Solar Energy Materials and Solar Cells 190 (2019) 12–19

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Solar Energy Materials and Solar Cells

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

Experimental study of thermophysical properties and thermal stability of T

quaternary nitrate molten salts for thermal energy storage
⁎
Lu-lu Zoua,b, Xia Chena,b, , Yu-ting Wua,b, Xin Wangc, Chong-fang Maa,b
a
Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education, College of Environmental and Energy Engineering, Beijing University of
Technology, Beijing 100124, China
b
Key Laboratory of Heat Transfer and Energy Conversion, Beijing Education Commission, College of Environmental and Energy Engineering, Beijing University of
Technology, Beijing 100124, China
c
College of Mechanical Engineering and Applied Electronics Technology, Beijing University of Technology, Beijing 100124, China

A R T I C LE I N FO A B S T R A C T

Keywords: Renewable energy has been rapidly developing because of the increasing severity of pollution and energy crises.
Molten salt In particular, solar thermal power generation technology has been attracting considerable attention globally due
Thermophysical properties to its large scale, low unit cost, and environment-friendliness. Thus, it has been quickly progressing. The in-
Thermal stability termittence and instability of solar energy can be solved by combination of solar thermal power with heat
Concentrating solar power
storage technology. Mixed molten salts stand out as heat transfer and storage materials due to their wide
temperature range, low vapor pressure, high heat capacity, low viscosity, and economical environmental pro-
tection. In the present study, a new kind of quaternary nitrate molten salt was presented. The salt was Hitec salt
with Ca(NO3)2 additive and has a low melting point, high decomposition point, and low cost. The thermo-
physical properties of the proposed salt, such as melting point, decomposition point, crystallization point,
specific heat, density, thermal conductivity, and thermal stability, were measured. Results showed that the
melting, crystallization, and decomposition points of the Hitec salt with Ca(NO3)2 additive were 83.1 °C,
163.1 °C, and 628.5 °C, respectively. The proper working temperature range of the new salt was 200–565 °C,
which was wider than those of Hitec salt (200–450 °C) and solar salt (290–565 °C). The average specific heat and
thermal conductivity of the Hitec salt with Ca(NO3)2 additive were approximately 1.52 J/(g K) and 0.655 W/
(m K), respectively, which showed better heat storage and heat transfer performance than did Hitec salt (1.40 J/
(g K) specific heat, 0.350 W/(m K) thermal conductivity) and solar salt (1.50 J/(g K) specific heat, 0.520 W/(m K)
thermal conductivity). An experimental study was conducted on the stability of mixed molten salts at 565 °C for
1200 h and 120 times for quenching/heating at 200–500 °C, and the Hitec salt with Ca(NO3)2 additive exhibited
good thermal stability.

1. Introduction
Energy is the material basis for human survival and social devel-
opment. With the improvement of material and spiritual life, people are
becoming continuously aware of the serious consequences of the large-
scale use of fossil fuels, that is, accelerating resource depletion and
global environment deterioration. Renewable energy is being devel-
oped due to severe pollution and energy crises. The development and
utilization of new and renewable energy resources are important for
sustainable development and the protection of the Earth's ecological
environment, on which humanity depends.
Solar thermal power generation technology has attracted significant
global attention due to its large scale, low unit cost, and environmental
friendliness; thus, it has been developing rapidly [1]. The intermittence
and instability of solar energy can be solved by combination of solar
thermal power with thermal energy storage (TES) technology [2]. TES
is an important means of addressing the power output volatility and
other issues of concentrating solar power (CSP) and serves as a key part
of solar thermal power systems [3]. TES accumulates energy when
production exceeds demand and supplies this energy during peak per-
iods. Compared with mechanical or chemical storage technologies, TES
generally has several advantages, such as lower capital cost [4–8] and
high operating efficiency [9]. The selection of good performance and
low-cost heat transfer and heat storage media can reduce the cost of an

⁎
Corresponding author at: Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education, College of Environmental and Energy
Engineering, Beijing University of Technology, Beijing 100124, China.
E-mail address: xiachen@bjut.edu.cn (X. Chen).

https://doi.org/10.1016/j.solmat.2018.10.013
Received 28 June 2018; Received in revised form 12 October 2018; Accepted 15 October 2018
Available online 26 October 2018
0927-0248/ © 2018 Elsevier B.V. All rights reserved.
L.-l. Zou et al. Solar Energy Materials and Solar Cells 190 (2019) 12–19

entire CSP and improve heat storage efficiency, which is a key technical Table 1
problem that needs an urgent solution. Experimental instruments.
Water, conduction oil, air, molten salts, and concrete are commonly Name Parameters
used thermal storage materials. However, the steam pressure of water is
high, the upper-limit temperature of conduction oil is low, metals are Electronic balance Type: ML204
Maximum weighing range: 220 g
unsafe, the thermal storage property of air is unsatisfactory, and the
Readability: 0.0001 g
cost of concrete is high. Therefore, these materials are unsuitable for Weighing technology: MonoBloc
thermal storage. Molten salts are widely adopted as heat transfer and Linear error: 0.2 mg
storage materials in commercial CSP applications because they have Muffle furnace Type: SX-G16103
better thermal properties than do other candidates. Molten salt has high Rated power: 8 kW
Rated voltage: 380 V
energy density per specific volume, high thermal inertia, low corrosion
Rated temperature: 1000 °C
rates with common piping materials, and reasonable cost; this material Synchronous thermal analyzer Type: STA-449F3
also increases the Rankine cycle efficiency of power block steam tur- Temperature: − 150–2000 °C
bines and improves the global efficiency of plants [10–12]. Heating/cooling rate: 0.001–50 K/min
Weighing capacity: 35,000 mg
Solar salt (60 wt% sodium nitrate (NaNO3) and 40 wt% potassium
Weighing resolution: 0.1 μg
nitrate (KNO3)), Hitec salt (7 wt% NaNO3 + 53 wt% KNO3 + 40 wt% Differential scanning calorimetry (DSC)
sodium nitrite (NaNO2)), and Hitec XL® salt (48 wt% calcium nitrate resolution: < 1 μW
(Ca(NO3)2) + 45 wt% KNO3 + 7 wt% NaNO3) are extensively used Field emission scanning electron Type: SU-8020
molten salts [12–14]. Their crystallization points are 220 °C, 142 °C, microscopy Two electronic resolutions: 1.0 and 1.3 nm
Acceleration voltage: 0.1–30 kV
and 120 °C, respectively [14,15]. The universal disadvantages of these
Observation rate: 20–8000,000 (Negative
salts are their relatively high crystallization point and low decomposi- output)
tion point. Additional hardware must be installed, such as heat tracing, 60–2000,000 (Monitor output)
insulation, and emergency water dilution systems [11], to avoid the risk Laser thermal conductivity Type: LFA 457
of freezing due to sudden temperature drops. Molten salt with low analyzer Temperature: 125–500 °C
Heating/cooling rate: 0.01–50 K/min
melting point and low cost should therefore be developed. Laser energy: 18.5 J/pulse
In the present study, a new kind of quaternary nitrate molten salt Thermal diffusivity range:
with low melting point, high decomposition point, and low cost was 0.01–1000 mm2/s
presented. Its thermophysical properties, namely, melting point, de- Thermal conductivity range: 0.1–2000 W/
mK
composition point, crystallization point, specific heat, density, thermal
Thermo-gravimetry analyzer Type: STA 409 PC
conductivity, long-term thermal stability, and large-temperature-dif- Temperature range: RT–2000 °C
ference thermal stability, were measured. The feasibility of the new Heating/cooling rate: 0.001–50 K/min
molten salt as a heat transfer and storage medium for CSP was also Weighing capacity: 35,000 mg
comprehensively analyzed. Weighing resolution: 0.1 μg
DSC resolution: < 1 μW
Melt physical property tester Type: RTW-10
2. Method Maximum temperature: 1500 °C
Temperature measurement accuracy:
2.1. Quaternary nitrate molten salt preparation ± 0.5 °C
Maximum heating power: 10 kW

A new kind of quaternary nitrate molten salt, Hitec salt with Ca

(NO3)2 additive, was presented. Its constituents were 16.67 wt% Ca
(NO3)2·4H2O + 44.17 wt% KNO3 + 5.83 wt% NaNO3 + 33.33 wt%
NaNO2. The concrete steps for the two methods are discussed in the
subsections below.
① The four well-weighed components are thoroughly mixed, ground,
and placed in a drying oven for constant-temperature drying.
② The mixed salt is rapidly heated to 500 °C after pre-melting to
300 °C at 10 K/min in a muffle furnace for 24 h to remove crystal
water and completely melt and blend the mixture.
③ The products are naturally cooled until the salt mixture solidifies
to a white mass, which is then ultrafine-pulverized into powder and
kept in a sealed desiccator with desiccants in preparation for sub-
sequent experiments.
prevent sample loss. The melting point, freezing point, and latent heat
of melting were obtained through analysis of the DSC curves.
2.3.2. Decomposition point
For determining the decomposition point, the mixture was heated
from 30 °C to 800 °C at 10 K/min heating rate under N2 purging at
50 mL/min by using STA. The measuring principle of STA used for
decomposition point was thermogravimetric analysis. This technique
determines the relationship between the mass and the temperature of a
substance with use of a thermobalance under a controlled temperature.
Fig. 1 illustrates the basic structure of a thermobalance, which is an

2.2. Experimental reagents and instruments

See Table 1.

2.3. Experimental method

2.3.1. Melting point, freezing point, and latent heat of melting

The samples were tested with a synchronous thermal analyzer (STA)
for obtaining the corresponding DSC and thermogravimetric (TG)
curves. The mixture was heated from 40 °C to 500 °C at 15 K/ min
heating rate and 500–100 °C at 8 K/min cooling rate under N2 purging
at 20 mL/min. Alumina crucibles with perforated lids were used to Fig. 1. Basic structure of thermobalance.

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L.-l. Zou et al. Solar Energy Materials and Solar Cells 190 (2019) 12–19

important part of automatic and continuous weighing and recording. A

thermobalance requires inert gas protection and operates in an inert gas
environment. Thus, N2 was used to evaluate the decomposition point of
the molten salts. Graphite crucibles with lids were used for adaptation
to high test temperatures and preventing spillage of the mixture from
the crucible at high temperatures. The decomposition point was de-
termined by analysis of the TG curves, and the degradation of salt was
observed when the mass dropped due to the formation of gaseous
products.

2.3.3. Specific heat

The specific heat was obtained by comparison with a standard
sapphire with a known specific heat using STA. The calculation formula
was as follows:
Hms
Cp, st = Cp, s,
hmst (1)
Fig. 2. DSC curves of Hitec salt with Ca(NO3)2 additive.
where Cp,st is the specific heat of the sample to be tested, J/(g·K); Cp,s is
the specific heat of the standard sample, J/(g·K); mst is the mass of the
sample to be tested, g; ms is the mass of the standard sample, g; H is the salt is 163.1 °C, which is 14.8% higher than that of the Hitec salt
DSC signal difference between the reference material and a reference (142 °C) [14] and solar salt (221 °C) [16].
empty crucible, μV; and h is the DSC signal difference between the
sample to be tested and the reference empty crucible, μV. 3.2. Decomposition point

2.3.4. Density The decomposition temperature was measured by using an extra-

The density of molten salt nanofluids was experimentally in-
vestigated in this study. Archimedes’ principle was applied in de-
termining the density of the molten salt nanofluids. According to
Archimedes’ principle, the buoyancy of an object immersed in a liquid
is equal to the gravity of the liquid of the same volume discharged by
the object. In this study, the change in the volume of a platinum ball in
air and in the molten salt nanofluids was measured, thereby yielding
the density of the molten salt nanofluids.
2.3.5. Thermal diffusivity and thermal conductivity
The thermal diffusivity of the mixture was measured by a laser flash
analyzer (LFA). Thermal conductivity was calculated as follows:
λ = α∙ρ∙Cp,
where λ is the thermal conductivity, ρ is the density, and Cp is the
specific heat.
2.3.6. Thermal stability
Long-term thermal stability testing was conducted under 565 °C
working condition. The mixture was rapidly heated to 565 °C using a
muffle furnace, kept at this temperature for 1200 h, and sampled every
100 h.
Cycle thermal stability testing was conducted under a hea-
ting–cooling cycle (200–500 °C) working condition. The mixture was
rapidly heated to 500 °C using a muffle furnace, cooled to 200 °C, ra-
pidly heated to 500 °C again, and was cycled back and forth for 120
cycles. Sampling was performed every 20 cycles.
The prepared samples under the above conditions were dried and
kept in a sealed desiccator for subsequent experiments. The long-term
and cyclic thermal stabilities were analyzed by measurement of the
repeatability of the thermophysical properties.
polation starting point method on the basis of international standard
ISO 11358, which was automatically obtained by use of a synchronous
thermal analyzer (STA-449F3). The decomposition point could be ob-
tained from the TG curve, as shown in Fig. 3, which directly determined
the maximum working temperature of the Hitec salt with Ca(NO3)2
additive. An analysis of the TG curve in Fig. 2 determines the decom-
position point of the mixture to be approximately 628.5 °C, which is
11.2% higher than that of the Hitec salt (535 °C). The proper working
temperature range of the Hitec salt with Ca(NO3)2 additive is
200–565 °C, which is higher than those of the Hitec salt (200–450 °C)
[14] and solar salt (290–565 °C).
X-ray diffraction (XRD) maps of Hitec salt with Ca(NO3)2 additive
before and after decomposition are shown in Figs. 4 and 5, respectively.
(2)
NaNO3, NaNO3, and NaNO2 are detected. NaNO2 has a strong water
absorption capacity and absorbs moisture from the air during the test.
The structure of NaNO2 with crystal water after water absorption is
unknown and does not correspond to the database. Several peaks in
Fig. 4 are not detected in the corresponding phase, which may be re-
lated to Ca. No change is observed on the peak structures of NaNO3,
NaNO3, and NaNO2 after the decomposition of the Hitec salt with Ca
(NO3)2 additive (Fig. 5). However, the peaks related to Ca disappear,
and the peak of Ca(OH)2 is depicted in Fig. 5. Evident changes are
observed on Ca(NO3)2 before and after the decomposition of the Hitec

3. Results and discussion

3.1. Melting and crystallization point

The heating and cooling DSC curves of the Hitec salt with Ca(NO3)2
additive are shown in Fig. 2. The melting point and latent heat of this
new salt are 83.1 °C and 71.75 J/g, respectively. The melting point of
the Hitec salt with Ca(NO3)2 additive is 35.6% lower than that of the
Hitec salt (129 °C) [14,16,17]. The crystallization point of the proposed Fig. 3. TG curve of Hitec salt with Ca(NO3)2 additive.

14
L.-l. Zou et al.
Fig. 4. XRD map before decomposition of Hitec salt with Ca(NO3)2 additive.
Fig. 5. XRD map after decomposition of Hitec salt with Ca(NO3)2 additive.
salt with Ca(NO3)2 additive.
3.3. Specific heat
Fig. 6 shows the specific heat of the Hitec salt with Ca(NO3)2 ad-
ditive. The average specific heat of the proposed salt is approximately
1.52 J/(g K), which is similar to that of solar salt (1.50 J/(g K)) and
8.6% higher than that of the Hitec salt (1.40 J/(g K)) [14,16]. Eq. (3)
expresses the linear equation at the temperature range of 220–450 °C
for the Hitec salt with Ca(NO3)2 additive.
Fig. 6. Specific heat of Hitec salt with Ca(NO3)2 additive.
15
Solar Energy Materials and Solar Cells 190 (2019) 12–19
Fig. 7. Density of Hitec salt with Ca(NO3)2 additive.
Cp =1.77878–7.55155×10-4t 220°C≤t ≤450°C (3)
3.4. Density
As shown in Fig. 7, the density of the Hitec salt with Ca(NO3)2
additive has a linear relationship with temperature, gradually de-
creasing from 2.061 g/cm3 to 1.763 g/cm3 as the temperature increases
from 200 °C to 500 °C. The density of the Hitec salt with Ca(NO3)2
additive is 1.763 g/cm3 at 500 °C, which is slightly higher than that of
solar salt (1.752 g/cm3) and Hitec salt (1.723 g/cm3) at 500 °C. Eq. (4)
provides the linear equation at the temperature range of 220–450 °C for
the Hitec salt with Ca(NO3)2 additive.
ρ=2022744-9.43393×10-4t 220°C ≤t ≤ 450°C (4)
3.5. Thermal diffusivity and conductivity
The thermal diffusivity of the Hitec salt with Ca(NO3)2 additive (as
measured by LFA) and its fitted values are shown in Fig. 8. Eq. (5)
expresses the linear equation for the liquid state of the mixture at the
temperature range of 200 °C–500 °C.
α=-0.02076+7.37143×10-4t 250°C≤t≤500°C (5)
The thermal conductivity of the Hitec salt with Ca(NO3)2 additive,
which was calculated using Eq. (2), and its fitted values are shown in
Fig. 9. Eq. (6) provides the linear equation for the liquid state of the
mixture at the temperature range of 200–500 °C.
Fig. 8. Thermal diffusivity of Hitec salt with Ca(NO3)2 additive.
L.-l. Zou et al.
Fig. 9. Thermal conductivity of Hitec salt with Ca(NO3)2 additive.
λ=3.83349-0.02857+8.07852×10-5t 2-7.24056×10-8t 3,250°C≤t ≤500°C
The thermal diffusivity and thermal conductivity of the Hitec salt
with Ca(NO3)2 additive fluctuate only slightly over the test temperature
range of 200 °C–500 °C, which can be approximated as constant in low-
accuracy computation.
The average thermal conductivity of the Hitec salt with Ca(NO3)2
additive is 0.655 W/(m K), which is 26.0% and 87.1% more than those
of the solar salt (0.520 W/(m K)) and the Hitec salt (0.350 W/(m K))
[14,16].
3.6. Long-term thermal stability
Good high-temperature thermal stability is required for large-scale
practical applications of molten salt as heat transfer and storage ma-
terial. To verify the long-term thermal stability of the Hitec salt with Ca
(NO3)2 additive at high temperatures, the mixture was subjected to
565 °C working condition for 1200 h. A few samples were obtained, and
their thermophysical properties were monitored at set intervals. The
results show that the Hitec salt with Ca(NO3)2 additive has good long-
term thermal stability at high temperatures. The melting points, TG
curves, and decomposition points of the samples are shown in
Figs. 10–12. The melting point of the Hitec salt with Ca(NO3)2 additive
fluctuates from 93.0 °C to 95.9 °C in 1200 h; these figures are higher by
11.9% to 15.4%, respectively, compared with the initial melting point
of 83.1 °C. The decomposition point of the Hitec salt with Ca(NO3)2
additive fluctuates from 604.7 °C to 620.4 °C in 1200 h; these points are
lower by 1.3% to 3.8%, respectively, compared with the initial de-
composition point of 628.5 °C.
Fig. 10. Melting points of Hitec salt with Ca(NO3)2 additive at 565 °C.
Solar Energy Materials and Solar Cells 190 (2019) 12–19
Fig. 11. TG curves of Hitec salt with Ca(NO3)2 additive at 565 °C.
(6)
Fig. 12. Decomposition point of Hitec salt with Ca(NO3)2 additive at 565 °C.
Several fluctuations are observed in the melting and decomposition
temperatures, as shown in Figs. 10 and 12, and these fluctuations are
caused by the following conditions. A gap separating the sample and
the bottom of the instrument affected the measurement results. The
instrument has high accuracy when measuring the parameters of pure
substances. For instance, the accuracy of the instrument is less than 1%
in measuring the melting point of bismuth and aluminum. By contrast,
the Hitec salt with Ca(NO3)2 additive is a mixture. Although the molten
salt is mixed consistently, a slight difference affected the result because
the instrument is sensitive. At present, no method has been identified
for solving these problems, and no standards are applied for errors in
measuring the physical parameters of molten salt. Errors can be mini-
mized by increasing the number of experiments. Data are measured
three times, and the obtained results in the experiment are averaged to
minimize errors.
The specific heat of the sample in the liquid state at the temperature
range of 250–500 °C is shown in Fig. 13. The average specific heat of
the sample fluctuates in the range of 1.69–1.80 J/g.
The thermal conductivity of the sample in the liquid state at the
temperature range of 250–500 °C was measured by LFA and is plotted in
Fig. 14. The average thermal conductivity of the sample fluctuates in
the range of 0. 51–0.88 W/(m K).
The mass of molten salt under high and constant temperature is the
intuitive embodiment of its thermal stability. A mass loss experiment
was conducted for the Hitec salt with Ca(NO3)2 additive under a con-
stant temperature condition of 500 °C. A certain amount of the initial
melting sample weighing 63.1508 g was collected and then placed in a
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L.-l. Zou et al. Solar Energy Materials and Solar Cells 190 (2019) 12–19

Fig. 13. Specific heat of Hitec salt with Ca(NO3)2 additive at 565 °C.
Fig. 16. Melting point of Hitec salt with Ca(NO3)2 additive in heating–cooling
cycle experiment.

of the sample is 63.1329 g, which is 0.03% less than the initial mass.
The small fluctuations in quality is because of the strong water ab-
sorption capacity of Ca(NO3)2 and the high evaporation temperature of
water. The absorption and evaporation of water caused the small
fluctuations in the quality of the sample.

3.7. Heating–cooling cycle thermal stability

Heat transfer and storage materials are repeatedly heated and

cooled in practical applications. The constant thermal properties in
large-temperature-difference environments are favorable for heat
transfer and storage materials. To verify the heating–cooling cycle
thermal stability of the Hitec salt with Ca(NO3)2 additive, experimental
quenching/heating was conducted 120 times at 200–500 °C. The mix-
ture was subjected to large-temperature-difference cycles (200–500 °C)
Fig. 14. Thermal conductivity of Hitec salt with Ca(NO3)2 additive at 565 °C.
120 times. The thermophysical properties of the mixture during the
experiment were monitored, and the Hitec salt with Ca(NO3)2 additive
exhibited good thermal stability in the large-temperature-difference
cycles. The results are as follows.
The melting point, TG curves, and decomposition point of the
sample in the large-temperature-difference cycle experiment are shown
in Figs. 16–18. The melting and decomposition points of the sample
fluctuate near 96 °C and 616 °C, respectively. The repeatability of the
TG curves of the samples is good. The melting point of the Hitec salt
with Ca(NO3)2 additive is 95.7 °C after 120 runs of the large-tempera-
ture-difference cycle experiment, and this melting point is 13.9% higher

Fig. 15. Mass of Hitec salt with Ca(NO3)2 additive under 500 °C.

muffle furnace. The sample was rapidly heated to 500 °C, and the
constant temperature of 500 °C was set. The sample was removed from
the furnace every 24 h, cooled, and weighed. The mass loss curve of the
Hitec salt with Ca(NO3)2 additive is shown in Fig. 15.
The amount of the initial melting sample is 63.1508 g before the
mass loss experiment. The quality of the sample during 600 h in the
experiment tends to be stable. The lowest mass of the sample is Fig. 17. TG curves of Hitec salt with Ca(NO3)2 additive in heating–cooling
62.8390 g, which is 0.49% less than the initial mass. The highest mass cycle experiment.

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L.-l. Zou et al. Solar Energy Materials and Solar Cells 190 (2019) 12–19

Fig. 20. Thermal conductivity of Hitec salt with Ca(NO3)2 additive in hea-
ting–cooling cycle experiment.
Fig. 18. Decomposition point of Hitec salt with Ca(NO3)2 additive in hea-
ting–cooling cycle experiment.
t
∫t12 Cp dt
Cp = ,
than the initial melting point. The decomposition point is 617.9 °C after t2 − t1 (8)
120 runs of the large-temperature-difference cycle experiment, and this t
result remains unchanged and reflects a decrease of merely 1.6% ∫t12 Cp dt
Qsensible = ,
compared with the initial decomposition point. 3600 (9)
The specific heat and thermal conductivity of the sample in the li- where t1 is the minimum operating temperature (°C) and t2 is the
quid state at the temperature range of 250–500 °C are shown in Figs. 19 maximum operating temperature (°C).
and 20. The average specific heat of the samples fluctuates in the range Sensible heat storage cost can be calculated on the basis of Eq. (10).
of 1.53–1.69 J/g, and the average thermal conductivity of the sample
fluctuates in the range of 0.56–0.79 W/(m K). PC
TC =
Qsensible (10)
3.8. Sensible heat storage cost The unit prices of the raw materials were provided by Xiaxian Yunli
Chemical Co., Ltd. in September 2018. The sensible heat storage costs
The sensible heat storage technology of molten salt has a simple of the solar salt (t2 = 565 °C, t1 = 290 °C), Hitec salt (t2 = 450 °C, t1 =
principle, mature technology, flexible heat storage method, low cost, 200 °C), and Hitec salt with Ca(NO3)2 additive (t2 = 565 °C, t1 =
and suitability for large-scale commercial applications; this technology 200 °C) were calculated to be 6.4, 5.0, and 3.7 $/kW·h, respectively.
has been applied in solar thermal power generation [18]. Therefore, the The sensible heat storage cost of the Hitec salt with Ca(NO3)2 additive
sensible heat storage cost of mixed nitrate should be calculated for heat was the lowest, being 42.2% and 26.0% less than those of the solar salt
transfer and storage materials. and the Hitec salt.
The unit price can be calculated on the basis of Eq. (7).
4. Conclusions
PC = ∑ Mi×PCi, (7)
where Mi is the mass fraction of each component and PCi is the unit Hitec salt with Ca(NO3)2 additive, a new quaternary nitrate molten
price of each component ($/kg). salt with low melting point, high decomposition point, and low cost,
Integral average specific heat and sensible heat storage value can be was presented in this study. The thermophysical properties of this salt,
calculated by Eqs. (8) and (9). namely, melting point, decomposition point, crystallization point,
specific heat, density, thermal conductivity, and thermal stability, were
measured. An experimental study was also conducted on the stability of
the mixed molten salt at 565 °C for 1200 h and 120 times for
quenching/heating at 200–500 °C. The conclusions were as follows.

① The melting, crystallization, and decomposition points of the

Hitec salt with Ca(NO3)2 additive were 83.1 °C, 163.1 °C, and
628.5 °C, respectively. The proper working temperature range of the
proposed salt was 200–565 °C, which was higher than those of the
Hitec salt (200–450 °C) and solar salt (290–565 °C).
② The average specific heat of the Hitec salt with Ca(NO3)2 additive
was approximately 1.52 J/(g K), which was similar to that of solar
salt (1.50 J/( g K)) and 8.6% higher than that of Hitec salt (1.40 J/(
g K)). The average thermal conductivity of the Hitec salt with Ca
(NO3)2 additive was 0.655 W/(m K), which was 26.0% and 87.1%
more than those of solar salt (0.520 W/(m K)) and Hitec salt
(0.350 W/(m K)).
③ The thermophysical properties of the Hitec salt with Ca(NO3)2
Fig. 19. Specific heat of Hitec salt with Ca(NO3)2 additive in heating–cooling
additive were relatively stable after exposure to constant high
cycle experiment.

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L.-l. Zou et al.
temperature (565 °C) for 1200 h and after undergoing 120 large-
temperature-difference cycles (200–500 °C), which showed good
long-term and heating–cooling cycle thermal stabilities.
④ The sensible heat storage cost of the Hitec salt with Ca(NO3)2
additive was 3.7 $/kW h, which was 42.2% and 26.0% less than
those of the solar and Hitec salts, respectively.
Acknowledgements
This work was sponsored by the Research Program of Beijing
Natural Science Foundation No.3151001, the National Key Basic
Research Program of China (973 Program) No. 2015CB251303, and
National Natural Science Foundation of China No.51706005.
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