Renewable Energy 145 (2020) 84e92

Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Polyethylene glycol/silica (PEG@SiO2) composite inspired by the

synthesis of mesoporous materials as shape-stabilized phase change
material for energy storage
Bingmeng Li a, Dan Shu a, Ruifang Wang a, Lanlan Zhai a, *, Yuye Chai a, Yunjun Lan a,
Hongwei Cao b, Chao Zou a, **
a
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325027, PR China
b
State Grid Henan Electric Power Research Institute, Zhengzhou, 450052, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Inspired by the common preparation method of mesoporous silica where polyethylene glycol (PEG) was
Received 13 October 2018 used as template to obtain porous silica, PEG/silica (PEG@SiO2) composite as shape-stabilized phase
Received in revised form change material for energy storage was well prepared. In this paper, PEG was used as phase change
9 May 2019
material (PCM) to store and release thermal energy and SiO2 acted as the supporting matrix. Various
Accepted 28 May 2019
Available online 29 May 2019
techniques were employed to characterize the structural and thermal properties of PEG@SiO2. The results
indicate that PEG was encapsulated in SiO2 shell with physical interactions. The phase change enthalpy of
PEG@SiO2 is 164.9 J/g in the melting process and 160.1 J/g in the solidifying process with the mass
Keywords:
Polyethylene glycol/silica composite
fraction of 97 wt%. It is a considerably exciting result as the value is so close to pristine PEG’s (178.6 J/g).
Porous materials PEG@SiO2 exhibited excellent thermal reliability based on the results of undergoing the heating-cooling
Latent heat cycle 100 times. Also, PEG@SiO2 had a good thermal stability within its working temperature range. This
Energy storage study provides a general approach for increasing the loading of PCMs in porous materials and thus the
Thermal properties energy storage capability.
Phase change material © 2019 Elsevier Ltd. All rights reserved.

1. Introduction interest of researchers, since their thermal properties were better

Since the 1970s, the energy and environmental problems have
gradually aroused people’s attention. Therefore, people began to
exploit renewable energy sources and improve energy efficiency. At
present, the use of phase change materials (PCMs) is an effective
way to store latent heat in the form of phase change enthalpy [1e4].
As one of the PCMs, PEG has been widely investigated for thermal
storage due to its suitable phase change temperature, high latent
heat capacity and high thermal and chemical stability after long-
term utility period [2,5,6]. However, the leakage in the melting
process has limited its applicability in energy storage [6e8].
One of the common solutions is to develop various supporting
matrixes, such as polymers [7,9] and inorganic porous materials
[6,10e17] to prevent the leakage of melted PEG. PEG/inorganic
porous materials composites for energy storage have drawn great
* Corresponding author.
** Corresponding author.
E-mail addresses: zhaill@wzu.edu.cn (L. Zhai), zouchao@wzu.edu.cn (C. Zou).
than those of PEG/polymer composites [18]. PEG/inorganic porous
materials are usually prepared by physical methods such as ab-
sorption blending, and impregnation [6,10e14,16,19]. Karaman
et al. [15] prepared a form-stabilized PEG/diatomite composite PCM
by vacuum impregnation method, and 50 wt% PEG was incorpo-
rated into the pores of diatomite without any seepage. The melting
and freezing latent heats of the composite PCM were 87.09 J/g and
82.22 J/g, respectively. Zhang et al. [16] prepared PEG/silica sheets
(GS) PCM by mixing GS with PEG at 70
C for 4 h. The highest
enthalpy of the composite was 136.3 J/g and the mass fraction of
PEG was 80 wt%. Wang et al. [6] prepared PEG/silica fume (SF)
composites by physically blending after a series of complex pre-
treatment of SF. The highest PEG loading was 47.9% and the highest
value of enthalpy was 81.3 J/g. From these reports, the values of
phase change enthalpy were rather low compared with that of pure
PEG, which means the energy storage capacity of these PCMs was
not desirable. Since PEG is absorbed into the pores by capillary force
[6] in the above investigations, the amount of PEG absorbed is
significantly confined by the absorption capability of porous

https://doi.org/10.1016/j.renene.2019.05.118
0960-1481/© 2019 Elsevier Ltd. All rights reserved.
 B. Li et al. / Renewable Energy 145 (2020) 84e92
materials [12]. So the energy storage capability is influenced by the
absorption capability of supporting materials.
To improve the absorption capability of supporting materials for
higher phase change enthalpy and better energy storage capacity of
PEG/porous materials, some measures were took during the syn-
theses process, such as vacuum and outgassing. It was reported by
Wang [20] that graphite was dried in a vacuum oven at 70
C for
20 h, and heated in a furnace at 900
C for 50 s. Then PEG/graphite
blends were prepared by physically blending for 3 h. The maximum
weight percentage of PEG was 90% with the latent heat of 161.2 J/g.
Tian et al. [21] mixed PEG and methanol with silica gel (SG) which
was outgassed for more than 3 h. The mixture was heated slowly in
a water bath at 55
C about 9 h to obtain shape-stabilized PEG/SG
composites. The pore fillingness of the composites was 80% and the
highest enthalpy was 168.84 J/g. Though the enthalpy value of the
composites and the mass fraction of PEG were improved after the
pretreatment of porous materials, an amount of extra energy and
time were consumed to increase the absorption capability of
porous materials. Moreover, it was reported that the phase change
enthalpy of PEG/porous materials was quantitatively correlated
with the average pore diameter and the pore geometrical shape of
the supporting materials [21e23] indicating that the absorption
capability essentially depends on the pore structure of porous
materials. Pretreatments including vacuum and outgassing are not
effective ways to improve the absorption capability of supporting
materials, as the pore structure was ignored in the above reports. So
the phase change enthalpy or the energy storage capacity of PEG/
porous materials cannot be efficiently increased, no matter how
PEG was impregnated into the pore by these conventional syn-
theses methods. Then the applications of PEG/porous materials in
latent heat storage system are still restrained [24]. To avoid the
influence of the absorption capability of porous materials, it has
been widely reported that PCMs were encapsulated into SiO2 shell
by sol-gel method through hydrolysis and condensation
[18,25e29]. However, most of these reports focused on n-alkane
PCMs whose thermal properties are totally different from those of
PEG. Moreover, surfactants and catalysts were adopted which have
negative effect on the encapsulation ratio and encapsulation effi-
ciency [27,28]. The values of the latent heat of the PCM@SiO2
composites decreased significantly in comparison of those of the
corresponding pure PCMs.
Recently, the synthesis of mesoporous oxides using PEG sur-
factant as structure-directing (templating) agent has been exten-
sively studied and substantially reported [30e34], in which PEG is
surrounded by hydrolyzable precursors, and then encapsulated
into inorganic oxide framework during the process of hydrolysis
and condensation. To obtain mesoporous structure, PEG usually
needs to be calcined at high temperature or washed with solvents
at the end of the synthesis process of mesoporous oxides. In this
paper, PEG was packaged into silica framework to prepare PEG@-
SiO2 composite in the light of the synthesis method of mesoporous
silica without the elimination process of PEG. The mass fraction of
the packaged PEG can be increased to the desired contents by the
variation of the experimental conditions. The reported preparation
by physical blending costs much more time (4 h-9 h) and higher
temperature (55e70
C), with the pretreatment of vacuum or out-
gassing for more than 3 h. In our work, the whole process of the
preparation is much simple to operate at low cost without any
pretreatment of supporting materials. PEG plays two roles during
the preparation of PEG@SiO2, energy storage material and surfac-
tant. Additional surfactant and catalyst were avoided, which will
decrease the phase change enthalpy as foreign substance for the
crystallization of PEG. This preparation method can eliminate the
negative effect on both the absorption and the encapsulation of
PEG. It benefits higher mass fraction of PEG and thus higher phase
85
change enthalpy. Moreover, To the best of our knowledge, the
preparation of PEG@SiO2 inspired by the synthesis of mesoporous
materials as shape-stabilized PCM for energy storage has not been
reported. The morphology, microstructure and thermal properties
of the PEG@SiO2 were investigated by various techniques. Higher
phase change enthalpy and energy storage capability of PEG@SiO2
were illustrated. PEG@SiO2 exhibited excellent thermal stability
and reliability. Therefore, the facile synthesized composite with
comprehensive properties is potential to be applied in energy
storage devices such as solar-thermal energy conversion and stor-
age systems.
2. Experimental section
2.1. Materials
PEG with an average molecular weight of 6000 (PEG 6000),
tetraethoxysilane (TEOS) (>99%, GC grade) and isopropyl alcohol
(IPA, 99.9%, GC grade) were purchased from Aladdin Reagent Co
(Shanghai, China). N, N-dimethyl formamide (DMF) (99.5%, GC
grade) was obtained from Guangdong Guanghua Sci-Tech Co, Ltd.
Deionized water was used throughout the experiments.
2.2. Preparation of PEG@SiO2
PEG@SiO2 was prepared based on the common synthesis
method of mesoporous silica. 5.30 g PEG, 8.64 g deionized water,
3.02 g DMF and 3.02 g IPA were mixed with the molar rate PEG:
H2O: DMF: IPA ¼ 0.0184:10:0.86:1.05. The solution was then stirred
vigorously for 0.5 h at room temperature. Thereafter, 10 g TEOS was
added to the mixture under stirring for 1 h at room temperature.
Afterwards, the products were washed by absolute ethanol five
times and subsequently dried at 50
C for a week to completely
eliminate the unencapsulated PEG and residual solvent. At last, the
composite was obtained. The as-made bulk composite was calcined
at 500
C for 5 h to obtain the supporting material for comparison.
The schematic illustration of preparation is shown in Fig. 1.
2.3. Sample characterization
Morphological analysis was undertaken using SEM (FEI Nova
Nano SEM 200). Energy dispersive X-ray spectroscopy (EDS)
coupled with SEM was used to analyze the chemical composition.
High-resolution transmission electron microscopy (HRTEM), high-
angle annular dark-field (HAADF), scanning transmission electron
microscopy (STEM), and EDS were performed on JEOL 2100F mi-
croscope. Composition analysis was performed by EDS (oxford
INCA). The samples for TEM and STEM-EDS were collected by
placing a drop of sample dispersed in absolute ethanol onto carbon-
film-supported copper grids. The surface areas, pore volume and
pore size distribution of the calcined sample were determined at
77 K using a BELSORP-mini II instrument (Bel Japan Inc.). The
calculation of pore size was performed using the Bar-
retteJoynereHalenda (BJH) method applied to the adsorption data
of the N2 sorption isotherms. An FT-IR spectrometer (Perkin Elmer,
USA) was used to characterize the prepared composite. The crystal
structures and crystallization properties were studied using wide
angle X-ray diffraction (WAXD) (Bruker, D8 advance, Cu Ka radia-
tion using a curved graphite receiving monochromate), with a step
of 0.02
at a speed of 4
/min from 10
to 80
at room temperature.
Differential scanning calorimetry (DSC) was carried out to measure
the phase change temperature and enthalpy of the samples using
Q1000 (TA Instrument, USA) at heating/cooling rate of 10
C/min
from 10
C to 110
C in nitrogen atmosphere. The thermal analysis
was performed by a thermogravimetric analysis Diamond TG-DTA/
86 B. Li et al. / Renewable Energy 145 (2020) 84e92

Fig. 1. Schematic illustration of preparation of PEG@SiO2.

Fig. 2. (a) SEM micrograph and (b) EDS result of the prepared composite, (c) and (d) SEM micrograph and (b) EDS result of the supporting material after calcination.
 B. Li et al. / Renewable Energy 145 (2020) 84e92 87

Spectrum GX (Perkin Elmer, USA) in nitrogen atmosphere and ox-

ygen atmosphere, respectively. The samples were scanned over the
temperature range from room temperature to 800
C at a heating
rate of 10
C/min.

3. Results and discussion

3.1. Morphologies, microstructure and chemical composition

The morphology and structure of the prepared samples were

investigated by FE-SEM (Fig. 2). As polymer, PEG tends to melt
during the focus of electron gun of SEM and experience the
melting-solidification process. While no PEG was found being
outside the sample or leaking from the inside of the sample during
the SEM observation, indicating unencapsulated PEG was elimi-
nated completely by rinse in the preparation. It can be found most
particles in aggregation are round and a few of larger particles are
irregular in shape without obvious crack and pores (Fig. 2a).
Innumerable pores appeared after the prepared sample was
calcined at 500
C for 5 h (Fig. 2c). The sizes of these pores are
uniform with dozens of nanometers (Fig. 2d). It proves that these
uniform pores had been full of PEG. They were derived from the
vacancy left by PEG after it was eliminated by calcination. These
uniform pores used to accommodate PEG emerged after PEG was
eliminated by calcination. EDS results demonstrates that the sup-
porting material is composed of O and Si (Fig. 2b, e), implying that
supporting material is SiO2.
The morphology and structure of the as-prepared composite
were further characterized by TEM. It is obviously seen most of
these particles interpenetrated (in Fig. 3a). The particles are
approximately spherical with the size of about 20 nm (Fig. 3b). The
detailed structural information of the microsphere was observed by
Fig. 3. TEM micrographs of the prepared composite, (a, b) TEM, (c, d) lattice-resolved
the lattice-resolved HRTEM. Calculated from the line profile in HRTEM, (c1-c3, d1-d2) line profile integrated along the region enclosed in the yellow
Fig. 3c (1e3) and 3d (1e2), enclosed from the yellow rectangle area rectangle in (c, d).
in Fig. 3c and d, one can get a series of lattice spacing, 3.83 Å, 3.89 Å,
4.60 Å, 4.06 Å and 4.0 Å, which well coincide with those of PEG
crystals. It means the composite contains PEG crystal. Furthermore, PEG 6000, the prepared composite and the supporting material
it is preliminarily speculated that PEG crystal was sheltered by SiO2 obtained by calcination were measured by FT-IR shown in Fig. 6. In
from the focus of electron gun considering the results of SEM and Curve (a), the peak at 958 cm1 indicates deformation vibrations of
TEM. SieOH group. The stretching vibration of SieO and the asymmetric
Chemical analyses with nanoscale spatial resolution were per- and symmetrical stretching vibration of SieOeSi are at 790 and
formed to clarify the sample compositions and elemental distri- 1061 cm1, respectively, which could be attributed to the charac-
butions in individual. Fig. 4 displays STEM-EDS elemental mapping. teristic absorption bands of SiO2. These characteristic peaks suggest
EDS data collected from all points in the sample exhibits the exis- that SiO2 was obtained and PEG was thoroughly removed by
tence of Si, C and O elements. Due to the interference of carbon film calcination. In Curve (b), the peaks at 3150e3559 cm1 represent
on copper grid and oxygen absorbed on sample, the relative the vibration eOH which indicates the presence of hydroxyl ions
elemental ratio for Si/C/O in composite is hard to determine. The and/or adsorbed water [35]. The strong absorption peak at
2D-projected elemental maps for three elements, shown in 2880 cm1, 1468 cm1, 1359 cm1 and 841 cm1 are assigned to
Fig. 4bed, demonstrate the evenly distribution of those elements eCH2 in PEG molecular chain. The peak at 1094 cm1 is attributed
among the entire composite and no technical noticeable to CeOeC [35]. For the spectra of the composite (Curve (c)), the
separation. main peaks of the characteristic functional groups of PEG and SiO2
To further research into the porous structure and pore-size also appeared in the spectra of the composites with only a slight
distribution of the supporting material, nitrogen adsorption- shift of peak positions and change of relative intensity. There are no
desorption isotherms were measured to ascertain the specific additional peaks for the composite. It suggests the composite
surface area and pore size of the microspheres. It can be found that consists of PEG and SiO2. In addition, physical interactions exist
the size of the mesopores is uniform which is further confirmed by between PEG core and SiO2 wall, and no chemical reactions occur
its corresponding pore-size distribution (inset in Fig. 5). The surface during the composite formation. As the composite was washed
area of the calcined sample was relatively high (562.83 m2 g1) with absolute ethanol several times to remove the PEG adhering to
from Fig. 5. The BJH plot shows that the pore size distribution of the the outside of SiO2 shell, it can be suspected that PEG has been
calcined sample is very narrow and the peak pore diameter is encapsulated into the pore of SiO2 from the FT-IR results. According
12.12 nm. It certified that mesoporous structure was obtained after to the results of SEM, TEM and FT-IR, PEG@SiO2 composite was
the calcination of PEG. A large amount of PEG can be encapsulated successfully synthesized.
in the uniform mesopores as the values of pore volume
(1.2516 cm3g1) and surface area are very high, which benefits the
energy storage capability.
88 B. Li et al. / Renewable Energy 145 (2020) 84e92

Fig. 4. STEM micrographs of the prepared composite, (a) dark field image, (bed) STEM-EDS elemental maps.

Fig. 5. Nitrogen adsorption-desorption isotherms and BJH pore size distribution plot (inset) for the calcined sample.
 B. Li et al. / Renewable Energy 145 (2020) 84e92
Fig. 6. FT-IR spectra of (a) the supporting matrix obtained by calcination, (b) PEG 6000,
(c) the prepared composite.
3.2. Crystal structure
The crystal structure was investigated by XRD. Fig. 7 shows the
XRD patterns of PEG 6000, PEG@SiO2 and SiO2 obtained by calci-
nation. In Fig. 7a, the broad peak indicates a typical amorphous
structure of SiO2. From Curve (b), two notable sharp peaks at 19.2

and 23.4
are assigned to PEG crystal. Besides, the 2q position of the
PEG peaks shows no significant change in PCMs, indicating that the
crystal structure of PEG has not been destroyed after PEG was
encapsulated in SiO2 pore. These findings also indicate that physical
interactions exist between PEG and SiO2. And physical interactions
between PEG and SiO2 would prevent the leakage of the melted
PEG from the SiO2 container. The XRD results further verified PEG
was encapsulated in SiO2 cell with physical interactions, which
consisted with the results of FT-IR. Some information of crystal
structure was obtained (Table 1) according to the JCPDS card No.
49e2097 of PEG. The values of the lattice spacing of sharper peaks
(Fig. 7) are 4.652 Å, 4.044 Å, 4.025 Å, 3.830 Å, 3.411 Å, and 3.323 Å
respectively. The values are in good agreement with the TEM
Fig. 7. XRD patterns of (a) porous SiO2 obtained by calcination, (b) PEG 6000, (c) the
prepared PEG@SiO2.
89
Table 1
Crystal structure information of PEG.
2q 19.062 21.961 22.066 23.205 26.102 26.806
d (Å) 4.652 4.044 4.025 3.830 3.411 3.323
results. It corroborates PEG had crystallized in SiO2 pore without
obvious disturbance of SiO2 container on regular arrangement for
crystallization.
3.3. Energy storage property and reliability
The phase change enthalpy of pristine PEG and the prepared
PEG@SiO2 were measured with DSC as the phase change enthalpy
is always considered as a most reliable indicator to evaluate the
thermal energy storage capacity for PCMs. Fig. 8 shows that the
curves of pristine PEG and PEG@SiO2 are greatly similar, both of
them undergoing phase transition with high transition enthalpy.
The melting and crystallization temperature of PEG@SiO2 respec-
tively are 60.4
C and 37.9
C, which are close to those of pristine
PEG (61.7
C and 35.3
C). The phase change enthalpy of PEG@SiO2
reaches 164.9 J/g in the melting process, and 160.1 J/g in the solid-
ifying process. It is considerably exciting results as the values are so
close to pristine PEG’s (178.6 J/g and 167.1 J/g). It can be extrapo-
lated that about more than 92.3 wt% PEG was sealed inside of SiO2
pore with 164.9 J/g being divided by 178.6 J/g [36]. The enthalpy
value of PEG@SiO2 is a little lower than that of pristine PEG because
it is only PEG sealed inside of SiO2 pore that can crystallize for
energy storage. SiO2 is merely used as supporting material and do
not undergo phase change in the operating temperature range. The
minor difference of the temperature and enthalpy between pristine
PEG and PEG@SiO2 was caused by the physical interactions
confirmed by FT-IR and XRD results, which were likely to restricted
the crystal arrangement and orientation of PEG molecular chains in
SiO2 pore. Thus the regularities of crystal region decreased and
lattice defect increased. As the higher the degree of crystallinity, the
more energy is absorbed or released. So the melting and crystal-
lizing enthalpy and temperature of the prepared PEG@SiO2 are a
little lower than those of pristine PEG.
The enthalpy value of 164.9 J/g is much close to that of the PEG/
single-walled carbon nanotubes (PEG/SWCNs) nanocomposite
(179.4 J/g), whose value has been the highest in literature up to now
Fig. 8. DSC curves of PEG 6000, PEG@SiO2 and PEG@SiO2 after 100 melting/solidifying
cycles.
90 B. Li et al. / Renewable Energy 145 (2020) 84e92
Table 2
Phase change temperature and enthalpy of pristine PEG and PEG@SiO2.
PCMs Melting process Solidifying process
DHM(J/g) TM(
C) DHc(J/g)
PEG6000 178.6 61.7 167.1
PEG@SiO2 164.9 60.4 160.1
100th cycle 165.3 60.4 160.5
[17]. However, the attainment of the largest phase change enthalpy
of PEG/SWCNs is at the expense of other kinds of energy. For
example, the whole fabrication procedure was carried out at higher
temperature and intensive ultrasonication was essential to reduce
the SWCNs aggregates. Moreover, the toxic solvent toluene was
used to prepare PEG/SWCNs, which is rather harmful to the health
and the environment.
PEG@SiO2 has excellent cycling performance based on the re-
sults of undergoing the heating-cooling cycle 100 times. The DSC
curve of the first melting and solidifying process is almost coin-
cided with that of the 100th for PEG@SiO2 (Fig. 8), which means
that the absorbed/released heat and phase change temperature in
the first cycle are similar to that of the 100th cycle. Corresponding
thermal properties of PEG@SiO2 after thermal cycling were pre-
sented in Table 2. After repeated cycle of 100 times, TM (melting
temperature) and Tc (crystallization temperature) of PEG@SiO2
respectively changed by 0
C and 0.3
C, which are negligible for
PEG@SiO2 application in energy storage. Moreover, the values of
phase change enthalpy of melting and crystallization respectively
changed by 0.24% and 0.25%, which are also acceptable for energy
storage application. The above testing results indicate that syn-
thetic PEG@SiO2 has excellent heat storage reliability.
3.4. Thermal stability
Thermal stability plays a significant role in thermal energy
storage applications since it is a critical parameter for PEG@SiO2.
Fig. 9 presents the TGA thermograms of PEG 6000 and the prepared
PEG@SiO2 tested in nitrogen atmosphere and oxygen atmosphere.
As shown in Fig. 9, a tremendous decrease occurred from 300
C to
440
C and the weight loss percent is about 94 wt%. It is ascribed to
the decomposition of PEG molecule. As for PEG@SiO2, weight loss
occurred at about 300
C, indicating that PEG@SiO2 has a good
thermal stability within its working temperature range. Moreover,
the weight loss of PEG@SiO2 occurred earlier than that of pure PEG.
Fig. 9. TGA curves of PEG and PEG@SiO2 measured in nitrogen atmosphere and oxygen atmosphere.
It was probably due to the physical interaction between PEG and
SiO2 which is weaker compared with the intermolecular force in
pure PEG.
Tc(
C)
According to the TGA curves of PEG and PEG@SiO2 measured in
oxygen atmosphere, pure PEG was completely oxidized to carbon
35.3
dioxide at 250
C as the weight loss of PEG was nearly 100%. While
37.9
38.2 2.7 wt % of PEG@SiO2 was left at 400
C. It can be concluded that the
weight percentage of PEG in PEG@SiO2 is 97.3 wt% because the net
weight loss corresponds to the evaporation of oxidized PEG. From
the TGA results tested in oxygen atmosphere, the load of PEG in
PEG@SiO2 is 97.3 wt%, which is much close to the reported highest
value so far [14]. High phase change enthalpy of PEG@SiO2 was thus
obtained for it is proportional to the mass ratio of PEG in the
composite. The results measured in oxygen atmosphere sustain
that PEG based shape stabilized PCMs with just a small contents of
supporting materials were successfully synthesized. PEG was
encapsulated in SiO2 as much as possible in this study.
The theoretical enthalpies of melting and solidifying process for
PEG@SiO2 can be determined by DHtheo ¼ 97.3 wt%*DHpure [36e38].
They are 173.8 J/g and 162.6 J/g, respectively. The actual enthalpies
values (shown in Table 2) of the prepared PEG@SiO2 are a little
lower than their corresponding theoretical values, 5.1% and 1.5%
decreased comparing with the theoretical enthalpies. The minor
difference between the theoretical enthalpies and the actual en-
thalpies results from the degreased crystallinity of the encapsu-
lated PEG. The free movement and aggregation of some PEG
molecules was restricted, as these molecules were absorbed on the
inside surface of SiO2 by the physical interaction between them. As
a result, the crystal arrangement and orientation of PEG molecule
decreased, which explained why the experimental phase change
enthalpy is smaller than the theoretical value. The restriction is so
small that it is likely not to be chemical interaction but belongs to
weak physical interactions, certified by FT-IR, XRD analysis.
4. Conclusions
PEG@SiO2 was successfully prepared as shape-stabilized PCM
for energy storage, based on the common preparation method of
mesoporous silica. The synthesis process of PEG@SiO2 is greatly
efficient and simple. SiO2 and PEG were used as supporting mate-
rial and energy storage medium, respectively. PEG was encapsu-
lated in SiO2 pore with physical interactions, which kept PEG@SiO2
in stable shape and prevented the leakage of the melted PEG during
the phase change process. Physical interactions are so weak that
 B. Li et al. / Renewable Energy 145 (2020) 84e92
PEG has crystallized in SiO2 pore with tiny disturbance of SiO2 wall
in regular arrangement for crystallization. The weight percentage of
PEG in SiO2 is 97.3 wt%, which is almost as high as the reported
highest value so far. PEG@SiO2 stores and releases massive latent
heat when it undergoes phase transition. The phase change
enthalpy of PEG@SiO2 reaches 164.9 J/g in the melting process, and
160.1 J/g in the solidifying process. It is considerably exciting results
as the values are so close to pristine PEG’s (178.6 J/g and 167.1 J/g).
Moreover, PEG@SiO2 has excellent heat storage reliability based on
the results of undergoing the heating-cooling cycle 100 times. After
repeated cycle of 100 times, TM (melting temperature) and Tc
(crystallization temperature) of PEG@SiO2 respectively changed by
0
C and 0.3
C. The values of phase change enthalpy of melting and
crystallization respectively changed by 0.24% and 0.25%. These
changes are acceptable for energy storage application. PEG@SiO2
also has good thermal stability within its working temperature
range as the weight loss occurred at about 300
C. In summary,
PEG@SiO2 composite with high energy storage property, proper
phase change temperature, and remarkable thermal stability and
reliability is applicable for thermal energy storage such as solar
energy utilization, waste heat recovery, and other thermal energy
storage systems. Moreover, this work not only presented a shape-
stabilized PCM with great thermal properties, but also provided a
new method for increasing the loading of PCMs in porous materials
and thus the energy storage capability.
Acknowledgement
This work was financially supported by the National Natural
Science Foundation of China (grant numbers 51772218, 51572199,
51302194); the Public Interest Project Foundation of Zhejiang
(grant number 2015C31130); the Key Lab Photovolatic & Energy
Conservation Materials of Chinese Academy of Sciences (grant
number KF201603); and the scientific fund of State Grid Corpora-
tion of China (grant number 52170215000F).
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