The Thermal Stability of Molten

Lithium–Sodium–Potassium
Rene I. Olivares1
Research Scientist
CSIRO Energy Centre,
Mayfield West, Newcastle,
NSW 2304, Australia
e-mail: Rene.Olivares@csiro.au
Chunlin Chen
Steven Wright
CSIRO Process Science and Engineering,
Clayton, Melbourne, Vic 3169, Australia
Carbonate and the Influence of
Additives on the Melting Point
The thermal stability of a molten LiNaK carbonate salt, potentially suitable for thermal
energy storage, was studied up to a temperature of 1000  C. The salt investigated was the
eutectic Li2CO3–Na2CO3–K2CO3 in the proportions 32.1–33.4–34.5 wt. % and the study
was done by simultaneous differential scanning calorimetry (DSC)/thermogravimetric–mass
spectrometric (TG–MS) analysis in gas atmospheres of argon, air, and CO2. It was found
that (i) under a blanket gas atmosphere of CO2 the LiNaK carbonate salt is stable up to at
least 1000  C. (ii) In an inert atmosphere of argon, the salt evolves gaseous CO2 soon after
melting and begins to decompose at between 710  C and 715  C with acceleration in the
CO2 evolution rate from the melt. An increase in the rate of weight loss is also observed af-
ter 707  C. (iii) Under a blanket atmosphere of air, the gaseous CO2 evolution from the salt
is observed to commence at 530  C, the onset of decomposition detected by DSC analysis at
601  C and the rapid rate of weight loss determined by TG analysis at 673  C. The melting
point of the LiNaK carbonate studied was between 400  C and 405  C. Thermodynamic
modeling with Multi-Phase-Equilibrium (MPE) software developed in CSIRO Process
Science and Engineering indicated that additives such as NaNO3, KCl, and NaOH lower
the melting point of the LiNaK carbonate eutectic, and this was experimentally verified.
[DOI: 10.1115/1.4006895]

Keywords: molten salts, thermal energy storage, heat transfer fluid, thermal stability,
carbonates

Introduction called MPE using the CALPHAD method [7,8] for the calculation
of multiphase equilibrium in high temperature systems. A broad
A desirable medium for thermal energy storage (TES) and
range of solution models for application to slag, alloys, matte, and
energy transfer in concentrating solar power towers (CSP), is a
solid solution systems have been included in MPE [9]. This soft-
molten salt that has a low melting point and can sustain high tem-
ware has been successfully applied in the design and/or optimiza-
peratures before thermally decomposing. Salts that have been
tion of various base metal production processes. One of the recent
identified and used in experimental or commercial solar thermal
developments has been to extend MPE model capability to cover
plants as a TES medium or a heat transfer fluid (HTF) involve
the molten salt phases such as nitrate, carbonate, sulfate, chloride,
mainly nitrate-based systems that can only be used at tempera-
etc., and to use this software for designing a molten salt system
tures below 600  C [1–4]. Operating these salts at higher than
with low melting point and high thermal stability, which could be
600  C may be possible by rigorous control of the atmosphere
used as a TES medium or an HTF in solar thermal plants. In the
under which they are used [5]. However, a salt that is stable at
present work, MPE was used for modeling the thermal stability of
higher temperatures than 700  C is needed to make effective use
molten LiNaK carbonate and the effect of some additives on its
of, for example, high temperature closed-loop Brayton power
melting point.
cycles or Rankine cycles using supercritical steam to potentially
The model required the inclusion of interaction parameters
increase the heat-to-electricity conversion efficiency.
between nitrates, chlorides, hydroxides, and carbonates and these
The possibility of replacing molten nitrate salts with mixed
were obtained and optimized by reproducing published phase
carbonates has been identified [6] where the operation at tempera-
diagrams [10]. With the optimized database, the MPE was used to
tures of between 700  C and 850  C would be possible. In
calculate the chemical equilibrium under various conditions and
Ref. [6], at least 15 lithium–sodium–potassium carbonates blends
to predict the effect of additives on the melting point.
with melting points between 400  C and 410  C and thermal sta-
Thermodynamic solution models can better predict binary sys-
bility between 800  C and 850  C are reported. Although thermal
tems than higher order systems. This because most of the solution
stability is influenced by the atmosphere under which it is eval-
models are binary parameter based models, where the parameters
uated, Ref. [6] does not specify the conditions under which
are obtained by fitting the available phase diagrams and thermo-
thermal stability was measured in the experiments.
dynamic data. With the binary parameters, it is possible to esti-
mate the thermodynamic properties and phase diagrams of ternary
Thermodynamic Modeling. Since the early 1990s, CSIRO and higher order systems. The available data of higher order sys-
has been developing a thermodynamic modeling software package tems, when they exist, can be used to refine the representation of
higher order thermodynamic properties.
1
Corresponding author. The objective of the modeling component in the present work
Contributed by the Solar Energy Division of ASME for publication in the
JOURNAL OF SOLAR ENERGY ENGINEERING. Manuscript received November 23, 2011;
is on estimating the effect of hydroxide on the melting point
final manuscript received May 6, 2012; published online June 26, 2012. Assoc. Edi- of eutectic LiNaK carbonate, therefore of particular importance
tor: Manuel Romero Alvarez. is to have a good representation of the carbonate–hydroxide

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 Fig. 1 Hydroxide and carbonate interactions optimized by fitting published phase diagrams [10]
interactions. There are some higher order phase diagram data on
carbonate systems without hydroxide; however, the detailed
development of the model/database of carbonate system was
beyond the scope of the present work which is mainly focused on
the experimental study.
Figure 1 demonstrates the capability of the model with opti-
mized parameters to reproduce published phase diagrams, while
Fig. 2 shows model predictions of the effect of adding hydroxide
to an LiNaK carbonate mix. This shows, for example, that the
melting point of LiNaK carbonate can be reduced from 396  C to
350  C with the addition of approximately 16 wt. % of potassium
hydroxide.
Experiments were carried out where each of 10 wt. % of
NaNO3, KCl, and NaOH was added in turn to the LiNaK carbon-
ate eutectic, with the aim of lowering the melting point as
predicted by thermodynamic modeling. The overall effect of the
additions on the thermal stability was also investigated. The
experiments were carried out using a eutectic 32.1 wt. % Li2CO3,
33.4 wt. % Na2CO3, and 34.5 wt. % K2CO3 prepared from high
grade purity chemicals. The high temperature stability was eval-
uated in three different atmospheres (argon, air, and CO2) by mon-
itoring the following:
Fig. 2 Model prediction of the effect of hydroxide on the
melting point of LiNaK carbonate
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• The temperature at which the commencement of rapid weight
loss is observed by TG analysis.
• The temperature after melting at which an endothermic peak
of decomposition is detected by DSC.
• The temperature at which the commencement of the evolu-
tion of CO2 is detected by means of MS analysis.
A combination of these three criteria is used in ascertaining the
limits under which molten LiNaK carbonate could work as either
a TES medium of an HTF.
Experimental Procedures
A mixture of pure reagent grade Li2CO3–Na2CO3–K2CO3 in
the weight proportions 32.1–33.4–34.5, predried at 105  C, was
melted in a muffle furnace and allowed to equilibrate in air at
500  C before casting into a stainless steel mould to quench and
solidify. A small subsample from the solidified salt was used for
simultaneous DSC/TG–MS experimentation. The experiments
were carried out from room temperature up to 1000  C at a
heating-rate of 10  C/min in atmospheres of argon, air, and CO2.
About 30–35 mg subsample was loaded into a 100 ml Al2O3
crucible in a SETARAM DSC/TG-SETSYS Evolution analyzer
coupled with a Pfeiffer Quadstar-422 mass spectrometer. After
the atmosphere around the sample had been first purged and
refilled with the desired gas, the gas flow was maintained at a rate
of 20 ml/min for the duration of the experiment.
At the end of each experiment, the Al2O3 crucibles containing
the sample and reference were found to have stuck to the base of
the DSC platinum sensor. This was due to a build-up of condensed
salt vapors and the crucibles had to be removed by soaking the
platinum sensor for several hours in hot water. Once detached, the
sensor and DSC assembly had to be thoroughly cleaned and
heated under a flow of air to 1500  C to remove any residue. The
DSC/TG baseline was subsequently verified before a new experi-
ment was done.
Experimental Error and Uncertainty. Calibration of the
DSC was done as per standard method for this type of analysis
using the certified reference materials (CRM); In, Pb, Al, and Au
to cover the temperature range 150–1050  C. The calibration was
done in an inert atmosphere of argon gas flowing at 20 ml/min.
The properties of the certified reference materials are listed in
Table 1 where the DSC measurements after calibration are
also given. For the temperature range of interest in the present
Transactions of the ASME
 Table 1 Standard CRM—DSC calibration

Certified Measured Errora Certified energy Measured energy

CRM melting T ( C) melting T ( C) T ( C) of melting (J=g) of melting (J=g) Errora energy (J=g)

In 156.59 151.18 5.41 28.51 28.45 0.21

158.47 1.88 28.18 1.17
Pb 327.47 326.52 0.95 23.00 22.98 0.73
326.74 0.73 23.07 0.07
Al 660.33 658.60 1.73 401.30 395.44 1.73
661.62 1.29 403.62 1.29
Au 1064.18 1067.36 3.18 64.50 64.59 0.09
a
Error is the difference between the measured value and that of the CRM.

experiments, (300  C to 750  C), the errors in the temperature
measurements are considered low at 62  C.
Results
The experimental results for testing of the molten LiNaK car-
bonate salt under the different blanket atmospheres of argon, air,
and CO2 are shown in Figs. 3–5, respectively. The figures show a
combination of the MS–ion current intensity for the evolution of
CO2 lines 44 amu and 12 amu, the rate of weight loss dTG trace
in mg/min, the thermogravimetric weight loss TG trace in mg,
and the differential scanning calorimetry DSC trace.
In an inert atmosphere of argon, Fig. 3 shows that CO2 gas is
evolved from the salt at 405  C soon after melting at 401  C and
the onset of decomposition is detected by a small endothermic
peak of 76 J/g between 715  C and 1000  C. Over the whole tem-
perature range up to 1000  C, a total weight loss of 5.1% is meas-
ured in this experiment. From the melting point at 401  C and up
to 700  C, the rate of salt vaporization (dTG trace) is less than
0.01 mg/min, which then increases rapidly as the temperature
increases in conjunction with salt decomposition taking place as
depicted by the increase in CO2 evolution rate at 711  C.
For the experiment in air, shown in Fig. 4, the evolution of CO2
gas is observed to occur at temperatures higher than 530  C prior
to the onset of decomposition detected by DSC at 601  C with a
large endothermic peak of 360 J/g between 600  C and 900  C.
This larger endothermic peak reflects a faster rate of decomposi-
tion than that observed under an atmosphere of argon gas in
Fig. 3. Over the whole temperature range up to 1000  C, a total
weight loss of 6.7% is measured in this experiment. Between the
melting point at 405  C in this atmosphere and up to about 670  C,
the rate of salt vaporization is slightly higher, about 0.015 mg/
min, than that for the experiment in argon. After 700  C, the va-
porization rate increases rapidly (dTG trace) as the temperature
increases in conjunction with salt decomposition taking place as
indicated by the increase in the rate of CO2 evolution.
With the experiment under a blanket of CO2 gas, shown in
Fig. 5, the thermal stability of the LiNaK carbonate salt is clearly
demonstrated to have improved. Over the temperature range up to
1000  C, a small total weight loss of only 1.4% is measured in
this experiment and it mostly corresponds to the vaporization of
the salt. Between the melting point at 405  C in this atmosphere
and up to 1000  C, the rate of salt vaporization (dTG trace) is
small, at about 0.0075 mg/min at 700  C and increasing to
approximately 0.010 mg/min at 1000  C. The DSC trace only
shows the endothermic peak of melting and it is very stable up to
1000  C. There is probably a small evolution of CO2 from the
salt, but the background ion current intensity in this gas atmos-
phere is too high to allow accurate detection. Figure 5 indicates
that the MS lines (44 amu and 12 amu) for CO2 detection are flat
suggesting that no salt decomposition has occurred over the whole
temperature range.

Fig. 3 DSC=TG-MS analysis for thermal decomposition of LiNaK carbonate salt in argon
atmosphere

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 Fig. 4 DSC=TG-MS analysis for thermal decomposition of LiNaK carbonate salt in air
atmosphere

The results for the experiments with the LiNaK carbonate salt,
collected from Figs. 3 to 5, in the different atmospheres of argon,
air, and CO2, are summarized in Table 2 for ease of comparison.
The published data on melting point of the lithium–sodium–
potassium carbonate eutectic can be found in reported literature
ranging from 394  C to 399  C and this generally determined by
the technique used and the accuracy of the mix preparation. In the
present experiments, a master salt was prepared by premelting the
lithium–sodium–potassium carbonate mix and the melting point
was determined by the conventional method when using DSC
analysis and gave 400  C when the blanket atmosphere was argon
gas and 405  C when the blanket gas atmosphere was CO2. The
gas cover was having an effect on the melting point. For the
comparative studies involving additions aimed at lowering the
melting point, the gas cover atmosphere was argon gas so that the
measurements were consistent.
Additions of NaNO3, KCl, and NaOH. The effect of com-
pounds aimed at lowering the melting point of the LiNaK carbon-
ate eutectic is shown in Fig. 6 for 10 wt. % addition of NaNO3, in
Fig. 7 for 10 wt. % addition of KCl, and in Fig. 8 for 10 wt. %
addition of NaOH. To facilitate the comparisons, these experi-
ments were carried out under a blanket gas atmosphere of argon
rather than CO2 given that it was necessary to also be able to
detect their effect on thermal stability and the need to have high

Fig. 5 DSC=TG-MS analysis for thermal decomposition of LiNaK carbonate salt in

CO2 atmosphere

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 Table 2 Summary data for the effect of atmosphere on thermal decomposition of LiNaK carbonates salt

Vaporization rate
Heat of TG rapid Total wt. % (mg=min) at Suggested
Melting Heat of DSC onset of decomposition CO2 evolution weight loss at suggested useable
Atmosphere T ( C) melting (J=g) decomposition J=g 44–12 amu loss after 1000  C useable temperature temperature

Argon 401 221 715  C 76 405–405  C 707  C 5.1a 0.010 707  C

Air 405 223 601  C 360 530–566  C 673  C 6.7a 0.015 673  C
CO2 405 257 Stable > 1000  C nd nd 788  C 1.4b 0.0075 788  C
a
Weight loss is a combination of salt vaporization and salt decomposition.
b
Weight loss is mainly due to salt evaporation in this atmosphere.

sensitivity to detect CO2 evolution from the melt and not being
affected by the background.
Figure 6 shows that the addition of 10 wt. % NaNO3 lowered
the melting point of the LiNaK carbonate eutectic from 401  C to
388  C. The melting process though becomes incongruent with a
small solid/solid (a/b) type transformation at 128  C and some
amount of liquid forming at 319  C that corresponds to the melt-
ing of the NaNO3 portion added. The melting point of the carbon-
ate is detected by the DSC endothermic event at 388  C. The
evolution of NO (30 amu) commencing at 528  C and the evolu-
tion of NO2 (46 amu) at 646  C both indicate that the decomposi-
tion of NaNO3 is taking place first despite the presence of the
LiNaK carbonate. The decomposition of LiNaK carbonate is
noted later by the evolution of CO2 (44 amu) at 649  C and an
acceleration in the rate of weight loss. Weight loss is observed to
commence at 634  C in this case and the bulk of the decomposi-
tion, as detected by DSC, at 662  C. The total weight loss at the
end of the experiment was 13 wt. %.
Figure 7 shows that the addition of 10 wt. % KCl marginally
lowered the melting point of the LiNaK carbonate eutectic from
401 to 396  C. In this case, an early evolution of CO2 is detected
at 235  C coinciding with a small exothermic event beginning at
301  C prior to melting, although no weight loss is detected. The
further evolution of CO2 observed after 436  C and acceleration in
the rate after 652  C coinciding with a broad endothermic
event starting at 548  C, all indicate that the LiNaK carbonate is
decomposing. Rapid weight loss begins at 744  C in this case and
the total weight loss at the end of the experiment is 9 wt. %.
The addition of 10 wt. % NaOH is shown in Fig. 8. It can be
seen that NaOH has a greater effect in lowering the melting point
of the LiNaK carbonate eutectic from 401  C to 326  C. Although
some evolution of CO2 is first detected at 477  C closely linked to
an endothermic DSC event at 524  C, no weight loss is observed.
Only after 667  C does acceleration in the evolution rate of CO2,
followed by a second sharper endothermic event at 725  C, indi-
cates that the bulk of decomposition is taking place with a rapid
rate of weight loss observed to commence at 780  C. The total
weight loss in this case is 11.6 wt. % at the end of the experiment.
The results collected from Figs. 6 to 8 are further summarized in
Table 3 for ease of comparison.
Discussion
The results presented here show that in the case of the molten
carbonate eutectic, 32.1 wt. % Li2CO3–33.4 wt. % Na2CO3–34.5
wt. % K2CO3, the thermal stability can be significantly influenced
by the gaseous atmosphere blanketing the salt. Although the melt-
ing point of this salt is quite high at between 401  C and 405  C in
these experiments, from the point of view of high temperature sta-
bility a blanket of CO2 is to be preferred for operation at tempera-
tures higher than 700  C and up to 1000  C. A salt vaporization
rate of about 0.0075 mg/min at 788  C and about 0.01 mg/min at

Fig. 6 DSC=TG-MS analysis for the effect of 10 wt. % NaNO3 addition to LiNaK carbonate
salt in argon atmosphere

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 Fig. 7 DSC=TG-MS analysis for the effect of 10 wt. % KCl addition to LiNaK carbonate
salt in argon atmosphere

Fig. 8 DSC=TG-MS analysis for the effect of 10 wt. % NaOH addition to LiNaK carbonate
salt in argon atmosphere

1000  C may need to be tolerated equivalent to a salt loss to the top
space of between 1.08  105 and 1.44  105 kg/day; this is in
fact a very small evaporation rate. Because at temperatures higher
than 788  C under a CO2 atmosphere the vaporization rate is
increased, this temperature may be the practical limit for use of
lithium–sodium–potassium carbonate eutectic as a TES medium. In a
closed system, however, condensation of the vapors in the freeboard of
the storage tank can be expected to return the salt to the liquid phase.
In atmospheres of air and argon the salt was less stable, com-
pared to a CO2 atmosphere, as shown by the gas evolved and the
weight loss curves from the combined DSC/TG–MS analysis. In
air, the practical limit assessed was 670  C compared with a
temperature of 700  C if protected by a blanket atmosphere of
argon. In both cases, the rate of salt vaporization is also higher
than that under a protective atmosphere of CO2. The latter may
again not necessarily be a problem if working in a closed system,
so long as the condensed salt vapors return to the bulk of the mol-
ten salt as they cool-down and do not stick or adhere to the walls
of the containment material in the freeboard of the storage unit
potentially forming accretions.
Thermodynamic analysis based on CSIRO Process Science and
Engineering MPE modeling suggested that additions such as

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 Table 3 Summary data for the effect of additions to LiNaK carbonate eutectic (argon atmosphere)
DSC events other
Heat of than melting
System Melting T ( C) melting (J=g) endothermic=exothermic
LiNaK (CO3) 401 221 — 715
þ10 wt. % NaNO3 388 187 128  C (endo) and 319  C (endo)
þ10 wt. % KCl 396 205 301  C (exo)
þ10 wt. % NaOH 326 204 524  C (endo)
a
Total weight loss is a combination of salt vaporization and salt decomposition.
NaNO3, KCl, or NaOH could be used to lower the melting point
and this was verified experimentally. The best result was obtained
by means of NaOH addition where 10 wt. % content was shown to
lower the LiNaK carbonate melting point from 401  C to 326  C
without significant impact on thermal stability up to 780  C. The
addition of NaNO3 and KCl resulted in a more complex thermal
behavior with no significant advantage, and in the case of NaNO3
it was observed to decompose from the salt independent of the
carbonate. In all these cases, the results show that a more compli-
cated thermogram is obtained and although the effect on lowering
the melting point of the LiNaK carbonate eutectic predicted by
thermodynamic modeling was corroborated, the overall thermal
behavior and high temperature stability were significantly com-
promised by the additions.
The high melting point of the eutectic LiNaK carbonate studied,
although this work shows that it can be reduced significantly by
the addition of NaOH, is still quite high and might not be practi-
cal. Particularly considering that in a CO2 atmosphere the NaOH
would not be stable and will be converted to Na2CO3 leading to
an increase in melting point and the presence of water vapor
would be necessary to counteract this effect. The viscosity of the
ternary LiNaK carbonate melt has been measured and reviewed
by Ejima et al. [11] and has values of 40 mPa s just above the
eutectic temperature to value of 4.3 mPa s at 800  C. This viscos-
ity is higher, but of comparable magnitude to that measured for
the binary potassium nitrate, sodium nitrate eutectic composition
[12,13] which is considered as the base melt for solar towers.
An approach considering a cascading arrangement, similar to
that proposed by Michels and Pitz-Pal [14] for latent heat storage
in parabolic trough solar power plants, could be considered by
including a lower melting point salt such as HITEC1 being molten
for the temperature range between 145  C and 565  C coupled with
the LiNaK carbonate for temperatures higher than 400  C and up to
1000  C by controlling the atmosphere. Shin et al. [15] showed that
the ternary LiNaK carbonate eutectic could be used as a latent heat
storage system in the range 395–400  C over many cycles of stor-
age and discharge without overcooling and without significant cor-
rosion of the 316 stainless steel used to contain the mixture.
A significant issue when using molten carbonates at higher tem-
perature than 400  C is the requirement to find compatible alloys and
materials of containment for this corrosive salt. In exploratory
corrosion studies, Coyle et al. [16] showed that a number of
commercially available alloys such as HASTELLOY X, CABOT
214, HAYNES 188, HAYNES 556, INCONEL X750, and Nickel
alloys 600 and 800 significantly resist corrosion in eutectic molten
lithium–sodium–potassium carbonate. Yet detailed studies will still
have to be carried out to specifically quantify corrosion rates for the
intended application, given that in most cases some of these alloys may
still corrode during service at a rate of several millimeters a year [16].
Conclusions
The investigation carried out here demonstrates that the thermal
stability of the eutectic lithium, sodium, and potassium carbonate
1
7 wt. % NaNO3, 53 wt. % KNO3 and 40 wt. % NaNO2, Reg. U.S. Patent - Coastal
Chemical Company.
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DSC event bulk of TG, rapid weight loss Total weight loss
decomposition begin, T ( C) at 1000  C (wt. %)a
707 5.1
662 634 13.0
548 744 9.0
725 780 11.6
is significantly influenced by the gas atmosphere under which it is
measured. Under a blanket gas atmosphere of CO2, the molten
LiNaK carbonate is stable up to at least 1000  C; whereas in an
inert atmosphere of argon or an atmosphere of air, the thermal
stability is significantly lower.
The thermal decomposition was evaluated by means of three
criteria that take into consideration:
(1) The temperature at which rapid weight loss is observed to
commence by TG.
(2) The temperature after melting at which an endothermic
peak of decomposition is detected by DSC.
(3) The temperature at which the evolution of CO2 is detected
by means of MS analysis.
A combination of these three criteria suggests that molten
lithium–sodium–potassium carbonate eutectic could be used as
thermal energy storage and heat transfer media up to 1000  C
under CO2, at 700  C in argon and 670  C in air.
Thermodynamic modeling with CSIRO MPE software indicated
that the melting point of the LiNaK carbonate could be lowered by
additives such as NaNO3, KCl, or NaOH and this was verified exper-
imentally. However, complex thermal behavior regarding stability is
displayed in their presence and this warrants further study.
Acknowledgment
The authors wish to acknowledge helpful discussions held with col-
leagues at CSIRO Process Science and Engineering in relation to this
work, in particular Dr. Shouyi Sun of high temperature processing.
This project has been supported by the Australian Government
through the Australian Solar Institute (ASI). The Australian
Government, through ASI, is supporting Australian research and
development in solar photovoltaic and concentrating solar power
technologies to help solar power become cost competitive with
other energy sources.
Nomenclature
CSP ¼ concentrated solar power
DSC ¼ differential scanning calorimetry
HTF ¼ heat transfer fluid
MPE ¼ multiphase equilibrium
MS ¼ mass spectrometry
TES ¼ thermal energy storage
TG ¼ thermogravimetric
References
[1] Gil, A., Medrano, M., Martorell, I., Lazaro, A., Dolado, P., Zalba, B., and
Cabeza, L. F., 2010, “State of the Art on High Temperature Thermal Energy
Storage for Power Generation. Part 1—Concepts, Materials and Modellization,”
Renewable Sustainable Energy Rev., 14, pp. 31–55.
[2] Kenisarin, M., 2010, “High-Temperature Phase Change Materials for Thermal
Energy Storage,” Renewable Sustainable Energy Rev., 14, pp. 955–970.
[3] Medrano, M., Gil, A., Martorell, I., Potau, X., and Cabeza, L. F., 2010, “State
of the Art on High Temperature Thermal Energy Storage for Power Generation.
Part 2—Case Studies,” Renewable Sustainable Energy Rev., 14, pp. 56–72.
[4] Ren, N., Wu, Y., Wang, T., and Ma, C., 2011, “Experimental Study on Opti-
mized Composition of Mixed Carbonate for Phase Change Thermal Storage in
Solar Thermal Power Plant,” J. Therm. Anal. Calorim., 104(3), pp. 1201–1208.
NOVEMBER 2012, Vol. 134 / 041002-7
 [5] Olivares, R., “The Thermal Stability of Molten Nitrite/Nitrates Based Salt for So-
lar Thermal Energy Storage in Different Atmospheres,” Solar Energy (accepted).
[6] Wu, Y., Ren, N., Wang, T., and Ma, C., 2011, “Experimental Study on Opti-
mized Composition of Mixed Carbonate Salt for Sensible Heat Storage in Solar
Thermal Power Plant,” Sol. Energy, 85(9), pp. 1957–1966.
[7] Lukas, H. L., Fries, S. G., and Sundman, B., 2007, Computational Thermody-
namics: The CALPHAD Method, Cambridge University Press, Cambridge, UK.
[8] Spencer, P., 2008, “A Brief History of CALPHAD,” CALPHAD: Comput. Cou-
pling Phase Diagrams Thermochem., 32, pp. 1–8.
[9] Zhang, L., Jahanshahi, S., Sun, S., Chen, C., Bourke, B., Wright, S., and Somer-
ville, M., 2002, “CSIRO’s Multi-Phase Reaction Model and Its Applications in
Industry,” J. Met., 54, pp. 51–56.
[10] Cook, L. P., and McMurdie, H. F., 1989, Phase Diagrams for Ceramists, The
American Ceramic Society, Inc., Columbus, OH, Vol. VII, pp. 63–68.
041002-8 / Vol. 134, NOVEMBER 2012
Downloaded From: http://solarenergyengineering.asmedigitalcollection.asme.org/ on 01/28/2016 Terms of Use: http://www.asme.org/about-asme/terms-of-use
[11] Ejima, T., Sato, Y., Yamamura, T., Tamai, K., Hasebe, M., Bohn, M. S., and
Janz, G. J., 1987, “Viscosity of the Eutectic Li2CO3-Na2CO3-K2CO3 Melt,” J.
Chem. Eng. Data, 32(2), pp. 180–182.
[12] Bowcott, J. E. L., and Plunkett, B. A., 1969, “Diffusion of the Ag(I) Ion
Sodium and Potassium Nitrate Melts,” Electrochim. Acta, 14, pp. 363–372.
[13] Bradshaw, R. W., 2010, “Viscosity of Multi-Component Molten Nitrate Salts—
Liquidus to 200  C,” Sandia National Laboratories, Report No. SAND2010-1129.
[14] Michels, H., and Pitz-Pal, R., 2007, “Cascade Latent Heat Storage for Parabolic
Trough Solar Power Plants,” Sol. Energy, 81, pp. 829–837.
[15] Shin, B., Kim, S. D., and Park, W. H., 1990, “Ternary Carbonate Eutectic (Lith-
ium, Sodium and Potassium Carbonates) for Latent Heat Storage Medium,”
Sol. Energy Mater., 21, pp. 81–90.
[16] Coyle, R., Thomas, T., and Lai, Y. G., 1986, “Exploratory Corrosion Tests on
Alloys in Molten Salts at 900  C,” J. Mater. Energy Syst., 7(4), pp. 345–354.
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