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From anisotropic graphene aerogels to electron-

and photo-driven phase change composites†
Cite this: DOI: 10.1039/c6ta07587h
Guangyong Li,ab Xuetong Zhang,*a Jin Wanga and Jianhui Fang*b

Received 2nd September 2016
Accepted 3rd October 2016
DOI: 10.1039/c6ta07587h
www.rsc.org/MaterialsA
To overcome fatal shortcomings of organic phase change materials (PCMs), such as leakage during work,
low thermal conductivity and shortage of multiple driving ways, we propose a novel strategy to synthesize
structurally, mechanically, electrically and optically anisotropic graphene aerogels (AN-GAs) by using
gaseous hydrogen chloride to in situ solidify ordered graphene oxide liquid crystals followed by chemical
reduction, supercritical fluid drying and annealing in an Ar atmosphere in sequence. The confined pore
space and aligned wall structure of the resulting AN-GAs have benefited crystallization of organic phase
change molecules and thus highly efficient phase change composites (PCCs) are fabricated with long
durability and good strength. The resulting PCCs can also be driven either by applying a small voltage
(1–3 V) with high electro-heat efficiency (up to 85%) or by irradiating with weak sunlight (0.8–1.0 sun)
with high photo-heat efficiency (up to 77%).

serve as the PCM hosts with anisotropic electrical/optical

Introduction
Latent heat storage of phase change materials (PCMs) is
considered as an extremely promising way to utilize thermal
energy coming from the surrounding environment, solar irra-
diation, waste heat produced by vehicles and electronic prod-
ucts, etc.1,2 Multiple driven techniques are demanded for PCMs
with fast-heating as well as slow-radiating characteristics to
utilize latent heat in ever-increasing application elds.2–4
However, due to low thermal/electrical conductivity, pale color,
and easy leaking in the melted state, neither electrical nor
optical ways can be used to drive the organic PCMs.5 Recently,
3D conducting/light-absorbing porous networks, such as metal
foams, carbon nanotube sponges and graphene aerogels, have
been used to serve as hosts for organic PCMs to make phase
change composites (PCCs),6–9 which gives the possibility to
achieve latent heat storage driven either optically or electrically.
However, all of these 3D porous networks were isotropic, which
still signicantly restricted the phase change performance of
the resulting PCCs. In fact, electrically driven PCMs particularly
need porous hosts with a higher conductivity along the fast
heating direction, while optically driven PCMs particularly need
porous hosts with a larger light-absorbing surface perpendic-
ular to the light irradiation direction. All these urgent require-
ments have forced scientists to develop porous frameworks to
a
Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences,
Suzhou 215123, China. E-mail: zhangxtchina@yahoo.com
b
Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444,
China. E-mail: jhfang@shu.edu.cn
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c6ta07587h
properties.
Aerogels, an extremely important class of isotropic porous
materials with extraordinary capillary force,10 have been ideal
hosts for PCMs to prevent leaking during phase change tran-
sition.3,6,7,9,11–13 However, two critical issues should be overcome
before aerogels can achieve practical applications in the
multiple driven PCCs: (1) intrinsically low thermal conductivity
of the aerogels themselves could not guarantee fast heating of
the PCCs, and thus the aerogels with high thermal conductivity
have to be developed, and (2) the intrinsically isotropic porous
structure of the aerogels could not guarantee the best phase
change performance of the resulting PCCs as mentioned above,
and thus anisotropic aerogels have to be developed. Lately,
Tsuguyuki Saito14 reported an anisotropic aerogel, for the rst
time, with a 3D ordered nanober skeleton prepared from
a nanocellulose liquid crystal precursor; however the ordered
aerogel still has heat-insulation and thus could not be applied
in the eld of latent heat storage. Recently, the discovery of
graphene oxide liquid crystals (GO-LCs) and orientational
ordering of graphene oxide sheets in aqueous dispersions have
provided a great opportunity to design aligned porous archi-
tectures, such as lms15 and bers16,17 with excellent thermal,
electric and mechanical properties.18–20 Nevertheless, the
growth of ice and the absence of a sol–gel process have resulted
in an inhomogeneous graphene framework.
To overcome fatal shortcomings of organic PCMs, such as
leakage during work, low thermal conductivity and shortage of
multiple driving ways, herein we have presented a novel strategy
for the rst time to synthesize structurally, mechanically, elec-
trically and optically anisotropic graphene aerogels (AN-GAs) by
using gaseous hydrogen chloride to in situ solidify ordered

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Journal of Materials Chemistry A
GO-LCs followed by chemical reduction, supercritical uid
drying and annealing in an Ar atmosphere in sequence, and
then organic PCMs have been successfully lled into these AN-
GAs to fabricate electron- and photo-driven PCCs with low drive,
high efficiency and long durability. The aligned walls together
with conned pores of the AN-GAs have directed preferential
orientation of the organic PCMs with high crystallinity. The
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existence of the AN-GA frameworks can signicantly enhance
the mechanical strength of the PCMs regardless of direction
(although there are differences in different directions). The
work presented here, to the best of our knowledge, is the rst
report on anisotropic graphene aerogel-based multiple driven
PCCs. Our work also gives much inspiration to design more
anisotropic aerogels as hosts for multiple driven PCCs.
Experimental
Materials
Graphite powder (1 mm) was purchased from Qingdao Tianheda
Graphite Co., Ltd, Qingdao, China. P2O5, K2S2O7, 30% H2O2,
HCl (aq), HI and H2SO4 were obtained from Sinopharm
Chemical Reagent Company. Paraffin and commercial PCC
were obtained from Shanghai Joule wax Co., Ltd. Gaseous
hydrogen chloride was obtained via the volatilization of
hydrochloric acid (35–37 wt%).
Preparation of GO-LCs
Graphene oxide (GO) sheets were prepared from graphite
powder by a modied Hummers method reported in our
previous study.19 Liquid crystalline GO was prepared by centri-
fugation of the GO dispersion at high speed (10 000 rpm) for
about 3 h.
Preparation of the AN-GA
The resulting GO liquid crystal (
25 mg mL1) was loaded into
a mould (plastic box) and was driven to have a long-range order
via owing (repeatedly tilting the plastic box containing the GO
liquid crystal). The mould was aged in gaseous hydrogen chlo-
ride (HCl (g)) for 6 h to obtain the GO hydrogel, aer that the
10 wt% HI (serving as the reducing agent) solution (the volume
of HI solution is the same as that of the GO-LC) was spread over
the GO hydrogel and allowed to stand for 12 h at room
temperature. Followed by washing at least 4 times with absolute
ethyl alcohol to replace the water and the residual HI in the
hydrogel network, supercritical drying with CO2 (40  C, 10 MPa)
for 12 h, and annealing at 600  C in an Ar atmosphere for 3 h,
the AN-GA was obtained.
Preparation of the AN-GA–paraffin composite
Both the AN-GA and paraffin were heated to 80  C (above the
melting point of paraffin, 48  C) in a vacuum oven and were
placed for 3 h for the AN-GA to infuse with paraffin. Aer the
AN-GA was submerged in the melting paraffin, the system was
allowed to cool until the paraffin was solidied, and then the
excess paraffin adhered on the composite surface was removed
with a knife. The paraffin loading in the composite was
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determined by measuring the weight difference of the AN-GA
before and aer infusion.
Electric-to-thermal energy conversion and storage
The cylinder-shaped samples (AN-GA and PCC) were connected
to a regulated DC power supply (ATTEN, APS3005Dm) with two
Cu wires, each wire was attached to the undersurface of the
cylindrical sample with silver paste to ensure good electrical
contact; silica coating was covered on the silver paste to insulate
the heat in the axial direction. The temperature evolution of the
sample was measured by using a thermocouple and recorded by
using a data collection system using the same conguration.
Photo-to-thermal energy conversion and storage
The rectangular samples (AN-GA and PCC) were placed in
a transparent and sealed plastic box, and then directly illumi-
nated by simulated solar light from a tungsten–halogen lamp
ltered by a IV cut-off lter (Eddmund Optics, 54047) and
a daylight blue lter (HOYA LB120) using a Keithley 2400 source
meter. The temperature evolution of the samples was measured
and recorded with a thermometer (FLUKE, 54IIB).
Characterization
Raman spectra were recorded on a LabRAM HR Raman spec-
trometer with a 50 mW He–Ne laser operating at 632 nm with
a CCD detector. X-ray diffraction (XRD) patterns were recorded
on a D8 Advanced spectrometer with a scanning rate of 0.05 s1
over an angular range of 5–65 (2q). The morphology of the
samples was examined by SEM (Hitachi S-4800) with an accel-
eration voltage of 5–15 kV. The paraffin and the composite were
coated with Au nano-powder under a current of 20 mA for
2 min. Transmission Electron Microscopy (TEM) measurement
was carried out on a Tecnai G2F20 S-Twin with an acceleration
voltage of 200 kV. The pore size distribution and average pore
diameter of the aerogels were analyzed by the BJH nitrogen
adsorption and desorption method (ASAP 2020, Micromeritics,
USA). The surface area of the aerogels was determined by the
Brunauer–Emmett–Teller (BET) method, based on the amount
of N2 adsorbed at pressures 0.05 < P/P0 < 0.3. Thermal gravi-
metric analysis (TGA) and DTG were carried out using a TG
209F1 Libra (NETZSCH) analyzer with a heating rate of 10  C
min1 in a nitrogen atmosphere. DSC analysis was performed
on a DSC 200F3 NETZSCH with a heating and cooling rate of
10  C min1. Lateral thermal diffusivity was measured by using
a Netzsch LFA 457 laser ash thermal diffusivity apparatus
operating at room temperature. Thermal conductivity of the AN-
GA and its composite was calculated from the equation l ¼
arCP, where a is the thermal diffusivity, r is the density of the
sample and CP is the heat capacity. The heat capacity of the AN-
GA was measured by LFA; the heat capacities of the AN-GA–
paraffin and pure paraffin were measured by DSC. The electric
resistances of the aerogel and its composites were measured by
using a CHIChief 600D electrochemical workstation, and the
electric conductivity can be calculated by the equation: k ¼ IL/
US where k is the electric conductivity, I is the current which
crosses the sample, U is the voltage applied in the sample, L is
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the length of sample the current goes through, and S is the cross
area of current. The stress–strain curves were recorded by using
an Instron 3365 tensile testing machine.
Results and discussion
Assembling the anisotropic graphene aerogels
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The synthetic pathway of the AN-GA is shown in Scheme 1A.
First of all, uniform GO-LCs with macroscopic and microscopic
colorful textures (Fig. S1, ESI†) were obtained from the uniform
GO suspension via high-speed centrifugation.21–23 According to
Onsager's theory,19,24 the competition between orientational
entropy and excluded volume entropy can promote the forma-
tion of stable liquid crystalline orders (Fig. S2†). When the GO-
LC was aged in the presence of gaseous hydrogen chloride (HCl
(g)), the HCl (g) dissolved and diffused into the GO-LC slowly
with immediate ionization, which restrained ionization of the
carboxylic acid groups attached on GO sheets, and thus led to
gradual formation of a dynamic hydrogen-bonding network due
to the coupling effect. With the increase of hydrogen ions, the
dynamic hydrogen-bonding network (Fig. S3†) was “in situ
frozen” and the liquid crystal GO hydrogel with colorful texture
(Fig. S4†) was obtained. Aer chemical reduction with HI,
supercritical uid drying with CO2 and annealing at 600  C in
an Ar atmosphere in sequence, the corresponding AN-GAs with
different shapes and sizes as shown in Fig. 1a were obtained.
The cutting section plane of the aerogel exhibited metallic
shininess, indicating a high reduction degree and uniform
macrostructure. Moreover, the anisotropic GO aerogels (AN-
GOAs) with a uniform and smooth cutting section plane were
also successfully obtained (Fig. S5†) by the supercritical CO2
drying of the LC-GO hydrogel, which indicated that the LC-GO
hydrogel structure was stable. In addition, the AN-GOA can be
transferred into the uniform GO solution just by mechanical
agitation in deionized water (Fig. S6b†), which indicated that
there was no other cross-linkers except hydrogen bonds.
Scheme 1 (A) Schematic description of the AN-GA synthesis derived
from liquid crystals with the assistance of the solid hydrogen-bonding
network based on vapor diffusion and the sol–gel process. (B) Illus-
tration of the fabrication process in which the melting paraffin fills in
the AN-GA to make a composite that can be driven either electrically
or optically for heat storage.
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Fig. 1 (a) Pictures of the as-synthesized AN-GA (left) and the section
plane after cutting (right) and (b) illustration of the AN-GA in two
directions for SEM imaging. (c) TEM image and electron diffraction
pattern of the AN-GA. (d–f) SEM images of the AN-GA in the axial
direction at different magnifications. (g–i) SEM images of the AN-GA in
the radial direction observed from different positions.
The resulting AN-GAs as well as the AN-GOA were charac-
terized by transmission electron microscopy (TEM), N2
adsorption–desorption test and XRD. As shown in Fig. 1c and S7
and S8,† single- or few-layered graphene sheets exhibited a at
state with some straight wrinkles that evenly distributed over
the whole sheets, reecting the nature state of graphene sheets
with some wrinkles in solution.25,26 All the edges of graphene
sheets were clear and smooth, similar to graphene sheets in the
liquid crystal which was observed by real-time confocal laser
microscopy.19 Furthermore, we also observed from Fig. S7a†
that two edges of the different GO sheets were half connected
and half separated in parallel, which might attributed to the
coupling effect of the carboxylic acid group.27 From nitrogen-
sorption spectra, a steep increase in N2 uptake at low relative
pressure (P/P0 < 0.02) could be observed, (Fig. 2b and S9†),
which suggested a microporous structure (0.35–0.7 nm) in the
aerogel, and the ratio of micropore areas to total ones reached
9.6% (for the AN-GOA) and 12.7% (for the AN-GA), respectively
(more details see Table S1 in the ESI†). We considered that the
micropores derived from the nature wrinkle of the GO in solu-
tion with least partial overlapping. Moreover, the mesopores
(
4 nm) of the graphene-based aerogel with a type IV adsorp-
tion isotherm might be attributed to monolayer–multilayer
adsorption. The XRD patterns of both the AN-GOA and AN-GA
(Fig. 2c) have a sharp peak, further revealing the regular packing
of graphene sheets with a longer correlation length in the
anisotropic aerogel.15 Moreover, the decrease of interlayer
spacing from 0.9 nm (2q ¼ 9.8 ) of the AN-GOA to 0.35 nm (2q ¼
25.4 ) of the AN-GA indicates the elimination of functional
groups in the reduction process.
The vapor diffusion method through HCl (g) to crosslink LC-
GO promised the gelation without mechanical stirring, and
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Fig. 2 (a) Polarized Raman spectra of the AN-GOA and AN-GA, (b)
nitrogen adsorption and desorption isotherms of the AN-GA, and (c)
XRD patterns of the AN-GOA and AN-GA. (d) XRD patterns of pure
paraffin, 80  C treated paraffin and the composite. (e) Compressive
stress–strain curves of the AN-GA in different directions. (f)
Compressive stress–strain curves of AN-GA–paraffin and the
commercial PCM.
thus allowed maintaining intrinsic ordering of liquid crystals in
the resulting aerogel, which could be conrmed directly from
the eld emission scanning electron microscopy (FESEM)
imaging. Along the axial direction (along the arrangements of
graphene sheets and pore channels, Fig. 1b), the graphene
sheets were piled up to form regular wrinkle-bands with aligned
honeycomb-like pores (macropore diameter 4 < 1 mm) and led to
a folded zone (Fig. 1d–f and S10a–f†). Along the radial direction
(normal to the arrangements of graphene sheets and pores,
Fig. 1b), the aligned pore channels and the smooth pore walls
were observed from the cross-section images (Fig. 1g–i and
S10g–i†). All of these exhibited a totally different morphology
compared to the common graphene aerogel (Fig. S11†).
Furthermore, the SEM images also exhibited an open and
tubular structure, and the cell walls were extremely thin with
a translucent state, containing only single or few layers of gra-
phene. The AN-GOA also showed a highly ordered lamellar
structure with 3D ordered interconnected pores and walls
(Fig. S6a†), which corresponded to orientational graphene
nano-sheets of the GO-LCs.
Fig. 2a shows the Raman spectra of the anisotropic aerogel.
The intensities of the G- and D-bands of the aerogel were 3–4
times higher in the axial direction than those in the radial
direction. This meant that there was higher resonance in the
axial direction, indicating an ordered alignment of graphene
layers in the anisotropic aerogels.28–30 In addition, the increase
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of the intensity ratio of the D peak to G peak in the Raman
spectra, from 0.99 of the AN-GOA to 1.42 of the AN-GA, sug-
gested the recovery of the conjugated structure via the reduction
process.
The anisotropic mechanical properties of the resulting aer-
ogels were investigated as shown in Fig. 2e. For the axial
direction, the curve could be divided into three linear regimes:
the rst (3 < 2%, Young's modulus E ¼ 6.25 MPa) and the second
(3 ¼ 2–21%, E ¼ 2.88 MPa) regimes were elastic deformation,
and the third one was plastic deformation (3 > 21%, E ¼ 0.41
MPa). The SEM image showed that compressing the aerogel in
the axial direction resulted in conversion from initially at pore-
walls into a buckled fold (Fig. S12†), similar to the deformation
of the aligned CNT array,31 which further reected long-range
uniform alignment of graphene in the axial direction. For the
radial direction, the curve showed two regions, a linear elasticity
region and a yield region as shown in Fig. S13,† similar to the
regular graphene aerogel's behavior. In comparison with the
axial direction (E ¼ 6.25 MPa), the radial direction showed
higher compressive modulus (E ¼ 8.3 MPa) in the rst linear
elastic deformation, and both of them were higher than those of
the graphene aerogels reported elsewhere.16,32 Based on SEM
images of the AN-GA deformation under pressure in two
directions, the deformation mechanisms were proposed as
illustrated in Fig. S14.†
Thermal conductivity as a function of graphene orientation
along two directions was described and is shown in Fig. 3a and
b. Along the axial direction, the thermal conductivity (l) of the
AN-GA was as high as 1.71  0.2 W m1 K1, about eight times
higher than that in the radial direction (0.22  0.05 W m1 K1),
suggesting that the AN-GA was an excellent thermal conducting
host for PCMs in comparison with a commercial SiO2 aerogel
(0.018 W m1 K1)11 and nanocellulose/graphene oxide foam
(0.021 W m1 K1).33 The l value of the AN-GA in the axial
direction was signicantly above the value of the regular gra-
phene aerogel (0.1  0.01 W m1 K1)34 and comparable to that
of the isotropic CVD-graphene foam (1.47 W m1 K1),6 which
might be related to the thermal properties of graphene sheets
and the aligned microstructure in the cell wall (Fig. 3a). The
thermal conductivity in the radial direction was smaller and
similar to that of the regular graphene aerogels, possibly due to
the existence of air layers (0.01 W m1 K1) and more interface
resistances between the wall and the air. The electric conduc-
tivity behaviors were also anisotropic. The electric conductivity
could reach 341.3 S m1 in the axial direction by a four-probe
method, about 4–5 times higher than that of self-assembled
graphene aerogels35 (
87 S m1), cross-linked graphene aero-
gels32 (
1  102 S m1) and emulsion-templated graphene aer-
ogels34 (64  2 S m1), while the electric conductivity of our
aerogel in the radial direction was
65–105 S m1, comparable
to that of the regular graphene aerogels reported elsewhere.32,34,35
Phase change composites based on the anisotropic graphene
aerogel
Based on these results, the AN-GAs might be ideal hosts for
PCMs with multiple means to drive latent heat storage. Thus,
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Fig. 3 (a) Schematic illustration of the aerogel thermal conductivity in
the axial and radial directions with oriented pores and walls. (b)
Thermal conductivity values of the AN-GA and AN-GA–paraffin in
different directions. (c) TGA curves of the pure paraffin, the
commercial composite and the AN-GA–paraffin. (d) DSC melting and
freezing curves of the pure paraffin (1st and 2nd), AN-GA–paraffin
composite, and commercial PCC. (e) The measured latent heats of
pure paraffin (1st and 2nd), AN-GA–paraffin composite, and
commercial PCC. (f) The measured latent heat of the AN-GA–paraffin
composite during 45 melting–freezing cycles, the inset shows the
DSC curves of the AN-GA–paraffin composite tested for 45 cycles.
paraffin was used to fabricate a series of AN-GA derived PCCs
(AN-GA–paraffin, see Scheme 1B). As shown in Fig. S15,† the
well-maintained aligned graphene structure in the composite
was unchanged aer lling paraffin: the graphene sheets were
wrapped by paraffin, and the massive crystals (induced lump-
crystals of paraffin along aligned channel-like pores) also stood
in the aligned pore channels, which was totally different from
the crystal structure of the pure paraffin (Fig. S16†). According
to the literature,36 the pores with a diameter of less than 13 mm
should have enough capillary force to hold the PCM without
leakage during phase transition. As the pore diameter of our
aerogels was less than 1 mm, the AN-GA was therefore an
effective host for fabricating PCCs without leakage during the
phase change process. This could be demonstrated by heating
AN-GA–paraffin and pure paraffin at
100  C; as shown in
Fig. S17,† the former remained stable without leakage, but the
latter became uidic. From compressive stress–strain curves as
shown in Fig. 2f, the AN-GA–paraffin also exhibited excellent
mechanical strength: the brittleness of the paraffin was reduced
signicantly in the presence of the AN-GA and the corre-
sponding PCC was compressed with nearly vefold strain in
comparison with that of the commercial PCC.
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The crystallization of paraffin and PCC was investigated by
XRD. It is clearly shown in Fig. 2d that two sharp intensive
diffraction peaks at 2q ¼ 21 and 24.2 were observed for the
pure paraffin, which were attributed to the typical diffractions
of (110) and (200) crystal planes of the monoclinic paraffin,
respectively.37 However the intensity of the (110) in the AN-GA–
paraffin composite (underwent 80  C treatment during the
lling process of the paraffin) enhanced signicantly and that
of the (200) decreased sharply, suggesting that preferential
orientation of paraffin molecules with high crystallinity formed
in the pore channel of the AN-GA. Furthermore, the 80  C-
treated paraffin possessed the same peaks but with signicantly
decreased intensities, indicating that the secondary crystalli-
zation of the paraffin was limited in the absence of ordered
conned space.
Thermal stability of paraffin in the AN-GA was measured by
TGA as shown in Fig. 3b and S18.† The degradation step
occurring at temperature between 200 and 450  C belonged to
the thermal degradation of paraffin, and the remaining could
be attributed to the AN-GA framework. This is because the AN-
GA had a very high degradation temperature (Fig. S19†). The
paraffin loading percentage in AN-GA–paraffin was up to 94% as
calculated from the TGA result, which was comparable to the
maximum loading amount reported recently (>90%)13 and
much higher than that of the commercial PCCs (77%).
Phase change behavior was characterized by differential
scanning calorimetry (DSC), as shown in Fig. 3d. The pristine
paraffin melting curve showed an onset at 49.3  C with a peak
position at 58.2  C. The DSC curve of the AN-GA–paraffin
showed a lower melting onset (47.8  C) and a similar solidi-
cation point of 46.05  C. In addition, incorporation of a gra-
phene network resulted in delayed peak temperatures of the
heating and cooling of paraffin, which shied from 54.4  C and
40.75  C, to 64.7  C and 29.7  C, respectively. For the pristine
paraffin, the melting enthalpy (DHm ¼ 207 J g1) was higher
than the freezing enthalpy (DHf ¼ 192 J g1) in the rst cycle
(1st) as shown in Fig. 3e, mainly due to the change of the crystal
structure, but in the second cycle (2nd), the melting enthalpy
(DHf ¼ 190.2 J g1) became lower than the freezing enthalpy
(DHf ¼ 193 J g1), which was similar to that of most of the
PCMs.13 The phase enthalpy of AN-GA–paraffin (DHm ¼ 193.7 J
g1 and DHf ¼ 198.2 J g1) exhibited only a partial loss (
6.4%)
in comparison with paraffin (1st), nearly corresponding to the
graphene loading percentage as calculated from the TG curve,
but higher than that of the pure paraffin (2nd). Taking XRD
analysis aforementioned into consideration, we could further
conrm that the paraffin in the AN-GA possessed a higher
crystalline degree. In addition, the 45 cyclic DSC curves of the
AN-GA–paraffin were virtually identical as shown in Fig. 3f,
which indicated the excellent cyclic stability of the composites.
In comparison with the cyclic DSC curves of the pure paraffin
and the commercial PCC (Fig. S20†), we could nd that the AN-
GA skeleton was not disrupted and the crystal structure of
paraffin was well maintained during the cyclic solid–liquid
transition process.
Since air in the AN-GA was replaced by paraffin (0.21 W m1
1
K ), with a paraffin loading of
94%, the thermal conductivity
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of the AN-GA–paraffin signicantly increased up to 2.99 W m1

K1 in the axial direction as shown in Fig. 3b, which represented
a nearly 15-fold increase in comparison with that of pure
paraffin, and higher than that of the aligned CNT–n-eicosane
(90 wt%) composite.9 The thermal conductivity of AN-GA–
paraffin in the radial direction could reach
1.2 W m1 K1.
The thermal conductivity difference between the axial and the
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radial directions was reduced to nearly three times as the air

was replaced with the paraffin. Similarly, the alignment of
graphene sheets in the composite also gave it a high electric
conductivity in the axial direction and a large electric conduc-
tivity difference (axial/radial reached to
5) along different
directions. To further study electrical properties, we measured
the electric resistance of the AN-GA and AN-GA–paraffin in the
axial direction by a current–voltage (I–V) test as shown in
Fig. S21,† and the result indicated that the electrical resistance
increased slightly aer introduction of paraffin into the AN-GA,
from 1.06 U of the aerogel to 1.22 U of the composite. The
corresponding electric conductivities were 297 S m1 and 258.7
S m1, respectively, indicating that a slight structural defor-
mation had occurred for the AN-GA being lled with paraffin.
The resistance of a PCC with 94% paraffin content still
approached that of a pure graphene aerogel, indicating that the
paraffin introduction had played a negligible role in disturbing
the original graphene network.
Electric-to-thermal energy conversion and storage
For an AN-GA placed at room temperature, applying a constant
voltage of 0.5 to 3 V (electric circuit showed in Fig. 4a) caused an
abrupt increase in sample temperature during the initial 60 s
and reached an equilibrium state where heat dissipation from
the AN-GA to the environment balanced input energy (Fig. 4b).
Correspondingly, a larger voltage resulted in a higher equilib-
rium temperature. When the applied voltage was withdrawn,
the sample temperature dropped sharply close to the environ-
mental temperature. All these observations indicated that the
AN-GA possessed a fast-response electro-thermal effect. When
a similar voltage (1.0–3.0 V) was applied to the AN-GA–paraffin
composite as shown in Fig. 4c, the temperature increased
rapidly in the initial stage, until a plateau with a minimum
slope that corresponded to start and termination of the paraffin
phase change process was reached. Aer phase change nished,
the composite temperature increased rapidly again until
reaching the equilibrium state. When a lower applied voltage
(e.g. 0.5 V) was applied, there was no inection point in the
temperature curve, indicating that the paraffin in the composite
had not melted during this period. Thus a critical voltage for
a complete phase change was about 1.0 V, which was a quite low
critical triggering voltage. Under higher voltage, the melting
process became more shortened; therefore heat loss from the
heated composite (exposed to air) to the environment was
reduced and thus resulted in an enhanced efficiency. The
electro-to heat storage efficiency is about 50.5% under 1.5 V and
85.4% under 3.0 V as shown in Table S2,† exhibiting much
better performance in electric-to-heat conversion in comparison
with CNT sponge3 (40.6% under 1.5 V), anisotropic carbon
Fig. 4 (a) Schematic illustration of the electro-driven phase change
composite device circuit. (b) The temperature–time relationship of the
AN-GA under applied voltages of 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0 V,
respectively. (c) The temperature–time relationship of AN-GA–
paraffin under the same voltage conditions. (d) Schematic illustration
of the photo-driven phase change composite device circuit. (e) The
temperature–time relationship of the AN-GA under illumination by
simulated sunlight (AM 1.5) at intensities of 0.7 sun, 0.8 sun, 0.9 sun and
1.0 sun. (f) The temperature–time relationship of AN-GA–paraffin
under the same illumination conditions.
nanotube array9 (38.9% under 1.7 V) and carbon aerogel7 (71.4%
under 15 V). Aer withdrawing the applied voltages, all the curves
immediately dropped to the freezing point of paraffin (
48  C),
and the second plateau appeared in each curve, which was
associated with the solidifying process of the PCM. The ratio of
the plateau length of the solidifying process to the melting one
was bigger under higher voltage, about 3 times under 1.5 V and
25 times under 3.0 V, suggesting that the thermal energy could be
generated in a very short time and released very slowly for a long
time. This indicated that AN-GA–paraffin was an excellent elec-
tron-driven latent heat storage composite in comparison with an
aligned CNTA–n-eicosane composite.9
Photo-to-thermal energy conversion and storage
The AN-GA–paraffin could be considered as an excellent photo-
capturer due to the following reasons: (1) the absorption of
individual graphene layers was
2.3% of the white light,38 (2)
large thermal interface between graphene sheets and paraffin
molecules, and (3) the graphene–paraffin–graphene sandwich
junction structure might act as a microcavity, which could
enhance the light absorption.39–41 Consequently, a rectangular
AN-GA–paraffin sample could adsorb sunlight vertically (radial
direction) through the graphene basic plane (the wall of the
aerogel pore) and a corresponding device for photo-to-heat

J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2016


Paper
energy conversion is illustrated in Fig. 4d. The sample was placed
under simulated solar illumination (AM 1.5, 100 mW cm2) with
controlled intensities of 0.7, 0.8, 0.9 and 1.0 sun, respectively.
During the light radiation, the temperature of the AN-GA abruptly
increased and reached a stable state with a equilibrium
temperature (
70  C under 1.0 sun and
60  C under 0.9 sun), as
shown in Fig. 4e, suggesting that the AN-GA could be used as an
Published on 03 October 2016. Downloaded by UNIVERSITY OF NEW ORLEANS on 20/10/2016 07:40:19.
ideal photo-capturer for solar–thermal-conversion of phase
change composites. When the incident light was switched off, the
temperature was quickly dropped with a manner similar to the
withdrawal of voltage as shown in Fig. 4b. When an AN-GA–
paraffin composite (
92% loading of paraffin, 1.4  1.7 cm2) was
exposed to light, phase change occurred at temperature close to
48  C under light intensities of 0.8, 0.9, and 1.0 sun, as could be
seen from the plateau in each curve; no phase change was
observed under 0.7 sun (Fig. 4f). Similarly, the heat release from
the composite could be observed aer turning off the light. The
photo-to-thermal conversion efficiency was about 77% as calcu-
lated from stored-energy divided by the irradiating energy
received by the sample over the working time (Table S3†). This
indicated that the resulting AN-GA–paraffin was an excellent
photo-driven latent heat storage composite in comparison with
the literature reported elsewhere.42,43
Conclusion
In conclusion, 3D porous graphene aerogels with a highly
anisotropic network originating from GO-LCs were prepared via
combination of vapor diffusion and a sol–gel method followed by
supercritical CO2 drying and thermal annealing in sequence. The
resulting aerogels showed high thermal conductivity (1.71 
0.2 W m1 K1) and high electricity conductivity (341.3 S m1)
with outstanding anisotropy (
8 times difference in thermal
conductivity and 3–5 times difference in electrical conductivity
investigated from two orthogonal directions). We have found that
the conned pore space and aligned wall structure of the result-
ing AN-GAs beneted crystallization of the organic phase change
molecules and thus highly efficient PCCs were fabricated with
long durability and good strength. What's more, the resulting
PCCs could be driven either by applying a small voltage (1–3 V)
with high electro-heat efficiency (up to 85%) or by irradiating with
weak sunlight (0.8–1.0 sun) with high photo-heat efficiency (up to
77%). Our work might offer a possibility to develop next-genera-
tion energy systems with smart performance for electric devices,
solar energy utilization, thermal management, etc.
Acknowledgements
This work was nancially supported by the National Natural
Science Foundation of China (51572285, 21373024, and
21404117) and the Natural Science Foundation of Jiangsu
Province (BK20151234).
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