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Energy Procedia 105 (2017) 4185 4191

The 8th International Conference on Applied Energy ICAE2016

Thermal stability of the eutectic composition in NaCl-CaCl2-

MgCl2 ternary system used for thermal energy storage
applications
Lichan Du a, Heqing Tian a, Weilong Wang a,*, Jing Ding a,*, Xiaolan Wei b, Ming Song b
a. School of Engineering, Sun Yat-Sen University, Guangzhou 510006, China
b. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China

Abstract

The ternary eutectic chloride salt (NaCl-CaCl2-MgCl2) was designed and prepared for thermal energy
storage over 550 in a concentration solar power system. The melting temperature and fusion enthalpy
of the eutectic salt were measured experimentally using the Differential Scanning Calorimeter (DSC)
technique which were determined to be 420.83 and 201.50 J/g, respectively. The thermal stability
including the short-term and the long-term thermal stability of the ternary system was investigated by the
Thermo-gravimetric Analyzer (TGA) technique and the DSC technique. The thermal properties of the
eutectic mixture kept stable during the short-term thermal cycling test. The weight loss of the eutectic salt
was less than 5%, and the melting temperature and fusion enthalpy changed slightly as the temperature
increased below 650 in the long-term isothermal stability study. The thermal stability test revealed that
the ternary eutectic system demonstrated excellent thermal stability below 650 which was taken as the
upper limit temperature of the ternary system. The eutectic composition was characterized by the X-Ray
Diffraction (XRD) technique before and after thermal treatment to provide preliminary analysis on the
mechanism of thermal instability. The results suggested that the ternary eutectic chloride salt was a
potential candidate for applying in high-temperature thermal energy storage.
2017
2016TheTheAuthors. Published
Authors. by Elsevier
Published Ltd. This
by Elsevier is an open access article under the CC BY-NC-ND license
Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and/or peer-review under responsibility of ICAE
Peer-review under responsibility of the scientific committee of the 8th International Conference on Applied Energy.
Keyword: Ternary eutectic salt; Thermal stability; Melting temperature; Fusion enthalpy; TGA.

1. Introduction

* Corresponding author. Tel.: +8620-3933-2320; fax: +8620-3933-2319.

E-mail address: wwlong@mail.sysu.edu.cn, dingjing@mail.sysu.edu.cn

1876-6102 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the scientific committee of the 8th International Conference on Applied Energy.
doi:10.1016/j.egypro.2017.03.892
4186 Lichan Du et al. / Energy Procedia 105 (2017) 4185 4191

Thermal energy storage has been emphasized greatly nowadays with the energy consumption
increasing rapidly. Molten salts as phase change materials are being studied extensively for thermal
energy storage and heat transfer applications due to the desirable thermal characteristics such as wide
operating temperature range, low vapor pressure, moderate heat capacity, low viscosity and excellent
thermal stability[1]. The most common molten salts include chlorides, fluorides, carbonates and nitrates,
among which molten nitrate salts have been used widely as thermal energy storage media for solar energy
applications because of their low melting point and high thermal stability. Solar Salt (NaNO3/KNO3:
40/60 wt%) and HITEC (NaNO3/KNO3/NaNO2: 7/53/40 wt%) are two popular molten salts as thermal
energy storage media in concentrated solar power plants[2-4]. In the power generation system, the Rankine
cycle efficiency rises with the steam output temperature as well as the heating fluid temperature.
Unfortunately, Solar Salt was found to be stable below 600 and the upper limit temperature of HITEC
was 450 in long-term use and up to 528 in short-term use[5-7], which restricts their application at
higher temperature.
Molten chloride salts are the primary candidates for high-temperature thermal energy storage with
excellent characteristics of low unit cost, high heat storage capacity, appropriate working temperature
(400~1000 ). Numerous studies have been conducted on molten chloride salts regarding novel molten
salts design, preparation and thermo-physical properties. However, the thermal stability of molten salts is
also a very important property that needs to be considered to ensure their long cyclic life.
In our previous work, a novel ternary eutectic chloride salt (NaCl-CaCl2-MgCl2) was developed with
higher upper limit temperature for high-temperature thermal energy storage applications[8]. In practical
applicationthe thermal stability is critical to the use of molten salts as thermal energy storage media. In
this paper, the thermal stability of the ternary eutectic chloride salt was studied extensively by the
Thermogravimetric Analyzer (TGA) technique and the Differential Scanning Calorimeter (DSC)
technique, including the short-term and the long-term thermal stability. Subsequently, the eutectic
composition of the eutectic salt was characterized by the X-Ray Diffraction (XRD) technique before and
after the stability experiments to analyze the mechanism of thermal instability.

2. Experimental and methodology

2.1. Materials

The ternary eutectic chloride salt (NaCl-CaCl2-MgCl2) was prepared experimentally by static melting
method with mixing corresponding amounts of sodium chloride, calcium chloride and magnesium
chloride (AR, >99% pure) according to the eutectic composition. All the three salts were pre-dried in an
oven at 120 for 24 h and were used without further purification.

2.2. Experimental procedure

The melting point and fusion enthalpy of the ternary eutectic chloride salt were measured using the
DSC/TGA synchronization analyzer (SDT Q600, TA Instrument Inc., USA). The sample was heated
continuously from 50 to 1000 with a heating rate of 20 /min in argon atmosphere and the flow rate
of the gas was maintained at 100 ml/min in the experiments. And then, a TG-DSC curve was made, from
which the melting point, fusion enthalpy and weight loss change with temperature would be obtained.
The short-term cycling thermal stability of the ternary eutectic chloride salt was determined by the
TGA apparatus. Prior to the thermal stability experiment, the sample was pretreated at 150 for 30 mins
to remove the residual moisture absorbed during the molten salt preparation. And then, the sample was
 Lichan Du et al. / Energy Procedia 105 (2017) 4185 4191 4187

heated through 12 cycles in the process of measurement where a temperature range was set from 200 to
600 with a heating rate of 20 /min. All the measurements were conducted in argon atmosphere with
a flow rate of 100 ml/min. A weight loss vs. temperature curve for 12 thermal cycles was used to assess
the short-term cycling thermal stability of the eutectic salt.
The long-term isothermal stability of the ternary eutectic chloride salt was studied by isothermally
heating for different time (10, 20, 30, 40, 50, 60 and 70 h) at various temperatures (500, 550, 600, 650
and 700 ). The weight of the sample after thermal treatment was determined by using an electronic
weighing balance, and the melting point and fusion enthalpy were measured by the DSC/TGA
synchronization analyzer subsequently.
The specimens were ground into powder to be tested by XRD analysis to study the mechanism of
thermal instability of the ternary eutectic chloride salt.

3. Results and discussion

3.1. Characteristics of the ternary eutectic chloride salt

Fig. 1 showed the heat flow and weight loss of the ternary eutectic chloride salt with temperature. A
endothermic peak was identified from the DSC plot, and the onset temperature and the peak temperature
of phase transition were 420.83 and 430.10 , respectively. The onset temperature was taken as the
melting point of the molten salt. The fusion enthalpy of the eutectic mixture determined from the area
under the endothermic peak was 201.50 J/g. Fig. 2 indicated the weight loss rate of the ternary system. It
showed that the weight loss rate was 0.03217 wt%/ at 700 and started to increase rapidly at this
temperature in accord with the TG plot, which turned out that the ternary eutectic chloride salt had been
unstable when the temperature was beyond 700 .

Fig. 1 The TG-DSC curve of the ternary eutectic chloride salt Fig. 2 Weight loss of the ternary eutectic chloride salt

3.2. Short-term cycling thermal stability

The short-term cycling thermal stability of the ternary eutectic chloride salt was demined by weight
loss. The measurement result of the cyclic thermal stability was plotted in Fig. 3. As shown in the figure,
weight loss was obviously observed and decreased with the thermal cycles until the sixth thermal cycle,
which were 4.62, 2.29, 0.98, 0.44, 0.20 and 0.05% separately. After that, there was almost no weight loss
in the following thermal cycles. These results implied that the ternary eutectic chloride salt was thermally
stable during the test temperature range, and the recyclability was also verified in its whole lifetime for
4188 Lichan Du et al. / Energy Procedia 105 (2017) 4185 4191

thermal energy storage applications. And it turned out that the major weight loss in the first cycles was
attributed to the loss of moisture which was picked up during the process of sample loading.

Fig. 3 Weight loss of for short-term cycling thermal stability Fig. 4 Weight loss for long-term isothermal stability

3.3. Long-term isothermal stability

The long-term isothermal stability of the ternary eutectic chloride salt was studied by isothermally
heating for different time at various temperatures. The weight loss of the sample after certain thermal
treatment was shown in fig. 4. The total weight loss at 500, 550, 600 and 650 were 1.94, 2.10, 4.14 and
4.20% separately after durative heating for 70 h, being less than 5%. However, the weight loss at 700
was 8.02% which was much higher than 5%. The results above demonstrated that the ternary eutectic
chloride salt was stable below 650 and started to degrade at 700 which had a good agreement with
the trend in Fig.2. Figs. 5-7 showed the DSC curves of the ternary eutectic chloride salt at 500, 600 and
700 for different heating time, and Fig. 8 represented the curves for 70 h heating at different
temperatures. It can be seen from the figures that the curves below 650 were almost the same, meaning
that the melting point and fusion enthalpy was hardly changed. Whereas there were two endothermic
peaks at 437 and 469 appearing in the DSC curve at 700 for 70 h heating, indicating that the ternary
eutectic chloride salt was unstable at 700 . The detailed data about the melting point and fusion
enthalpy of the original salt and the ternary eutectic salt after thermal treatment at 500, 650 and 700
was presented in Table 1. Considering all the analysis results of the thermal stability experiments
synthetically, 650 was taken as the upper limit temperature of the ternary eutectic chloride salt.

Fig. 5 DSC curves of the ternary eutectic chloride salt at 500 Fig. 6 DSC curves of the ternary eutectic chloride salt at 600
 Lichan Du et al. / Energy Procedia 105 (2017) 4185 4191 4189

Fig. 7 DSC curves of the ternary eutectic chloride salt at 700 Fig. 8 DSC curves of the ternary eutectic chloride salt for 70 h
heating

Table 1. Melting points and latent heat capacities of the ternary eutectic chloride salt before and after long-term isothermal stability
experiments

Original 500 650 700

Temperature
Salt 30 h 50 h 70 h 30 h 50 h 70 h 30 h 50 h 70 h
Onset 420.83 421.69 421.01 422.89 422.50 422.98 423.32 430.11 430.91
Temperature ()
Peak Temperature 430.10 429.20 428.86 429.91 531.74 432.50 432.50 437.84 439.89
()
Fusion Enthalpy 201.50 194.50 206.90 203.10 200.80 195.70 198.60 152.30 156.30
(J/g)

Fig. 9 XRD patterns of the ternary eutectic chloride salt Fig. 10 XRD patterns of the ternary eutectic chloride salt
for 70 h heating at 700

3.4. X-ray diffraction studies

In order to analyze the mechanism of thermal instability of the ternary eutectic chloride salt, XRD
technique was utilized to study the phases before and after long-term isothermal stability experiments. Fig.
9 and 10 showed the XRD patterns of the eutectic mixture before and after certain thermal treatments,
three major phases were all observed in angles corresponding to the pure compound of each component in
4190 Lichan Du et al. / Energy Procedia 105 (2017) 4185 4191

the ternary system. However, the intensity of magnesium chloride peak decreased and the magnesium
oxide peak appeared at 700 . Therefore, we concluded that a little moisture was picked up during the
process of sample loading, and the thermal decomposition reaction happened to the generated magnesium
chloride hexahydrate at high temperature[9].

4. Conclusions

The melting temperature and fusion enthalpy of the ternary eutectic chloride salt measured
experimentally were 420.83 and 201.5 J/g, respectively. The thermal stability of the ternary system
was determined experimentally. In the short-term cycling thermal stability experiment, the eutectic salt
showed almost no weight loss after first two thermal cycles, reflecting excellent short-term cycling
thermal stability. The total weight loss at 500, 550, 600 and 650 were 1.94, 2.10, 4.14 and 4.20%
separately after durative heating for 70 h in long-term isothermal stability study, being less than 5%.
Moreover, the melting point and fusion enthalpy of eutectic mixture had almost no change below 650
and started to degrade at 700 . Based on these results, the upper limit temperature of the ternary
eutectic chloride salt was 650 . From the X-ray diffraction analysis, the mechanism of thermal
instability turned out to be the thermal decomposition mechanism of MgCl26H2O at 700 .

Acknowledgements

This work was supported by the funding of Nature Science Foundation of China (51436009), Nature
Science Foundation of China (U1507113), Science and Technology Planning Project of Guang Dong
Province (2015A010106006), and Science and Technology Program of Guang Zhou (201510010248).

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