any
randomly distributed functional groups act as molecular doping to
graphene, destroying the perfect 2D crystallinity of graphene and giving
unavoidable phonon scattering caused by the sp3 bonds created by
functionalization different from the typical sp2 bonds.
The smallest “functional group” is a hydrogen atom. Unfortunately,
it is shown that even a hydrogen coverage of 2.5 % may decrease the TC
of graphene by ∼40 % [67]. Large size groups may be more severe to
Fig. 7. (a) TC versus measured temperature for suspended graphene on Si3N4 substrate in air with grain sizes of 0.5, 2.2 and 4.1 μm. (b) SEM images of graphene with
different grain size synthesized at controlled operating temperature and pressure. (Reproduced with permission from Ref. [63]).
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Materials Science & Engineering R 142 (2020) 100577
reduce the TC of graphene. For example, randomly distributed methyl
and phenyl groups are found to decrease TC of graphene of up to 50 %
with a functional group coverage regime of as few as 1.25 % [68] (see
Fig. 8). Detailed analyses show the rapid TC drop depends closely on
the angular momentum of the functional groups. That is, the high an­
gular momentum rotates the unsupported sp3 bonds and thus the
phonon mean free paths are reduced.
The effect of alkyl functional groups on the TC of GO sheets was
investigated by Aref et al. [69] by using a reverse NEMD simulation
method. The results show that, since functionalization of GO has in­
tensified phonon scattering [69], its TC decreases dramatically after
alkylation and deteriorates with increasing chain length of the func­
tional groups. In another NEMD simulation study on fluorinated gra­
phene [70], Huang et al. found that the TC was dependent on the
structure (zigzag or armchair) of graphene and the distribution of
fluorine atoms. Hence, TC decreases rapidly with increasing fluorine
coverage from 0 % to 20 %, stabilizes from 20 % to 70 %, and then
increases quickly when the coverage approaches 100 %. These results
agree with the fact that the functionalization induced TC reduction is
caused by phonon scattering at the interface of fluorinated and non-
fluorinated graphene regions, and when fluorine coverage increases to
100 %, there are no interfaces. However, it must be noted that the fully
fluorinated graphene possesses only 40 % the TC of pristine graphene.
Apart from the mono-layer graphene, it has also been confirmed that
functional groups can also reduce the TC of bi-layer graphene (BLG)
sheets [71].
2.6. Effects of size and layer number
Chen et al. experimentally investigated TC of CVD fabricated SLG
with different diameter ranging from 2.9 to 9.7 μm, and obtained TC of
suspended graphene between 2600–3100 W/m·K with no clear size ef­
fect [16]. This observation is attributed to the relatively large mea­
surement uncertainty as well as grain boundaries, wrinkles, defects,
and/or polymeric residue which are possibly present in the tested
samples.
Theoretically, the lateral size of a graphene ribbon is critical to
maintain high TC of graphene since the edge can scatter phonons. A
recent experimental study showed that for porous graphene nano-mesh
with feature size of ∼10 nm, the thermal conduction would be dra­
matically altered due to phonon-edge scattering. The neck width be­
tween pores is critical. Specifically, the TC of graphene nano-mesh with
8 nm neck width can be as low as ∼78 W/m·K that is the lowest value
for suspended graphene obtained by MD simulation [72]. Mahdizadeh
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

Fig. 8. Effect of degree of (a) −CH3 and (b)

–C6H5 functionalization on TC. S is the degree
of functionalization and defined as the ratio of
sp3 hybridized carbon atoms to the total carbon
atoms. The error bars are obtained from mul­
tiple MD simulations of statistically in­
dependent functionalized GNRs for a given
functional group coverage regime.
(Reproduced with permission from [68]).

and Goharshadi studied the heat transport of a series of GNRs with 2 nm

width and 2−30 nm length [73]. Their results show that the TC decays
exponentially with GNR length from 3500 W/m·K at 2 nm to a limiting
value of ∼1500 W/m·K at 30 nm. Majee and Aksamija obtained TC of
suspended GNRs with a constant ribbon width, showing a logarithmic
divergence for ribbon length < 100 μm [74]. By contrast, Nika et al.
found that the long mean free path of long wave-length acoustic pho­
nons in graphene could lead to an unusual non-monotonic dependence
of TC on ribbon length (Fig. 9a) [75]. For a graphene ribbon with a
width of 5 μm, the maximum TC occurs at a ribbon length of ∼100 μm,
then gradually reduces to a steady constant value at a length of ∼1000
μm. Detailed discussion reveals that the TC-GNR length relationship is
actually associated with the ribbon width. With infinitely wide ribbons,
the monotonic dependence of TC on length is obtained (Fig. 9b). Be­
sides, the TC of graphene ribbon depends on its width. Unlike the length
effect, the mechanism of width effect in graphene is mainly due to the
limitation of the directional edge on phonon transmission [76].
Layer number is obvious for graphene to be distinct from graphite.
Fig. 10. Measured TC as a function of the number of atomic planes in FLG. The
Thus, it is believed that interlayer phonon coupling affects TC of gra­ dashed straight lines indicate the range of bulk graphite thermal conductivities.
phene. Cao et al. reported monotonously decreasing TC for graphene The blue diamonds were obtained from the first-principle theory of thermal
with increasing layers [77]. However, calculation gives an un­ conduction in FLG based on actual phonon dispersion and accounting for all
reasonably low TC of graphene with 500 W/m·K for single-layer gra­ allowed three-phonon umklapp scattering channels. The green triangles are
phene and ∼300 W/m·K for 5-layer graphene [77]. For bi-layer GNRs, Callaway–Klemens model calculations, which include the extrinsic effects
Liu et al. [78] showed that the TC depends weakly on the stacking characteristic of thicker films (Reproduced with permission from Ref. [19]).
pattern, with the thermal conductivities of AA-stacked bi-layer GNRs (For interpretation of the references to colour in this figure legend, the reader is
slightly higher than those of AB-stacked. However, again low TC values referred to the web version of this article.)
of 100−500 W/m·K of these graphene ribbons are obtained. Such small
values may be due to the small domains used in MD modelling. conduction crossover is clearly demonstrated as the number of atomic
In an experimental study, Ghosh et al. [19] found that, at room- planes changes from 2 to about 8. Sadeghi et al. conducted a systematic
temperature, the TC changes from ∼2800 to 1300 W/m·K as the investigation on TC of MLG on an amorphous substrate. It is found that
number of layers in graphene increases from 2 to 4 (see Fig. 10). This even after the graphene thickness is increased to 34 layers, its TC is still
phenomenon can be explained by the through-plane coupling of the higher than that of graphite [79]. Hence, it is believed that MLG can be
low-energy phonons, and changes in the phonon umklapp scattering. even better than graphite platelets in order to achieve high TC in
The TC obtained is reasonable and the 2D graphene to 3D graphite heat polymer composites.

Fig. 9. (a) Dependence of TC of rectangular

GNR on ribbon length L shown for different
specularity parameters p. The specularity
parameter determines the fraction of diffu­
sively scattered phonons at the edges and is
related to the edge roughness. The width is
fixed at d = 5 μm. (b) Dependence of TC of
rectangular graphene ribbon on the ribbon
length L shown for different ribbon width d.
The specularity parameter is fixed at p = 0.9.
Note in both (a) and (b) an unusual non-
monotonic length dependence of TC, which
results from the exceptionally long mean free
path of the low-energy phonons and their
angle-dependent scattering from the ribbon
edges (Reproduced with permission from Ref.
[75]).

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X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

2.7. Effects of folding, twisting and wrinkles 3. Modelling TC of graphene/polymer composites

The common deformations of graphene (e.g., folding, twisting and Developing composite materials with desirable properties through
wrinkles) may remarkably affect its TC. Higher flatness ratios lead to traditional trial-and-error method is not only time-consuming and
higher TC. A low flatness ratio causes substantial degradation in TC costly but also difficult to obtain valuable insights on materials design.
[80], which in turn may markedly limit the thermal conductivity en­ An optimum way toward real high-performance composites is to clearly
hancement (TCE) in graphene/polymer composites since twisting, define the factors determining the properties of a composite through
folding and wrinkles of high aspect ratio graphene cannot be totally analytical and numerical simulations and then to fabricate the com­
avoided in the matrix. posites by taking all the factors into full account. That is, analytical and
It has been shown that folding can severely modulate the thermal numerical simulations can inform what should be done to optimize and
transport properties of GNRs [81]. TC may be greatly decreased up to what is not necessary from the scientific perspective.
70 % in comparison with that of its flat counterpart although no defects Traditionally, the TC of composite materials can be modelled using
are actually introduced to the graphene during folding. The more the some homogenization approach, e.g., effective medium theory. The
ribbons are folded, the more the thermal conductivities are reduced effective medium theory was first developed analytically to obtain ef­
because of the strong scattering of low frequency phonon modes at the fective TC values of homogeneous spherical particle filled composites,
folds (see Fig. 11). In a study by NEMD simulation [82], a more drastic and then gradually extended to model different types of fillers [71].
effect is illustrated. Although perfect graphene may possess a TC of up Although graphene/polymer composites did not attract much interests
to 2212 W/m·K, TC of folded graphene sheets with macroscopic thick­ until 2006 [88], Nan et al. developed an analytical model/formula
ness is only 71.4 W/m·K, which is ∼3.3 % of perfect graphene struc­ which can consider the filler shape, orientation and interface thermal
ture. resistance. It is most suitable to estimate the effective TC (kc ) of com­
Other deformations, such as twisting and wrinkles, will undoubtedly posites with graphene as filler [89]. That is,
reduce substantially the TC of graphene [81–87]. Using the non-equi­
3 + f [2 11 (1 L11) + 33 (1 L33 )]
librium Green’s function, which is another atomic simulation method k c = km
for phonon transport, it is shown that the thermal conductance of GNRs 3 f (2 11 L11 + 33 L33 ) (1)
can be, controllably and reversibly, modulated over more than 55 % at with
room temperature by adjusting the twisted angle. The tuning range of
c c
the twisted angle depends on the width and length of the graphene k11 km k33 km
11 = , 33 = ,
ribbon under study. The reduction of the thermal conductance mainly
c
km + L11 (k11 km ) c
km + L 33 (k33 km ) (2)
comes from the phonon scattering due to the inhomogeneous force
constant in the twisted nanoribbons [83]. NEMD simulations on gra­ c
kf c
kf
k11 = , k33 =
phene with wrinkles and pristine graphene show lower TC for the 1 + L11 kf / km 1 + L33 kf / km (3)
former owing to the increased phonon scattering and decreased phonon
lifetime. Also, the TC of graphene wrinkles is insensitive to temperature 2
1
L33 = 2 L11 = 1 2 cosh
in the range of 200−600 K caused by the dominance of low frequency 2( 2 1) 2( 2 1)3/2 (4)
phonon modes in the vertical direction along the wrinkle textures,
which is distinctly different to pristine graphene [86]. where kc is isotropic TC due to random dispersion of graphene in a
polymer matrix, km and kf are thermal conductivities of matrix and

Fig. 11. (A) Simulation structures of multiple folded GNRs. The structures in (a), (c), (e) and (g) are GNRs before relaxation and have 0.74 nm in inter-lamellar space.
(a) GNR with 3 folds; (b) relaxed GNR with 3 folds and 0.24 nm inter-lamellar space; (c) GNR with 4 folds; (d) relaxed GNR with 4 folds and 0.37 nm inter-lamellar
space; (e) GNR with 5 folds; (f) relaxed GNR with 5 folds and 0.34 nm inter-lamellar space; (g) GNR with 6 folds; (h) relaxed GNR with 6 folds and 0.27 nm inter-
lamellar space. The heat bath with high temperature and low temperature are shown in red and blue, respectively. There are two substrates for each GNR. One is on
the top layer and the other is below the bottom layer. (B) Relative TC modulation by compressing the inter-lamellar space with different folds in GNRs. The value 1.0
of relative TC corresponds to 111.5 W/m·K which is TC of the flat zigzag GNR. The sizes of all GNRs are the same, which are 0.71 nm in width and 21.3 nm in length
(Reproduced with permission from Ref. [81]). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)

8
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

graphene, respectively, and kiic = (i = 1, 3) is equivalent TC of the
graphene composite along the x- and z- directions. f is graphene volume
fraction and ρ (=a3/ a1) is aspect ratio, defined as the ratio of thickness
to diameter, of graphene. = (1 + 2 ) , where = ak /a3 and
ak = km/Gk ; Gk is interfacial thermal conductance of graphene/polymer
matrix. The thermal conductivities of graphene/polymer composites
can be predicted using Eqs. (1)–(4) with kf , f and Gk known.
Although Nan et al.’s model can estimate TC of graphene compo­
sites, it needs the intrinsic TC value of graphene as an input. As de­
scribed in Section 2, unlike bulk materials, the external factors induced
during composites processing can affect the intrinsic properties of
graphene. As such, in theory, an atomic scale approach has to be used to
model the thermal transport in graphene/polymer composites. Hence,
MD simulations have been extensively used to evaluate TC of graphene/
polymer composites [67,79,85,90–103]. In the following subsections,
the main factors which determine TC of graphene/polymer composites
by MD simulations will be discussed.
3.1. Interfacial thermal transport and interfacial thermal conductance
It is well established that the filler/matrix interfacial thermal con­
ductance is critical to determine the TC of a composite. Poor thermal
coupling between filler and matrix usually results in limited thermal
conductance enhancement of the composite due to the serious mis­
match of the phonon spectra of the interface components [90]. The
degree of mismatch of the phonon vibration at the interface can be
evaluated by the calculated vibration power spectrum (VPS) which
reflects the atomic vibration energy (that is, the essential part of
thermal energy). At the interface between two dissimilar materials, the
similarity of VPS usually determines the interfacial thermal con­
ductance. Larger overlap between VPS gives larger interfacial thermal
conductance (or smaller resistance). As an example, Fig. 12 shows the
VPS of a composite of graphene and paraffin matrix (C30H60). The
coupling between the through-plane of graphene and polymer in the
low frequency range (2−16 THz) contributes to the main interfacial
thermal transport; however, there is minimal VPS spectra overlap, in­
dicating weak vibrational match or high interfacial thermal resistance
in the graphene/paraffin composite.
Interfacial interaction enhancement effectively increases the inter­
facial thermal conductance across the graphene/polymer interface. The
functionalization of graphene with organic molecules facilitates strong
interaction with the polymer matrix, which, in turn, greatly restrains
the vibrational mismatch between graphene and polymer matrix. In
general, there are two approaches to functionalize graphene: covalent
functionalization and non-covalent functionalization [104].
thermal conductance becomes significant, and the initial morphology of
the grafting chains gives a large difference on enhancement of inter­
facial thermal conductance. In addition, grafting of aligned long PE
chains onto graphene gives a much higher improvement of the inter­
facial thermal conductance compared to the grafting of random long PE
chains on graphene. As revealed by Shen et al. [106], these results are
due to the aligned PE chains having more segments which interact
strongly with the polymer matrix and such aligned PE chains also
possess intrinsically higher TC than the random PE chains.
MD simulations show that the grafting of polymer chains onto the
graphene surface can significantly enhance the interfacial thermal
conductance across the graphene/polymer interface. However, it is
difficult in practice to graft polymer chains onto the basal plane of
graphene because all the bonds of graphene are saturated on this plane.
Moreover, MD simulations demonstrate that the covalent grafting of
polymer chains on 5 % carbon atoms of the basal plane of graphene
gives ∼60 % decrease of TC of graphene due to the destruction of the
perfect 2D crystallinity of graphene [92].
An alternative way to solve this problem is, instead of grafting
polymer chains onto the basal plane of graphene, through covalent
functionalization at the edges of graphene, which will not compromise
the intrinsic high TC of graphene but increase the thermal conductance
across the graphene/polymer interface. Konatham and Striolo ex­
amined the effect of grafting branched alkanes on the interfacial
thermal conductance across a graphene/octane interface [91]. MD si­
mulations show that the graphene/ octane interfacial thermal con­
ductance increases by ∼3 times, benefiting from the improved coupling
of the vibrational mode between functionalized graphene and octane.
As displayed in Fig. 14, the VPS traces of graphene and octane show
that the spectra of pristine graphene and octane do not couple. But the
VPS plots of functionalized graphene by short branched alkanes and
octane overlap at several frequencies.
As mentioned above, covalent functionalization techniques can ef­
fectively reduce the interfacial thermal resistance (that is, the inverse of
conductance) between graphene and polymer matrix in the composite.
Simultaneously, the diverse covalent functional groups give different

3.1.1. Effect of covalent functionalization on interfacial thermal

conductance
Wang et al. investigated the effect of grafting of polyethylene (CnH2n
+1, PE) chains on the interfacial thermal conductance of a graphene/PE
interface [105]. It is concluded from Fig. 13 that grafting of PE chains
can enhance the interfacial thermal conductance across the graphene/
polymer interface. For example, at a grafting density of ∼0.0144/Å2,
the interfacial thermal conductance increases to 144 ± 15 MW/m2K
from 56 ± 4 MW/m2K of the pristine graphene/polymer interface. In
addition, the increase of grafting density improves the enhancement of
the interfacial thermal conductance. It is also concluded that the length
and initial morphology (Fig. 13c,d) of grafting chains show important
effects on the interfacial thermal conductance. When short PE chains
(i.e., n = 8, 12) are grafted onto graphene, the increase of interfacial
thermal conductance is not significant; and the initial morphology of
the grafting chains shows a marginal difference in the improvement of
the interfacial thermal conductance. This is because the grafted PE
short chains have weak interaction with the polymer matrix, resulting Fig. 12. VPS spectra of carbon atoms of paraffin and graphene. The VPS
in poor thermal coupling between the graphene and polymer. With spectrum of graphene is decomposed into in-plane and through-plane direc­
longer grafted PE chains (i.e., n = 16), the increase of interfacial tions. (Reproduced with permission from Ref. [90]).

9
X. Huang, et al.
amount of reduction on interfacial thermal resistance in the graphene/
polymer composites. Wang et al. studied the effect of different covalent
functional groups [e.g., butyl (−C4H9), carboxyl (−COOH) and hy­
droxyl (−OH)] on the reduction of interfacial thermal resistance of
graphene/epoxy composites [107]. These functional groups were con­
sidered randomly dispersed on both sides of graphene with coverage of
carbon atoms varying from 1.19 % to 9.52 %. Defining the interfacial
thermal resistance across the pristine graphene and epoxy as RK0, the
simulation results showed that the interfacial thermal resistance ratio
(RK/RK0) between functionalized graphene and epoxy was less than 1,
indicating reduction of interfacial thermal resistance between functio­
nalized graphene and epoxy resin. The reduction increased with in­
creasing coverage of covalent functionalization and the butyl group
gave the largest reduction among the three functional groups. In an­
other study, Zabihi and Araghi compared the effects of three functional
groups (phenyl, methyl and hydrogen) on the interfacial thermal re­
sistance of graphene/paraffin composites [108]. It found that each
covalent functionalization group reduced substantially the interfacial
thermal resistance, and the phenyl group was most effective to enhance
thermal transport across the graphene/ paraffin interface [108].
Although functionalization of graphene can effectively decrease the
interfacial thermal resistance, it may not enhance TC of the composites
because the functionalization can also deteriorate the intrinsic TC of
Fig. 14. VPS spectra of carbon atoms in octane, (a) pristine graphene (GS 216, which means the graphene sheet has 216 carbon atoms) and (b) short branched
alkanes functionalized graphene. (Reproduced with permission from Ref. [91]).
10
Materials Science & Engineering R 142 (2020) 100577
Fig. 13. Scheme illustrating the initial mor­
phology of PE chain grafted onto the surface of
a graphene sheet (a) aligned and (b) random.
Effects of grafting density on interfacial
thermal conductance across the graphene/
polymer interface with different initial PE
chain morphologies: (c) aligned and (d)
random. (Reproduced with permission from
Ref. [105]).
graphene. For example, the TC of a pristine graphene sheet embedded
in epoxy resin can be reduced by ∼50 % compared to the intrinsic TC
of free-standing graphene owing to the large phonon energy reduction
weakened by the matrix. TC reduction of functionalized graphene was
relatively small (e.g., ∼10 %) when embedded; but the functionaliza­
tion of graphene may deteriorate its TC by over one order of magnitude,
whether the graphene is free-standing or embedded in the matrix, due
to the increased phonon scattering from the functional groups. Shen
et al. discovered [109] that graphene functionalization is effective in
enhancing TC of composites with small lateral sizes of graphene, while
TCE is ineffective when graphene has a large size. Therefore, a critical
size theory was proposed based on the effective medium theory, which
could identify the predominant factors controlling the TC of graphene/
polymer composites. In this theory, it is necessary to functionalize
graphene to improve the interface conductance and TC of the composite
when the size of graphene is smaller than the critical value (e.g., a few
μm). However, the intrinsic high TC of pristine graphene is more im­
portant when the size of graphene is larger than the critical value, and,
in this case, functionalization is unnecessary. Shen et al. compared the
effect of four types (oxygenated group [−OH], fluorine [-F], amine
[-NH2] and triethylenetetramine [TETA]) of graphene functionalization
on the TCE of epoxy resin [109]. It was found that functionalization by
amino groups, particularly TETA, was most effective among the four
X. Huang, et al.
functional groups. This can be understood since covalent bonding im­
proves the interfacial thermal conductance and the long TETA chains
enhance the vibrational coupling of phonons because of their penetra­
tion into the epoxy. The enhanced interfacial thermal conductance in
functionalized graphene compensated its low TC, resulting in higher TC
of the composite when the lateral size of graphene was smaller than the
critical value [109].
3.1.2. Effect of non-covalent functionalization on interfacial thermal
conductance
Compared to covalent functionalization, non-covalent functionali­
zation can be realized much easier. Also, no defects or adatoms are
introduced to the basal plane of graphene during the functionalization,
which is conducive to preserving the intrinsic high TC of graphene.
These features make non-covalent functionalized graphene sheets pro­
mising to prepare polymer composites with enhanced TC. Typical non-
covalent functionalization of graphene is through the absorption of
molecules containing aromatic structures on the basal surface of gra­
phene via π-π interaction. For example, pyrene derivatives have been
widely used to non-covalently functionalize graphene. Lin and Buehler
studied the effect of non-covalent functionalization of graphene by alk-
pyrene molecules on the interfacial thermal conductance of graphene/
polymer interface [95]. Three alk-pyrene derivatives were used as non-
covalent linkers between graphene and model matrix (i.e., octane).
Simulation results showed that only C8-pyrene could increase the in­
terfacial thermal conductance across the graphene/octane interface (22
% increment). This result was caused by the different orientation of the
alkyl chains of pyrene derivatives. The simulation results showed that
C8-pyrene had the highest degree of parallel alignment along the basal
surface of graphene, hence maximizing the through-plane phonon
transport via carbon-hydrogen bond vibrations. In another MD simu­
lation investigation, functional pyrenes, such as 1-pyrenebutylamine, 1-
pyrenebutyric acid and 1-pyrenebutyl were found to have a similar
effect on reducing the interfacial thermal resistance between graphene
and paraffin [110]. In addition, it was found that the reduction of
thermal resistance increases as the coverage of functional molecules
becomes higher. At 26−28 wt.% of functional pyrene molecules, the
interfacial thermal resistance between graphene and paraffin can be
reduced by 16–17 %.
The effects of non-covalent functionalization of graphene by three
polycyclic aromatic hydrocarbons on the graphene/epoxy interfacial
thermal resistance were studied [107]. In this MD simulation study,
functional molecules were attached to both sides of graphene and the
functionalization coverage was defined as the ratio of total number of
functional molecules to the number of carbon atoms in the graphene. It
found that the presence of non-covalent functional molecules resulted
Fig. 15. Interfacial thermal conductance (Gκ) plotted against (a) interfacial van der Waals interaction, and (b) across graphene/polymer interface versus polymer
density. (Reproduced with permission from Ref. [90]).
11
Materials Science & Engineering R 142 (2020) 100577
in reduced graphene/epoxy interfacial thermal resistance, and the re­
duction increased markedly with increasing coverage of functionaliza­
tion. However, the three types of polycyclic aromatic hydrocarbons did
not show different effect on the reduction of interfacial thermal re­
sistance. The vibrational density of states (VDOS) of graphene was re­
distributed after non-covalent functionalization and became better
coupled with the VDOS of epoxy, which was the main mechanism for
the reduced graphene/epoxy interfacial thermal resistance [110].
Van der Waals interaction between graphene and polymer matrix
also affects the contact strength of graphene and polymer, giving dif­
ferent interfacial thermal conductance values across the graphene/
polymer interface. Luo and Lloyd examined the effect of van der Walls
interaction between graphene and polymer on their interfacial thermal
conductance [90], which displayed significant enhancement as the van
der Walls interaction became stronger (Fig. 15a). This result indicates
that high TC graphene composites can be fabricated by selecting a
suitable polymer matrix that has an intense interaction with graphene
through van der Walls forces.
Increasing the polymer density provides stronger van der Waals
forces at the graphene/polymer interface and consequently stronger
thermal coupling at the interface is expected. Luo and Lloyd also stu­
died the role of polymer density on interfacial thermal conductance
[90]. Fig. 15b shows that there is a fairly rapid increase of thermal
conductance across the graphene/polymer interface with increasing
polymer density.
3.1.3. Effect of defect/doping on interfacial thermal conductance
Defects of graphene affect the graphene/polymer interfacial thermal
conductance. Li et al. studied the effect of four different types of defects
on graphene/epoxy interfacial thermal conductance [101]. Fig. 16
shows that SW and MV defects can markedly enhance the interfacial
thermal conductance. When the SW defect concentration is increased
from no defects to 13 %, the interfacial thermal conductance is in­
creased from 135.54 ± 5.82 to 162.64 ± 4.84 MW/m2K; and as the
removed atoms of MV defects is increased from no defects to 56, the
interfacial thermal conductance is increased from 135.54 ± 5.82 to
163.78 ± 7.10 MW/m2K [101]. These results can be understood be­
cause the introduced defects in graphene facilitated the VDOS curves to
overlap. The impact of carbon isotope doping on graphene/polymer
interfacial thermal resistance was also studied using MD simulation. It
found that the graphene/epoxy interfacial thermal resistance was in­
sensitive to 13C isotope doping in graphene [17,111] since the VDOS for
13
C-modified graphene exhibited only small differences when compared
to graphene based on 12C [107].
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

Fig. 16. Interfacial thermal conductance be­

tween graphene and epoxy resin with different
defects. The dashed blue horizontal lines in­
dicate interfacial thermal conductance of the
composites with defect-free graphene.
(Reproduced with permission from Ref. [101]).
(For interpretation of the references to colour
in this figure legend, the reader is referred to
the web version of this article.)

3.2. Effect of interfacial thermal conductance on TC of composites are in the majority; second, the graphene platelets have many defects,
resulting in lower TC than expected; and third, the graphene platelets
Larger interfacial thermal conductance indicates less thermal energy prepared in this study have higher interfacial thermal resistance with
loss at the graphene/polymer interface, and thus higher TC of compo­ the polymer matrix than that used in the calculations.
sites can be obtained. Wang et al. studied the effect of interfacial Although many studies have revealed that an increased number of
thermal conductance on TC of graphene composites [105]. As shown in graphene layers would result in a reduction of TC of suspended or free-
Fig. 17, the TC of graphene/polymer composites clearly increases with standing graphene [19,77], this is quite different with graphene/
increasing interfacial thermal conductance Gκ. Further, TC due to the polymer composites in which MLG sheets possess large lateral sizes but
increase of interfacial thermal conductance is stronger at higher gra­ similar aspect ratios as SLG sheets. MD simulation results (Fig. 19a)
phene volume fraction (e.g., f > 4 vol.%). have shown that the thermal conductivity of graphene/epoxy compo­
sites are enhanced significantly with increasing number of graphene
3.3. Effects of graphene size, dispersion and volume fraction on TC of layer that is consistent with experimental results [114]. Specifically, as
shown in Fig. 19b, the TCE factor (i.e., c k m ) of epoxy composites
k k
composites m
fabricated with 20-layer GNPs, at similar aspect ratio (∽200), is higher
Because of the usually low intrinsic phonon scattering, the TC of than those of composites containing 1-layer and 5-layer GNPs. It is
graphene generally increases with sample size. This has also been noted that compared to TC values of MLG and SLG epoxy composites
confirmed by NEMD simulation, which shows that the TC of graphene given in Fig. 18, the simulated TC values of these composites obtained
increases almost linearly with size below a critical value [93]. This in Fig. 19 show an opposite trend. This is because the TC of embedded
critical value depends on the sample quality. Thus, TC of graphene/ SLG and MLG are assumed to be the same in the effective medium
polymer composites increases rapidly with the size of graphene sheets model in Ref. [93], which we believe is not accurate.
when the size is smaller than this critical value. Hu et al. investigated
the graphene size and volume fraction dependence of the composite TC 3.4. Graphene-polymer interactions induced reduction of TC of graphene
and evaluated the interfacial thermal conductance [93]. As displayed in
Fig. 18, the TC of graphene/polymer composites increases rapidly with Apart from the aforementioned factors influencing the TC of gra­
graphene size and then reaches an upper limit, which is consistent with phene/polymer composites, a factor which can be inadvertently ig­
the size dependence of TC of pristine graphene sheets [75]. However, in nored is the variation of TC of graphene itself after being introduced
graphene framework/polymer composites, higher TC can be achieved into a polymer matrix. This should be considered in the MD
by size-dependent modulation of graphene sheets at a relative lower
graphene loading. Hou et al. reported that a quasi-isotropic graphene
framework fabricated by vacuum filtration could impart high in-plane
and through-plane thermal conductivities to epoxy composites. More­
over, the quasi-isotropic arrangement can be achieved by modulating
smaller lateral size graphene sheets [112].
Graphene/polymer interfacial area increases with graphene volume
fraction. However, the increase of thermal energy loss in graphene/
polymer interface is usually much lower than the heat transport en­
hancement, finally resulting in the increase of TC in the composites
[93,113]. As shown in Fig. 18b, at a given graphene volume fraction,
the MLG sheets (5-layer) can be regarded as the aggregation of SLG (1-
layer), leading to reduced thermal conductive paths in the composite.
Also, the TC of graphene decreases with increasing number of graphene
layers. Together, these factors explain why higher TC of composites can
be achieved with SLG fillers instead of MLG. In Fig. 18a, it is noted that
the upper limit of TC is achieved at a smaller size of SLG than that of
MLG, thus confirming that well-dispersed graphene sheets have higher
TCE efficiency in polymer composites. In the investigation by Yu et al.
[94], MLG/polymer composites displayed TC values much lower than
the expected values calculated using Eqs. (1–4). Three factors cause Fig. 17. TC of graphene composites versus graphene/polymer interfacial
these large discrepancies. First, graphene platelets have a wide layer thermal conductance (Gκ). Here L is the length of graphene and f is the graphene
number distribution and the platelets with layer number larger than 5 volume fraction. (Reproduced with permission from Ref. [105]).

12
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

Fig. 18. (a) TC of polymer composites with 1.0 vol.% graphene versus graphene sheet size and (b) TC of graphene composites versus graphene volume loading. TC
values of graphene and polymer matrix were set as 1000 W/m·K and 0.298 W/m·K, respectively. The interfacial thermal conductance was set at 30 MW/m2K, which is
calculated from MD simulation. (Reproduced with permission from [93]). The experimental data are for MLG/polymer composites reproduced from Ref. [94].

calculations. The simulation results obtained by Mortazavi et al. show

that, compared to free SLG, the TC of SLG in epoxy can be decreased by
30 % due to the interfacial interaction between graphene and epoxy
[92]. The main mechanism underlying this phenomenon is the overlap
of the phonon spectra of carbon atoms for graphene and epoxy, which
causes phonon scattering of graphene in a wide range of frequencies
and hence reduction of its intrinsic thermal conductivity.

4. TC of graphene/polymer composites: Influence of graphene

types

4.1. TC of GO/polymer composites

Apart from their high TC, graphene sheets also have high electrical
conductivity so that graphene/polymer composites usually exhibit sig­
nificantly enhanced electrical conductivity even at very low graphene
loadings [118,119]. This restrictively limits their applications to parts
and devices requiring a high level of electrical insulation [120,121].
As a derivative of graphene, GO is an electrically insulating material
possessing much higher TC in comparison with polymers. Hence, it can
be used to enhance TC of polymer composites yet retaining the elec­
trically insulating properties of the composites [122–124]. Kim et al.
studied the thermal and electrical conductivities of GO (prepared by the
Hummers method and the C:O ratio is 1.8) filled epoxy composites
[125]. As shown in Fig. 20, the GO fillers enhance the TC of epoxy
matrix and retain the electrical insulating properties. At 3 wt.% GO, the
TCE factor is ∼0.9 and the electrical conductivity is of the same order
of magnitude as neat epoxy. Wang et al. found that incorporation of 5 Fig. 20. TC, TCE factor and electrical conductivity of GO/epoxy composites.
Results shown are taken from test data provided in Refs. [125,127].
wt.% GO into epoxy increased the composite TC to ∼1.0 W/m·K, giving

Fig. 19. (a) Simulation results showing the ef­

fects of layer number (n) and lateral size of
graphene on TC of epoxy composites with 1.0
vol.% graphene. (b) Experimental data (unfilled
symbols: blue star from [114], red circle from
[94], blue diamond from [115], red triangle
from [116], and black right-pointing triangle
from [117]) and MD simulation results (solid
curves) showing TCE (in %) of epoxy composites
with graphene aspect ratio and the effect of
layer number (n = 1, n = 5 and n = 20) but
similar lateral size. (Reproduced with permis­
sion from Ref. [114]). (For interpretation of the
references to colour in this figure legend, the
reader is referred to the web version of this ar­
ticle.)

13
X. Huang, et al.
a TCE factor of ∼4.0 [126]. However, detailed structural analyses of
the GO fillers and electrical measurements of the composites were not
given so that improved understanding of the mechanisms involved
could not be obtained. For example, the GO fillers might be partially
reduced during the fabrication process, leading to further increase of
the TCE of composites.
It should be noted that even at moderate temperatures, the reduc­
tion of GO can happen within the polymer matrix [128–130]. This issue
should be considered because the reduction of GO not only enhances
the TC more effectively but also gives a significant variation of elec­
trical properties of the composites (e.g., electrical conductivity, di­
electric constant, etc.), particularly those highly loaded with GO. An
investigation on TC of GrO-NH2/epoxy composites revealed that the
oxidation degree of GrO-NH2 played a critical role [131]. GrO-NH2
refers to (3-aminopropyl) triethoxysilane modified graphite oxide,
where -NH2 groups were introduced to establish covalent interactions
between GrO and epoxy resin. In detail, Fig. 21 indicates that the mildly
oxidized GrO-NH2 exhibits edge functionalization and a strong TCE
[131]. This is caused by the edge-functionalized GrO sheets which
provide a preferential thermal conduction pathway for high efficiency
heat transfer in epoxy. Over-oxidation of GrO results in weak TCE in
GrO/epoxy composites, while TCE can become stronger when the over-
oxidated GrO is reduced.
GO cannot be dissolved in many organic solvents including N, N-
dimethylformamide (DMF), tetra-hydrofuran (THF) and N-methyl-2-
pyrrolidone (NMP), which makes the preparation of their polymer
composites difficult [132]. To disperse GO in organic solvents, func­
tionalization is required. This will also contribute to the TC value of
their composites [122]. Tseng et al. studied glycidyl methacrylate-
functionalized GO on the TC of polyimide (PI) composites [130]. As
shown in Fig. 22a, composites with functionalized GO (f-GO) exhibit
significantly enhanced TC in comparison to those with as-prepared GO.
Although the electrical resistance of the composites with high f-GO
loading decreases more when compared with the corresponding as-
prepared GO composites, both types of composites still have high
electrical resistance (see Fig. 22b).
Aminopropylisobutyl polyhedral oligomeric silsesquioxane (Ap-
POSS) has been used to modify GO for improved solubility in organic
solvents and enhanced dispersion in epoxy matrices. Ap-POSS-GO
shows great influence on TCE but only marginal impact on electrical
insulation [122]. For instance, adding 0.5 wt.% Ap-POSS-GO improves
the TC of epoxy by 57.5 %, but the same content of GO only yields a
16.7 % increase on TC of epoxy. However, the epoxy composite with
0.5 wt.% Ap-POSS-GO displays a slight decrease of the electrical
Fig. 21. TC of GrO-NH2/epoxy composites with GrO fabricated with different ratio of KMnO4 to graphite. Here, GrO refers to graphite oxide. The dash line
corresponds to TC (0.157 W/m·K) of neat epoxy resin. (Reproduced with permission from Ref. [131]).
14
Materials Science & Engineering R 142 (2020) 100577
resistivity in comparison with neat epoxy [122].
4.2. TC of RGO/polymer composites
4.2.1. Effect of RGO loading
GO is highly oxidized graphene, where oxygen atoms are bound to
carbon in the basal plane and at the edges of graphene, resulting in
large amounts of hydroxyl, epoxy and carboxyl groups. The oxygen-
containing functional groups form numerous tetrahedrally bonded sp3
carbon clusters, yielding strong phonon scattering and hence GO
usually exhibits low TC. Reduction of GO produces a high fraction of
large-size sp2 carbon clusters, in which the phonons travel with slight
scattering and therefore RGO exhibits higher TC compared to GO. Thus,
the TC of RGO composite is usually determined by several factors:
loading level, surface functionality and structural property [133].
Using thermally reduced GO, Yavari et al. prepared 1-octadecanol-
based phase change composites (PCCs) [134]. At 4 wt.% fraction of
RGO, TCE factor of PCCs is ∼1.4. Xue et al. revealed that TC of RGO/
porous poly(vinyl alcohol) (PVA) composites shows an almost linear
increase from 0.31 W/m·K for neat PVA to 0.54 W/m·K at 2 wt.% RGO.
It is also shown that RGO disrupts the chain configuration of PVA
molecules, resulting in free volume reduction that may be responsible
for the increase in TC [135]. In addition, RGO has been used to improve
the TC of silicone grease and a TCE factor of 1.0 is obtained at 1.0 wt.%
RGO [136]. The reduction of GO and hence the TCE of RGO composites
depend strongly on the reduction method used and the reaction con­
ditions of temperature and chemical agent employed. For example, with
3.0 wt.% RGO, reduced by the microwave treatment of GO (C:O =
3.2:1), in polycarbonate (PC), only a small TCE factor of 0.20 is ob­
tained [137]. Further, marginal increase of TC is found in poly(vinyli­
dene fluoride) (PVDF) filled with hydrazine hydrate reduced GO (< 7.0
wt.%) [138]. The low TCE may be attributed to the weak reduction
capability of the method/reagent used, resulting in low C:O ratio and
high defect density [137–139]. In fact, annealed composites at high
temperatures show high TC since RGO is further reduced within the
polymer matrix [137]. Lee et al. revealed that the thermal conductance
of RGO/silicone composites not only is affected by thermal reduction
induced morphological and structural changes of RGO but is also sig­
nificantly affected by the phenolic group density on the basal plane of
RGO. The phenolic groups can decrease the interfacial thermal re­
sistance between RGO and silicone [133].
4.2.2. Effect of covalent functionalization of RGO
RGO has the tendency to agglomerate and is generally incompatible
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

Fig. 22. (a) TC and (b) surface electrical resistance of GO/PI and f-GO/PI composites based on data provided in Ref. [130].

with most polymers, exhibiting poor dispersion and high interfacial
thermal resistance. To overcome these disadvantages, covalent func­
tionalization of RGO is usually used to enhance its dispersion and re­
duce the interfacial phonon scattering [140]. To achieve strong RGO/
polymer interaction, RGO functionalized by polymer chains have often
been adopted. Both the edges and basal plane of RGO are functionalized
to enhance the dispersion and interfacial interaction with the polymer
matrix. Polyester functionalized RGO (f-RGO) is prepared by grafting
polyester chains onto the edges of GO via esterification between hy­
droxyl terminations of polyester and carboxyl groups of GO edges [141]
and then reduced. By this method, the sp2 conjugated structure is lar­
gely preserved. The TCE factor is 1.90 at 1.5 vol.% RGO loading, re­
vealing a great enhancement of polyester grafted RGO (C:O = 5.5:1).
The influence of polymer chain length grafted on the RGO edges on TCE
is also studied [141]. Amino-terminated polyethylene-glycol (PEG) of
different chain length is used to functionalize RGO to enhance the TC of
polyamide 6 (PA6) composites. The through-plane TC increases with
increasing PEG chain length.
Bis(3-aminopropyl)-terminated poly(ethylene glycol) (NH2-PEG-
NH2) has been used to disperse RGO in cellulose to prepare composites
with significantly improved in-plane TC which increases to 9.0 W/m·K
at 6.0 wt.% RGO from 2.47 W/m·K of neat cellulose, yielding a TCE
factor of ∼2.60. The high TCE is attributed to the hydrogen bonding
between cellulose and f-RGO, the uniform dispersion of f-RGO, and the
alignment of RGO along the in-plane direction [142]. It is also reported
that the PEG chain length has significant impacts on both through-plane
and in-plane thermal conductivities of RGO/PA6 nanocomposites
[143]. The through-plane TC increases with increasing NH2–PEG–NH2
chain length; but the in-plane TC has a maximum value of 9.71 W/m·K
at a certain length of the NH2–PEG–NH2 chain [143].
Functionalization of RGO at the basal plane is also found to be
useful to improve the TCE of polymer composites. Typically, the in­
troduction of polystyrene (PS) chains onto the basal plane of RGO is
conducted via diazonium addition and succeeding atom transfer radical
polymerization (ATRP) [144]. The merit of this method is that the
grafting density and grafted chain length can be well controlled, facil­
itating the investigation of their effects on TC of PS composites. Addi­
tion of PS-f-RGO provides strong TCE which can be 1.60 even at a low f-
RGO loading of 2.0 wt.%. In general, the grafted chains in functiona­
lized graphene can act as thermal conductive pathways in the gra­
phene/polymer interface. However, as mentioned before, functionali­
zation can also deteriorate the intrinsic TC of RGO [109]. Hence, there
may exist an optimum grafting density for the highest TCE in the
composites. It is found in experiments that RGO with a lower PS
grafting density (Mn = 81600, Mn/Mw = 1.56, weight loss at 600 °C =
55.4 %) results in a higher TCE [144]. At a higher grafting density (Mn
= 21300, Mn/Mw = 1.60, weight loss at 600 °C = 49.6 %), TCE due to
the improved graphene/matrix interface may be offset by the reduced
TC of f-RGO [97,144]. Hence, it is expected that the maximum TC of
composites with polymer grafted graphene occurs at a medium grafting
density due to the competing effects between the improvement of in­
terfacial thermal conductance and the reduction of in-plane TC of
graphene.
Compared to grafting of organic polymers, the functionalization of
graphene by small molecules such as coupling agents are more con­
venient. Thus far, silane coupling agents (SCA), titanate coupling agents
(TCA) and antioxidants have been used to functionalize RGO in order to
improve the thermal conduction of RGO/polymer composites
[145,146]. Fig. 23 shows the effect of TCA functionalized RGO on TCE
of RGO/PA composites. Clearly, at 5 wt.% RGO and over, TC of f-RGO/
PA composites reaches 5.10 W/m·K from 3.34 W/m·K of RGO/PA
composites, yielding in a 53 % increase.
4.2.3. Effect of non-covalent functionalization of RGO
Although covalent functionalization of RGO can improve greatly
RGO/polymer thermal interfacial conduction, it may also result in
significant reduction of the TC of the f-RGO due to the introduction of
defect-sites with the conjugated basal plane of RGO. By contrast, non-
covalent functionalization of RGO does not generate defects within the
graphene basal plane structure. As a result, the intrinsic high TC of
graphene can be well retained.
Aromatic molecules are usually used to non-covalently functionalize
RGO via strong π-π or van der Waals interactions with the basal plane of
RGO. Pyrene (Py) derivatives are often used to functionalize RGO
through π-π interactions between Py and RGO [147]. For example, Py
terminated poly(glycidyl methacrylate) (Py-PGMA) prepared by ATRP
is used to functionalize RGO for enhancing TC of epoxy composites. The
pendant oxirane functional groups react with epoxy, thus improving the
compatibility between RGO and epoxy matrix. Fig. 24 shows epoxy
Fig. 23. TC of PA composites filled with rGO or TCA functionalized rGO.
(Reproduced with permission from [145]).

15
X. Huang, et al.
composites with Py-PGMA-RGO having much higher TC values com­
pared to the epoxy composites filled with pristine RGO, particularly at
relatively high filler loading. At 4 parts filler per hundred parts (phr) of
epoxy, for example, Py-PGMA-RGO/epoxy composite has a TC of
1.91 W/m·K, giving a thermal enhancement factor of ∼8.6. Also, this
TC is ∼20 % higher than that of RGO/epoxy composite with the same
filler content of 4 phr. Another example is RGO-based linear low-den­
sity polyethylene (LLDPE) nanocomposites, wherein Py-grafted LLDPE
(Py-LLDPE) and maleated LLDPE (MA-LLDPE) were chosen as two
different matrices for comparison. The π-π interaction between Py and
RGO yielded much improved dispersion of RGO in Py-LLDPE, and
hence RGO/Py-LLDPE displayed higher TCE values [148].
4.2.4. Effect of composites processing methods
The thermal conductivity of polymer composites depends closely on
the composite morphology, in particular, the filler dispersion state
[1,149]. Thus, the TC of polymer composites can be enhanced by
controlling the filler dispersion. Past investigations on the processing-
structure-property relationships of RGO/natural rubber (NR) compo­
sites showed that the TCE is dramatically affected by the composite
microstructure (i.e., the dispersion state of RGO), which is mainly
controlled by the processing method [150]. Fig. 25 presents the mi­
crostructure and TC of RGO/NR composites prepared by latex mixing,
solution curing and mill mixing methods. The composites prepared by
latex mixing exhibited a “web-like” dispersion morphology of RGO in
NR matrix (images a, b), and this “web-like” morphology was preserved
during the curing process in a solution containing peroxide (images c,
d), whereas the RGO platelets were uniformly dispersed in the milled
composites (images e, f). The network morphology facilitated phonon
transport along the RGO, thus giving higher TC in the composites
prepared by latex mixing and then solution treated.
RGO coated PMMA (RGO@PMMA) balls with diameters of
200−300 nm were used as core-shell fillers in epoxy matrix. The TC of
epoxy composites with 1.0 wt.% RGO@PMMA balls was increased 7-
fold compared to neat epoxy. By contrast, incorporation of 1.0 wt.%
RGO only increased TC of epoxy composite by ∼ 3-fold [151]. Using
the π–π interaction between polydopamine (PDA) coated GO (GO-PDA)
and PS microsphere, Yuan et al. prepared electrically insulating but
thermally conductive GO/PS nanocomposites [152]. GO-PDA formed a
3D interconnected structure in the nanocomposites, which resulted in
an in-plane TC of 4.13 W/m·K and a through-plane TC of 4.56 W/m·K at
a low GO-PDA loading (i.e., 0.96 vol.%).
Apart from using latex mixing and core-shell fillers, many other
methods have also been developed to construct interconnected 3D RGO
structures in thermally conductive polymer composites [153]. In gen­
eral, these preparation methods can be divided into two types: self-
assembly method and template method. The self-assembly of GO starts
from the phase separation to develop an interconnected 3D structure,
and the liquid phase acts as a spacer to avoid parallel overlap of GO
sheets and to help form interlinked pores [153]. As an example, the
preparation of interconnected 3D RGO-based composites can be de­
scribed below: First, an isotropic RGO sponge is prepared by thermal
treatment of GO solution and the reduction of GO may be conducted by
thermal or chemical methods. Second, GO or RGO aerogel is obtained
by freeze drying. Third, thermally conductive composites are prepared
by infiltrating the aerogel with polymers such as epoxy resin and
polydimethyl-siloxane (PDMS) pre-polymer. Using this fabrication
technique, Conrado and Pavese prepared epoxy composites with 1.25
wt.% RGO and obtained an 80 % higher TC compared with neat epoxy
[154]. While the processing method is simple, the spontaneous self-
assembly of GO cannot produce efficient overlap of RGO, coupled with
the low RGO content, the TCE of the composites suffers.
The template strategy utilizes commercially available polymer or
metal foam as skeleton to prepare 3D RGO structure. A typical study
was demonstrated by Qin et al. [155] (see Fig. 26). Here, melamine-
formaldehyde foam is dipped into GO suspension and then the excess
16
Materials Science & Engineering R 142 (2020) 100577
GO is removed by centrifugation from the pores. This process results in
coating of the foam skeleton by GO. After chemical reduction of GO, a
3D RGO continuous network is obtained based on the skeleton. Note the
uncoated skeleton surface is very smooth, but GO and RGO coated
skeleton surfaces become rough and exhibit crinkled texture due to the
flexibility of GO and RGO sheets. Finally, thermally conductive com­
posites are prepared by pouring PDMS pre-polymer into the RGO coated
foam. The merit of this method is that the orientation and density of
RGO can be easily controlled in the composites by controlling the foam
dipping time in GO suspension and by pressing the RGO coated foam
from different directions. As the unidirectional compression ratio of the
RGO coated foam is increased to 95 % from 0 %, the in-plane and
through-plane (or cross-plane in Fig. 26c) TCs increase to 1.68 W/m·K
and 0.76 W/m·K, respectively, from 0.175 W/m·K at zero compression,
corresponding to an increase of RGO to 2.6 wt.% from 0.13 wt.%, and
an increase of orientation to 20° from 1° [155]. In the case of 3D
compression and a compression ratio of 70 %, the isotropic TC increases
to a maximum of 2.19 W/m·K, equivalent to a RGO loading of 4.82 wt.
% [155].
Compared to constructing 3D interconnected RGO structures,
aligning RGO in one direction is more effective to improve the heat
transfer in the aligned direction. Zhao et al. reported the preparation of
high in-plane thermally conductive poly(p-phenylene benzobisoxazole)
(PBO) composite films in which RGO was self-aligned along the in-
plane direction. The RGO/PBO composite films exhibit an in-plane TC
of 50 W/m·K at 5.0 vol.% RGO [156]. Luo et al. prepared RGO/epoxy
composite films with high anisotropic TC. In their study, bulk RGO with
an aligned laminated structure in the in-plane direction was first pre­
pared by vacuum-assisted self-assembly of modified RGO in suspension.
Then, the composite film was obtained by infiltrating epoxy resin into
the bulk RGO followed by thermal curing. The composite film exhibits
in-plane and through-plane TCs of 1.32 W/m·K and 0.17 W/m·K, re­
spectively [157]. Kumar et al. fabricated thermoplastic RGO/PVDF-HFP
(poly(vinylidene fluoride-hexafluoropropylene) films by solution
casting and chemical reduction, which exhibited an in-plane TC of
∼19.5 W/m·K at a RGO loading of 27.2 wt.% [158]. Recently, the
electrospinning technique has received considerable attention in pre­
paring thermally conductive polymer composites since it can align fil­
lers along a certain direction [159]. RGO/PI nanocomposites were
prepared by electrospinning technique and the TC of PI with 5.0 wt.%
modified RGO is 4 times higher than that of pristine PI [160].
Despite the high in-plane TC achieved, most of the aforementioned
anisotropic composite films with aligned RGO display low through-
plane TC. To overcome this difficulty, Lian et al. developed a strategy to
prepare composites with high through-plane TC [161]. They con­
structed vertically aligned and interconnected RGO networks in epoxy
Fig. 24. TC of Py-PGMA-RGO/epoxy and RGO/epoxy composites versus RGO
content. (Reproduced with permission from [147]).
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

Fig. 25. TEM images showing the dispersion of RGO in the RGO/NR nanocomposites: (a, b) uncured RGO/NR nanocomposites prepared by direct latex co-coa­
gulation; (c, d) solution-treated RGO/NR nanocomposites; and (e, f) milled RGO/NR nanocomposites. Here, “solution treatment” refers to a process to cure the rubber
but preserve the morphology obtained by latex co-coagulation. (g) TC of RGO/NR composites prepared by different processing methods. (Reproduced with per­
mission from Ref. [150]).

matrix by four steps: (a) formation of GO liquid crystals; (b) oriented
freeze casting, (c) high-temperature reduction in Ar, and (d) infiltration
with epoxy resin. The composites showed a high through-plane TC of
2.13 W/m·K at 0.92 vol.% RGO, exhibiting a high TCE factor of ∼12.0
compared to neat epoxy [161].
4.2.5. Comparative study
To gain deep insights into TCE of GO or RGO composites, Fig. 27
summarizes reported TCE factors in different GO/RGO composites. It
can be concluded that, apart from the RGO/PC composites [137],
generally, TCE shows that f-RGO > RGO > f-GO > GO. In some cases,
RGO even exhibits comparable enhancement with f-RGO. This could be
caused by the high reduction degree and/or large size of RGO [109].
High temperature annealing was found to be very effective to im­
proving the quality of RGO [23,162–164]. Studies on the role of an­
nealing temperature on the TC of RGO/1-octadanol composites showed
that, as the annealing temperature was increased, the defects such as
oxygen-containing groups could be removed and the crystallinity of
RGO fully recovered [165]. As shown in Fig. 28, the intensity of D band
at 1350 cm−1, which represents lattice detects of RGO, decreases with
increasing annealing temperature up to 2000 °C. Starting from 2200 °C,
the D band disappears and RGO becomes defect-free graphene. As a
result, TCE in the composites increases with annealing temperature of
RGO up to 2000 °C and becomes stable when the annealing temperature
is higher than 2200 °C. Compared to RGO (prepared by rapidly heating
graphite oxide by Hummers’ method, e.g., > 2000 °C/min), defect-free
graphene (RGO annealed at > 2200 °C) exhibits much higher TCE in
the composites. This study shows the importance of high intrinsic TC of
the filler to enhance the TC of polymer composites.
4.3. TC of FLG/polymer and MLG/polymer composites
Defect-free SLG have several merits when used as fillers in matrix
for preparing highly thermally conductive polymer composites: ultra­
high intrinsic TC, lightweight and high aspect ratio. However, defect-
free SLG has not been widely used for this purpose owing to a few
persistent difficulties. For example, (a) large-scale production of defect-
free SLG is too expensive; (b) compared to suspended pristine SLG, the

17
X. Huang, et al.
Fig. 27. Reported TCE factors for different GO/RGO composites. h-PS-f-RGO1
and l-PS-f-RGO2 are RGO grafted with high and low density of PS chains and
RGO was prepared via reduction of GO by hydrazine hydrate (100 °C, 14 h)
[144]. Polyester-f-RGO was polyester grafted chemically reduced GO [141].
RGO was prepared by rapid thermal extension of graphite oxide [126,134]. GO
was prepared by modified Hummers method [125,130]. Py-PGMA-RGO was
non-covalent f-RGO by Py-PGMA [147]. PGMA-f-RGO was PGMA grafted RGO
[130].
SLG added to a polymer matrix shows significantly reduced TC due to
the flexural (through-plane acoustic) ZA (Z: through-plane transverse
and A: acoustic) phonon suppression; and (c) high flexibility can give
substantial wrinkling of graphene sheets in polymer matrix, leading to
an increased number of interfaces across the graphene. By contrast, FLG
18
Materials Science & Engineering R 142 (2020) 100577
Fig. 26. (a) Schematic showing the
preparation process of RGO compo­
sites. SEM images and photos of (b)
melamine–formaldehyde foam [MF],
(c) GO coated foam [GO@MF], and (d)
RGO coated foam [RGO@MF]. (e) TC
(κ) and orientation degree versus com­
pression ratio of 1D compressed com­
posites. (f) TC and RGO content versus
compression ratio of 3D compressed
composite. (g) TC versus compression
ratio of 1D compressed composites
fabricated by different dipping times.
(Reproduced with permission from Ref.
[155]).
sheets are more suitable fillers to prepare highly thermal conductive
polymer composites because of their ease of production, high intrinsic
TC and low densities of wrinkles (i.e., difficult to fold).
The superiority of FLG sheets in enhancing TC of polymer compo­
sites was demonstrated by the experimental work of Shahil and
Balandin in which liquid-phase-exfoliated defect-free graphene/MLG
hybrids were used to enhance the TC of epoxy resin [116]. The absence
of a disorder-induced D band in the Raman spectra (see Fig. 29) has
confirmed a highly ordered structure of liquid phase exfoliated gra­
phene/MLG hybrids. At 10 vol.% graphene/MLG hybrid loading, TC of
epoxy composites reaches 5.1 W/m·K corresponding to a TCE factor of
∼23. By contrast, traditional fillers, such as graphite and carbon black,
can only yield a weak TCE factor of their composites (< 2.5). It is noted
that the graphene hybrids prepared by higher centrifugation rates gave
higher TC values of the composites since higher centrifugation rates
lead to higher fractions of few-layer-graphene in the hybrids, hence
forming more compact graphene networks in the composites.
Graphene produced by liquid phase exfoliation is almost defect free,
but the method is not scalable. To produce high-quality graphene filler
at large scale, a graphite intercalation compound method was devel­
oped. GFs with low oxygen content (∼2.1 %) were fabricated using this
method and Raman spectra (Fig. 30) only displayed a weak D band
peak [117]. Non-covalently functionalized GFs (f-GFs) were used to
enhance the TC of epoxy resin. Fig. 30 shows composites with 10 wt.%
f-GFs have a TC of 1.53 W/m·K, which is much higher than the values of
composites filled with GO, graphite, CNTs and carbon black. Compar­
ison of Figs. 29 and 30 shows that, compared to liquid-phase-exfoliated
defect-free graphene/MLG hybrids, the f-GFs produced by the graphite
intercalation compound method yield much lower TCE factors in the
composites. Although slight oxidation of the f-GFs may be an important
reason, the effect of filler size, size distribution and aspect ratio cannot
be excluded.
Another way that can be scaled up easily to fabricate defect-free FLG
X. Huang, et al.
for polymer composites is by ball milling. Using this well-established
industrial grinding technique, FLG dispersion can be quickly obtained
from graphite with high yield [166]. Using melamine and Darvan-I
(sodium polynaphthalene sulphonate) as exfoliating agent and surfac­
tant, George et al. produced defect-free FLGs (2∼5 layers) by planetary
ball milling of graphite in water and dispersed them as fillers in NR
latex to fabricate composites with high TC [167]. At 37 ℃, the resulting
composites with < 1.43 wt.% original graphite exhibit TCE factors of
4.86 and 9.83 when 200 g and 500 g weights are applied, respectively
[167].
At a given graphite content, reduction of layer number can facilitate
the formation of more compact thermal conductive paths in composites.
Based on this idea, re-exfoliation of re-expanded graphite was used to
produce SLG and FLG. Using graphene produced by this method, a large
TCE was found in epoxy composites [168]. As shown in Fig. 31, while
graphene prepared by this method gives defects (Raman spectra of
graphene shows a strong D band), the composites show much higher
TCE compared with those filled with sonication exfoliated expanded
graphite and graphite powder. At a graphene loading of ∼10.0 wt.%,
TC of epoxy composites reaches 4.0 W/m·K, exhibiting a TCE factor of
Fig. 29. (a) Raman spectra of graphite, bi-layer graphene (BLG) and MLG. (b) TCE factors of epoxy composites with graphite, carbon black and graphene/MLG
hybrids. In Graphene-MLG-Hybrid Epoxy A and B, the sonication time used for graphene preparation is 12 h and 10 h, respectively, and centrifugation rates for
graphene preparation are 15,000 rpm and 5000 rpm, respectively. (Reproduced with permission from Ref. [116]).
19
Materials Science & Engineering R 142 (2020) 100577
Fig. 28. (a) Raman spectra of RGO and an­
nealed RGO at different temperature. TC and
TCE factors of RGO/1-octadanol composites:
(b) composites with different loading of pris­
tine RGO, (c) composites with 5% RGO an­
nealed at different temperature, and (d) com­
posites with different loading of RGO annealed
at 2200 °C. (Reproduced with permission from
Ref. [165]).
23.6. By contrast, composites with the same loading of sonication ex­
foliated expanded graphite has a > 50 % lower TC of 1.84 W/m·K.
A proper comparative study on TCE of different graphene filler is
highly desirable to understand the factors that determine TC of gra­
phene/polymer composites. However, such a study cannot be done
properly with so many factors influencing the final TC of a composite,
including graphene size, size distribution, thickness, thickness dis­
tribution, aspect ratio and defects, etc. Even if the same method was
used, the geometric properties of graphene might be strongly affected
by the different preparation conditions, e.g., sonication time, etc.
Despite this, many efforts have been made to explore the factors af­
fecting TC of graphene/polymer composites. Warzoha and Fleischer
attempted to reveal the effects of geometric properties of graphene on
TC of paraffin composites [169]. As shown in Fig. 32, the TCE of the
composites increases with increasing graphene thickness and diameter.
It is believed the results can be explained in terms of the graphene
bending stiffness that depends on its thickness. Thinner graphene tends
to form more interfaces within the paraffin due to the ease of folding
(i.e., thin graphene has low bending stiffness). This is a reasonable
explanation. Similarly, Kim et al. also revealed that graphene with large
X. Huang, et al.
Fig. 30. (a) Raman spectra of graphite, graphene and f-GFs. (b) TC of epoxy composites with GO, graphite, MWNT (multi-walled CNT), carbon black and f-GFs.
(Reproduced with permission from Ref. [117]).
lateral size and thickness could enhance TC of composites more than
small-sized graphene because of the reduced filler/matrix interface
[170]. However, Goli et al. reported that TC of graphene/paraffin
composites with 1.0 wt.% SLG can reach ∼15 W/m·K from 0.25 W/m·K
of pristine paraffin, i.e., a TCE factor of 60 (Fig. 32b) [171]. To date,
this is one of the reported maximum TCEs in composites with low
graphene loading. Moreover, paraffin composites with 20 wt.% of dif­
ferent graphene thickness exhibit comparable TC values. These results
further reflect the complexity of TCE of polymer/graphene composites.
That is, the TCE of graphene-based polymer composites is influenced by
multiple factors.
As TC of graphene is highly anisotropic and the in-plane TC is much
higher than the through-plane TC, it is expected that, at the same
graphene loading, the formation of aligned graphene can enhance in-
plane or through-plane TC of composites more efficiently as confirmed
by many studies [156,158,172–175]. Thus, Li et al. prepared aligned
MLG/epoxy composites through two steps (Fig. 33): (a) An ethanol/
water solution of graphene was vacuum-filtrated, yielding self-assembly
of aligned graphene; and (b) epoxy resin and curing agent were im­
pregnated into the aligned graphene and cured [176]. The aligned
graphene/epoxy composites exhibit strong anisotropic thermal con­
ductivities. For example, at 40 °C, the TCs of in-plane and through-
plane are, respectively, 16.75 and 5.43 W/m·K. For comparison, com­
posites having randomly dispersed graphene have a low TC of 1.84 W/
m·K. Using an evaporation induced self-assembly method, Zeng et al.
prepared graphene/oxidized cellulose (OC) nanocomposite films with
highly oriented structures [177]. The preparation process includes the
following 4 steps: (a) GO/OC solution was heated at 180 °C for 6 h in a
Teflon-lined autoclave; (b) DMF was added into the cooled rGO/OC
Fig. 31. (a) Raman spectra of graphite and graphene prepared by re-exfoliation of re-expanded graphite. (b) TC of epoxy composites with graphene prepared by re-
exfoliation of re-expanded graphite, sonication exfoliated expanded graphite, and graphite. (Reproduced with permission from Ref. [168]).
20
Materials Science & Engineering R 142 (2020) 100577
solution to form a proper concentration; (c) epoxy adhesion agent was
gently added and the solution stirred at room temperature; and (d) the
final solution was drop-cast on a Teflon mould and heated at step-in­
creased temperatures. The resultant graphene/OC nanocomposite films
comprise long-range well-aligned rGO layers, which are separated by
the OC planar layers. The nanocomposites films exhibit an in-plane TC
of 25.66 W/m·K at 4.1 vol.% rGO loading, resulting in a TCE factor of
72.35 [177].
Owing to the lack of functional groups on FLGs, their interaction with
most polymers is low, which results in poor dispersion and weak heat
transfer across the FLG/polymer interface. To overcome these problems,
efforts were made to form interconnected 3D FLG structures in the
polymer matrices, which usually displayed much higher TCE factors
compared to randomly dispersed FLG. Li et al. developed a spray drying
method to prepare FLG/SBR (styrene-butadiene rubber) composites that
could not be processed by traditional methods due to the weak FLG/SBR
interactions [178]. FLG loading up to 15.0 vol.% was introduced to form
an interconnected 3D FLG structure in SBR, yielding not only a high TCE
factor of 13.30 (that is, TC increased from 0.20 W/m·K of SBR to 2.92 W/
m·K of FLG/SBR) but also excellent electromagnetic shielding of 45 dB at
8–12 GHz [178]. Fang et al. developed a method to increase the interac­
tion between FLG foam and PDMS matrix [179]. PDA was first coated onto
the FLG foam skeleton and then amino-silane was introduced by reaction
with PDA. The modified FLG foam was compressed before infiltration with
PDMS and the obtained PDMS composites with 11.62 wt.% FLG exhibited
an in-plane TC of 28.77 W/m·K and a through-plane TC of 1.62 W/m·K
[179]. Using Ni foam as a template and CVD, Shen et al. [180] prepared
epoxy composites with 3D interconnected FLG through several steps in­
cluding Ni foam stacking and compression, FLG growth by CVD, Ni
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

Fig. 32. TC of graphene/paraffin composites. Tables below the figures show the geometric parameters of the corresponding graphene filler. (Reproduced with
permission from Ref. [169,171]).

etching, infiltration by epoxy and then curing. The interconnected FLG
exhibited certain orientation degree along the in-plane direction de­
pending on the applied compressive stress when they were packed densely
through the plane, yielding high loading (up to 8.3 wt.%) but uniform
dispersion of FLG within epoxy. With only 2.2 wt.% FLG, the composites
exhibited a TC higher than 5.0 W/m·K along the in-plane direction, and
when FLG was increased to 8.3 wt.% this became 8.8 W/m·K. Such a high
TC is ∼43 times higher than that of neat epoxy resin (∼0.2 W/m·K)
[180].
4.4. TC of 3D structured graphene/polymer composites
When dispersed in a composite, graphene sheets may be pre­
ferentially aligned in the direction of applied load, usually resulting in
low through-plane TC of the composite [181]. To obtain a composite
with high isotropic TC, random dispersion of highly filled graphene is
preferred. However, the loading of randomly dispersed graphene sheets
is usually limited because of its influence on other properties (e.g.,
mechanical, processing, etc.) of the composite [174]. Large 3D

Fig. 33. (a) Schematic illustrating the preparation process of epoxy composites with aligned graphene (AG) and dispersed graphene (DG). (b) Raman spectrum of the
graphene used and (c) temperature dependence of TC of graphene/epoxy composites. (Reproduced with permission from Ref. [176]).

21
 Table 1
Summary of TC and TCE factor of GNP-based polymer composites.
Graphene Raw materials Preparation method Lateral size Thickness Aspect ratio Loading Matrix TC TCE factor Ref.
X. Huang, et al.

filler (W/m K)

GNP NFG, Thermal exfoliation of intercalated NG at 800 °C 0.35 μm 1.7 nm 25 vol.% Epoxy resin 6.44 30.00 [94]
500 μm
GNP NFG, Thermal exfoliation of intercalated NG at 800 °C 0.35 μm 1.7 nm 5.4 vol.% Epoxy resin 1.45 6.21 [94]
500 μm
GNP NFG, Thermal exfoliation of intercalated NG at 800 °C ∼ 1 μm ∼ 25 ± 5 10 wt.% Epoxy resin ∼ 0.42 1.09 [184]
< 43 μm
GNP NFG, Thermal exfoliation of intercalated NG at 800 °C ∼ 1 μm ∼ 35 ± 10 10 wt.% Epoxy resin ∼ 0.88 3.38 [184]
< 78 μm
GNP NFG, Thermal exfoliation of intercalated NG at 800 °C Several to > 15 1−100 nm ∼ 290 ± 10 wt.% Epoxy resin ∼ 2.0 8.95 [184]
180–420 μm μm 50
GNP EG Chemical exfoliation & mechanical exfoliation 25 wt.% Cellulose 30.25 [211]
0.53
GNP NFG, Thermal exfoliation of intercalated NG at 800 °C Several to > 15 1−100 nm 350 ± 100 10 wt.% Epoxy resin ∼ 1.52 6.56 [217]
500–850 μm μm
Oxidized NFG, Thermal exfoliation of intercalated NG at 800 °C plus nitric acid Several to > 15 350 ± 100 10 wt.% Epoxy resin ∼ 2.08 9.03 [217]
GNP 500–850 μm treatment μm
GNP NFG Mechanical cleavage of NG ∼5 μm ∼ 60 nm 10 wt.% PE 5.9 11.00 [199]
GNP NFG Thermal exfoliation of intercalated NG at 600 °C 3.9 μm Several to 100 nm 16 wt.%, Epoxy resin 2.27, 10.35, [115]
20 wt.% 4.27 20.35
GNP NFG Thermal exfoliation of intercalated NG at 600 °C plus silane 3.9 μm Several to 100 nm 16 wt.%, Epoxy resin 3.27, 15.35, [115]
functionalization 20 wt.% 5.86 28.30
GNP EG In situ intercalated EG by caprolactam onium ion 12 wt.% PA 6 2.49 6.78 [205]
GNP NFG, Thermal exfoliation of intercalated NG at 900 °C plus separation 16 wt.%, Epoxy resin ∼ 3.55, 15.21 [218]
500 μm by a 50 mesh sieve 20 wt.% ∼ 4.3 18.63

22
GNP NFG, Thermal exfoliation of intercalated NG at 900 °C plus separation 16 wt.%, Epoxy resin ∼ 2.3, 9.50, [218]
500 μm by a 100 mesh sieve 20 wt.% ∼ 4.3 18.63
GNP NFG, Thermal exfoliation of intercalated NG at 900 °C plus separation 16 wt.%, Epoxy resin ∼ 1.5, 5.84 [218]
500 μm by a 150 mesh sieve 20 wt.% ∼ 4.3 18.63
GNP NFG Thermal exfoliation of intercalated NG at 800 °C 0.5−2 μm 25 nm 4.25 vol.% Silicone grease 1.05 7.07 [136]
GNP GO Thermal exfoliation of graphite oxide at 48 μm ∼3 nm 5.3 wt.% PEG 1.35 4.63 [219]
1050℃ followed by annealing at 2200℃under argon
atmosphere
GNP Commercially available 5 μm 6–8 nm 20 wt.% PCa 1.13 ∼4.90 [220]
GNP NFG Thermal exfoliation of intercalated NG 15 μm 5−10 nm ∼ 1500 20 vol.% HDPE ∼ 1.1 [221]
GNP NFG Thermal exfoliation of intercalated NG 15 μm 5−10 nm ∼ 1500 4.25 vol.% Nylon 66 ∼ 4.1 ∼ 12.66 [221]
GNP NFG Thermal exfoliation of intercalated NG 5 μm ∼ 5 – 10 nm 5 wt.% Epoxy resin ∼ 0.45 1.14 [188]
GNP NFG Thermal exfoliation of intercalated NG < 1 μm ∼ 5−10 nm 5 wt.% Epoxy resin ∼ 0.25 0.19 [188]
GNP Graphite oxide Ball mill of GO for 10 h and heated in a microwave oven at 1000 1−5 nm 1.5 wt.% Silicone 2.7 12.00 [222]
W
GNP NFG, Thermal exfoliation of intercalated NG at 1100 °C 2.7 wt.% Paraffin 2.75 10.00 [223]
∼ 700 μm
GNP NG Microwave thermal exfoliation of intercalated NG 15 μm 10 nm 5 vol.% Paraffin 2.41 8.64 [187]
GNP Graphite oxide Mechanical exfoliation of GO < 10 μm 20 wt.% PVDF 0.562 2.12 [138]
f-GNP GNP Surface hydroxylation of GNP 40 μm 250 30 wt.% Epoxy resin 1.698 8.00 [192]
GNP Commercially available 10 ± 7 μm 5−20 nm 725 ± 125 17 vol.% Epoxy resin ∼ 3.28 17.22 [185]
GNP Commercially available 19 ± 9 μm 9−20 nm 1255 ± 145 17 vol% Epoxy resin 3.86 20.44 [185]
GNP Commercially available 20 ± 7 μm 15−100 nm 568 ± 298 17 vol.% Epoxy resin 4, 21.20 [185]
24 vol.% 12.40 68.00
GNP Commercially available 34 ± 20 μm > 100 nm 340 ± 200 17 vol.% Epoxy resin ∼ 2.72 30.0 [185]
GNP Commercially available 2 ± 1 μm 5−20 nm 175 ± 25 Epoxy resin ∼ 0.65 [223]
GNP Commercially available 15 μm 10 wt% PEIb 3.2 16.00 [209]
GNPb Commercially available 40 μm 250 29.3 vol.% PPSc 4.41 19.00 [210]
GNP Commercially available 3−7 μm 20−60 nm 10 wt.% Epoxy resin 0.668 2.69 [224]
(continued on next page)
Materials Science & Engineering R 142 (2020) 100577
 Table 1 (continued)

Graphene Raw materials Preparation method Lateral size Thickness Aspect ratio Loading Matrix TC TCE factor Ref.
filler (W/m K)
X. Huang, et al.

GNP Commercially available 40 μm 250 25 wt.% Epoxy resin 2.67 14.22 [197]
GNP Commercially available 5−10 μm 4−20 μm 10 wt.% Eicosane 2.0 4.00 [225]
GNP Commercially available 5−10 μm 4−20 μm 5 wt.% Paraffin 0.7 1.69 [216]
GNP Commercially available 1.5−10 μm ∼ 12 nm 12 wt.% Epoxy resin 0.73 3.50 [226]
GNP Commercially available ∼25 μm ∼6 nm 0.53 wt.% PA 66 0.53 1.65 [227]
0.65 wt.% 0.65 2.25
0.94 wt.% 0.94 3.70
1.32 wt.% 1.32 5.60
GNP NFG Ultrasonic treatment and homogenized at high pressure by 5 wt.% Silica gel sheets 0.43 1.10 [228]
homogenizer, repeated 20 times.
GNP Commercially available 5−25 μm 6−10 nm 16.7 wt.% PPd 0.8−1.0 4.00 [229]
GNP Commercially available 50 μm 17.6 vol.% HDPE ∼4.13 [204]
GNP NFG, Liquid phase exfoliation of NG 1.5 μm 20 wt.% PTFEe 4.02 13.00 [230]
∼20 μm
Modified GNP Commercially available and pre-treated with a coupling agent 0.17 wt.% Silicone rubber 0.20 [231]
GNP KH-550 0.33 wt.% 0.40
0.67 wt.% 0.50
GNP Commercially available 5−7 μm < 30 layers 1 wt.% PVDF 0.27 0.17 [232]
5 wt.% 0.48 1.09
10 wt.% 0.75 2.26
20 wt.% 1.64 6.13
f
GNP Commercially available 5−10 μm 4−20 nm 1 wt.% Polymer bonded 2.799 5.40 [233]
explosives
GNP Commercially available 40 μm 250 30 wt.% Epoxy resin 1.35 5.70 [192]
GNP Commercially available 1.5−10 μm 0.35−12 nm 55 wt.% Epoxy resin ∼8 35 [234]

23
2−8 μm 0.35−3 nm ∼3.2
GNP Commercially available 3−5 μm < 10 layers 0.43 vol.% Natural rubber 0.79 5.08 [235]
f-GNP Graphite oxide Surface functionalization of GO 3 wt% Epoxy resin 0.67 4.03 [236]
GNP Commercially available 7 μm 7 vol.% Linear PP ∼0.225 [237]
7 μm Branched PP ∼0.24
100 μm Linear PP ∼0.4
100 μm Branched PP ∼0.35
Modified GNP EG Ultrasonic treatment and modification with atmospheric- 0−20 μm < 100 nm 20 wt.% Epoxy resin 1.73 8.11 [238]
pressure plasma
GNP Commercially available 1−5 μm 3 nm 1.51 wt% Polyethylene glycol 1.03 2.32 [239]
GNP Commercially available 8 μm 20 vol.% PBT/PCh 5.82 (in-plane) 24.3 [240]
1.06 (through- 3.61
plane)
Modified GNP GNP GNP modified with polydopamine 10 wt.% Polyvinyl alcohol 13.4 43 [241]
f-GNP GNP Decorated with silica nanoparticles 10−15 μm 1−3 nm 2 wt.% PDMS 0.497 1.55 [242]
GNP NFG Liquid-phase exfoliation ∼400 nm ∼1.6 nm 4 wt.% PDMS 0.93 4.00 [243]
GNP Commercially available 5 μm 1.5 nm 1 wt.% Glass fiber-epoxy resin ∼0.38 [244]

Note: aPolycarbonate; bPolyether imide; cPolyphenylene sulphide; dPolypropylene; ePolytetrafluoroethylene, fComposites consist of a majority of powerful explosive crystals and a small portion of polymer binder; gTCA
functionalized; hpolybutylene terephthalate/polycarbonate blend.
Materials Science & Engineering R 142 (2020) 100577
X. Huang, et al.
graphene structure, e.g., aerogels, can markedly increase the TC of
composites at a low graphene loading. However, the size of aerogels is
often too small for industrial applications and the preparation is usually
complicated. In addition, the composite shape may be limited by the
aerogel configuration and the infiltration process of the composite is
largely restricted by the pore structure of the aerogels and the viscosity
of the matrix or their precursors. 3D structured graphene fillers can
overcome these shortcomings of the graphene sheets and large 3D
graphene structure. Using 3D interconnected graphene microsphere as
filler, Li et al. prepared epoxy composites with high through-plane TC at
low loading. Owing to the interconnected 3D network of graphene
microspheres, the epoxy composite with 1.0 wt.% loading gave the
maximum through-plane TC of 0.96 W/m·K, yielding a TCE factor of
4.31 [182]. Zhou et al. prepared thermally conductive epoxy compo­
sites using 3D graphene as filler, which was prepared by fragmenting
the large graphene foam [183]. The TC of 3D graphene/epoxy com­
posites increased to 0.52 W/m·K at 0.27 wt.% graphene loading, which
is 2.74 times that of neat epoxy resin. Fang et al. recently reviewed the
progress on the preparation strategies of 3D structured graphene for
TCE of composites [174]. For details, interested readers may refer to
this article.
4.5. TC of GNP/polymer composites
GNPs (called graphene nanoplatelets or graphite nanoplates), re­
ferred to as 2D graphite materials with a thickness less than 100 nm
[15], have been widely used as fillers to achieve high TC polymer
composites. The main advantage of utilizing GNPs is their ease of
preparation in comparison to SLG or MLG, particularly at large scale.
GNPs prepared by different methods have been used to prepare polymer
composites with high TC.
Thermal exfoliation of intercalated natural graphite is the most
common method for the preparation of GNPs. Here, natural flake gra­
phite (NFG) was first intercalated by a mixture of sulphuric and nitric
acids. Then, the intercalated graphite was subjected to a sudden high
temperature (e.g., several hundred to 900 °C) heat treatment. After
sonication of the thermal exfoliated graphite in a solvent, GNPs could
be successfully obtained. Several factors, e.g., heat treatment
24
Materials Science & Engineering R 142 (2020) 100577
temperature of intercalated graphite, size of starting NFG, surface
modification and separation of GNPs, etc. could affect very much the TC
of polymer composites. Table 1 summarizes reported TC values and
TCE factors of GNP-based polymer composites. In the following, the
influence of preparation method, size, aspect ratio, functionalization of
GNP and the composite processing methods on TC of GNP composites
will be discussed in detail.
4.5.1. Effects of preparation method, size and aspect ratio of GNPs
It has been shown from previous research that the preparation
method, size and aspect ratio of GNPs show significant influence on the
TCE of polymer composites. The effect of heat treatment temperature of
intercalated graphite on the exfoliation of NFG and TC of GNP/epoxy
composites was studied by Yu et al. [94]. Three temperatures (200, 400
and 800 °C) were employed to exfoliate the intercalated graphite. As
shown in Fig. 34a, epoxy composites with GNPs exfoliated at higher
temperature yield greater enhancement of TC. This is caused by the
increase of heat treatment temperature, giving rise to reduced number
of graphene layers, which, in turn, increases the thermal conductive
paths in the composites.
Because GNPs are made from NFGs, the effect of the starting gra­
phite flake size on the final lateral dimension of exfoliated GNPs and TC
of GNP/epoxy composites should be considered. Sun et al. [184] found
that, under the same exfoliation conditions, NFGs with larger lateral
size undergo higher exfoliation degree, giving higher aspect ratios of
GNPs. Hence, epoxy composites with GNPs prepared from large-sized
NFGs produce high TC (Fig. 34b,c). However, as noted from Fig. 34c,
composites with GNPs having ultra-high aspect ratio (GNP-D, 500−850
μm) may exhibit low TC. This is explained by the fact that NFGs with
too large size cannot be homogeneously intercalated, yielding in­
complete exfoliation. Using commercially available GNPs as fillers,
Shtein et al. studied the effects of geometry parameters of GNPs on TC
of epoxy composites [185]. It is also found that the aspect ratio of GNPs
is the most important parameter controlling the composite TC. Higher
aspect ratios are more effective in enhancing TC of polymer composites.
To investigate the effect of GNP size on TC of polymer composites,
Debelak and Lafdi prepared GNPs of different sizes by separating the
exfoliated GNPs by using sieves of 150, 100 and 50 mesh, respectively
Fig. 34. (a) TC at 30 °C for epoxy composites
with 5.4 wt.% GNPs. GMP (average lateral size
≈ 30 μm, average thickness ≈ 10 μm), GNP-
200: GNPs exfoliated at 200 °C (average lateral
size ≈ 1.7 μm, average thickness ≈ 60 nm),
GNP-400: GNPs exfoliated at 400 °C (average
lateral size ≈ 1.1 μm, average thickness ≈ 25
nm), and GNP-800: GNPs exfoliated at 800 °C
(average lateral size ≈ 0.35 μm, average
thickness ≈ 1.7 nm). (Reproduced with per­
mission from Ref. [94]). (b, c) Average-aspect-
ratios of GNPs prepared from different starting
natural graphite and TC of epoxy composites
with GNPs prepared from different starting
NFG. (Reproduced with permission from Ref.
[184]). (d) TC of epoxy composites versus gra­
phite content (i.e., GNPs) having different size.
(Reproduced with permission from Ref. [186]).
X. Huang, et al.
[186], and their products were labelled small, medium and large.
Fig. 34d shows that except at very low and very high loadings, epoxy
composites with larger GNPs generally exhibit higher TC. Also, the TC
of composites with large GNPs increases almost linearly with increasing
GNP loading. These results are caused by large GNPs having high aspect
ratios, thus enhancing the TC of the composites. Other researchers have
also confirmed that high aspect ratio GNPs are more effective to in­
crease the TC of epoxy composites [187,188].
Using expanded graphite as starting materials, Song et al. [189,190]
and Veca et al. [191] developed a method to prepare GNPs whereby the
expanded graphite was prepared by three steps: (a) sonication treat­
ment in alcohol/water mixture, (b) intercalation in sulphuric acid/ni­
tric acid mixture, and (c) long-time sonication treatment. Using these
GNPs they prepared highly filled epoxy [191], ethylene-vinyl acetate
copolymer (EVA) [190], PI [190] and PVA [189] composites. Since only
thermal diffusivities of these composites were given, complete TC
analysis was impossible to conduct.
4.5.2. Effect of functionalization of GNPs
Filler surface functionalization has been widely used in the pre­
paration of polymer composites with enhanced TC. But there is less
attention on the role of GNP functionalization on the TC of composites.
SCAs have been used to functionalize GNPs. In the work of Ganguli
et al., at 8 wt.% GNPs, the thermal conductivities of epoxy composites
filled with functionalized and non-functionalized GNPs are 1.24 and
0.58 W/m·K, respectively [115]. Gu et al. also reported that at 30 wt.%
GNPs, epoxy-terminated silane functionalized GNP/epoxy composite
has a TC of 1.70 W/m·K that is higher than 1.35 W/m·K of the pristine
GNP composite [192]. Chen et al. designed a Diels-Alder reaction route
to functionalize pristine graphite by acrylic acid (AA) and they docu­
mented a TC of 21.3 W/m·K in PVA composite with 30 wt. % functio­
nalized graphite. This is much higher than 14.1 W/m·K of composites
with the same loading of pristine graphite [193]. These results meant
that surface functionalization of GNPs gives stronger interfacial adhe­
sion between graphite and epoxy and/or reduced acoustic impedance
mismatch at the graphite/epoxy interface.
4.5.3. Effect of composites processing methods
Achieving excellent dispersion of GNPs in composites is not only
important to enhance the TC but is also vital to obtain other desirable
attributes (e.g., mechanical properties). However, GNPs tend to ag­
gregate during dispersion because of the strong van der Waals interac­
tion; and efforts have been made to obtain excellent dispersion of GNPs
by developing effective composite processing methods.
In general, melt compounding and solution mixing are two com­
monly used methods to fabricate graphene/polymer composites.
Compared to melt compounding, solution mixing is more effective to
prevent stacking of graphene layers in polymer matrices [194]. Araby
et al. found that hydrophobic GNPs (∼3 nm thick) could be uniformly
Fig. 35. Effects of GNP loading and processing time on TC and TCE factors of epoxy composites prepared by ball milling and sonication methods. (Reproduced with
permission from Ref. [197]).
25
Materials Science & Engineering R 142 (2020) 100577
dispersed in styrene-butadiene rubber (SBR) solution since the solution
environment provided more interlayer spacing for elastomer molecules
to intercalate and retain the high aspect ratio of GNPs [195]. However,
in highly filled composites, melt compounding under high shear forces
are more effective to reduce the agglomeration of fillers. Hence, com­
bined processing techniques have been used to enhance the TC of
polymer composites with high graphene loading. Ren et al. prepared
graphene/PA composites by combining the benefits of solution mixing
and melt compounding, which gave a through-plane TC of 3.55 W/m·K
in those composites with 20 wt.% graphene loading [196].
Guo and Chen investigated the effects of processing methods on TC
of commercially available GNP-based composites [197]. Ball milling
and sonication were used to disperse GNPs in epoxy. As shown in
Fig. 35, in general, the TC of the composites exhibits strong dependence
on processing time. Ball milling seems much more effective to achieve
higher TC than sonication methods. The existence of a maximum in the
processing time dependent TC means that both processing methods not
only improve the dispersion of GNPs but also reduce the size of the
GNPs. These results indicate that maintaining a well-controlled balance
between the dispersion and large size of GNPs is important to maximize
the TC of GNP-based composites. Similar findings have been found in
other studies [198], indicating that ball milling is promising for prac­
tical production of thermally conductive composites filled with GNPs.
Aligning GNPs along a specific direction is an efficient way to en­
hance TC in that direction. Several methods have been developed to
prepare polymer composites with aligned GNPs through applications of
electric field, magnetic field, mechanical strain, melt flow and two-roll
milling. Mechanical strain with low drawing rate ∼40 μm/min was
used by Saeidijavash et al. to align GNPs in PE. At a strain of 400 % and
7.0 wt.% GNPs, a TC of 5.10 W/m·K is achieved for aligned GNP/PE
composites, which is ∼5 times higher than that of strain-free compo­
sites (1.10 W/m·K) [199]. Fig. 36a shows how two-roll milling is used to
mix polyolefin elastomer (POE, ethylene content 8.5 wt.%) and natural
graphite (NG) and through the strong shear force obtain the orientation
of NG flakes along the in-plane direction. After hot-pressing, the lami­
nated samples (A and B) produce highly anisotropic thermal con­
ductivities, Fig. 36b. The TC along the aligned GNP direction reaches
13.27 W/m·K at 49.30 vol.% NG [200]. An L-shaped tube (like equal
channel angular extrusion used in metals) is used to prepare PVDF
composites with oriented GNFs (6−8 nm thickness), Fig. 36c. Sliced
circular disks exhibit a TC along the oriented GNF direction of
∼10.0 W/m·K at 25 vol.% as shown in Fig. 36d [201].
External compressive forces on the composites during curing
(thermoset matrices) or consolidation (thermoplastic matrices) can
align the fillers, reduce the inter-filler distance and effect of voids,
hence the TC can be markedly increased and anisotropic. These results
clearly depend on the level of the applied compression. Ohayon-Lavi
et al. reported the effect of compression on TC of epoxy composites with
hybrid fillers comprising GNPs and graphite flakes [202]. A high TC of
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

Fig. 36. (a) Schematic showing the prepara­

tion process of NG/POE composites. (b) NG
concentration dependent TC of POE/NG com­
posites. Inset in (b) shows the anisotropic
factor of TC as a function of NG content.
(Reproduced with permission from Ref. [200]).
(c) Schematic showing the fabrication process
of PVDF composites with aligned GNFs using
an L-shaped tube. Photos in the bottom right
side show a cylindrical PVDF composite with
orientated GNFs (oGNF), and the sliced and
polished disk-type samples for TC tests. (d) TC
of PVDF composites with randomly dispersed
GNF and oriented GNF and TC predicted by the
Hashin-Shtrikman (H-S) model. (Reproduced
with permission from Ref. [201]).

Fig. 37. (a) Illustrations for ideal GNP (GnP) exfoliation and dispersion in IMF process. (b) TC of GNP/HDPE composites prepared by IMS, IMF and HPIMF plotted
against GNP loading. (c) TC of IMF samples versus degree of foaming (DP). (Reproduced with permission from Ref. [204]).

26
X. Huang, et al.
27.5 W/m·K was obtained for the compressed (at 250 bar) epoxy
composite with 30 wt.% GNPs and 40 wt.% graphite flakes. This value
is much larger than the TC of 16.0 W/m·K for the non-compressed
composite.
Applying an electric or magnetic field is the conventional way to
align solid inclusion in a dielectric liquid or polymer melt. The align­
ment of GNPs in epoxy resin by an AC electric field was investigated by
Wu et al. [203]. However, the GNP alignment only exhibits marginal
enhancement of TC when the GNP content is lower than 0.8 vol.%.
Here, TC of epoxy composites with aligned GNPs is 0.45 W/m·K com­
pared to ∼0.40 W/m·K of the same composites with randomly dis­
persed GNPs. Starting from 0.8 vol.%, TCE decreases in epoxy compo­
sites with aligned GNPs as the GNP loading is increased [203].
Magnetic field induced alignment of GNPs also gives very marginal
increase in the TC of GNP/PVDF composites [138]. The maximum TC of
the composites with aligned GNPs reaches 0.587 W/m·K at 20 wt.%
GNP, which is only 4.5 % higher than that of composites with randomly
dispersed GNPs. In both cases, the marginal increases in TC may be
caused by the low GNP loading and the high viscosity of the GNP/
polymer systems (melt or solution), which have greatly limited the
formation of connected thermally conductive pathways.
Hamidinejad et al. [204] demonstrated a supercritical fluid (SCF)
assisted fabrication strategy for thermally conductive GNP/HDPE (high
density polyethylene) composites by using injection moulding. Three
methods were used: (a) injection-moulded solid (IMS, traditional in­
jection moulding process without SCF treatment and foaming), (b) in­
jection-moulded foam (IMF, 0.4 wt.% supercritical N2 injected into the
barrel), and (c) high-pressure-injection-moulded foam (HPIMF, 0.4 wt.
% supercritical N2 injected into the barrel). For IMF, the SCF can in­
tercalate the layered graphite and weaken the bonding force of GNPs,
making exfoliation easier. Also, the plasticizing effect of SCF can en­
hance the likelihood for the macro-molecular chains to penetrate the
interlayer regions of GNPs owing to the enhanced mobility of the
macromolecules and increased interlayer distances of the GNPs. During
the phase transition, expansion of SCF can further separate and ex­
foliate the platelets. Fig. 37 shows the ideal process for exfoliation and
dispersion of GNPs for the IMF case [204]. The SCF-treated HDPE
composite with 17.6 vol.% GNP shows a TC of 3.75 ± 0.12 W/m·K,
which is much higher than that of the IMS counterpart (2.09 ± 0.03 W/
m·K). Note that the degree of foaming must be controlled due to the low
TC (0.026 W/m·K) of air and its strong phonon scattering effect [88]. In-
situ intercalation polymerization was also used by Meng et al. to pre­
pare thermally conductive GNP/PA6 composites [205]. First, capro­
lactam onium ion (CL⊕) formed by -caprolactam and H+ of 6-ami­
nocaproic acid could intercalate into the interlayer of expanded
graphite (EG) via π-π interaction. Then, the GNP/PA6 composites were
synthesized by in situ polymerization. In this way, TC of GNP/PA6
Fig. 38. (a) TC and (b) electrical conductivity of epoxy composites versus GNP loading (lateral size: 20 ± 7 μm, thickness: 15-100 nm, aspect ratio: 568 ± 298).
(Reproduced with permission from Ref. [185]).
27
Materials Science & Engineering R 142 (2020) 100577
composites could reach 2.49 W/m·K with 12 wt.% EG, much higher
than that of composites fabricated by melt blending or without CL⊕
intercalation [205].
4.5.4. Percolation phenomenon in GNP/polymer composites
The electrical percolation phenomenon of composites comprising
electrically conductive particles within an insulating matrix can be
predicted and clearly observed in numerous experiments, which can be
described by the abrupt change of electrical conductivity when the
conductive fillers begin to form conductive networks through electron
hopping or tunnelling [206]. However, the existence of a thermal
percolation in composites is still controversial because phonon heat
conduction contributes to the main heat transfer. Shtein et al. claimed
that a thermal percolation can be found in GNP/epoxy composites
[185]. It can be seen from Fig. 38a that, below the percolation
threshold of ∼18 vol.%, the TC increases slowly with increasing GNP
loading caused by the isolated GNPs and the large GNP/epoxy inter­
facial thermal resistance. Above this percolation threshold, most of the
heat is transferred via the connected GNP network, yielding a rapid
thermal conduction enhancement as the loading increases. In this case,
the TC of the composites may be limited by the high thermal boundary
resistance at the filler/filler interface or filler/matrix interface, while
the through-plane TC of GNP is still one to three orders of magnitude
higher than that of epoxy matrix. Considering the electrical con­
ductivity of GNPs is more than 15 orders of magnitude higher than that
of epoxy, it is reasonable to observe in Fig. 38b a lower electrical
percolation threshold at 5 vol.% in these GNP/epoxy composites [185].
Kargar et al. [207] also claimed the existence of thermal percolations in
graphene/epoxy composites and gave a thermal percolation threshold
of ∼30 vol.% that is again much higher than the electrical percolation
threshold of ∼10 vol.%. As mentioned earlier, the large percolation
threshold differences may be attributed to the different thermal and
electrical conduction mechanisms, and the different ratios of thermal
and electrical conductivity of fillers to matrix, and the large interfacial
thermal resistance. Later, Naghibi et al. reported that there exists a
thermal percolation threshold of 1.9 vol.% in non-curing mixtures of
graphene (grade H-15, XG-Sciences) and mineral oil TIMs, wherein
addition of 1.9 vol.% of graphene increases the TC to 1.2 W/m·K from
0.3 W/m·K of pure mineral oil [208]. Several studies also reported the
existence of critical filler loadings in thermally conductive composites
[185,209,210]. However, the linear increase of TC with filler loading
was also frequently found in polymer composites
[94,116,192,211–214].
4.5.5. Comparative study
Besides 2D nano-carbon fillers, 1D nano-carbon fillers, such as CNTs
and carbon nanofibres (CNFs), also have ultrahigh intrinsic thermal
X. Huang, et al.
conductivity [215]. Fan et al. compared the TCE of commercially
available GNPs, multi-walled CNTs (MWCNTs) and CNFs in eicosane
(C20H42) composite materials at loading levels lower than 1.6 vol.%
[216]. GNPs are found to show much higher efficiency of TCE when
compared with other nano-carbon fillers, exhibiting promising poten­
tial for the preparation of thermally conductive composite materials.
Compared to 1D CNTs and CNFs, the superiority of GNPs in enhancing
the TC of composites originates from their unique 2D planar structure,
which gives reduced nano-carbon/polymer thermal interface re­
sistance. In another study [214], the effects of relatively high loadings
(< 20 wt.%) of several different carbon allotropes (i.e., CB, CNT, GNP,
graphite, pitch-based carbon fiber [PCF] and EG) on the TC of poly­
merized cyclic butylene terephthalate composites were investigated.
The results (Fig. 39) showed that the morphology (sizes and shapes) of
the fillers plays an important role on the TCE of polymer composites.
However, among these diverse fillers, micro-sized 1D PCF and EG dis­
play superiority in enhancing the TC of composites because of the de­
creased phonon scattering at their interfaces [214]. All the results in­
dicate that decreasing interfaces between filler and matrix reduces the
interface thermal resistance and weakens the phonon scattering.
5. TC of graphene/polymer composites: Influence of hybrid fillers
Graphene-based fillers together with other fillers are often jointly
used as hybrid fillers to enhance the TC of polymer composites. The
utilization of hybrid fillers has three main goals:
(a) Maximize the TC and TCE at a certain filler loading to take ad­
vantage of the synergetic effects. Here, composites processing may
become much easier and other properties, such as mechanical
flexibility of polymer, can be largely preserved.
(b) Further improve the performance of functional polymer composites
by enhancing the TC through addition of graphene. For example, to
meet the requirements of thermal management, packaging mate­
rials may need to be filled by both reinforcement fillers and
Fig. 39. SEM images of (a) CB, (b) CNT, (c) GNP, (d) graphite, (e) PCF and (f) EG. TC of polymerized cyclic butylene terephthalate composites with different carbon
filler. (Reproduced with permission from Ref. [214]).
28
Materials Science & Engineering R 142 (2020) 100577
thermally conductive graphene fillers.
(c) Use graphene fillers to improve the TC of polymer composites and
simultaneously use other fillers to suppress electrical conduction,
thus fabricating thermally conductive but electrically insulating
polymer composites.
5.1. Synergetic effects of GNP and other fillers
Synergetic effects are to utilize fillers with different sizes and/or
different dimensions to realize the formation of long-range thermally
conductive paths at relatively low total filler loading. As a typical 2D
filler, GNPs have been widely used together with other fillers, such as
0D nanoparticle, 1D CNT, 2D BN and RGO, to synergistically enhance
the TC of polymer composites [245–251]. Yu et al. found synergetic
effects on TCE in PC composites containing GNP/CNT hybrid fillers. At
a filler loading of 20 wt.%, TC of composite with hybrid fillers is in­
creased to 1.39 W/m·K from 1.13 W/m·K of GNP composite [220]. Si­
milar synergetic effect was found in a comparative study of epoxy
composites with individual fillers and hybrid fillers (Fig. 40). At a filler
loading of 10 wt.%, the epoxy composites with single-walled CNT
(SWCNT) gave a TC of 0.85 W/m·K and with GNP showed a TC of
1.49 W/m·K, while the composites with hybrid filler (i.e., GNP/SWCNT)
exhibited a maximum TC of 1.75 W/m·K at a GNP:SWCNT ratio of 3:1
(Fig. 40a) [245]. The synergetic effects are attributed to the replace­
ment of CNT/CNT or GNP/GNP point contacts by linear contacts be­
tween CNT and GNP (Fig. 40b). However, the synergetic effects shown
in [245] can only be found in composites with hybrid loading from 5 to
20 wt.%; and in the work of Huang et al., the synergetic effect of GNP
and CNT at high filler loading can be achieved [252] (see Fig. 40d). As
displayed in Fig. 40c, the synergetic effect of TC is seen to be much
stronger at higher hybrid filler loading (> 25 wt.%). The effects were
found to originate from the enhanced random dispersion of GNPs in­
duced by the presence of CNTs. That is, GNPs tend to orientate along
the in-plane direction; but the introduction of MWCNTs restrains the
orientation of GNPs and improves their dispersion. The realization of
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

Fig. 40. (a) TC of epoxy composites with GNPs and GNP/SWCNT hybrid fillers. (b) Schematic illustrating the GNP/SWCNT network in composites. (c) TC of epoxy
composites with individual filler and hybrids. (d) Synergistic effect of hybrids reported in different investigations. (Reproduced with permission from Ref. [245,252]).

strong synergetic effects at high hybrid filler loading was attributed to
the unique sample preparation method, which guaranteed high sample
quality.
Unlike CNT/GNP mixtures as hybrids, CNT grafted GNP
(CNT@GNP) is also utilized as hybrids to enhance the TC of epoxy
[253]. The composites with 20 wt.% CNT@GNP hybrids show 300 %
and 50 % enhancement of the through-plane TC compared to those
composites with individual CNTs and GNPs, respectively. Additionally,
compared to the composites with mixed CNT/GNP (2.15 W/m·K), a
higher TC (2.41 W/m·K) is obtained in CNT@GNP composites. This is

Fig. 41. (a) Schematic showing the prepara­

tion process of PS composites with three dif­
ferent structures. (b) TC of PS composites
versus filler loading. (Reproduced with per­
mission from Ref. [249].) SEM image showing
(c) the UGF-CNT hybrid foam structure and (d)
the tip of Al2O3 layer covered single CNT
bundle. (e) TC of different composites. (Re­
produced with permission from Ref. [254]).

29
X. Huang, et al.
because the simply mixed CNT/GNP are separated in the composites
due to the density difference, whereas CNT@GNP cannot separate in
the composites.
Constructing interconnected GNP networks can improve the TCE in
composites. Here, by introducing other fillers, e.g., CNTs, in the matrix
or growing thermally conductive fillers on GNPs, the TCE can be in­
creased. Indeed, high TCE has been found in composites having a GNP
network and MWCNT/PS particles, designated (MWCNT/PS)@GNPs
[249]. Fig. 41a shows 3 different hybrid composites: (a) MWCNT/
GNPs/PS with randomly dispersed MWCNT and GNPs in PS, (b)
(MWCNT@GNPs)/PS with a GNPs/MWCNT hybrid network and seg­
regated PS particles, and (c) (MWCNT/PS)@GNPs. Compared to GNPs/
PS, for composites with higher than 3.5 wt.% total loading of fillers as
in Fig. 41b, (MWCNT/PS)@GNPs exhibit synergistically enhanced TC;
however, the other two hybrid filler cases, MWCNT/GNPs/PS and
(MWCNT@GNPs)/PS, yield lower TC values. The synergistic effect
between MWCNT/PS particles and GNP network may be caused by the
double-network bridging effect and the increased density of filler net­
work [249]. Kholmanov et al. showed that the TC of UGF (UGF: ultra-
thin graphite foam) based erythritol composites could be increased by
growing long CNTs onto the graphite skeleton [254]. SEM images
shown in Fig. 41c,d reveal the UGF-CNT hybrid foam structure: CNT
bundles exhibit curved shapes and the bundle tips are covered by an
Al2O3 layer. As shown in Fig. 41e, the TC of UGF-CNT/erythritol
composites is increased from 2.26 ± 0.3 W/m·K of the UGF/erythritol
composites to 4.09 ± 0.3 W/m·K. However, TC decreases to 2.90 W/
m·K from 4.09 W/m·K when ground UGF-CNT powder is used as hybrid
filler [254]. The enhanced TC of UGF-CNT/erythritol composites is
attributed to the lower interfacial thermal resistance between CNTs and
UGF, which can be achieved through direct connections between
themselves.
5.2. GO- and RGO-based hybrid fillers
GO can be dissolved in water to form hydrogels via assembly and
thus 3D architecture (i.e., foam, skeleton, aerogel) of GO or RGO can be
easily constructed by drying the hydrogels. Combining the lightweight
and tuneable density, the interconnected structure makes GO or RGO
3D architecture attractive for high efficiency TCE in polymer matrix. In
addition, other highly thermally conductive fillers, such as BN, GNP,
CNT and FLG, can be introduced to further increase the TC of compo­
sites [255–257]. Using ball milled GO-BN hybrid, Yao et al. prepared
3D RGO-BN skeleton to study the TCE of epoxy (Fig. 42a) [258]. First,
BN-GO hybrid suspension was directionally frozen and 3D inter-con­
nected BN-GO skeleton ice was prepared by low-temperature vacuum
30
Materials Science & Engineering R 142 (2020) 100577
drying. Composites were subsequently obtained by infiltration of the 3D
interconnected BN-GO skeleton with liquid epoxy and followed by
curing. N, N-dimethylbenzylamine was used as the curing and reducing
agent, which simultaneously converted GO into RGO during the curing
process. At 5.17 vol.% of skeleton (Fig. 42b), BN-GO plates in the
skeleton curl because of the limited space for ice crystal growth. At
higher GO loading, the increased solution viscosity restricts the move­
ment of BN-GO plates and some particles are embedded within the ice
crystals, finally producing a homogeneous interconnected structure
(Fig. 42c). Composites with 13.16 vol.% BN-RGO show a maximum
through-plane TC of 5.05 W/m·K, which is much higher than those
values of composites with randomly dispersed BN (R-h-BN) and BN-
RGO (R-BN-RGO). These results also confirm that the added BN-RGO
hybrids have contributed to forming thermally conductive pathways in
the through-plane direction. An et al. [259] prepared highly anisotropic
RGO/BN hybrid aerogels by hydrothermally treating the GO/BN sus­
pension, air-drying and finally high-temperature annealing. RGO were
self-assembled to a long-range ordered network with high anisotropy
during hydrothermal treatment, while BN distributed between the
aligned RGO could avoid volume shrinkage of RGO aerogel during air-
drying. The RGO/BN (GO:BN = 5:1) hybrid aerogel composites exhibit
a TC of 3.06 W/m·K, which is much higher than 0.87 W/m·K of BN
composites. Also, TC of RGO/BN hybrid aerogel composites increases
with increasing annealing temperature and gives a through-plane TC of
11.01 W/m·K at 2000 °C. By GO-assisted gelation and following hot-
pressing, Li et al. prepared flexible and thermally conductive natural
rubber composite films, which displayed an in-plane TC of 16.04 W/
m·K when the ratio of natural rubber:GO:BN is 1:25:10 [260]. Shao
et al. reported a large enhancement effect of BNNSs on TCE of RGO/
PA6 composites [261]. 3D BNNSs/RGO framework was self-assembled
by introducing BNNSs into the 3D RGO framework; and PA6 composites
were prepared by in-situ polymerization of PA6 in the 3D framework. It
was found that incorporating 1.6 wt.% BNNSs in the composites with
6.8 wt.% 3D RGO could increase TC by 87.6 %, reaching 0.89 W/m·K.
Zhao et al. reported a remarkable synergistic effect between FLG
and RGO foam in enhancing the TC of PDMS composites [262]. FLGs
were added to 0.2 vol.% RGO foam/PDMS composite. At 2.7 vol.%
FLGs, TC of FLG/RGO/PDMS composite reaches 1.08 W/m·K, which is
80 % and 184 % higher than those of 2.7 vol.% FLG/PDMS and RGO/
PDMS composites, respectively. It is, however, noted that graphene-
based hybrid fillers may have a negative effect on TCE. Zhang et al.
studied the thermal and electrical conductivities of epoxy composites
filled with fullerene decorated RGO (fullerene@RGO) [263]. Although
the electrical conductivity increase of highly loaded fullerene@RGO
composites can be more than 17 orders of magnitude (i.e., from 10−14
Fig. 42. (a) Illustration of the fabrication of 3D
BN-RGO/epoxy composites. (b) SEM images of
cross-section of 3D BN-GO skeleton with 5.17
vol.% and the content of GO is 3.4 wt.% of BN-
GO hybrid. (c) SEM images of cross-section of
3D BN-GO skeleton with 13.16 vol.% and the
content of GO is 3.4 wt.% of BN-GO hybrid. (d)
TC of epoxy composites with R-h-BN, R-BN-
RGO, 3D BN-RGO. (Reproduced with permis­
sion from Ref. [258]).
X. Huang, et al.
to ∼3 × 103 S/m), TC only gives a two-fold increase (i.e., from 0.30 to
0.66 W/m·K). Such a TCE (i.e., 1.2) is much lower in comparison with
the various reported RGO/epoxy composites. It is believed that the low
TCE is mainly caused by phonon scattering of fullerene/RGO interface
and an isolation effect of fullerene on graphene/graphene contact. The
latter isolation effect has been indirectly proven in a comparative in­
vestigation on the TC of composites with fullerene@RGO and a physical
mixture of fullerene and RGO [263].
GO or RGO solution can be used to prepare anisotropic composite
films by filtration or solution casting. Other fillers like MWCNT and BN
nanosheet (BNNS) are also used to further enhance the TC or impart
multi-functionalities to the GO/RGO composites [264,265]. Hence,
RGO-encapsulated SiO2 (RGO@ SiO2) were used as fillers to fabricate
multifunctional epoxy composites, which not only gave enhanced TC
but also much improved dielectric and thermal-mechanical properties
[266]. Zhang et al. studied PVA composites with enhanced in-plane TC
and excellent mechanical properties based on the synergistic effects of
functionalized BNNSs/GO network at relatively low loading [267].
Also, some GO/RGO hybrid systems were used to increase both flame
retardancy and TC of composites. Al2O3/f-RGO/epoxy ternary compo­
sites possessed both higher TC and improved flame retardancy perfor­
mance relative to Al2O3/epoxy composites [268]. Silver nanowires and
flame-retardant functionalized RGOs could also enhance both TC and
flame retardancy of epoxy composites owing to the effects of bridging
and catalytic charring of the functionalized RGOs [269].
Vertically aligning graphene sheets in a composite can maximize the
TCE along the through-plane direction [270]. Using this strategy, Li
et al. prepared epoxy composites with ultrahigh through-plane TC
[271]. Typically, they prepared highly aligned and graphitized gra­
phene aerogels by (a) directional-freezing GO hydrogels, (b) freeze-
drying and (c) graphitizing at 2800 °C. The epoxy composite with 0.75
vol.% vertically aligned graphitized graphene aerogel exhibited a
through-plane TC of 6.57 W/m·K, which is 37 times higher in com­
parison with neat epoxy resin. Taking this further with hybrids, as
shown in Fig. 43a, An et al. prepared vertically aligned hybrid foams by
(a) hydrothermal reduction of a GO/GNP suspension, (b) air-drying and
(c) annealing at different temperature [272]. During the hydrothermal
reduction step, the RGO sheets formed a vertically aligned inter­
connected network and prevented the shrinkage of the RGO foams
during the air-drying process. The graphitization of the hybrid foams at
2800 °C removed the oxygen-containing groups and healed the defects
of RGO. These factors resulted in vertically aligned high-quality hybrid
graphene foams with an ideal porous architecture so that the epoxy
composites with 19.0 vol.% hybrid graphene foam displayed an ultra­
high through-plane TC of 35.5 W/m·K (Fig. 43b) [272].
5.3. TC of electrically insulating polymer composites with graphene as filler
The introduction of graphene-based fillers into a polymer matrix
31
Materials Science & Engineering R 142 (2020) 100577
enhances the TC, and simultaneously, in most cases, the electrical
conductivity will also be increased. However, for some TIMs under high
voltage and as underfills in electronic packaging, electrical insulation is
an essential requirement [273,274]. Thus, any electrical conductivity
enhancement must be avoided. A conventional method is to use gra­
phene-based hybrids as thermal conductive fillers for the polymer
composites. For example, alumina coated RGO [275,276], alumina
coated GNPs [277,278], silica coated RGO [279,280], silica coated
graphite [281,282], silicon carbide (SiC) coated graphite [283], alu­
minium nitride (AlN) coated GO [284] and Al(OH)3 coated GO
[125,127] have been reported as effective fillers for preparation of
thermally conductive but electrically insulating polymer composites.
Silica nanoparticles coated RGO have been used to prepare ther­
mally conductive but electrically insulating epoxy composites [279].
Composites with 1.0 wt.% silica coated RGO display a TCE factor of
0.61 in comparison with epoxy resin (from 0.20 W/m·K of epoxy to
0.32 W/m·K of the composite) and well-preserved electrically insulating
properties (i.e., electrical resistivity > 109 Ω·cm). The silica layer ef­
fectively prevents the electrons from hopping or tunnelling from one
graphene sheet to another, resulting in high electrical resistivity of the
composites. However, it is noted that the nanoparticles (e.g., silica,
alumina) used to coat graphene usually have much lower TC than
graphene. Together with their abovementioned insulation effect, a de­
creased efficiency of TCE is unavoidable. Kim et al. indeed found that
epoxy composites with Al(OH)3 coated GO show much lower TC in
comparison with epoxy composites with uncoated GO [125,127]. By
contrast, however, several studies reveal that composites with coated
graphene exhibit higher TC compared to those filled with uncoated
graphene [28,29,279,283]. Sun et al. reported an alumina coated GNP
(Al2O3@GNP) network synthesized by a solution-assisted deposition
method and found significant TCE in Al2O3@GNP/epoxy composites
compared to GNP/epoxy composites [277]. Hsiao et al. [279] explained
these results by suggesting that the coatings improved the graphene
dispersion and decreased the elastic modulus mismatch between gra­
phene and epoxy. In addition, whereas pristine RGO sheets might be
easily rippled and wrinkled, the nanoparticle coating would tend to
flatten the graphene sheets. Therefore, long TC pathways could be
formed along the nanoparticle coated graphene, giving high TC of the
composites. Indirect proof comes from studies on TC of composites
filled with uncoated graphite and silica coated graphite [285], where
lower TC is obtained in epoxy composites with silica coated graphite
flakes. Note that both silica coated and uncoated graphite flakes have
intrinsic flat structures. This implies that the coating would increase the
thermal resistance between the graphite sheets. By dispersing PDA
coated GO (GO@PDA) into a PS microsphere suspension, Yuan et al.
prepared 3D GO interconnected PS nanocomposites. As shown in
Fig. 44a, the nanocomposite with 0.96 vol.% GO@PDA exhibits both
high through-plane (4.56 W/m·K) and in-plane (4.13 W/m·K) thermal
conductivities. Moreover, the same nanocomposite shows an excellent
Fig. 43. (a) Schematic illustration showing the
fabrication process of epoxy composite with
high through-plane TC, including (a) hydro­
thermally assembling GO and GNP in the
aqueous suspension to form vertically aligned
RGO/GNP hybrid foams, (b) air-drying the
hybrid foams, (c) thermally annealing the hy­
brid foams to form aligned graphene aerogels,
and (d) infiltrating epoxy into the graphene
aerogels. (b) TC of annealed air-dried graphene
hybrid foams (GHF)/epoxy composites at dif­
ferent annealing temperature. (Reproduced
with permission from Ref. [272]).
X. Huang, et al.
Fig. 44. (a) TC and (b) electrical resistivity of GO@PDA/PS composites. (Figures were replotted using the test data provided by the authors of Ref. [152]).
electrically insulating property in Fig. 44b (> 1014 Ω·cm) [152].
In addition, as an insulating material, GO has been used to further
increase the TC of traditional thermally conductive but electrically in­
sulating composites [258,286,287]. For example, Huang et al. used GO
as a modifier of AlN and found the encapsulation of AlN by GO sig­
nificantly enhances the TC of epoxy composites when the AlN loading is
low (< 55 vol.%) [288]. But when the AlN loading is very high (i.e.,
beyond the percolation threshold), introducing GO imparts a sub­
stantial increase of viscosity (i.e., low flowability) of the uncured epoxy
composites. Hence, the composites contain pores and voids, yielding
low TC.
5.4. TC of conventional thermally conductive polymer composites by
graphene-based fillers
Since traditional filler composites often have low TCE factors, gra­
phene-based fillers can be used as a second filler to enhance their TC.
The first successful example is the increased TCE of silver/epoxy
composites by graphene. It was shown that adding a small amount of
graphene can result in significant enhancement of TC in silver/epoxy
composites [289]. As shown in Fig. 45a, it is clear that traditional
silver/epoxy composites have a TC of 1.67 W/m·K. After the addition of
32
Materials Science & Engineering R 142 (2020) 100577
5 vol.% graphene, however, the TC of epoxy composites increases re­
markably to 9.9 W/m·K with a TCE factor of ∼5.0. Another example is
f-RGO filled BN/PI composites. Fig. 45b shows BN has low TCE factors
up to 50 wt.% loading in the composites. The introduction of 1.0 wt.%
f-RGO results in a TC of 2.11 W/m·K from 0.74 W/m·K [290]. For ad­
hesives, low filler content is more attractive because it almost does not
change the viscosity and the curing conditions. Messina et al. [248]
investigated the effect of a small amount of GNPs on the thermal and
electrical conductivities of a commercial conductive adhesive com­
prising epoxy resin and ∼78 % sliver platelets and has a TC of 2.5 W/
m·K. Starting from 0.005 wt.% GNPs, TC is increased to 4.0 W/m·K and
further rises to a maximum value of 11.8 W/m·K at 0.01 wt.% GNPs
(Fig. 45c). A remarkable enhancement of TC can also be observed at
0.03 and 0.06 wt.% GNPs. Beyond 0.2 wt.% GNPs, however, the TC is
significantly reduced. This trend agrees with that of electrical con­
ductivity (that is, the reciprocal of electrical resistivity) versus GNP
loading (Fig. 45d) [248]. The decreased enhancement of TC at higher
GNP loading is associated with the agglomeration of excessive fillers
and/or introduction of defects such as voids and pores.
Fig. 45. (a) TC of silver/epoxy composites
versus graphene loading. (Reproduced with
permission from Ref. [289]). (b) TC of PI
composites with individual BN or RGO (f-BN:
TCA modified BN). (Reproduced with permis­
sion from Ref. [290]). (c) Effects of GNP
loading on TC and (d) electrical resistivity of
the commercial conductive adhesive com­
prising epoxy resin and ∼78 % sliver platelets.
(Reproduced with permission from Ref. [248]).
X. Huang, et al.
6. Applications of thermally conductive graphene/polymer
composites
The high TC of graphene/polymer composites presents opportu­
nities for a wide range of different applications. Among these, elec­
tronic packaging materials, PCMs, TIMs and circuit board materials are
the most important, since they utilize high TC of the composites for
effective thermal dissipation. The effects can be clearly and visibly il­
lustrated when they are compared to non-thermally conductive mate­
rials. (See, for example, thermal images of LED on graphene-BN/
polymer composites versus FR4 printed circuit board substrates in
Fig. 46b). However, as most studies on graphene-based composites for
electronic packaging materials and TIMs are often similar to routine
materials research which are mainly focused on materials character­
ization, measurements of thermal and electrical conductivities, and
other physical and mechanical properties, we will not adopt this ap­
proach to avoid overlaps with preceding sections. Since applications are
the ultimate goal of materials research, we will review recent in­
vestigations on graphene-based TIMs (i.e., polymer composites/
greases/fluids), PCMs and battery separators as three examples to shed
light on future potential use of graphene-based highly thermally con­
ductive polymer composites.
6.1. Thermal interface materials
TIMs are used to reduce the thermal contact resistance between two
surfaces, such as the surface of heat-sinks and the surface of a packed
Central Processing Unit (CPU) schematically shown in Fig. 47. They
include thermal fluids, thermal grease (pastes), resilient thermal con­
ductors and solders (applied in the molten state) [292]. TC is a critical
parameter for TIMs [293–298]. When commercial TIMs are filled with
∼4.0 wt.% graphene, the temperature rise can be reduced by ∼10 °C in
the CPU after 15 h operation. This temperature reduction is commer­
cially important for practical applications because a decrease of tem­
perature rise of ∼20 °C can increase the device lifetime by an order of
magnitude [299].
Fig. 46. (a) Photo of FR4 printed circuit board and graphene-BN/polymer composites having a LED mounted on top of each; and (b) thermal images of the LED
mounted on two different substrates. (Reproduced with permission from Ref. [291]).
33
Materials Science & Engineering R 142 (2020) 100577
When graphene/polymer composites are used as TIMs, the most
popular matrix is epoxy resin. The TCE achieved is better than the
traditional carbon materials, such as graphite and CB. Besides, some
flexible graphene-based polymer composites with high TC also have
great potential in thermal management in many fields [300]. In fact,
when SLG and MLG are jointly used, the TCE is much more effective
due to the synergistic effects obtained (Fig. 29). Indeed, most graphene/
polymer composites with high TC can be considered or used as TIMs.
Surprisingly, few studies have been conducted on grease/paste
based graphene composites as TIMs despite demonstrations that gra­
phene can be an excellent filler for TCE. At a low filler loading of 2.0
vol.%, the TC of commercial thermal grease is increased from an initial
value of ∼5.8 W/m·K to 14 W/m·K [116]. Though the matrix is a
commercial thermal grease with decent high TC, the final TCE achieved
by adding graphene is still very remarkable. The graphene used is
fabricated from natural graphite via ultrasonic-assisted liquid exfolia­
tion, followed by centrifugation separation. Hence, it is believed to be
multi-layered and with high quality. In another study [136], RGO is
found to be the most effective filler to enhance the heat transfer
properties of silicone, and GNP is slightly inferior. However, silicone
grease containing RGO exhibits a high viscosity because of its porous
structure, thus GNP is still the best choice to fabricate grease with high
filler loading and a TC of ∼1.0 W/m·K can be achieved with 4.25 vol.%.
Therefore, thermally conductive grease with graphene as filler pos­
sesses better thermal performance than GNP with thickness of tens of
nanometers [301,302]. However, they also induce a high viscosity in
the grease and seriously suppress their processibility.
As for thermally conductive fluids, graphene materials are not an
excellent choice for applications because their high-aspect-ratio will
lead to significant unacceptable increase in viscosity of the fluids. But
advantages do exist. For example, the high aspect ratio may enhance
the TCE, and GO can be well dispersed in fluids without even surfac­
tants. To maintain a stable dispersion, low filler loadings, e.g., 0.1 wt.
%, are normally used. Indeed, the stability of the thermally conductive
fluids obtained are decent: in 2 months (6, 5, 3 months are reported), no
obvious concentration change is observed [303–305]. The base fluids
X. Huang, et al.
are usually water, ionic liquid, propyl glycol or liquid paraffin. Gen­
erally, a low filler loading has a limited effect on the TCE. For example,
when graphene is 0.25 wt.%, the enhancement efficiency is only 33.9 %
at 20 ℃; and when the temperature is increased to 40 ℃, the en­
hancement is up to 47.5 % [306]. The enhancements achieved in other
reports are close to these values [117,218,304,307–317]. Dramatically
increased viscosity and instability at higher filler loadings are believed
to be the obstacle to achieve better performance [310]. Nonetheless,
Wang et al. reported the viscosity of an ionic liquid with graphene
added might be lower than that of the base fluid due to the self-lu­
brication effect of graphene [318]. Fortunately, the fluid viscosity
would decrease sharply at high temperature [319].
It should be noted that currently studies on graphene involved TIMs
focused primarily on material performance, while many related tech­
nical issues have not been fully considered. Some typical issues are:
mismatch of thermal expansion coefficients, simplification of installa­
tion process and reduction of installation pressure of TIMs among
others.
6.2. Phase change materials
Organic PCMs are normally used as latent heat energy storage and
release media for effective thermal management. Pristine PCMs usually
have a very low TC, which results in a slow transient temperature re­
sponse and reduced heat transfer efficiency [320,321]. To enhance TCs
and facilitate phase change of PCMs, enclosing graphene materials is a
means usually employed to increase the temperature during heating up
and decrease the temperature more rapidly during cooling of the whole
PCM [13,134,165,169,171,187,225,303,319,322–344]. Different from
conventional thermally conductive polymer composites, polymers with
phase transition functions, such as PEG, n-hexadecane, 1-octadecanol,
n-eicosane, n-dodecanol and paraffin are often used as matrices
[165,335,337,345–347].
The quality of graphene varies with different preparation methods,
which would result in diversified TCE of graphene/PCMs. For instance,
0.8–1.2 vol.% of 3D ultrathin-graphite foams embedded in PCM can
increase its TC up to 18-fold, while in other experiments, 4.0 wt.%
34
Materials Science & Engineering R 142 (2020) 100577
Fig. 47. (a) Schematic illustrating the action of
thermal interface material, which fills the gaps
between two contacting surfaces. The heat re­
moval improves with higher TC, smaller bond
line thickness and lower contact resistance of
the material. (Reproduced with permission
from Ref. [116]). (b) TC of a commercial TIM
with graphene. (c) Temperature rise versus
time inside a computer CPU using the com­
mercial TIM or graphene filled commercial
TIM. Inset in (c) shows the backside of a CPU
with TIM. (Reproduced with permission from
Ref. [299]).
randomly dispersed graphene leads to only 2.5-fold TC improvement
[13]. Moreover, thermal annealing (> 2200 ℃) is very effective to
obtain defect-free graphene [165]. A high TC of thermally annealed
defect-free graphene/PCM can reach 3.55 W/m·K with 10 wt.% gra­
phene. This is an enhancement efficiency of > 600 % compared to un-
annealed graphene/PCM composites at a similar filler loading, and a
16-fold increase to pure PCM (1-octadecanol). When defective pristine
graphene is used as fillers, a TC of only 0.55 W/m·K is obtained with 10
wt.% filler. This result clearly reveals the importance of graphene
quality.
Apart from the graphene quality, the number of graphene layers
also greatly affects the TC that can be obtained in graphene/PCM
composites [169]. Thus, the TCE factor varies from ∼2 to 25 at 20 vol.
% graphene whose number of layers is between 3 and 44. These results
are not only due to the relatively lower intrinsic TC of MLG but are also
caused by the interface thermal resistance, morphologies of graphene
with different layers in polymer matrix and the percolation threshold.
While common sense would suggest thin perfect graphene materials
are preferred fillers to achieve high TC in polymer composites, the
current best TCE is instead achieved with continuous 3D graphene
structures as fillers for PCM [13,338,348]. For example, with a very low
loading (0.8–1.2 vol.%) of ultrathin graphite foam, the TC of a PCM is
enhanced up to 18 times (∼2.8 W/m·K) and the influences on the
melting temperature or mass specific heat of fusion are negligible [13].
The ultrathin graphite foams were fabricated using Ni foam templates.
The main point to achieve a very high TC at very low filler fraction is to
utilize 3D continuous filler structure instead of dispersed fillers and to
anneal the fillers at very high temperature (3000 ℃). High temperature
annealing makes the continuous graphite struts possessing TC up to
840 W/m·K and the strut structure of the graphite fillers forms con­
tinuous thermal conductive paths in the PCM matrix. It is noted that,
here, the graphite foam has a wall thickness of hundreds of nanometers,
which is much thicker than even MLGs. This claims to give a graphite
strut/PCM interface insensitive to phonon scattering that is crucial to
achieving high TCE, since the interface phonon scattering greatly re­
duces the basal-plane TC of graphene materials. In another study, Min
et al. showed that at 3.6 ± 0.2 wt.%, the anisotropic high-quality
X. Huang, et al. Materials Science & Engineering R 142 (2020) 100577

graphene aerogel-based paraffin PCM composites exhibit a high
through-plane TC of 8.87 W/m·K, resulting in a TCE factor of 24.34 and
an exceptional latent heat retention of 98.7 % [349]. They prepared the
graphene aerogels in four steps: (a) fabricating vertically aligned
monoliths by freezing the suspensions of polyamic acid (PAA) salt and
GO, (b) freeze-drying, (c) imidization at 300 °C and (d) graphitization at
2800 °C.
The application of graphene filled PCMs for battery pack thermal
management is illustrated in Fig. 48 by Goli et al. [171]. Clearly, gra­
phene-filled PCMs show large reductions of temperature rise inside the
battery pack. Computer simulation also confirms the significant effect
of graphene filled PCMs on thermal management of battery pack. In the
case of graphene-filled PCMs, battery cylinders exhibit the lowest
temperature of ∼310 K–315 K. In combination with TC data shown in
Fig. 32, it can be concluded that the increased TCs in graphene-filled
PCMs significantly improve the thermal management capability of Li-
ion battery packs.
In addition, graphene filled PCMs with high TC have great potential
for high-power-density energy harvesting, such as solar-thermal energy
conversion [350,351]. These PCMs not only can improve the thermal-
diffusion-based charging rate, but also enable cost-effective thermal
management applications [352,353]. Wu et al. reported highly ther­
mally conductive PCMs with largely aligned GNP and their application
in thermal energy storage [354]. As illustrated in Fig. 49a,b, the heat
capacity of the PCM-based thermal energy harvesting device remains
quite stable after ∼100 cycles of charge and discharge. Moreover, the
TC of these PCMs can be tailored in the range of 4.4–35.0 W/m·K at
filler loading below 40 wt.%. The IR images shown in Fig. 49c also
reveal the excellent thermal management of such PCMs in power bat­
tery. It can be seen that the maximum surface temperature of the
wrapped power battery is 47.8 °C when the discharging rate is 2.3 C.
However, the non-wrapped power battery reaches 61.0 °C.
6.3. Battery separators
Separator is an important component of battery systems that elec­
trically isolate the cathode from the anode to avoid internal short cir­
cuits. However, low affinity to electrolyte and poor thermal properties
of commercial polyolefin separators have seriously undermined the
electrochemical behaviours and safety of batteries [355]. The applica­
tion of graphene-based materials in battery separators has been in­
vestigated due to its high TC and rich functional groups [356]. Typical
graphene/polymer composite separators can be divided into hybrid
separators and coated separators.
The polymers commonly used in developing hybrid separators in­
clude PAN [357], PMMA [358], PVDF [359] and PU [360]. PAN and
PMMA nanofiber separators incorporated with graphene were fabri­
cated by the electrospinning technique [358]. The TC of PAN and
PMMA nanocomposite fibers increased with graphene loading (Fig. 50).
At 8 wt.% graphene, the TC of PMMA and PAN composite fibers
reached 5.0 W/m·K and 2.7 W/m·K, respectively, which could improve
thermal management of batteries [361,362]. Besides TC, electrolyte
wettability, dielectric constant, and ionic conductivity of the nano­
composite separators also increasd with the addition of graphene. As for
coated separators, the batteries with graphene composite separators
display significant enhancement of electrochemical performance [363].

Fig. 48. (a) Setup for battery testing. Six 4 V Li-ion cells are placed in an Al battery pack, and each has a capacity of 3000 mA h. Graphene filled PCM (IGI-1260) is
used for cooling the Li-ion battery pack. (b) Measured temperature fluctuations at battery cathode, battery anode and battery pack and ambient temperature. (c) Rise
of temperature inside the battery pack of first ten charge-discharge cycles in the cases of no PCM, paraffin, PCM with 1 wt.% graphene and PCM with 20 wt.%
graphene. (d) Simulated temperature in the pack of a battery. (Reproduced with permission from Ref. [171]).

35
X. Huang, et al.
Fig. 49. (a) Schematic showing the heat design of the thermal energy harvesting system. (b) Thermal capacity versus cycle times of the thermal energy harvesting
system. The inset in (b) is a photo of the thermal energy harvesting system. (c) Surface temperature of two power battery units. The insets in (c) show the photos of
the tested power battery units and their IR images during the discharging process. (Reproduced with permission from Ref. [354]).
Fig. 50. TC of (a) PAN and (b) PMMA composite fibers plotted against gra­
phene nanoflake loading. (Reproduced with permission from Ref. [357]).
Li et al. studied a bi-layer composite separator by coating PA-grafted
GO molecular brushes onto the PP separator. The cells with these
composite separators exhibited long-term stability for over 2600 h at a
high current density (2 mA/cm2) [364]. Zhu et al. explored the effect of
RGO reduction on the electrochemical characteristics of Li-S cells with
coated separators [365]. It was found that RGO with higher reduction
degrees possessed better polysulfide rejection performance, which
provides a promising strategy in the RGO selection for battery separa­
tors. However, the detailed role and mechanism of the TC of separators
on battery performance was seldom reported.
7. Summary and outlook
For the development of highly thermally conductive polymer com­
posites, graphene materials as fillers have at least two key advantages:
36
Materials Science & Engineering R 142 (2020) 100577
the superb high TC and very high aspect ratio. The high aspect ratio
makes the utilization of the high TC of graphene more effective to
achieve high TC composites. However, it is noted that many problems
in current graphene/polymer composites are also associated with these
two advantages. Some of these problems are identified below:
(1) The extremely high TC of graphene is very sensitive to many fac­
tors. The large TC can only be preserved in perfect graphene
structure, defects and modification to graphene and even the in­
teraction between graphene and matrix will unavoidably result in
remarkable reduction of TC. This incurs two sub-problems: (a)
Graphene derived from different fabrication methods actually pos­
sesses different TC. Graphene fabricated by CVD, peeling graphite
or sonication exfoliation may have very high quality, but they have
extremely low yield or multi-layered structures. Highly yielded GO
or RGO is known to possess low TC caused by the defective struc­
tures and the quality of RGO which greatly depends on the reduc­
tion agents/methods used and high temperature post-annealing. (b)
The contradiction between surface modification and high TC of
graphene. Surface modification is of primary importance to im­
prove the interfacial affinity between graphene and polymer and
graphene dispersion in matrix. However, any functional groups
attached on graphene will induce local phonon scattering and in
turn ruin the intrinsic TC. Detailed studies on balancing these two
contradictions have been wanting to-date.
(2) High aspect ratio results in the serious problem of dispersion. While
theoretically high aspect ratio benefits TC achievable in composites
at high filler loading, the high viscosity of graphene/polymer melt
or solution mixture makes it very difficult to fabricate such gra­
phene/polymer composites. In addition, high aspect ratio induces
folding and twisting of graphene sheets which are difficult to
overcome, and in turn they may lead to serious reductions of TC of
the graphene sheets [80,84]. High aspect-ratio MLG with high
flatness should be better than thinner graphene sheets and thicker
graphite platelets to achieve high TC in polymer composites.
(3) There are no effective approaches to curb the interfacial thermal
resistance between graphene and polymer matrix as well as the
contact resistance between graphene sheets in the composites. A
X. Huang, et al.
graphene/polymer composite fabrication approach that has a high
potential to achieve high TC at low graphene loading is to use
graphene aerogel which is a self-supported structure of graphene
sheets. Although it is expected that the pre-formed thermal con­
ductive paths will give high TC of fabricated composites, the TC
values obtained by this method is still much lower than expected.
This is attributed to the high interfacial thermal resistance and
contact resistance which are not very well managed.
(4) Despite the high expectations, the advantages of utilizing graphene
in highly thermally conductive polymer composites have not been
well demonstrated. Actually, most data achieved with graphene are
not much superior to those by CNTs or thin graphite platelets.
Instead, an obvious observation is that the quality and formation of
thermal conductive paths are more important. Some CNTs and thin
graphite platelets possess much more perfect structure than GO and
RGO, which lead to even better performance. Also, 3D structure of
graphite/graphene platelets may be more effective than 2D thin
layer graphene for TCE [13,161,179,366–371], indicating the for­
mation of 3D thermally conductive paths in polymer composites is
more important than the thin structure of graphene.
(5) Graphene is highly electrically conductive and they also give sig­
nificant electrical conductivity enhancement of the polymer com­
posites when increasing the TC. In this case, the development of
thermally conductive but electrically insulating polymer compo­
sites is curtailed. Coating a high-electrical-resistivity layer, such as
inorganic nanoparticles and dielectric polymers, on graphene-based
fillers retains the electrical insulation of the composites. However,
TCE of the composites is also influenced by the additional inter­
facial and contact thermal resistances. In addition, these composites
cannot withstand high voltage applications due to the electrically
conductive nature of graphene [121,372].
Looking to the future, to achieve the desired high TC in polymer
composites with graphene as filler, the following issues should be ad­
dressed with good engineering solutions:
(1) High yield and large-scale production of high-quality graphene is
still on demand and is critical for the development of polymer
composites with high qualities. Today, almost all the methods de­
veloped for large-scale fabrication of graphene materials involve
severe conditions, yielding defective samples. The TC of these de­
fective graphene materials may be low to tens of W/m·K in spite of
the high intrinsic TC up to thousands of W/m·K of the perfect
graphene lattice. Therefore, most graphene currently used as fillers
for polymer composites actually does not truly justify the name of
“graphene” as far as TC is concerned.
(2) For processing and fabrication of graphene/polymer composites, it
is widely agreed that some methods, e.g., surface modification,
using graphene with large lateral sizes, etc., are very effective;
however, studies to avoid their negative effects are much fewer. For
example, surface modification on graphene is a typical double-edge
sword: while it can solve the problems of dispersion and interfacial
phonon scattering, it can also destroy the high intrinsic TC of gra­
phene. High aspect ratio graphene may increase the TCE factor, it
also imparts dramatically higher mixture viscosity, poor dispersion,
folding and twisting of graphene sheets, etc. Hence, it is possible to
use low aspect ratio graphene to achieve high TC in polymer
composites with better dispersibility than high aspect ratio gra­
phene. More basic work is needed on these issues to balance the
processing conditions.
(3) Great efforts are needed on 3D graphene/polymer composites. It is
a promising approach to achieve high TC with preformed 3D
thermal conductive paths. However, at present, as a result of
37
Materials Science & Engineering R 142 (2020) 100577
unsolved interfacial and contact thermal resistances, the expected
high TC has not been realized.
(4) Synergetic effects, which have been widely studied in polymer
composites, must be well designed to overcome the weakness of
graphene as a filler. First, synergetic effects greatly benefit forma­
tion of thermally conductive paths in polymer composites; second,
hybridizing graphene and other fillers with different dimensions
and particle sizes can improve the graphene dispersion in polymer
matrices by overcoming the adverse self-formed layered structure.
Hence, combining graphene with other highly thermally conductive
fillers may be the ultimate solution for current practical applica­
tions of graphene-based materials as thermally conductive fillers.
(5) Graphene has anisotropic TC and the in-plane TC can be more than
two orders of magnitude higher than the through-plane TC. Thus,
much research work had been done to obtain polymer composites
with anisotropic TC. Such methods include aligning graphene by
applying electric/magnetic field, electrospinning, mechanical
straining, injection moulding, two-roll milling, self-assembly, ice
template, filtration and solution casting. Using these methods, it is
possible to design and fabricate graphene/polymer composites with
either high in-plane TC or high through-plane TC. In the future,
particular attention should be given to practical industrial appli­
cations of these methods, but not just seeking the highest TC values.
Researchers should address the critical issue of what is the TC re­
quired for the particular end-use.
(6) The role of TC of graphene and its composites in practical appli­
cations should be investigated in depth. Hence, new measurement
and characterization techniques must be developed, which should
not only give TC of materials in service but should also reflect the
performance variation induced by the enhanced TC. One example is
graphene nanocomposite separators for batteries. While high TC
separators may improve the thermal management of batteries, the
detailed role and mechanism of how the TC improves the battery
performance has not been revealed.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ­
ence the work reported in this paper.
Acknowledgements
X.H. and G.W. gratefully acknowledge the supports from the
National Natural Science Foundation of China (Nos. U19A20105). Y.-
W.M. thanks the support from the Australian Research Grants Council
(DP130104648).
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from Purdue University in 2012. His research interests are
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in micro/nano scale thermal energy transport, thermo­
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41
X. Huang, et al.
Pingkai Jiang is a professor of Department of Polymer
Science and Engineering and the Director of Research
Center of Dielectrics and Electrical Insulation at Shanghai
Jiao Tong University. Jiang’s research focuses on polymer
nanocomposites for energy storage and dielectric applica­
tion and fire retardant materials for electrical insulation. He
received his Ph.D. in Electrical Materials and Insulation
Technology in 1995 from Xi’an Jiao Tong University.
42
Materials Science & Engineering R 142 (2020) 100577
Yiu-Wing Mai is University Professor in Mechanical
Engineering at the University of Sydney. He obtained his
PhD on fracture mechanics from the University of Hong
Kong. He previously worked in the US (University of
Michigan and NIST), the UK (Imperial College) and Hong
Kong (HKUST, CityU, HKU and PolyU). His current research
interest is on polymer nanocomposites and their functional
applications. He is a Fellow of the Royal Society of London
and the Australian Academy of Science as well as a Foreign
Member of the Chinese Academy of Engineering.