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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca
School of Materials and Energy, Guangdong University of Technology, 510006 Guangzhou, PR China
Center for Nanochemistry, Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable
Species, College of Chemistry and Molecular Engineering, Peking University, Beijing, PR China
b
a r t i c l e
i n f o
Article history:
Received 1 March 2014
Received in revised form 18 April 2014
Accepted 22 April 2014
Available online 29 April 2014
Keywords:
Binary nitrate salt
Expanded graphite
Ultrasonic
Thermal energy storage
Latent heat
a b s t r a c t
The binary nitrate salts/expanded graphite (EG) composite phase change material (PCM) were prepared
via adding different mass rate of EG to binary nitrate salts consisting of NaNO3 and KNO3 (6:4) by aqueous
solution method adopting ultrasonic. The morphology and chemical composition of EG and the composite PCM were characterized and investigated by X-ray diffraction (XRD), scan electron microscope (SEM),
energy dispersive spectrometer (EDS), transmission electron microscope (TEM), respectively. Laser thermal conductivity instrument and differential scanning calorimeter (DSC) were employed to measure
thermo physical properties. Drawing the conclusion from investigation, that EG had enhanced thermal
conductivity coefcient which largely increased to 4.884 W/(m K) and reduced total latent heat by mostly
11.0%. The morphology and phase structure results indicated that EG were well dispersed into and physically combined with molten salts. In general, the prepared composite PCM could be a suitable phase
change material for thermal energy storage.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Since serious shortage of energy resource and tremendous
requirement for renewable energy, phase change material (PCM)
with advantageous thermal properties has been applied to satisfy
the increasing demand [15]. Depending on the characteristics of
high latent heat, high specic heat and high thermal conductivity
and so on [6,7], PCM has played an important role in various elds
extensively [810].
In recent decades, several inorganic PCM and their mixtures
have been investigated for thermal energy storage [1113]. Due
to its better thermal properties, molten salts were usually used as
direct heat transfer medium in industrial applications [1416]. Various nitrate salts and their composite have attracted tremendous
researchers concern. The mixtures consisting of KNO3 , LiNO3 and
Ca(NO3 )2 with excellent thermal properties were proved to be a
promising PCM [17]. Iverson et al. [18] concluded that temperature
did not have a signicant effect on mechanical properties through
Corresponding author at: B58 100 West Waihuan Road, Guangzhou Higher Education Mega Center, 510006 Guangzhou, PR China. Tel.: +86 020 39322715;
fax: +86 020 39322715.
E-mail address: huangjiner@126.com (J. Huang).
http://dx.doi.org/10.1016/j.tca.2014.04.021
0040-6031/ 2014 Elsevier B.V. All rights reserved.
53
conductivity of binary nitrate salts and binary nitrate salts/EG composite PCM was measured by employing a laser heat conductive
instrument (Germany, NETZSCH, LFA 447) at room temperature.
The phase change temperature and latent heat of the nitrates and
nitrates/EG composite PCM were both measured by differential
scanning calorimetry (DSC; DSC-204, NETZSCH, Germany) under
a nitrogen atmosphere. The data were collected with a scan rate of
10 C min1 from room temperature to 260 C.
3. Results and discussion
3.1. Stripped graphite akes
The morphologies of EG and SGFs were observed by SEM as
shown in Fig. 1. As can be seen from Fig. 1a, EG has a 3D wormlike architecture within size of 150 m. The high-magnication
SEM photograph (Fig. 1b) of SGFs shows that EG altered to slices
in nanoscale after the ultrasonic.
The TEM photographs of SGFs from different angles were shown
in Fig. 2. As represented in Fig. 2a, SGFs were at and semitransparent slices with some wrinkles and folds. It could be observed
that its dimension was between 8 and 25 nm which corresponded
to observation of SEM photograph in Fig. 1b. As observed in Fig. 2b,
the folds with lamellar structure were slices as given in Fig. 1b.
The phase structure of EG and SGFs were characterized by XRD
as shown in Fig. 3. The sharp and intensive diffraction peaks at 26.3 ,
56.0 correspond to EG and SGFs, respectively. A third diffraction
peak of SGFs at 45.0 appeared particularly because ultrasonic made
structure of graphite ake into disorder.
2.2. Preparation
After being dried at 100 C, graphite intercalation compounds
were expanded through a rapid heating in microwave ovens as
reported in our previous work [31]. The expanded graphite was
prepared while the bright ame was out.
Potassium nitrate and sodium nitrate were put into an air oven
and dried at 120 C for 24 h respectively and then mixed at the mass
ratio of 6:4 uniformly. A mixture of binary nitrates salts was placed
into a crucible and then heated at 350 C for 30 min statically in
order to melt completely. Afterwards, the crucible was gradually
cooled down to room temperature. The molten salts were obtained.
Grinding the molten salts slowly and dissolved it in a breaker by
deionized water gradually. Then, EG was added into the previous
solution slowly under continuous stirring at different mass rate.
After the EG soaking into the solution, the solution was stirred by
the strong ultrasonic homogeneous instrument (SCIENTZ-IID) with
a power of 800 W for 1.0 h. Then, the breaker was put into a drying
oven and dried at 100 C for 24 h. By grinding the dried composite PCM, sample was obtained. Before drying of the solutions, one
was ltered and washed using deionized water until the stripped
graphite akes (SGFs) were enough visible. SGFs were obtained
after drying as mentioned.
2.3. Characterization and determination of thermal properties
X-ray diffraction (XRD; DMAX-Ultima IV, Rigaku Corporation,
Japan) was employed to identify the microstructure and chemical
composition of EG, SFGs and the composite PCM. The morphology and chemical composition of composite PCM were investigated
by scan electron microscope (SEM; S3400N, Hitachi, Japan) with
an energy dispersive X-ray spectroscopy detector, eld emission
scanning electron microscopy (FE-SEM; S-4800, Hitachi, Japan)
(EDS; EX-250, HORIBA, Japan) at room temperature. The morphology of SGFs was investigated with a high resolution transmission
electron microscope (HRTEM; JEM-2010HR, Jeol, Japan). Thermal
54
Fig. 1. Scanning electron microphotographs of (a) EG and (b) SGFs by coating condition at room temperature.
Fig. 2. Transmission electron microscope of SGFs from different angles at room temperature.
Fig. 3. X-ray diffraction pattern obtained for EG and SGFs at room temperature.
55
Fig. 4. The SEM images of binary molten salt and composite PCM samples at room temperature.
Table 1
The specic heat, thermal diffusivity and thermal conductivity coefcient of
samples.
No.
EG (wt.%)
Specic heat
J/(g K)
Thermal diffusivity
(mm2 /s)
Thermal conductivity
coefcient W/(m K)
1
2
3
4
5
0
0.5
1
1.5
2
2.351
2.485
2.586
2.593
2.6
0.477
0.573
0.639
0.791
0.93
2.27201
2.876
3.338
4.143
4.884
Fig. 5. X-ray diffraction pattern obtained for binary molten salt and composite PCM at room temperature.
56
Table 2
The parameters of phase change temperature and latent heat of samples.
No.
EG (wt.%)
1
2
3
4
5
0
0.5
1
1.5
2
Peak temperature ( C)
Peak temperature ( C)
130.6
130.1
130.4
130.0
130.2
17.26
19.95
18.69
18.71
17.51
223.2
225.6
224.8
224.7
225.3
142.2
128.7
128.4
128.1
124.4
159.46
148.65
147.09
146.81
141.91
57
the increasing mass rate of EG, it could be seen that specic heat
increased rst sharply and then slowly, however, thermal diffusivity and thermal conductivity coefcient increased almost linearly.
It can be indicated that EG have given a great rise to thermal
conductivity coefcient which largely increased to 4.884 W/(m K)
and a nearly 11.0% reduction to latent heat. During the tests, we
can conclude that the melting curves contain two phase change:
solidsolid phase change and solidliquid phase change. The
uctuation of phase transition temperatures was very insignicant
and the total latent heat of composite PCM had a reduction about
6.7811.01%. In general, the nitrate salts/EG composite PCM
is suitable for heat transfer and thermal energy storage as EG
enhanced the thermal conductivity of binary nitrate salts.
Acknowledgements
Fig. 8. DSC curves of binary molten salt and composite PCM samples.
that every curve had two transformation peaks and the peaks were
matched nearly at same temperatures. These results nearly correspond to the DSC proles of the mixture of NaNO3 and KNO3 [32].
Concluding from the analysis of XRD and SEM, the peak at about
130.4 C was formed by solid-solid phase change and the peak at
about 224.8 C was formed by solidliquid phase change.
The uctuation of phase transition temperatures was very
insignicant and reduction on the total latent heat of composite
PCM (PTLH) was slight, as compared to binary molten salt correspondingly. The reduction on the total latent heat of composite
PCM (PTLH) was calculated by comparing to the total latent heat of
binary molten salt (BTLH). A non-dimensional parameter formulated as Eq. (1) was used for presenting the reduction percentage
on the total latent heat of composite PCM to binary molten salt.
=
(BTLH PTLH)
BTLH
(1)
58
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