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Phase Change Materials Hot Paper
Highly Efficient Thermal Energy Storage Using a Hybrid
Hypercrosslinked Polymer**
Changhui Liu,* Jiahao Zhang, Jian Liu, Zengyi Tan, Yuqi Cao, Xia Li, and Zhonghao Rao
Abstract: In this work, an organic/inorganic hybrid polymer
containing siloxyl functional groups was synthesized and
applied to encapsulate phase change materials (PCMs). Owing
to the mild conditions of the hypercrosslinking reaction, which
only requires the addition of a catalytic amount of aqueous
alkaline solution, both organic and inorganic PCMs are
tolerated. It is noteworthy that the initial homogeneous state
of the reaction mixture allowed the ultimate encapsulation rate
of the PCMs and the uniform blending of the third nano-
additives with the aim of thermal conductivity enhancement.
Further study reveals that the presence of this hybrid hydro-
phobic polymer in a phase change composite endows the latter
with a unique self-cleaning property. This novel PCM encap-
sulation protocol is suitable for nanoparticles including
carbon-based nanomaterials, metal oxide nanoparticles, and
inorganic oxide nanoparticles. A thermal conductivity en-
hancement of 600 % was achieved along with 93.7 % light-to-
thermal conversion efficiency with a latent heat of 180 J g 1
without leakage.
Introduction
Depletion of fossil energy has become a critical issue with
the rapid development of industry and economy. The search
for new energy resource alternatives and improving the
energy conversion efficiency are continuous endeavors of
researchers.[1] Energy storage technology is considered as an
effective way to solve the problem of mismatch between
energy supply and application in terms of space and time.
Thermal energy storage (TES) plays a vital role among
various energy storage techniques.[2] TES can be used to
collect and store heat energy and release heat energy with the
demand in the future. The forms TES can be classified into
thermal chemistry energy storage, sensible heat energy
storage, latent heat energy storage or a combination of some
of them. Among the aforementioned forms, latent heat
energy storage,[3] also termed as phase change energy storage,
has been widely applied in practical due to the high energy
[*] C. Liu, J. Zhang, J. Liu, Z. Tan, Y. Cao, X. Li, Prof. Z. Rao
School of Electrical and Power Engineering
China University of Mining and Technology
Xuzhou, Jiangsu 221116 (China)
E-mail: liuch915@cumt.edu.com
[**] A previous version of this manuscript has been deposited on
a preprint server (https://doi.org/10.21203/rs.3.rs-152851/v1).
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.202103186.
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How to cite:
International Edition: doi.org/10.1002/anie.202103186
German Edition: doi.org/10.1002/ange.202103186
storage density, small temperature fluctuation during the
working stage.[4]
Phase change materials (PCMs) are functional materials
which can absorb or release thermal energy in the form of
latent heat within a certain temperature range.[5] PCMs can be
generally divided into four forms in terms of phase change
states, namely, solid-solid, solid–liquid, liquid–gas and solid–
gas.[6] Solid-gas and liquid–gas PCMs benefit from high phase
change energy storage density, however, the large volume
change of material during phase transition makes it is difficult
to be used in practical.[7] Solid-solid PCMs bearing the
advantages of small volume change and low degree of
supercooling,[8] but either suffer from low thermal energy
density or limited temperature scope.[9] Solid-liquid type
phase change is the most common and widest utilization form
because of its negligible volume change during the phase
transition process and high energy storage density. However,
people must face the problem of liquid leakage during the
phase change process associated with the poor thermal
conductivity. Therefore, a shape-stabilized phase change
material which generally constituted by a working material
and a supporting material has emerged an important protocol
for the use of solid–liquid phase change material.[10] Though
so many existed methods have been dedicated to seeking
a way for the solution of liquid leakage and poor thermal
conductive performance, the room for further improvement
still existed.[11] Such as sophisticated preparation process,
which generally requires the addition of extra chemicals or
harsh reaction conditions. The participation of supporting
materials will inevitably reduce the energy storage density as
the it has no contribution to the latent enthalpy.[12] Therefore,
an efficient way which could enhance the thermal conductiv-
ity on the premise of keeping the thermal energy storage
density is of highly demand.[13] As one of the most efficient
approach to address the above-mentioned problems, recently,
we used benzene and PPh3 as precursors to encapsulate
PCMs, in which an FeCl3 catalyzed, 1,2-dimethylmethane
aided intermolecular Friedel–Crafts reaction is the key
procedure to effect the encapsulation rate and impacts the
final thermal properties of obtained PCMs composite.[14] In
this process, we found moisture has a great influence on the
success of encapsulation reaction since FeCl3 is too sensitive
against water which would thus lead to the failure of Friedel–
Crafts reaction behind. To overcome this inherent drawback,
we envisioned that whether we could graft a functional group
who will easy to be crosslinked on the skeleton of monomer,
thus deemed to participate in the hypercrosslinked reaction
without the need of harsh reaction condition. In this work, for
the first time, we synthesized a -Si-O- containing polymer,
which could be crosslinked with each other under a mild
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Research Articles
condition and formed a porous structure after integrating with
a nanomaterial. More importantly, our study revealed that the
presence of -Si-O- group could serve as a micro water
reservoir which was able to prevent the loss of bounded water
from inorganic PCMs, which thus ensured a good encapsu-
lation efficiency and recyclability. Blending a third high
thermal conductivity component with PCMs composite is
a common way to enhance the thermal conductivity of PCMs
composites.[15] However, it also suffers the risk of phase
separation during the phase transition state, thus causes the
invalidation of the energy storage function. Wrapping PCMs
with a polymer is a good solution towards the problem, while
it should also face the solubility and compatibility between
PCMs and that of polymers.[16] In this work, we adapted
a homogeneous-to-heterogeneous protocol, mixing PCMs
with soluble linear polymer prior to PCMs holding process
and then initiates the hypercrosslinking reaction via a simple
alkaline treatment. This method was able to ensure the
utmost uniform and even mixing of PCMs and nanoparticle
and avoid the phase separation in the downstream real
application case. It is worth noting that our protocol is
allowed the incorporation with several different nanoparti-
cles, such as, graphene, SiC, carbon black (CB), SiO2, etc. Due
to the synergistic contribution from polymer and nanoparti-
cles, the highest thermal conductivity can achieve to 600 %
with a light-to-thermal conversion up to 93.7 % without
observation of liquid leakage during the energy storage
process with respect to both organic and inorganic PCMs.
Figure 1. Schematic illustration of the preparation of HP/CB-OPCMs composite. a) The synthetic concept of HP/CB-PCMs. b) Facile aqueous
alkaline aided encapsulation of PCMs via hypercrosslinking a hybrid polymer. c) 1H NMR spectra of different hybrid polymers (detailed data can
be seen in the Supporting Information).
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Results and Discussion
Preparation and Characterization of the New Materials
Our study commenced from the synthesis of the hybrid
polymer (HP). The reaction was carried out under a nitrogen
atmosphere by employing AIBN as a radical initiator. The
proportion of styrene (organic part) and silica-containing
styrene (inorganic part) was facilely tuned by the amount of
two different starting materials. After obtaining the HP, the
preparation of the PCMs composite was started. As a proof-
of-concept, the preparing technique was designed based on
a homogeneous-to-heterogeneous protocol with the aim at
solving the poor encapsulation efficiency along with the
compatibility problem between PCMs and thermal conduc-
tivity enhancement nanoparticle (Figure 1 a and b). In
addition, integration in 1H NMR shows a good agreement
with the proportion of the two parts and demonstrates the
reliability of our polymer preparation method (Figure 1 c and
Figure S1) To facilitate the optimization process, we firstly
fixed the mass of paraffin wax (PW), CB and the HP to study
the effect the proportion of these two different monomers
(Tables S2 and S3). As it is displayed in Table 1, the leakage of
PCMs was up to 8.7 % in the absence of a HP which is far to
satisfactory. The leakage rate drastically reduced to 4.28 %
owing to the contribution of the HP, it provides both binding
effect and more fertile pore to CB, which might act as
a holding material in the process. Our protocol exerts the
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Table 1: Different reaction parameters.

Entry Sample[a] Molar ratio of monomers Mass of polymer [g] Mass of CB [g] Leakage rate [%]
[a]
1 CB-PCMs – – 5 8.7
2 HP/CB-OPCMs (9:1)[b] 9:1 0.5 5 4.28
3 HP/CB-OPCMs (8:2)[c] 8:2 0.5 5 2.36
4 HP/CB-OPCMs (7:3)[d] 7:3 0.5 5 1.28
5 HP/CB-OPCMs (6:4)[e] 6:4 0.5 5 0.45
6 HP/CB-OPCMs (5:5)[f ] 5:5 0.5 5 0.3
7 HP/CB-OPCMs (5:5)[f ] 5:5 0.4 5 1.68
8 HP/CB-OPCMs (5:5)[f ] 5:5 0.3 5 2.63
9 HP/CB-OPCMs (5:5)[f ] 5:5 0.2 5 4.75
10 HP/CB-OPCMs (5:5)[f ] 5:5 0.1 5 5.88
11 HP/CB-OPCMs (5:5)[f ] 5:5 0.4 4 1.32
12 HP/CB-OPCMs (5:5)[f ] 5:5 0.3 3 3.54
13 HP/CB-OPCMs (5:5)[g] 5:5 0.5 5 7.9
[a] Unless otherwise stated, the mass of all added CB is 5.0 g and the melting phase transition temperature of PW is 60 8C. [b] For the preparation of
polymer, monomer A is styrene, monomer B is trimethoxy(4-vinylphenyl)silane, styrene (5.0 g), trimethoxy(4-vinylphenyl)silane (1.2 g), AIBN
(15.8 mg), and trichloromethane (10 mL). [c] A 0.75 g, B 0.404 g, AIBN 15.8 mg. [d] A 2.0 g, B 0.922 g, AIBN 6.3 mg. [e] A 1.0 g, B 1.43 g, AIBN
3.15 mg. [f ] A 1.0 g, B 2.15 g, AIBN 6.3 mg. [g] Control experiment: without alkaline treatment.

occurrence of hypercrosslinking reaction under alkaline
conditions on the premise of the presence of silica containing
monomer, which could couple with each other via a cascade
intermolecular electrophilic substitution and elimination and
thus delivers the hypercrosslinking reaction. Under this
consideration, we are interested in the concentration of
monomer B as it directly determines the hypercrosslinking
rate of the HP. As it is shown in Figure 2 g, the leakage rate
really displays a decline trend with the concentration rising of
monomer B, and the leakage rate could even lower to
a negligible level (0.3 %) after blending a HP with a 1:1 of
monomer A and monomer B. Owing to the relatively high
cost of the silica-containing monomer and the acceptable
0.3 % leakage rate, the continue increase on the proportion of
monomer B was not carried out. After knowing the trend on
the chemical composition of HP, we started to investigate the
effect of total mass of polymer. As it is predicted, the leakage
rate gradually increased with the weight decrease of the HP.
This result further demonstrates the function of the HP that it
was able to encapsulate PW during the phase transition
process (Figure 2 h). Additionally, compared with HP, CB
displayed a slight influence on the carrying performance of
the PCMs composite since the leakage efficiency kept almost
unchanged in the case of 0.4 g HP associated with 4.0 g CB
(entry 11) by a comparison with that case of 0.4 g HP and 5 g
CB (entry 7) (Figure 2 i). Further decreasing the total amount
of supporting materials unexpectedly led to the rising of
leakage rate which demonstrated the synergistic effect
between the polymer and CB (entry 12). Moreover, a control
experiment was carried out to illustrate the importance of the
hypercrosslinking reaction in the process. As shown in
entry 13, the PCMs composite gives a comparable encapsu-
lation performance with the sole CB supported PCMs
composite without the addition of a base solution, which
clearly demonstrated the occurrence of the hypercrosslinking
reaction and success of the encapsulation of PCMs after
alkaline treatment.
After determining the optimized preparation parameters
and the preparation procedure, structural analysis on the
obtained PCMs composite was carried out. As it is displayed
in Figure 2 a and Figure S4, SEM images of the PCMs
composites reveal that PCMs were either encapsulated on
the pore and surface of the supporting materials without the
observation of liquid state PW. This result also directly proves
the success of our solid–liquid PCMs shape-stabilization
protocol as the SEM taking temperature is much higher than
its phase change transition temperature. Other character-
ization, Fourier-transform infrared spectra (FTIR), X-ray
diffraction (XRD), and thermal gravimetric analysis (TGA)
(Figure 2 b, c and d), were also conducted to understand the
stability and chemical composition of the obtained PCMs
composite, all these analyses demonstrates the success of the
hypercrosslinking reaction and the highly effective PCMs
encapsulation (detail analysis can be seen in the Supporting
Information). Moreover, the influence of PW on the hyper-
crosslinking reaction was studied by means of BET analysis.
As it is shown in Figure 2 e, f and Table 2, the specific surface
area of the supporting materials become even higher than that
of materials prepared in the absence of PW and CB, which
further indicates the good compatibility between PW and the
supporting materials.
Thermal Physical Performance of the New Materials
With the optimized preparation method and the corre-
sponding PCMs composite, some thermo-physical properties
were studied. At the first, thermal conductivity of the
obtained PCMs composite was analyzed because it associates
with the energy storage and release response time and thus
determines the application efficiency. As it is depicted in
Figure 2 j, the thermal conductivity of HP/CB-OPCMs (5:5)
can achieve to 0.5–0.6 W m 1 K 1, which is approximately
250 % higher than that of pure PW (0.22–0.24 W m 1 K 1).
The instability of the thermal conductivity of liquid PW above
the melting point will lead to a great change in the phase
transition temperature of the composites. This result further
demonstrates the feasibility of our PCMs shape-stabilization

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Figure 2. Structure and porosity of HP/CB-OPCMs. a) SEM images of HP/CB-OPCMs (5:5). b) FT-IR images of HP/CB-OPCMs. c) XRD images of
HP/CB-OPCMs. d) TGA images of HP/CB-OPCMs. e) Nitrogen adsorption and desorption isotherms at 77.3 K of HP/CB-OPCMs. f) Pore size
distribution of HP/CB-OPCMs. g) Leakage rates of PCMs composite with different proportions of polymer monomers. h) Leakage rates of PCMs
composite with different proportions of supporting materials. i) Leakage rates of PCMs composite with different polymer masses. j) Thermal
conductivity of the HP/CB-OPCMs samples. k) Differential scanning calorimetry (DSC) curves of the melting and freezing process of pure PW and
HP/CB-OPCMs. l) Measured latent heat of HP/CB-OPCMs (5:5) during 500 melting–freezing cycles.

Table 2: Surface area and total pore characteristics of the as-synthesized

samples. effect on the formation of the thermal transportation means
led by the high thermal conductivity nano-additives.
Sample BET Pore Average pore
Energy storage density of the obtained PCMs composites,
surface area volume diameter [nm]
[m2 g 1] [cm3 g 1] represents in the form of latent heat enthalpy, was measured
by DSC. As it is shown in Figure 2 k, the energy storage
CB + HP 131.54 0.59 17.93
characteristics of PCMs with respect to both phase change
CB 121.83 0.85 27.91
CB + HP + PW 151.14 0.39 10.25
temperature and enthalpy were measured. It can be seen from
(washed PW) Table 3 and Figure S5, both pristine PW and shape-stabilized
PCMs show two peaks in melting and solidification process,
which were, respectively attributed to solid-solid phase
protocol that the participation of HP was able to prohibit the transition and solid–liquid phase transition. Through the
leakage of PCMs during the phase transition process without synergistic effect of CB and polymer, HP/CB-OPCMs (5:5)

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Table 3: Data for the DSC curves for the HP/CB-OPCMs samples.
Sample Melting process Freezing process
Onset [8C] Peak [8C] DHm [J g 1] Onset [8C] Peak [8C] DHm [J g 1]
PW 49.55 55.62 188.62 53.62 50.82 185.36
CB-OPCMs 49.96 55.98 87.48 57.52 49.90 84.95
HP/CB-OPCMs (9:1) 49.24 57.39 82.40 53.51 49.62 79.79
HP/CB-OPCMs (8:2) 49.63 55.35 82.46 53.69 50.82 80.11
HP/CB-OPCMs (7:3) 49.53 56.66 87.29 53.62 49.98 85.19
HP/CB-OPCMs (6:4) 48.74 56.81 88.34 53.44 50.28 87.33
HP/CB-OPCMs (5:5) 49.06 56.36 82.62 53.55 50.32 82.30
HP/CB-OPCMs (5:5)[a] 49.83 56.45 80.46 53.28 49.04 75.29
HP/CB-OPCMs (5:5)[b] 49.92 55.65 80.93 53.31 49.61 76.65
HP/CB-OPCMs (5:5)[c] 50.08 55.68 80.17 53.39 49.70 76.73
HP/CB-OPCMs (5:5)[d] 50.09 55.52 79.44 53.42 49.88 75.54
HP/CB-OPCMs (5:5)[e] 50.26 55.71 79.02 53.33 49.82 74.74
[a] DSC data after cycling 100 times. [b] DSC data after cycling 200 times. [c] DSC data after cycling 300 times. [d] DSC data after cycling 400 times.
[e] DSC data after cycling 500 times.

has a slight temperature variation during the phase transition
process, and the peak temperature of the melting process and
solidifying process shift from 55.62 8C and 50.82 8C to 56.36 8C
and 50.32 8C respectively. The reason responsible for this low
temperature change can be ascribed to the good affinity
between HP and PW, which further affects the vicinal organic
PW molecules in this three-dimensional network structure,
thus delaying the phase transition process of the PW. More
importantly, as it is shown in Figure 2 l and Table 3, this HP
carried PCMs shows a promising cyclability that it was able to
keep almost unchanged with respect to both phase transition
temperature and latent heat after 500 times melting and
solidification process. Moreover, leakage performance of the
PCMs composite was further determined by using a digital
camera along with an infrared camera. As shown in Figure S3,
the leakage-proof performance is quite in line with the
leakage rate calculated with an accurate balance. Considering
the excellent encapsulation efficiency, promising latent heat
storage and the charging-discharging reliability, this HP
supported PCMs composite possessing a great potential to
be used as an ideal thermal energy storage medium, especially
in practical scenarios.
Real Application of the New Materials
To test the practical feasibility of this HP encapsulated
PCMs composite, some application study was carried out. On
the first hand, thermal energy storage and release perfor-
mance of the obtained PCMs composite was studied using
a home-made setup (Figure 3 a and b). As can be seen from
Figure 3 c and d, neither T1 nor T2 could forward a prompter
response during the heat energy charging process for the HP
encapsulated PCMs composite than that of pristine PW
thanks to the superior thermal conductivity. However, when
the temperature approaches to the melting temperature, the
slope of temperature change of pristine PW overwhelms that
of shape-stabilized PCMs composite probably owing to the
thermal resistance deriving from the inherent swelling
property of carbon-based supported PCMs composite. Similar
phenomenon was observed in the thermal energy releasing
process as the temperature responses rapidly for the HP
encapsulated PCMs composite (Figure 3 e and f). Besides the
thermal energy storage and release property regarding the
obtained PCMs composite, light-to-thermal conversion per-
formance of this shape-stabilized PCMs composite was also
studied. As a kind of clean and sustainable energy, solar
energy has been applied in many fields. Whereas, the
instability of solar energy in time heavily limits its application
scope. Solar energy collection technology or the storage of
solar energy in materials and the conversion of solar energy
into another kind of energy could solve this shortcoming to
some extent. Figure 3 i is the photothermal conversion curve
of HP/CB-OPCMs (5:5) and pure PW recording from
a photothermal conversion device (Figure 3 g, detailed plat-
form can be seen in Figure S9 a). As seen in Figure 3 h and j,
the initial temperature of the two materials are the same
(30 8C), under a 110 mW cm 2 sunlight simulation condition,
the temperature of the sample and pure PW increased with
illumination time, but the temperature rise rate of the PCMs
composite is much prompter than that of pure PW owing to
the superior light response ability derived from CB inside.
Based on the temperature change curves of the HP encapsu-
lated PCMs composition and the latent heat of the PCMs
composite, the light-to-thermal conversion efficiency was
calculated to be 93.7 % (Note 3 in the Supporting Informa-
tion). Notably, light-to-thermal conversion of this PCMs
composite is quite promising considering its relatively low
thermal conductivity. As it is shown in Figure 3 k and
Table S1, previous study indicates that an enhanced thermal
conductivity is essential for light harvesting for the heat
transfer requirement. While, a higher thermal conductivity
will also lead to a harder energy conservation. From the
viewpoint of the relatively low thermal conductivity and
excellent light-to-thermal conversion efficiency, this PCMs
encapsulation protocol really provides a practical method for
the fabrication of solar utilization materials.
Additionally, the hypercrosslinked polymers not only help
encapsulate the PW but also good for the hydrophobicity of
the PCMs composite. Superhydrophobicity of materials has
drawn ample attention owing to its unique advantages, such as
self-cleaning, water-proof, anti-corrosion and so on. Surface

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Figure 3. Comparison of the energy storage and release performance of PW and HP/CB-OPCMs (5:5). a) Schematic diagram of the thermal
energy storage and release tests. b) The site and detail size of the thermocouples and heat storage chamber, and the thermal storage properties
of HP/CB-OPCMs (5:5) at site 1 (c) and site 2 (d) and the thermal release properties of HP/CB-OPCMs (5:5) at site 1 (e) and site 2 (f).
g) Schematic illustration of the light-to-thermal energy conversion and storage measuring platform. i) Light-to-thermal energy conversion curves
for pure PW and HP/CB-OPCMs (5:5). Heat transfer rate of PW and HP/CB-OPCMs (5:5) during h) light-on and j) light-off process.
k) Comparison of results reported by different scholars.[2a,c, 6c, 17]

modification or spraying are commonly used approaches for
the set of hydrophobicity, but they must face the inherent
shortcomings due to the susceptibility brought from physical
or chemical fragility of the micro structure. In this regard, we
used a homogeneous-to-heterogeneous strategy, by which an
even blending among the hypercrosslinked polymers, CB and
PW can be unambiguously expected, thus could ensure
a stable and long-term hydrophobicity. As shown in Figure 4
and Figure S9 b, a water contact angle analysis platform was
set and comprised by a testing unit, a high-speed camera and
a data analyzer unit. PCMs composite without the addition of
the hypercrosslinked polymer displays a water contact angle
to be 998 might be accounted by the intrinsic hydrophobicity
of PW and the rough surface due to the CB. Because of the
addition of HP, the water contact angle to can be significantly
increased to 1208, and it can be further increased to 1378 when
changed the polymer to a 5:5 monomer ratio (Figure 4 c, d
and h). Based on this interesting result, we proposed
a plausible mechanism that the silica content should be
helpful for the enhancement of hydrophilicity of the PCMs
composite. Silica-oxygen bond is a polar functional group
which will form a weak Vander Walls force with water
molecule and therefore produced a good compatibility with
water. However, the silica content also determines the
hypercrosslinking rate of the HP, it is predictable that the
hypercrosslinking skeleton features a hydrophobicity as its
main framework is constituted by organic alkane chain.
Owing to the bulker property of organic component com-
pared with silica group, the main contribution of this HP
should be hydrophobicity, and thats why the addition of the
HP was able to make a hydrophobicity increment (Fig-
ure 4 b). The presence of silica will allow the hydrophilicity
increase, in the meantime, it also leads to the enhancement of
hypercrosslinking and thus leads to hydrophobicity enhance-
ment. Out of this consideration, the final PCMs composite
displays a phenomenon of hydrophobicity increase compared
with that of PCMs without the addition of hypercrosslinked
polymer.
Characterization of Inorganic Materials
Comparing with organic PCMs, inorganic PCMs bearing
some unique advantages, such as high latent heat capacity,
good thermal conductivity, promising fire-proof performance,
non-toxicity and so on.[18] However, some specific shortcom-
ings of inorganic PCMs, for example, phase separation, large
supercooling degree, which will cause a large temperature
difference between charging and discharging process and thus
bring many problematic issues from the practical point of

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Figure 4. a) Schematic illustration of the contact angle platform. b) Experimental diagram of contact angle of CB-OPCMs. Photographs showing
the contact angle of a water droplet on c) CB-PCMs, d) HP/CB-OPCMs (9:1), e) HP/CB-OPCMs (8:2), f) HP/CB-OPCMs (7:3), g) HP/CB-OPCMs
(6:4), h) HP/CB-OPCMs (5:5).
view,[20] still heavily hamper the way of its widely application.
Shape-stabilization strategy provides a feasible venue for the
practical utilization of inorganic PCMs.[19] For example, Yang
et al.[21] obtained hybrid properties by combining sol-gel
method with interfacial polymerization, taking calcium hex-
ahydrate as the representative polychlorinated biphenyl of
salt hydrate as the core material, and using organic alkox-
ysilane as the medium of hydrophilic core material and
hydrophobic shell material. Fu et al.[22] developed a novel
phase change temperature-regulated composite phase change
material using sodium acetate trihydrate (SAT) and urea non-
eutectic mixture as phase change material and gas-phase SiO2
as supporting material and temperature regulator. Xiao
et al.[23] prepared a novel polycrystalline phase change hydro-
gel composed of NaAc·3 H2O, acrylamide-acrylic acid sodium
copolymer and CuS by a melting impregnation method.
Though some endeavors have been dedicated to the practical
use of inorganic PCMs, a simpler and more accessible way is
still highly desirable. In this work, a new HP aided homoge-
neous-to-heterogeneous protocol was developed, the out-
standing superiority of this protocol is mainly ascribed to its
compatibility towards water as the hypercrosslinking reaction
was initiated by just adding catalytic amount of aqueous
sodium hydroxide solution. We chose SAT as an inorganic
phase change material and subject to the preparation of the
PCMs composite using the above-mentioned homogeneous-
to-heterogeneous protocol (the detail preparation process can
be seen in the Supporting Information). As it is shown in
Figure S8, water loss phenomenon of SAT/CB composite was
clearly observed as the surface of the composite gradually
changed to white due to the precipitation of sodium acetate
under a heating condition (water loss process was recorded in
a video and shown in the Supporting Information). Interest-
ingly, water loss phenomenon alleviates significantly after
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adding the hybrid polymers during the preparation process.
More importantly, samples with different HP display different
performance regarding water loss, and the larger proportion
of silica containing monomer could deliver a better perfor-
mance on the restriction of water loss. Based on this
interesting phenomenon, we tried to explain the result in
molecular level. Firstly, the presence of silica group on the
skeleton of polystyrene could lead to the hypercrosslinking
reaction due to the cascade substitution and elimination
reaction between siloxyl groups, the proportion increase of
siloxyl groups would inevitably make the increase of the
hypercrosslinking rate among the pristine linear polymer
which thus results in the formation of a porous structure
bearing a larger specific surface area. On the other hand, the
presence of siloxyl group on the hypercrosslinked polymer
could act as a micro water conserver, similar with a water
sponge, which could thus restrain the bound water from loss
owing to it intrinsic hydrophilicity (Figure 5 f). To support our
hypothesis, some experiments were carried out. As it is seen
in Figure S10, the flow ability of the polymer was obviously
hindered after the addition of aqueous sodium hydroxide due
to the confinement of water in this hypercrosslinked polymer.
Moreover, the leakage rate of this inorganic phase change
material composite can be significantly reduced from 14.5 %
to 0.1 % after blending SAT and CB with HP. This result
clearly demonstrates the feasibility of this HP participated
homogeneous-to-heterogeneous phase change shape-stabili-
zation strategy, which could not only be applied in organic
PCMs but also feasible towards the synthesis of inorganic
shape-stabilized PCMs. As can be seen from Table 4, Fig-
ure 5 e, and Figure S11, supercooling degree of pure SAT is
about 15.98 8C, and by adding HP with CB after only 0.27 8C
of supercooling degree, it was basically eliminated the
supercooling phenomenon of sodium acetate. Additionally,
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Figure 5. Chemical structure and thermophysical performance of HP/CB-IPCMs. a) XRD images of HP/CB-IPCMs. b) FTIR images of HP/CB-
IPCMs. c) TGA images of HP/CB-IPCMs. d) DSC curves of the melting and freezing process of pure SAT and HP/CB-IPCMs. e) The supercooling
degree of HP/CB-IPCMs. f) Schematic diagram of water storage with HP. g) Bar graph showing the leakage rates of HP/CB-IPCMs with different
polymer mass. h) Bar graph showing the thermal conductivity of polymer composites with different nanoadditives. i) Bar graph showing the
leakage rates of polymer composites with different nanoadditives. j) Leakage rates of HP/CB-IPCMs with different proportions of polymer
monomers. k) SEM image of HP/CB-IPCMs (7:3).

Table 4: Data for the supercooling degree curves for the HP/CB-IPCMs Table 5: Data for the DSC curves for the HP/CB-IPCMs samples.
samples.
Sample Melting process
Sample Freezing process Onset [8C] Peak [8C] Hm [J g 1]
Theoretical Actual Supercooling
SAT 57.13 61.35 224.73
phase change phase change degree [8C]
CB-IPCMs 56.22 59.60 185.85
temperature [8C] temperature [8C]
HP/CB-IPCMs (9:1) 60.83 61.35 179.14
SAT 55.24 39.26 15.98 HP/CB-IPCMs (8.5:1.5) 55.41 61.54 174.64
CB-IPCMs 53.83 38.34 15.49 HP/CB-IPCMs (8:2) 54.75 61.54 176.87
HP/CB-IPCMs (9:1) 55.61 48.98 6.63 HP/CB-IPCMs (7.5:2.5) 57.30 61.30 176.49
HP/CB-IPCMs 55.22 54.06 1.16 HP/CB-IPCMs (7:3) 57.31 62.55 180.04
(8.5:1.5)
HP/CB-IPCMs (8:2) 54.53 54.21 0.32
HP/CB-IPCMs 53.35 53.08 0.27
(7.5:2.5) stabilization protocol (detailed demonstration can be seen in
HP/CB-IPCMs (7:3) 53.89 53.17 0.73
the Supporting Information).

the latent heat of inorganic PCM composite is up to Application of this Strategy

180.04 J g 1 (Table 5). Through research and analysis, the
reason is that the three-dimensional network structure
polymer formed through cross-linking not only serves as the
supporting material of inorganic PCMs, but also provides
more binding sites for inorganic PCMs in the solidification
process, so that inorganic hydrated salt can solidify better.
Some structural analysis along with thermo-physical proper-
ties study were also performed (Figure 5 a, b, c, d, g and k). all
of them verified the feasibility of this inorganic PCMs shape-
To broaden the application range of the polymer prepared
in this study in PCMs, we tested five kinds of thermal
conductive nanoadditives (graphene, titanium dioxide, cop-
per oxide, silicon carbide, and expanded graphite), which
were commonly used in the study of shape-stabilized PCMs to
demonstrate the general adaptability of this strategy. The
proportions of all materials are the same as the mass fractions
of each material in HP/CB-OPCMs (5:5), which well illus-
trates the feasibility of our strategy. As seen in Figure 5 i, the

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Research Articles
leakage rate of the composite with graphene added is only
0.07 % after three leakage tests. As shown in the Figure 5 h,
the thermal conductivity of PCM with graphene at room
temperature is 1.21 W m 1 K 1, which is almost 6 times higher
than that of pure PW. The thermal conductivity of the
composite with expanded graphite can also reach
0.86 W m 1 K 1, but its leakage rate is relatively high. For
the homogeneous-to -heterogeneous strategy, we only need
a simple treatment to “lock” the PCMs, thus achieving the
requirements of shape stabilized PCMs.
Conclusion
In this paper, a kind of polymer containing organic/
inorganic hybrid siloxyl functional group was successfully
synthesized and applied to the encapsulation of PCMs. Due to
the mildness of the hypercrosslinking reaction, only a small
amount of aqueous alkaline solution is required to be added
and leads to the tolerance towards both organic and inorganic
PCMs. More importantly, the homogeneous state of the
mixture guarantees the highest encapsulation rate of the
phase change material and the uniform blending of the
nanoadditives. Further studies revealed that the HP gave
PCMs a unique self-cleaning property, which makes it to be
good hydrophobicity to water droplets. In addition, the PCMs
encapsulation method was able to be adapted to different
nanoadditives, resulting in a 600 % increase in maximum
thermal conductivity and 93.7 % increase in light-to-thermal
conversion efficiency.
Acknowledgements
Thanks for financial support from the National Natural
Science Foundation of China (No. 51906252) and the Natural
Science Foundation of Jiangsu Province (NO. BK20190632),
China Postdoctoral Science Foundation (2019M661980).
Conflict of interest
The authors declare no conflict of interest.
Keywords: energy storage · hybrid materials ·
phase change materials · phase transitions · self-cleaning
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Manuscript received: March 3, 2021
Accepted manuscript online: April 1, 2021
Version of record online: && &&, &&&&

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Research Articles
Phase Change Materials

C. Liu,* J. Zhang, J. Liu, Z. Tan, Y. Cao,

X. Li, Z. Rao &&&&—&&&&

Highly Efficient Thermal Energy Storage

Using a Hybrid Hypercrosslinked
Polymer A hybrid hypercrosslinked polymer was materials via a novel homogeneous-to-
prepared that is capable of encapsulating heterogeneous encapsulation strategy.
both organic and inorganic phase change

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These are not the final page numbers!