Energy Storage Materials 13 (2018) 88–95

Contents lists available at ScienceDirect

Energy Storage Materials

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

Hybridizing graphene aerogel into three-dimensional graphene foam for MARK

high-performance composite phase change materials
Jie Yanga, Guo-Qiang Qia,b, Rui-Ying Baoa, Kongyang Yib, Menglin Lib, Lan Pengb, Zhi Caib,
⁎ ⁎
Ming-Bo Yanga, Dacheng Weib, , Wei Yanga,
a
College of Polymer Science and Engineering, Sichuan University, State Key Laboratory of Polymer Materials Engineering, No. 24 South Section 1, Yihuan
Road, Chengdu, 610065, China
b
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, 220 Handan Rodd, Yangpu
District, Shanghai 200433, China

A R T I C L E I N F O A BS T RAC T

Keywords: Three-dimensional (3D) graphene foam (GF) produced by template-directed chemical vapour deposition (CVD)
Graphene foam has shown great potential for applications in composite phase change materials (PCMs) with enhanced thermal
Hybrid graphene aerogel conductivity and graphene aerogel (GA) has been proved to be effective supporting scaffold to improve the
Composite phase change materials shape-stability of organic PCMs. Here, hybrid graphene aerogel (HGA) is encapsulated in GF framework to
Solar energy conversion
obtain a 3D GF/HGA (GH) hybrid microstructure via combined self-assembly and CVD techniques. The thermal
conductivity of paraffin wax (PW)/GH composite PCMs increases by 574% and 98% compared with pure PW
and PW/GF composite PCMs, respectively. Meanwhile, PW/GH composite PCM exhibits better shape stability
than PW/GF composite PCM, high thermal energy storage density, good thermal reliability and chemical
stability. PW/GH composite PCMs also realize efficient light-to-thermal energy conversion and storage owing to
the excellent photoabsorption. This study sheds light on the development of the composite PCMs with good
comprehensive properties, which are potentially to be used widely in energy storage systems.

1. Introduction Nevertheless, three major drawbacks of organic PCMs such as

With the rapid industrial development and growing population, the
global energy crisis and greenhouse effect are also heading upwards. In
order to relief such pressure and avoid the excessive dependence of fossil
fuels, the development and utilization of renewable sources of energy,
especially the solar energy which is inexhaustible, abundant and clean, have
become a hot topic. However, solar energy is discontinuous and varies with
period of generation [1–4]. Therefore, the development of energy-storage
materials for storing solar thermal energy has attracted a great deal of
interest in recent years [5,6]. Organic phase change materials (PCMs)
storing or releasing thermal energy in the form of latent heat during phase
transition process are one of the effective advanced energy storage
techniques for solar energy conversion and storage owing to their high
storage capacity, adjustable phase transition temperature, desirable thermal
and chemical stability, no corrosivity, low or negligible supercooling degree,
etc. [7–10]. Therefore, organic PCMs exhibit tremendous potential for
applications in buildings, smart textiles, waste heat recovery, air-condition-
ing systems, thermal management for electronics/batteries, solar energy
conversion, etc. [9,11–18].
polyethylene glycol (PEG) and paraffin wax (PW) are their inherently
low thermal conductivity, poor shape-stability above the melting point
and weak photoabsorption during solar energy conversion, which un-
desirably suppress the practical application possibility and working
efficiency [19,20]. Great efforts have been dedicated to solving these
problems and fabricating high-performance composite PCMs by introdu-
cing functional materials and structures. In the past few decades, various
supporting materials including graphene oxide (GO) [21,22], expanded
graphite (EG) [23], polymers [2,24–27], diatomite [28,29], expanded
vermiculite [30,31], etc., and thermally conductive fillers such as graphene
[8,32,33], EG [34–37], graphene nanoplatelets (GNP) [38,39], boron
nitride [40,41], etc., have been used to improve the shape-stability and
thermal conductivity of organic PCMs, respectively. Carbon materials
[19,42–46], dye [47,48], polydopamine [49] have been proved to be able
to effectively improve the photoabsorption of the composite PCMs. It has
been found that constructing three-dimensional (3D) graphene based
structural materials contributes to simultaneously overcoming these three
shortcomings and endowing the composite PCMs with excellent compre-
hensive performance [18,50].

⁎
Corresponding authors.
E-mail addresses: weidc@fudan.edu.cn (D. Wei), weiyang@scu.edu.cn (W. Yang).

https://doi.org/10.1016/j.ensm.2017.12.028
Received 8 October 2017; Received in revised form 27 November 2017; Accepted 30 December 2017
Available online 02 January 2018
2405-8297/ © 2017 Published by Elsevier B.V.
J. Yang et al.
Compared with graphene aerogel (GA) prepared from self-assembly
technique, graphene foam (GF) prepared by chemical vapor deposition
(CVD) technique can more efficiently enhance the thermal conductivity
of the composite PCMs. This is because the physical cross-links of GAs
are formed by the van der Waals contact, hydrogen bonding and π–π
stacking interactions [51,52], which still generate interfacial thermal
resistances among the two-dimensional (2D) graphene nanosheets,
while GF from covalently bonded graphene building block is a monolith
of 3D graphene network that provides continuous pathways for phonon
transport [53,54]. However, the large pore size of GF on a few hundred
micrometers scale is determined by the large pore size of the Nickel
(Ni) foam catalyst skeletons, which has a detrimental effect on the
shape-stability of organic PCMs. There is no denying that GA can
greatly improve shape-stability of the organic PCMs [55–57].
Meanwhile, GA also reduces the thermal resistance for the composites
from the PCM inside the large pores of GF.
In the present work, we are proposing to encapsulate hybrid
graphene aerogel (HGA) into 3D GF to optimize the structure of 3D
network for high-performance composite PCMs. Self-assembled HGA
with a dense 3D network is introduced into the GF framework with
large pores to construct a 3D hybrid GF/HGA (GH) microstructure by
combining self-assembly and CVD techniques, and the obtained GH is
then used to fabricate PW/GH composite PCMs. Compared with pure
PW and PW/GF composite PCMs, the heat transport properties and
shape-stability of PW/GH composite PCMs are greatly improved due to
the structural optimization of GH. Also, PW/GH composite PCMs not
only exhibit high phase change enthalpy and excellent thermal stability
but also realize solar-to-thermal energy conversion owing to the
improvement of photoabsorption.
2. Experimental section
2.1. Fabrication of GH
GO was synthesized from EG with improved Hummer's method
[58]. Firstly, 10 mL GO aqueous solution with a concentration of
5 mg mL−1 was prepared, and then 50 mg, 100 mg, 150 mg, 250 mg,
500 mg GNP (Knano Graphene Technology Co., Ltd., Xiamen, China)
were added into the solution to obtain a GO/GNP aqueous dispersion
via ultrasonication and mechanical stirring. Ni foam (Jilin Zhuoer
Metal Materials Co., Ltd., 130 PPI, thickness of 5 mm) was then
immersed into the GO/GNP aqueous dispersion. 1 mL L-ascorbic acid
aqueous solution with a concentration of 150 mg mL−1 was added in
and mixed uniformly. GO in the mixture was reduced at 95 °C for 3 h
followed by removing excess L-ascorbic acid with deionized water. It is
worth noting that the reduction of GO with L-ascorbic acid ensures the
structural stability of HGA inside the Ni foam framework. In CVD
growth process, the temperature of the whole system rises from room
temperature to more than 1000 °C within just a few minutes. If the GO
nanosheets are not reduced, the CO2 generated from the decomposition
of oxygen containing functional groups on GO sheets will yield
sufficient rapid pressure buildup during rapid heating, resulting in
great expansion and destruction of HGA network, which will also be
squeezed out of Ni foam [59,60]. Therefore, the reduction of GO in
advance plays an important role in the structural stability of HGA
inside Ni foam framework during CVD growth. Finally, Ni foam
supported HGA (Ni foam/HGA) was obtained after freeze drying.
A 3D framework composed of HGA and Ni foam covered with
graphene was prepared using CVD growth method and labeled as Ni-
G/HGA [61]. In brief, the reaction system was pumped to a pressure of
4 × 10−3 Torr and then backfilled with a gas mixture of Ar (500
standard cubic centimeters per minute (sccm)) and H2 (200 sccm) until
reaching the atmospheric pressure. In the first step, the Ni foam/HGA
placed in a quartz tube was heated to 1000 °C under a flow of the mixed
gas at atmospheric pressure. In the second step (carbon dissolution),
CH4 (10 sccm) was introduced to the chamber as the source of carbon.
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Energy Storage Materials 13 (2018) 88–95
Table 1
The component and density of GF and GH.
Samples GF GH1 GH2 GH3 GH4 GH5
GO/GNP ratio N/A 1:1 1:2 1:3 1:5 1:10
Density (mg cm−3) 5.5 35.2 39.0 41.8 49.3 57.1
The CH4 molecules decomposed at the Ni surface and carbon atoms
diffused into the metal. In the last step (carbon segregation), samples
were cooled down to room temperature to obtain Ni-G/HGA [62,63].
Note that CH4 and other carrier gas took their respective gas paths, and
they converged into a pipeline before entering the furnace chamber.
The next step was to etch the Ni foam template. The Ni-G/HGA was
drop-coated with poly(methyl methacrylate) (PMMA, Mw = 350,000,
Aldrich) solution (4 wt% in anisole) to prevent the structural collapse of
GH during this process, and then baked at 180 °C for 3 h. A layer of
PMMA as a supporting material coated the 3D GH skeleton, reinforcing
the graphene structure. The PMMA@GH was prepared by etching the
Ni foam templates in 3 M HCl solution at 80 °C overnight. Finally, the
PMMA layer coating the surface of GH skeleton was dissolved by using
acetone at 55 °C to obtain the free-standing GH. As shown in Table 1,
according to the different ratio of GO and GNP in the GO/GNP aqueous
dispersion, the as-prepared GH samples are labeled as GH1, GH2,
GH3, GH4 and GH5, respectively, and the densities range from
35.2 mg cm−3 to 57.1 mg cm−3. As a comparison, the original Ni foam
was also used as 3D scaffold templates directly for CVD growth of GF
with the same procedure and conditions.
2.2. Fabrication of the composite PCMs
The PW/GF and PW/GH composite PCMs were prepared by a
vacuum impregnation technique. PW purchased from Sigma Aldrich
was heated to 80 °C to melt, and the GH and GF were individually
immersed into the melted PW. After that they were placed in a vacuum
oven at 80 °C until no air bubbles emerged before cooling to room
temperature. The obtained PW/GH composite PCMs with different GH
are labeled as PW/GH1, PW/GH2, PW/GH3, PWGH4 and PW/GH5,
respectively. The whole process of fabrication of GH and composite
PCMs was detailedly illustrated in Fig. 1.
2.3. Characterization
The morphologies of the samples were determined by a field-
emission scanning electron microscope (SEM, Zeiss Ultra 55, German)
at an accelerating voltage of 10 kV. Thermal conductivity measure-
ments were conducted using a Hot Disk Thermal Constant Analyzer
(TPS 2500, Hot Disk AB Company, Sweden) by a transient plane heat
source method. Thermal infrared images obtained from an infrared
camera (Ti27, Fluke, USA) were used to evaluate the rate of thermal
response for the composites visually. A thermomechanical analyzer
(TMA, SDTS841e, Mettler Toledo, Switzerland) was used to character-
ize the shape-stability of pure PW and the composite PCMs. Moreover,
the shape-stability of the samples placed on a hot stage was also
investigated by observation of samples as the heating temperature
increases, followed by taking digital photographs. Characterization of
the latent heat and phase change temperature of the samples was
performed using a differential scanning calorimeter (DSC, TA Q20,
USA) at a heating/cooling rate of 10 °C min−1 in high purified nitrogen
atmosphere. The Fourier-transform infrared (FTIR) spectra of the
samples were obtained using a Nicolet 6700 FTIR spectrometer
(Nicolet Instrument Company, USA). The light-to-thermal energy
conversion test was carried out under simulated sunlight provided by
a CEL-HXUV300 xenon lamp with an AM 1.5 filter, and a CEL-NP2000
optical power meter (CEAULIGHT, China) and a paperless recorder
with thermocouples (OMEGA) were used to verify the light irradiation
J. Yang et al.
Fig. 1. Schematic illustration of the preparation of GH and PW/GH composite PCMs.
power and record the temperature, respectively. The optical properties
of pure PW and the composite PCMs were characterized on a UV–vis-
NIR spectrophotometer (Lambda 750, Perkin-Elmer, USA) with an
integrating sphere.
3. Results and discussion
3.1. The microstructures of 3D GH
GO and GNP are employed as supporting materials and thermally
conductive fillers, respectively, and the obtained HGA is used to
optimize the structure of GF and improve the properties of composite
PCMs. When GO is reduced, most of the oxygen containing functional
groups are removed and the π-conjugation is restored. The π-π
stacking interaction together with hydrophobic effect promotes partial
overlapping and interlocking of reduced GO nanosheets with each
other in 3D space to generate enough physical crosslink sites for the
formation of a porous framework [64]. Encapsulating HGA into Ni
foam to get Ni foam/HGA is the critical base in the whole process. The
microstructures of the samples obtained in each step are observed by
SEM. Fig. 2a and b show that HGA constructs a second network in Ni
foam and wraps the skeletons of Ni foam compactly. From the exterior,
the whole Ni foam is wrapped by HGA via the self-assembly process, as
shown in Fig. 2g and h. After CVD growth with Ni foam/HGA, the
surface of Ni foam is covered with a monolith of graphene, and the
HGA network inside can still be observed in Fig. 2c and d. After
etching, the 3D GH hybrid microstructure composed of GF framework
and a dense HGA network is obtained, as shown in Fig. 2e and f.
3.2. Heat transfer properties of PW and the composite PCMs
Fig. 3a shows the thermal conductivity of pure PW, PW/GF and
PW/GH composite PCMs. Pure PW exhibits a relatively low thermal
conductivity (0.27 W m−1 K−1), which is consistent with the value
reported in previous work [61]. The thermal conductivity of PW/GF
composite PCM rises to 0.92 W m−1 K−1 after introducing GF.
Compared with PW/GF composite PCM, the thermal conductivity of
PW/GH composite PCMs is improved further, and the enhancement of
thermal conductivity is greatly dependent upon the ratio of GO and
GNP. It is worth noting that PW/GH5 composite PCM exhibits a
thermal conductivity as high as 1.82 W m−1 K−1, which is enhanced by
574% and 98% compared with pure PW and PW/GH composite PCM,
respectively. The enhancement is mainly ascribed to the optimized 3D
GH hybrid microstructure. Besides GF, the HGA across the GF frame-
work of GH provides additional thermally conductive pathways, which
contributes to the obvious reduction of thermal resistance inside the
pores of GF and acceleration of the thermal transport. Therefore, PW/
GH composite PCMs show a greatly improved thermal conductivity,
which can further improve the thermal charging/discharging rates and
the working efficiency of the organic composite PCMs.
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Energy Storage Materials 13 (2018) 88–95
The infrared thermal images were provided to further demonstrate
the heat dissipation capability of the composite PCMs visually, as
shown in Fig. 3b. Pure PW, PW/GF and PW/GH5 were placed on a hot
platform with a constant temperature of 70 °C in the heating phase. It
can be seen that the temperature increase of PW/GH5 with the highest
thermal conductivity is the fastest among PW, PW/GF and PW/GHs,
intuitively indicating that the heat spreads the fastest from the bottom
to the top. As expected, PW/GH5 also exhibits the best heat transfer
rate during cooling. The higher thermal conductivity enables the
composite PCMs to absorb/release thermal energy more rapidly. This
result further demonstrates that the 3D graphene microstructure is
effective for the construction of the thermally conductive pathways
owing to the formation of the hierarchical structures comprising a
continuous GF framework and a dense HGA network.
3.3. Shape-stability of PW and composite PCMs
The shape-stability of the composite PCMs was characterized with
TMA and a leakage test by digital camera observation. TMA results
shown in Fig. 4a disclose the excellent shape-stability of the composite
PCMs. The dimension of pure PW starts to reduce at ca. 50 °C, and
then decreases rapidly with increasing temperature. When the tem-
perature increases to more than 70 °C, the melt leaks completely for
pure PW and the solid–liquid phase change emerges. On the contrary,
by impregnating PW into GF and GH, the dimensions of the resultant
PW/GF and PW/GH composite PCMs change little even a temperature
above 90 °C, indicating that the composite PCMs exhibit significantly
improved shape-stability due to the supporting effect of the 3D
graphene microstructure. A leakage test was also conducted by digital
camera observation to directly confirm the shape-stability of the
composites, as shown in Fig. 4b. When heated to 60 °C, pure PW
starts to melt with obvious leakage on the bottom, which is in
accordance with the TMA results. It is noteworthy that although
obvious dimension reduction of PW/GF composite PCM is not
observed in TMA tests, PW/GF composite PCM shows the sign of
leakage because of the large and open pores of GF. However, PW/GH
composite PCMs maintain the original shape without obvious liquid
leakage in the whole process, which is ascribed to the denser network
structure of GH compared with GF. Apart from the supporting effect of
GF framework, the HGA inside GF framework of GH contributes to
improving the shape-stability of PW/GH composite PCMs greatly.
Therefore, the 3D graphene microstructure accommodates well the
molten PW and endows the PW/GH composite PCMs with an out-
standing shape-stability.
3.4. Thermophysical properties of PW and composite PCMs
The thermophysical properties of pure PW and the composite
PCMs, including phase change temperatures, specific latent heat and
thermal reliability are described by the DSC curves in Fig. 5. It is
J. Yang et al. Energy Storage Materials 13 (2018) 88–95

Fig. 2. SEM images of (a) and (b) Ni foam/HGA, (c) and (d) Ni-G/HGA obtained after CVD growth, (e) and (f) GH obtained after etching. Photographs of (g) Ni foam and (h) Ni foam/
HGA.

obvious that there are two phase change peaks on both heating and
cooling curves for all samples, which correspond to the solid-solid and
solid-liquid phase transition of PW [65]. The phase change parameters
extracted from DSC curves, such as melting/crystallization tempera-
ture (Tm/Tc) and melting/crystallization enthalpy (ΔHm/ΔHc) of the
composite PCMs, are presented in Table 2. The phase change tem-
peratures of the composite PCMs are not affected by the introduction of
GF and GH, while their specific latent heat decreases monotonically
with the decrease of the GO/GNP ratio owing to the decrease of the
weight percentage of working substance. Although the thermal energy
storage densities of PW/GH composite PCMs are slightly lower than
that of PW/GF composite PCM, the PW/GH5 composite PCM with

Fig. 3. (a) Thermal conductivity of pure PW, PW/GF and PW/GH composite PCMs. (b) Thermal transport evolution of pure PW, PW/GF and PW/GH5 composite PCMs during heating
and cooling.

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J. Yang et al. Energy Storage Materials 13 (2018) 88–95

Fig. 4. (a) TMA curves of pure PW, PW/GF and PW/GH5 composite PCMs. (b) Photographs of pure PW, PW/GF and PW/GH composite PCMs at different temperatures.

Fig. 5. (a) DSC heating and cooling curves of pure PW, PW/GF and PW/GH composite PCMs. (b) The obtained mass specific heat of fusion normalized by the first heating cycle of PW/
GH5 composite PCM (The inset is the DSC curves of PW/GH5 composite PCM with 100 melting and cooling cycles). (c) FTIR spectra of PW/GH5 composite PCM before and after 100
thermal cycles.

Table 2
DSC heating and cooling parameters of pure PW, PW/GF and PW/GH composite PCMs.

Specimens PW PW/GF PW/GH1 PW/GH2 PW/GH3 PW/GH4 PW/GH5

Tc (°C) 48.2 47.8 47.4 48.3 47.7 47.3 47.6

ΔHc (J g−1) 162.0 157.9 152.4 154.7 153.1 145.8 139.2
Tm (°C) 56.5 57.1 56.4 56.0 56.6 57.2 57.3
ΔHm (J g−1) 164.5 161.0 156.2 158.1 156.1 148.7 145.2

superior thermal conductivity and shape-stability exhibits a relatively
high thermal energy storage density (145.2 J g−1). Obviously, the
balance between high performance and high latent heat is achieved
for the PW/GH composite PCMs in this work, which ensures the energy
conversion discussed later.
Thermal reliability of the composite PCMs was determined by
performing DSC thermal cycling tests. Fig. 5b shows the thermal
properties of the composite PW/GH5 after 100 melting and cooling
cycles. A negligible change of phase change temperatures and a slight
reduction of 1.8% in heat of fusion are observed, as shown in DSC
curves and the heat of fusion normalized by the first heating cycle. Also,
no changes of the characteristic peaks from the FTIR spectra (Fig. 5c)
are observed, indicating that the chemical structure of PW/GH5
composite PCM is stable over 100 melting and cooling cycles. Based
on the above results, the prepared shape-stabilized composite PCMs
show excellent thermal reliability and chemical stability after thermal
cycles.
3.5. Solar-to-thermal energy conversion of PW and composite PCMs
In order to verify the capacity of energy conversion of the high-
performance composite PCMs, we constructed a smart light-to-thermal
energy conversion system based on PW/GH composite PCM in this
work, as illustrated in Fig. 6a. Fig. 6b shows the light-to-heat
conversion curves of the samples under simulated solar illumination
at a controlled intensity of 100 mW cm−2. When the samples are
exposed to light radiation, the temperature of PW/GF and PW/GH
composite PCMs rises rapidly compared with pure PW. As irradiation
time increases, the inflection point and platform of the composite
PCMs emerge successively between approximately 53 and 60 °C,
demonstrating that the composite PCMs exhibit solid-liquid phase
change and the light radiation is converted to thermal energy stored in
them in the form of latent heat. Following the light off, the stored heat
is released from the composite PCMs due to the crystallization of PW,
resulting in the appearance of another temperature growth plateau
between approximately 60 and 55 °C. Conversely, no visible melting
and cooling plateaus are observed for pure PW in the whole process.
The above phenomena result from the difference that the black GF and
GH enhance the photoabsorption of PW/GF and PW/GH composite
PCMs over the whole UV–vis-NIR range, while pure PW exhibits
relatively weak photoabsorption, especially in the visible-light range, as
shown in Fig. 6c. In this work, GF and GH, behaving as a black body
due to its low reflection and effective light trapping, are effective
photon captors and molecular heaters, absorbing and converting solar
radiation into thermal energy [19,43].
The light-to-thermal conversion and energy storage efficiency (η) of
the composite PCMs can be estimated by the ratio of heat stored in
composite PCMs and the collected light radiation energy during phase
change period [42,43]. According to Eq. (1), the η of PW/GF and PW/
GH composite PCMs is calculated to be above 90%.

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J. Yang et al.
Fig. 6. (a) Schematic diagram of the light-to-thermal energy conversion and storage measuring system. (b) Light-to-thermal conversion curves and (c) UV–vis-NIR absorption spectra
of pure PW, PW/GF and PW/GH5 composite PCMs.
m·ΔH
η =
P·S·(te − to )
where m is the total mass of the sample, ΔH is the phase change
enthalpy obtained by DSC, P is the light irradiation intensity of
simulated light source (100 mW cm−2 @ AM1.5), S is the surface area
of the sample, to and te are the light-driven phase change time of the
sample before and after the phase change.
4. Conclusion
In conclusion, 3D GH hybrid microstructure was obtained by
optimizing the structure of GF via combining CVD and self-assembly
techniques and then applied to prepare PW/GH composite PCMs. The
fabricated GH hybrid microstructure is composed of GF framework and
the encapsulated dense HGA 3D network across the GF framework.
The composite PCMs not only exhibit significantly enhanced thermal
conductivity and shape stability, but also maintain relatively high
thermal energy storage density and desirably stable thermal repeat-
ability. Compared with pure PW, the thermal conductivity of PW/GH5
composite PCM is enhanced by 574%. Based on PW/GF composite
PCM, the shape stability of PW/GH composite PCM is further
improved. Additionally, PW/GH composite PCM exhibits a total
absorbance over the whole UV–vis-NIR range, and the light irradiation
can be utilized to drive the energy conversion and storage in PW/GH
composite PCM. This work provides a novel route to optimize the
structure of 3D GF and the properties of the corresponding composite
PCMs, and sheds light on the fabrication of promising candidate
composite PCMs for solar energy conversion applications.
Acknowledgements
This work was funded by the National Program for Thousand
Energy Storage Materials 13 (2018) 88–95
Young Talents of China, the National Natural Science Foundation of
(1) China (51422305, 21544001 and 51721091), Sichuan Provincial
Science Fund for Distinguished Young Scholars (2015JQO003) and
State Key Laboratory of Polymer Materials Engineering (Grant no.
sklpme2014-2-02).
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