Chemical Engineering Journal 420 (2021) 129906

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Chemical Engineering Journal

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

Synthesis of Sn@SnO2 core-shell microcapsules by a self-oxidation strategy

for medium temperature thermal storage
Nan Sheng a, Jiahui Lu a, Jingdong Hu a, Ruijie Zhu b, Laras Fadillah b, Cheng Wang c,
Chunyu Zhu a, *, Zhonghao Rao a, Hiroki Habazaki b
a
School of Electrical and Power Engineering, China University of Mining and Technology, Xuzhou 221116, China
b
Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, Kita-Ku Kita 13, Jo Nishi 8, Sapporo, Hokkaido 060-8628, Japan
c
School of Petroleum Engineering, Changzhou University, Chang Zhou 213164, China

A R T I C L E I N F O A B S T R A C T

Keywords: Latent heat storage using metals as solid-liquid phase change materials (PCMs) have been concerned for medium-
Phase change material temperature thermal energy storage. However, due to the leakage and corrosion problems during phase trans­
Latent heat storage formation, the use of metallic PCMs are greatly limited. Encapsulation of PCM microparticles to form micro­
Thermal energy storage
encapsulated PCMs (MEPCMs) is an effective strategy, which is unfortunately technologically difficult for
Thermal management
metallic PCMs. In this study, we develop metallic Sn MEPCMs coated by a stable SnO2 shell through a facile self-
Phase change capsule
oxidation method. Sn@SnO2 core-shell MEPCMs are fabricated by two steps: firstly, Sn microspheres are pre-
treated by vapor or water to form an oxide precursor shell on Sn microspheres; secondly, heat oxidation treat­
ment under O2 atmosphere is conducted to form a stable SnO2 shell. The Sn@SnO2 microcapsules exhibit a
melting point of ~232 ◦ C and latent heat of ~53 J/g. Importantly, the capsules present an excellent thermal
cycling stability, in which after 100 cycles of melting-freezing the phase change properties and core-shell
structure could be well retained. These results reinforce the promising application of microencapsulated Sn in
medium-temperature thermal storage.

1. Introduction heat storage [2,3].

In order to alleviate the energy crisis and climate warming due to the
excessive exploitation and utilization of fossil fuels, clean energies such
as solar energy and wind energy have recently received great attentions.
However, the wide application of those renewable energies is limited by
their intermittent and unstable natures, which induce the mismatch
between energy demand and supply in both time and location [1]. The
development of reliable thermal energy storage (TES) technologies is
very important for the efficient utilization of renewable energies, which
can fill the gaps between energy demand and supply. Latent heat storage
(LHS) using phase change material (PCM) is a promising TES technol­
ogy, which is based on the storage or release of latent heat when the
PCM undergoes the phase transition between the solid phase and liquid
phase. The obvious advantages of LHS, including high thermal storage
density, constant phase transition temperature and reversible/repeat­
able phase change behavior, have reinforced LHS-based TES systems
much more reliable and efficient as compared to conventional sensible
Currently, the technologies for low-temperature PCMs below 100 ◦ C
have been well established in preparation and application, while the
medium and high temperature PCMs over 100 ◦ C have been greatly
concerned which require the devotion of more efforts. The medium and
high temperature PCMs include mainly molten salts such as carbonates
[4,5], chlorides [6,7], nitrates [8] et al., and metal/alloys such as Cu [9],
Al-Si [10,11], Zn [12,13], Sn [14,15] et al. The medium and high tem­
perature PCMs, especially the metallic PCMs, have high heat storage
densities and high thermal conductivity, which could be used for me­
dium and high temperature TES systems in waste heat recovery,
concentrated solar power plants and so on. However, the use of metallic
PCMs as thermal storage media is significantly limited, because the
liquified metals could leak out and are highly corrosive and chemically
active [16,17]. Shape-stabilization strategies, including compositing
with porous supporting additives and encapsulation to make core-shell
capsules, have been widely investigated for the liquid-solid PCMs
[18–20]. The use of encapsulation technology to make core-shell nano/

* Corresponding author.
E-mail address: zcyls@cumt.edu.cn (C. Zhu).

https://doi.org/10.1016/j.cej.2021.129906
Received 31 January 2021; Received in revised form 22 March 2021; Accepted 14 April 2021
Available online 21 April 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
N. Sheng et al. Chemical Engineering Journal 420 (2021) 129906

Fig. 1. Experiment procedures for synthesizing Sn@SnO2 core-shell MEPCMs. (a) Vapor pretreatment and (b) water pretreatment.

micro/macro-capsules, which are consisted of PCM cores and stable
shells, has particularly got a lot of attentions. The core PCM is well
encapsulated by solid and stable shells, as a result the capsules can be
considered as solids even when the core PCM is in the liquid state. So far,
the preparation and application of capsules for low temperature PCMs
such as paraffin and salt hydrates have achieved many successes
[21,22]. However, the encapsulation of metallic PCMs is very difficult
because of their high corrosivity to the shell materials and the large
volume change during phase transition at high utilization temperature.
Recently, Zhang et al. [23] prepared Fe-core/SiC/C-shells capsules of
around 500 μm by a pouted bed CVD method, and the capsules can be
used at a high temperature more than 1100 ◦ C. Wei et al. [11] suc­
cessfully prepared the core(=Al–Si/Bi)/void/shell(=Al2O3) composite
microcapsules (with melting temperature of ~571.9 ◦ C to 631.9 ◦ C) by
using Al/Bi immiscible alloy powders as starting material and tetrae­
thoxysilane as SiO2 source, which smartly utilized the in-situ displace­
ment reaction between SiO2 and molten Al. Metallic Sn has a melting
point of 231.9 ◦ C, which is proper for medium temperature heat storage
with potential applications in medium temperature solar energy utili­
zation and waste heat recovery. Lai et al. [24] successfully coated silica
shells on particles of Sn and Sn-Zn alloys by a sol-gel method, and added
them to HITEC molten salt to form latent heat fluid, which was applied
to Stirling engine. The results shown that the heat transfer and heat
Table 1
Naming of the samples prepared in this study.
Pretreating Time After Pretreatment After Heat Oxidation Treatment
0 min pure-Sn pure-Sn-0
30 min vapor-30-pre vapor-30
90 min vapor-90-pre vapor-90
20 min water-20-pre water-20
storage properties of the microcapsules added molten salt fluid were
improved. These attempts on metallic phase change capsules give us
many encouragements for continuing to explore a facile and consoli­
dated method to prepare medium temperature Sn microcapsules.
In this study, we are focusing on the preparation of Sn@SnO2 core-
shell micro-encapsulated PCM (MEPCM) for medium temperature
thermal storage. The microcapsules are produced by two steps,
including the first vapor or water treatment and the subsequent heat
oxidation treatment. The formation mechanism, morphology/structure,
phase change properties and cycling stability are examined in details.
2. Experimental section
2.1. Preparation of MEPCMs
The raw material of Sn microspheres used in this study was pur­
chased from Shanghai Xiangtian Nano Materials Co., Ltd. The as-
obtained Sn microspheres were filtered to 45–50 μm before use.
Deionized water used in the experiments was purified by using a water
purification system (EPED, EQ201).
The whole synthesis procedure is illustrated in Fig. 1. As shown in
Fig. 1, the Sn@SnO2 core-shell MEPCMs were prepared by two steps. The
first step was the pretreatment of Sn microspheres, which involved two
different methods: (a) vapor pretreatment and (b) water pretreatment. For
vapor pretreatment (Fig. 1a), Sn particles were homogeneously dispersed
over a nylon mesh with hole size of 0.5 μm, which was fixed on a beaker
filled with deionized water. The beaker was heated on a magnetic stirring
hot plate and the deionized water was kept boiling for 30 min or 90 min,
respectively, to make steam go through the particles. For the water pre­
treatment (Fig. 1b), Sn particles were dispersed into deionized water and
heated to 80 ◦ C, keeping for 20 min. Subsequently, the samples were

(a) (b) (c)

vapor-90-pre vapor-90

water-20
Intensity(a.u.)

Intensity(a.u.)

Intensity(a.u.)

vapor-30-pre vapor-30

water-20-pre

pure-Sn-0
JCPDS No. 41-1445 SnO2
pure-Sn
JCPDS No. 41-1445 SnO2
JCPDS No. 04-0673 Sn JCPDS No. 04-0673 Sn
JCPDS No. 04-0673 Sn

25 30 35 40 45 50 55 60 65 70 75 25 30 35 40 45 50 55 60 65 70 75 25 30 35 40 45 50 55 60 65 70 75
2θ(degree) 2θ(degree) 2θ(degree)

Fig. 2. XRD patterns of the microparticles (a) pure-Sn, vapor-30-pre and vapor-90-pre, (b) pure-Sn-0, vapor-30 and vapor-90 and (c) water-20-pre and water-20.

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N. Sheng et al. Chemical Engineering Journal 420 (2021) 129906

Pretreating Time Raw material of pure Sn After Heat Oxidation Treatment

a-1 a-2 b-1 b-2 b-3

0 min

After Vapor Pretreatment After Heat Oxidation Treatment

c-1 c-2 d-1 d-2 d-3

30 min

e-1 e-2 f-1 f-2 f-3

90 min

After Water Pretrentment After Heat Oxidation Treatment

g-1 g-2 h-1 h-2 h-3

20 min

Fig. 3. SEM images of the microparticles after vapor or water pretreatment and after heat oxidation treatment. (a) Raw material of pure-Sn, (b) pure-Sn-0, (c) vapor-
30-pre, (d) vapor-30, (e) vapor-90-pre, (f) vapor-90, (g) water-20-pre and (h) water-20.

washed, filtrated and dried at 60 ◦ C over 12 h for further use. The second
step was heat oxidation treatment, during which the pretreated particles
were placed in an Al2O3 crucible and heated in a tube furnace from room
temperature to 500 ◦ C at a rate of 10 ◦ C min− 1 and kept at 500 ◦ C for 30
min under an oxygen gas flow of 50 mL min− 1. After the completion of heat
oxidation treatment, the samples were naturally cooled to room tempera­
ture. Besides, pure Sn particles were directly undergone the heat oxidation
treatment without any pretreatment as a reference sample. Table 1 listed
the names of all samples.
Fig 4. Cross sectional SEM image of the typical sample obtained after heat
oxidation treatment.
2.2. Characterization
The powder X-ray diffraction patterns of the samples were measured
by an X-ray diffractometer (XRD, BRUKER, D8 ADVANCE) using Cu Kα
radiation (λ = 0.15405 nm). The X-ray tube was operated at 40 kV and
30 mA. The X-ray diffractogram was recorded at 0.01◦ interval with a
scanning rate of 6◦ /min for the scanning angle (2θ) from 5◦ to 75◦ . The
morphology of the samples was observed by high resolution field-
emission scanning electron microscope (SEM, TESCAN, MAIA3 LMH).
X-ray energy dispersive spectrometry (EDS) analysis combined with
SEM observation was conducted to observe the elemental mapping of
the microcapsules. The cross section elemental distribution of Sn@SnO2
core-shell MEPCM was also analyzed by electron prob micro-analyzer
(EPMA, SHIMADZU, 8050G). As for the cross section observation, the
MEPCMs were mounted in resin and were carefully polished to get a
smooth cross-section surface by using abrasive paper, polishing fluid
and cloth in sequence.
To carefully identify the shell properties of the sample after water
treatment, the following confirmatory experiment was conducted by X-
ray photoelectron spectroscopy (XPS, JEOL JPS-9200). A piece of pure
Sn plate was polished carefully by abrasive paper, which was subse­
quently treated by hot water at 80 ◦ C. Both the polished Sn plate and the
hot water treated Sn plate were parallelly observed by XPS. By con­
trolling the Ar ion etching time, a series of spectra at different depths (0,
400 and 800 nm) were obtained for both samples.
To observe the heat oxidation behavior of the formation of final
microcapsules, the samples obtained after vapor and water treatment
were measured by a simultaneous differential scanning calorimetry
analyzer combined with a thermal gravimetric analyzer (DSC-TGA,
NETZSCH, STA449F5). The samples were placed in an Al2O3 crucible
and heated in O2 or N2 flow of 50 mL min− 1 respectively, which were
conducted at a heating rate of 10 ◦ C min− 1 to 500 ◦ C and kept at 500 ℃
for 30 min.
The thermal change behavior and phase change enthalpies of the
samples were measured by using a differential scanning calorimetry

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N. Sheng et al. Chemical Engineering Journal 420 (2021) 129906

(a)

(d)

10μm
Scan
line

(b) Sn
1 μm

Oxide layer
400
(e) Sn
15000
10μm
O
300
Intensity (counts)

Intensity (counts)
10000

(c) O 200

5000
100

0 0
0 1 2 3 4 5 6
Distance ( m)
10μm

Fig. 5. Cross sectional morphology and elemental analysis of the pre-treated sample water-20-pre. (a, d) cross-sectional image of water-20-pre, (b) EPMA mapping of
Sn, (c) EPMA mapping of O, (f) elemental line scan of Sn and O corresponding to image (d).

analyzer (DSC, TA900). In this measurement, 20 mg samples were
placed in an Al crucible and analyzed in a N2 flow rate of 250 mL min− 1
and a heating/cooling rate of 2 ◦ C min− 1. The cyclic stability of the
MEPCMs was evaluated by 100 times cycling test using DSC. For cycle
test, the MEPCMs were heated from 90 ◦ C to 280 ◦ C at a heating/cooling
rate of 20 ◦ C min− 1 in the N2 atmosphere. The thermal conductivity of
the samples was analyzed by a thermal conductivity analyzer (TC 3000,
Xiatech, Xian), during which the pure Sn powders and the Sn@SnO2
microcapsules were pressed at 10 MPa in a module to form pellets for
measurements. Each sample was measured more than five times to
achieve an average value.
3. Results and discussion
3.1. Material properties of the Sn@SnO2 MEPCMs
XRD analysis was carried out to identify the crystal phase composi­
tion of the samples obtained at different stages, as shown in Fig. 2. The
XRD patterns for pure-Sn, vapor-30-pre and vapor-90-pre are presented
in Fig. 2a, in which only a single phase of Sn (JCPDS No. 04-0673) was
detected for all samples. Even after the vapor treatment of Sn micro­
spheres, the samples do not indicate a second crystal phase. This might
be due to the amorphous nature and low content of the shell precursor
through the reaction between Sn and water. The careful observation of
the shell precursor will be discussed in following XPS and EPMA anal­
ysis. After heat oxidation treatment to 500 ◦ C under O2 flow, the samples
are consisted of SnO2 (JCPDS No. 41-1445) and Sn, as confirmed by XRD
patterns in Fig. 2b. As a comparison, the Sn microspheres were also
treated by another process in hot water at 80 ◦ C. Similar to the case of
vapor treatment, the XRD pattern (Fig. 2c) after water treatment in­
dicates a single crystal phase of metallic Sn, and after the subsequent
heat oxidation treatment, the XRD pattern indicates two crystal phases
of SnO2 and Sn.
The micromorphology and structure of the samples were observed by
SEM, with the results shown in Fig. 3. As shown in Fig. 3a, the raw
material of Sn particles are microspheres of around 50 μm with smooth

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N. Sheng et al. Chemical Engineering Journal 420 (2021) 129906

Fig. 6. XPS spectra of (a) O 1s and (b) Sn 3d for the pure Sn plate and the water-pretreated Sn plate.

Fig. 7. TG and DSC curves of the samples measured in O2 and N2 atmosphere.

surface, which also exhibits good dispersion. After the direct heat
oxidation treatment at 500 ◦ C, the pure-Sn-0 particles become rough,
wrinkled and agglomerated together as shown in Fig. 3b. The melting
point of Sn is around 232 ◦ C. During the heat treatment to 500 ◦ C under
O2 flow, the particles were oxidized on the surface to form a thin oxide
layer, and at above the melting point of Sn, the liquid Sn leaked from the
thin oxide layer, making the particles conglutinate and agglomerate.
After the heat oxidation treatment for pure-Sn, the particles cannot be
dispersed. Fig. 3c–f shows the SEM images of the samples formed by
using vapor pretreatment and after heat oxidation treatment under
different vapor treating time, respectively. The surfaces of vapor-30-pre
and vapor-90-pre are still smooth, in addition, the particles also show

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N. Sheng et al. Chemical Engineering Journal 420 (2021) 129906

Fig. 8. DSC results for pure-Sn. (a) is the melting-freezing curves for 5 cycles, (b, c) are the enlarged freezing and melting peak curves.

Table 2
The summary of phase change temperatures and enthalpy values of pure-Sn.
Sample Cycle Melting Freezing

Ts/◦ C TP/◦ C TE/◦ C Enthalpy/(J/g) TS/◦ C TP/◦ C TE/◦ C Enthalpy/(J/g)

pure-Sn 1st 227.5 233.2 237.2 55.2 173.1 146.3 135.4 55.2
2nd 228.7 233.2 237.0 55.0 171.0 146.4 133.7 55.0
3rd 228.9 233.2 237.0 54.9 169.0 146.7 132.9 54.9
4th 229.1 233.2 236.7 54.8 168.3 146.9 132.4 54.8
5th 229.0 233.2 236.7 54.8 167.7 147.1 132.1 54.8

TS is the starting temperature, TP is peak temperature and TE is ending temperature for melting or freezing.

Fig. 9. DSC results for the Sn@SnO2 capsules. DSC curves at the 5th, 50th and 100th cycles for (a) vapor-30, (b) vapor-90 and (c) water-20. (d) Is the 100th cycle DSC
curves of vapor-30, vapor-90 and water-20.

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N. Sheng et al. Chemical Engineering Journal 420 (2021) 129906

Table 3
The summary of phase change temperatures and enthalpy values of the microcapsules.
Sample Cycle Melting Freezing

T S/ C
◦
T P/ C
◦
TE/ C
◦
Enthalpy/(J/g) TS/◦ C TP/◦ C TE/◦ C Enthalpy/(J/g)

vapor-30 5th 226.6 232.9 237.4 53.9 166.4 143.9 134.7 53.8
50th 227.5 233.0 236.5 53.8 164.6 143.9 134.7 53.5
100th 227.7 233.0 236.4 53.0 163.0 143.9 134.7 53.0
vapor-90 5th 228.6 233.0 236.8 52.5 164.6 143.8 133.0 52.5
50th 228.7 233.0 236.3 52.5 162.6 143.9 130.9 52.5
100th 228.7 233.0 236.0 52.4 160.9 143.8 130.3 52.4
water-20 5th 226.8 233.2 237.3 53.1 166.9 143.6 137.6 53.1
50th 226.9 233.2 236.4 52.9 164.6 143.4 136.8 52.9
100th 228.1 233.2 236.4 52.8 164.7 142.8 136.4 52.8

(a )
(a) (b)
(b) (cc))

Fig. 10. A bar chart of the enthalpy values at different cycles for (a) vapor-30, (b) vapor-90 and (c) water-20.

good dispersion state, as presented in Fig. 3c, e. After heat oxidation
treatment at 500 ◦ C which was higher than the phase change tempera­
ture of Sn, the particles could still remain the original particle size and
shape, as shown in Fig. 3d, f, although the surfaces of the particles
exhibited rougher morphology than those of raw Sn particles (Fig. 3a, b).
From these images, no leakage can be found from the as-prepared
products, and the particles also exhibit good dispersion state.
Comparing vapor-30 and vapor-90, a similar surface morphology could
be observed for both samples, as shown in Fig. 3d, f. According to XRD
(Fig. 2a, b) and SEM (Fig. 3c–f) analysis, it is confirmed that the SnO2
shell was successfully formed on the Sn microspheres, forming the
Sn@SnO2 MEPCM. As for another treating method using hot water
pretreatment, very similar results to that by vapor treatment were ob­
tained. The SEM images for the samples obtained after water treatment
and subsequent heat oxidation are shown in Fig. 3g, h. After 20 min
water pretreatment, the surface morphology of the particles was also
still smooth. After heat oxidation treatment, the particle surface of
water-20 become rougher than before. The surface morphologies of the
MEPCMs are similar no matter the different treating process. The typical
cross section SEM image of the final product after heat oxidation
treatment is shown in Fig. 4, which indicates the obvious core-shell
structure with shell thickness of around 1–2 μm. The careful observa­
tion of the core-shell structure for the water treated sample is also shown
in Fig. 5. It is also observed that the shell become rough for the capsules
after heat oxidation treatment than that after water treatment, which is
consistent with the surface morphology observation in Fig. 3. These
results suggest that the Sn@SnO2 core-shell MEPCMs were successfully
prepared by the two-step methods, including vapor or water pretreat­
ment and the subsequent heat oxidation treatment.
3.2. Formation mechanism of the oxide precursor by the pretreatment
with water
Fig. 5 presents the cross sectional images and elemental analysis of
the pre-treated sample water-20-pre. The oxide shell of the water treated
sample is very thin as compared to the final heat oxidized sample. The
cross sectional SEM images (Fig. 5a, d) indicate that shell is smooth
compared to that in Fig. 4. Fig. 5b, c shows the EMPA mapping of Sn and
O, indicating that the surface of the particle is accumulated with O,
while the concentration of Sn is lower on the surface than in the core
part. The elemental line analysis from the core to surface is shown in
Fig. 5e, which further confirms the presence of a thin oxide layer on the
surface of a particle. From Fig. 5d, e it can be confirmed that the
thickness of oxide layer is around several hundreds of nanometers.
In order to further demonstrate the characteristics of the oxide pre­
cursor, we did the same hot water treatment of a carefully polished Sn
plate, which was further analyzed by XPS. It is noted that the charac­
teristics of the oxide precursor layer by vapor treatment are similar to
the hot water treated one. Fig. 6 exhibits the XPS depth profiles (0, ~400
and ~800 nm) of O1s and Sn3d for the samples of water treated Sn plate
and polished pure Sn plate. At the depth of 0 nm, the water treated Sn
plate shows stronger peaks of O1s and Sn3d, compared to those of pure
Sn plate. The O1s curves cover the bonding positions of O-Sn (530.9 eV)
and –O–H (532.8 eV) [25,26]. The O–Sn band refers to the lattice oxygen
in tin oxide, while the –O–H band corresponds to hydroxyl groups which
are attributed to the adsorbed water and hydrate water. The Sn3d curves
cover the bonding positions of Sn0 (e.g. ~484.9 eV) and Sn–O (e.g.
~486.8 eV), which refer to the bands of metallic Sn and tin oxide
respectively.
As for the polished pure Sn plate at the depth of 0 nm, the XPS curves
indicate obvious O1s peaks which is mainly located at the –O–H position
(the –O–H band is stronger than the O–Sn band), whereas the XPS curves
for Sn3d are very weak both for the Sn0 and Sn–O bands. At the depth of
~400 and ~800 nm, the peaks for O1s disappear, while the Sn3d peaks
are very strong which are located at Sn0 band. Those observation in­
dicates that the surface of the polished pure Sn plate was only weakly
oxidized with a very thin layer, and at the depth of ~400 nm the oxide
layer was not detectable. As for the water treated Sn plate at the depth of
0 nm, the XPS curves indicate very strong O1s peaks, in which the O-Sn
band is stronger than the –O–H band. In addition, the XPS curves for
Sn3d are also obviously observed, in which the Sn–O band is stronger
than the Sn0 band. At the depth of ~400 and ~800 nm, the peaks for O1s

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N. Sheng et al.
vapor-30
(a-1) (a-2)
vapor-90
(b-1) (b-2)
water-20
(c-1) (c-2)
Fig. 11. SEM images of the capsules after 100 melting-freezing cycles. (a) vapor-30, (b) vapor-90 and (c) water-20.
become weaker both for the O–Sn and –O–H bands, while the Sn3d
peaks become stronger at the Sn0 band and the Sn–O band peak become
weaker. Even at ~800 nm, the O1s peak is still detectable. Therefore, the
oxide layer is around several hundreds of nanometers, which is similar
to the EPMA analysis in Fig. 5. Considering that the absorbed water is
only observed on the surface for pure Sn plate, however, the peaks for
the –O–H bands can be still observed for the water treated Sn plate at the
depth of 800 nm, therefore the –O–H bands must be mainly attributed
hydrate water. Therefore, through the water/vapor treatment, the oxide
precursor shell should be in the form of SnO2⋅xH2O. This is also indi­
cated by the weight decrease in the TG analysis at temperature below the
melting point of Sn. The formation of the thin oxide precursor layer is a
weak reaction with the help of hot water or vapor, which can be written
in the following formula:
Sn + O2 + xH2O → SnO2⋅xH2O
3.3. Formation mechanism of the Sn@SnO2 MEPCMs by heat oxidation
treatment
To investigate the formation of SnO2 shell, the heat oxidation process
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Chemical Engineering Journal 420 (2021) 129906
(a-3)
(b-3)
(c-3)
to form the final capsules was also monitored by DSC-TGA analysis
under O2 flow, as shown in Fig. 7. As a comparison, the pre-treated
samples by water or vapor were also undergone the DSC-TGA analysis
under N2 flow. The samples were heated in a DSC-TGA apparatus at
10 ◦ C min− 1 to 500 ◦ C and kept at 500 ◦ C for 30 min. In the DSC curves,
all samples presented the typical endothermic peaks at around 232 ◦ C
during the temperature rise period, corresponding to the solid-liquid
phase change of Sn. In N2 atmosphere, TG curves for the water/vapor
pretreated samples could be divided into two stages. The first stage was
that the weight slightly decreased from room temperature to around
232 ◦ C, which might due to loss of absorbed/hydrated water on the pre-
formed shell. The second stage was that the weight increased linearly
and gradually above ~232 ◦ C, which might due to the slight oxidation of
Sn (weight increase of around 0.5%) because there was a small amount
of O2 in N2 flow (purity: 99.999%). In O2 atmosphere, TG curves for the
water/vapor pretreated samples could be divided into three stages. The
first stage was the slight weight decrease from room temperature to
around 232 ◦ C due to the loss of absorbed/hydrated water on the pre-
formed shell. The second stage was that the weight increased (~0.2%)
slightly and gradually until near 500 ◦ C due to the gradual oxidation and
thickening of the shells. The third stage was that the weight increased
dramatically (~2%) during the holding period at 500 ◦ C, indicating the
N. Sheng et al. Chemical Engineering Journal 420 (2021) 129906

SEM image EDS-mapping of Sn EDS-mapping of O

(a-1) (a-2) (a-3)

vapor-30

(b-1) (b-2) (b-3)

water-20

Fig. 12. Cross sectional SEM images and EDS elemental mapping of (a) vapor-30 and (b) water-20 after 100 cycles.

SEM image EPMA-mapping of Sn EPMA-mapping of O

(a) (b) (c)

10μm 10μm 10μm

counts counts
347 1547 2747 23 117 211

Fig. 13. Cross-sectional SEM image and EPMA Sn/O element distribution images for water-20 after 100 cycles.

quick oxidation and thickening of the SnO2 shell. Pure-Sn was also un­
dergone the same heat oxidation process as a comparison. Pure-Sn
shows a gradual weight increase during the temperature rise period
until 500 ◦ C, and a dramatic weight increase during the holding period
at 500 ◦ C. The oxidation of pure-Sn during the temperature rise period
was severer than those of the pre-treated samples. The pre-treated
samples with pre-formed thin shells could induce a gradual thickening
and stabilization of SnO2 shells, avoiding the breakage or crack of shells,
thereby the Sn@SnO2 MEPCMs were successfully prepared by the two-
step method, as confirmed by SEM images in Fig. 3d, f, h. However,
without the protection of pre-formed shells, the direct oxidation of pure-
Sn was sudden and uneven, and above the melting point of Sn, liquid Sn
would leak, making conglutinated and agglomerated particles, as shown
in Fig. 3b.
3.4. Heat storage and thermal cycling stability of the MEPCMs
DSC was used to measure the phase change temperature and latent
heat capacity of pure-Sn and MEPCMs as-obtained after heat oxidation
treatment. The DSC results of pure-Sn were shown in Fig. 8 and
summarized in Table 2. The latent heat capacity of pure-Sn was 55.2 J/g
and the peak temperature of melting was 233.2 ◦ C, as shown in Table 2.
The melting curves during the 5 cycles were almost overlapped. The
melting heat capacity and the melting phase change temperatures,
including starting temperature, peak temperature and ending tempera­
ture, showed no significant changes during the 5 cycles. However, for
the freezing process, with the increase of cycling number, the single
freezing curve gradually split into two peaks, presenting gradually
decreased freezing temperature. This indicates the instability of pure Sn
powders during cycling, presenting increased supercooling degree. It is
commonly recognized the encapsulated particles have higher super­
cooling degree due to the confinement effect at small size [27]. The pure
Sn powders of ~45–50 μm present a supercooling degree of around
87 ◦ C based on the melting/freezing peak temperatures. In comparison,
the supercooling degree for the Sn@SnO2 MEPCMs are around 89 ◦ C as
shown in the following measurement. The pure Sn powders were not
covered by a good protective oxide layer, thereby during cycling mea­
surement the powders could be partially oxidized due to the oxygen
residue in the DSC chamber, especially for the smaller particles. When
the smaller particles were oxidized and encapsulated, the freezing

9
N. Sheng et al.
temperature of those smaller oxidized particles would shift to the lower
temperature side, thereby with increasing cycling number the freezing
curve was split into two peaks in which a new small peak appeared at the
lower temperature side.
The melting-solidification cycling stability of the capsule samples
was conducted using DSC measurement. Fig. 9a–c show the DSC curves
at the 5th, 50th and 100th cycles for vapor-30, vapor-90 and water-20,
respectively. For each sample, the DSC curves were very similar during
the 100 cycles, indicating the good cycling stability for the capsules.
Fig. 9d presents the comparison of the DSC curves of the three samples at
the 100th cycle, in which the three curves were almost overlapped,
indicating the similarity of phase change properties for the three capsule
samples. The phase change parameters including phase change tem­
peratures and enthalpies were summarized in Table 3. These samples
exhibited melting peak temperature of around 233 ± 1 ◦ C, freezing peak
temperature of around 143 ± 1 ◦ C, and melting/freezing enthalpies
around 53 ± 1 J/g. For each sample, with the increase of cycling
number, the melting/freezing enthalpies decreased slightly, for
example, melting enthalpy was 53.9 J/g at the 5th cycle while the value
is 53.0 J/g at the 100th cycle for sample vapor-30. This decreasing ratio
of around 1.7% is in an acceptable range. These results indicate the good
thermal cycling stability of the as-prepared Sn@SnO2 core-shell
MEPCM. The comparison of enthalpy values in term of bar chart is
shown in Fig. 10.
To further investigate the thermal cycling stability of the capsules,
the morphology and structure observation were conducted. Fig. 11
shows the SEM images of those sample after 100 cycles. From these
images, it is seen that no breakage or crack of a capsule could be
observed. Those capsules could still present good dispersion state, and
no conglutination or agglomeration of particles were observed. The
surface morphologies were also similar to those of the as-prepared
samples as-shown in Fig. 3.
Fig. 12 shows the cross-sectional SEM images and the Sn/O
elemental distribution for the typical samples vapor-30 and water-20
obtained after 100 cycles of melting-freezing in DSC measurement.
Clear core-shell structure could be observed for both samples in the
cross-sectional SEM images (a-1, b-1). Elemental distribution further
confirmed the accumulation of Sn (a-2, b-2) in the cores and O (a-3, b-3)
in the shells, indicating the characteristic of metallic core and oxide shell
that is the Sn@SnO2 core-shell capsule. The core-shell structure was
further clearly observed by EPMA technique by selecting sample water-
20 after 100 cycles as an example, as shown in Fig. 11. As for a typical
cross section of a MEPCM as shown in Fig. 11a, the EMPA mapping in
term of Sn and O are presented in Fig. 11b, c. The color from black to
orange indicated the increasement of element content, as shown by the
count bars. From Fig. 11b, it was observed that the Sn element could be
detected in all areas of the microsphere. The core part with dark orange
color of high counts represented high content of Sn, while at the surface
the color was lighter with low counts which represented a relatively
ratio of Sn. Fig. 11c shows the EPMA mapping of O, in which O element
was accumulated on the edge of the microsphere, forming an oxide shell
coated on the Sn core. The thickness of the oxide shell was around 1–2
μm. All of these characterizations further confirmed the good cycling
stability of Sn@SnO2 MEPCMs, which is promising for long term
repeated use (Fig. 13.).
Finally, the thermal conductivity of the samples was also measured
by pressing the capsule powders to disks. The Sn@SnO2 MEPCMs have a
thermal conductivity of around 4.2 W/m⋅K, which is lower than the
counterpart of pure Sn powders of 5.6 W/m⋅K. It is normal that the
thermal conductivity of the compacted powders is lower than that of
pure bulk Sn (67 W/m⋅K).
4. Conclusion
In summary, the Sn@SnO2 core-shell microcapsules were success­
fully prepared using Sn microspheres of 45–50 μm by a facile two-step
10
Chemical Engineering Journal 420 (2021) 129906
self-oxidation strategy including vapor or water pretreatment and sub­
sequent heat oxidation treatment. The crystal phase, composition and
microstructure observation by XRD, SEM-EDS and EPMA analysis sug­
gested that the metallic Sn core was well coated with SnO2 shell of 1–2
μm. DSC thermal analysis indicated that the Sn@SnO2 capsules exhibi­
ted a melting point of ~232 ◦ C and latent heat of ~53 J/g. Thermal
cycling measurement illustrated that after 100 cycles of melting-
freezing, the phase change properties and core-shell structure of the
capsules could be well remained, particularly, no crack or leakage was
observed. Therefore, by solving the critical problems of leakage and
corrosion of metallic PCM, the newly developed Sn@SnO2 core-shell
MEPCMs are promising for application in middle-temperature thermal
energy storage.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported partially by National Natural Science
Foundation of China (No. 52006236), Natural Science Foundation of
Jiangsu Province (No. BK20200656), the Fundamental Research Funds
for the Central University (Grant no. 2020QN08) and China Postdoctoral
Science Foundation (Grant no. 2020M681764).
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