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Full Length Article

Molten carbonates for advanced and sustainable

energy applications: Part I. Revisiting molten
carbonate properties from a sustainable viewpoint
S. Frangini a,*, A. Masi a,b
a
b

DTE-PCU-SPCT, ENEA CR Casaccia, 00123, Rome, Italy

DAFNE, University of Tuscia, Via San Camillo de Lellis snc, 01100, Viterbo, Italy

article info

abstract

Article history:

In addition to the traditional fuel cell field, recent research on molten alkali carbonates is

Received 26 October 2015

increasingly directed towards their use as efficient reaction medium or for the preparation

Accepted 7 December 2015

of highly functional materials in advanced, low fossil-carbon and sustainable energy ap-

Available online xxx

plications. The expansion of renewable energy use, and particularly of solar power, appears to be a major driving force behind the new wave of molten carbonate studies.

Keywords:

However, since the relevant molten carbonate literature in the new field of sustainable

Molten salts

energy is still relatively small, this work is an attempt to stimulate further and more

Molten alkali carbonates

systematic investigations on molten carbonates by revisiting some of their characteristic

Electrolyte

properties from a modern and sustainable perspective. In particular, this work is specif-

Reaction media

ically focused on molten carbonate properties that are important for uses as electrolyte or

Sustainable energy

reaction media. Specific properties that have been considered as major indicator of technological sustainability include safe melt chemistry, thermal and moisture stability, high
electrical conductivity combined with low metallic corrosiveness, ease to regenerate,
tunable acid-base and redox properties, and catalytic activity in gasification and partial
oxidation reactions. From this analysis it can be concluded that molten carbonates are very
stable systems under a wide range of chemical conditions and mild to moderate temperature ranges, giving the possibility of designing ideal reaction and electrolyte media for
advanced chemical/electrochemical processes related to production, storage, conversion
and efficient uses of renewable energy, particularly of solar energy, in future low-carbon
energy scenarios.
Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

Introduction
High temperature molten salt technology is a strategic sector
of the modern-day industry [1]. An almost endless list of

industrial processes today exploit the unique functional

properties of molten salts such as thermal and radiolysis
stability, non-flammability, low vapor pressure, ionic and
thermal conductivity, heat transfer, solvent capability and

* Corresponding author. Tel.: 39 06 30483138; fax: 39 06 30486357.

E-mail address: stefano.frangini@enea.it (S. Frangini).
http://dx.doi.org/10.1016/j.ijhydene.2015.12.073
0360-3199/Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Frangini S, Masi A, Molten carbonates for advanced and sustainable energy applications: Part I.
Revisiting molten carbonate properties from a sustainable viewpoint, International Journal of Hydrogen Energy (2016), http://
dx.doi.org/10.1016/j.ijhydene.2015.12.073

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

catalytic activity. Extractive metallurgy was historically the

first sector to make a large-scale use of molten salts for the
electrolytic production of light metals like aluminum and
magnesium during the Industrial Revolution of the nineteenth
century. With the later advent of easy oil energy at the turn of
the new century, molten salts further expanded their crucial
role in the more demanding metallurgical processes of stainless steels and corrosion-resistant alloys. Only in the last few
decades, the interest for non-metallurgical uses of molten
salts, in particular as heat transfer and thermal storage fluids,
has steadily increased being driven by the arise of first molten
salt nuclear reactor [2] and solar power plant programs [3].
In this context, several molten salt systems including
molten alkali carbonates (MACs) were actively studied as
thermal storage media in the seventies and eighties [4,5].
During this period, the high versatility of MAC properties
attracted a broader attention for their use in other energyrelated technologies, including coal gasification [6], waste
disposal [7], gas cleaning [8,9], CO2 concentration [10] and fuel
cells [11,12]. Unfortunately, most of the above mentioned
research programs saw a substantial decline of interest over
the time, because of various technical and economic constraints impeding their further implementation and leading to
a concurrently declining interest also for the study of MAC
salts. The only remarkable exception was in the emerging fuel
cell field, where the study of alkali carbonate electrolytes
continued to grow fast, being driven by the high promise of
fuel cells to become the power source of choice in a sustainable energy future. In particular, the world oil crisis of the
seventies sparked outstanding research efforts to develop
molten salt fuel cells with the result that today the Molten
Carbonate Fuel Cell (MCFC) is an available technology in the
power marketplace [13]. This interest has generated over the
past two decades a copious amount of technical and scholarly
literature focusing almost exclusively on the study of functional properties and performance of molten carbonates as
MCFC electrolytes. Thus, apart from fuel cells, practical use of
alkali molten carbonates is today confined in a few niche
energy applications. For example, ternary mixtures of alkali
carbonate salts, known under the Cartecsal trade name, are
being used in the nuclear power industry for cleaning and
processing of uranium-containing alloys [14,15].
Over the past years rising concerns over energy and environment are placing strong pressure for a process chemistry
redesigned on more sustainable principles resulting in
increased research activities for those technologies that have
both the potential of lower energy consumption and environmentally benign properties. As a part of this broader sustainable scenario, interest for energy applications of MAC
salts has begun to creep up again after decades of languishing
research [16]. Very interestingly, the new emerging areas of
storage and conversion of energy has opened up new directions for molten carbonate research not only as efficient,
safe and sustainable reaction media, but also as component
for the preparation of highly functional solid materials in
advanced energy devices. For instance, carbonate-ion conducting solid electrolytes consisting of a molten carbonate
phase and solid ceria oxide phase are today actively studied
for hybrid high temperature fuel cell [17] and gas separation
membrane applications [18].

Chemical and physico-chemical properties of MAC salts

make them unique among the various classes of high temperature molten ionic systems based upon oxo-anion, halide
or pseudo-halide salts in terms of safety, chemical stability
and environmental benignity. Potential exists that a wider use
of MAC salts can help to design more sustainable high temperature molten salt media and therefore explain, at least in
part, the recent interest among researchers for the development of novel and sustainable molten salt processes specifically based on the use of MAC salts.
However, it is also felt that these long known properties of
carbonate salts could not simply justify all the observed new
research activities on these salts. A much more decisive factor
is likely related to the vigorous recent development of
renewable energy sources that could promote wide sustainability of MAC salt-based applications and technologies. In
fact, the rather wide working temperature range of MAC salts,
which stems from mild to moderate temperatures
(500e800  C), opens up the possibility of easy integration with
solar-derived sources of electrical and thermal energy, thus
offering a lot more options for a versatile design of MAC salt
processes with expected strong reduction of energy intensity
and environmental impact. At the same time, operations at
such wide temperature range allows to potentially exploit a
large spectrum of different chemical/electrochemical reactions, especially in conversion, storage and efficient use of
energy technologies such as fuel cells, electrolysis, gas separation and clean-up, CO2 chemical utilization and capture,
material processing.
This paper is intended to be the first of a two-part paper
series. General aspects of MAC salt chemistry and properties
of relevance for use of molten carbonates as sustainable
functional media will be highlighted in this work. A subsequent work (Part II) will focus on reviewing recent research
published in energy applications of MAC salts, including
research on advanced functional materials using molten
carbonates as key component.

MAC salt properties and sustainability

This work will focus on chemical and physico-chemical
properties of primary importance for a sustainable technological use of MAC salts. Comprehensive compilation of
molten carbonate physical and physico-chemical properties
can be found in Ref. [11].
Alkali molten carbonates are high temperature ionic salts
with melting temperatures above 700  C and boiling points
exceeding 1300  C. In general, MAC salt media are characterized by a suite of attractive properties such as high thermal
and chemical stability, insignificant vapor pressure, high ionic
conductivity and low metallic corrosiveness. Moreover,
several properties including the acid-base chemistry can be
finely tuned through slight change in temperature, gas atmosphere, alkali cation composition and special additive
formulation [11]. Table 1 identifies major advantages (and also
some limits) for a sustainable use of MAC salts as electrolyte
or chemical reaction media. Some of these properties will be
analyzed in more detail in the following paragraphs.
A general view on the potential of MAC salts as effective
media for high temperature processes can be readily obtained

Please cite this article in press as: Frangini S, Masi A, Molten carbonates for advanced and sustainable energy applications: Part I.
Revisiting molten carbonate properties from a sustainable viewpoint, International Journal of Hydrogen Energy (2016), http://
dx.doi.org/10.1016/j.ijhydene.2015.12.073

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

by comparing some physical properties of MAC salts with

water, a sustainable solvent media par excellence. Table 2
reports a subset of basic properties allowing a simple comparison between a widely used binary eutectic carbonate and
water. The molten carbonate data have been collected from
source [11], except for thermal conductivity data for which
much more accurate data have been found in Ref. [19].
Refractive index has been included as directly related to polarity and solvent properties. Since no refractive index could
be found in literature for molten carbonate systems, comparison has been made using refractive index value of a
structurally-similar molten nitrate salt [20]. Water properties
have been taken from source [21]. Focusing the attention on
the ionic conductivity, which is a key electrolyte property, it is
instructive to note that ionic conductivity shows the most
striking differences between the two media. Thus, specific
conductance of the binary LiK eutectic is very high, being
about 1.3 S cm1 at 650  C, which is nearly 10 times higher
than a 1 M KCl solution at 25  C. However, since no significant
differences exist in their equivalent conductance, ca.
140 S cm2 equiv1 [22], this means that ionic mobility values
must be of the same order of magnitude and that the higher
specific conductance of MAC salts is mostly related to the effects of ionic charge density. On the other hand, it can be
observed that other important solvent properties reported in
Table 2 (i.e, thermal conductivity, refractive index, O2 gas
solubility) that are independent from Coulomb force interactions become comparable with those of aqueous solutions. All these results can be interpreted as saying that MAC
salts are not only excellent as electrolyte but also as dissolving
media with a strong solvent affinity for ionic substances in a
way similar to water. Additionally, amphoteric and partially
covalent compounds can be also chemically dissolved under
specific conditions, for instance, by properly tuning salt acidbase properties. For instance, Licht has recently observed high

Table 1 e Summary of major advantages and limitations

for a sustainable use of MAC salt systems as electrolyte
and chemical reaction media in high temperature
processes.
Advantages
 Safe to handle
 Benign melt chemistry
 Chemical stability

 Basic/oxidizing properties
can be tuned
 Catalytic activity in reactions
of energy interest
 Thermal stability
 Insignificant vapor pressure
 Moisture-insensitivity
 High ionic conductivity
 Sufficiently large electrochemical
window
 Low corrosivity
 Easy to regenerate

Limitations
 Solidify to rock-like
hardness
 Salt residues are not
easy to remove
 Common low-melting
point eutectic mixtures
contain expensive Li2CO3
constituent

solubility of iron oxides in Li2CO3 from 750  C onwards, but not

in the analogous Na2CO3, K2CO3 salts or their mixtures, under
similar experimental conditions [23]. Although this was a
rather unexpected result based on prior literature, the unique
dissolving properties of Li2CO3 can be easily explained if one
considers the different acid-base properties of the salts. The
Li2CO3 salt is a much stronger base than Na2CO3 and K2CO3
[24] and therefore, differently from the other two salts, it is the
only one alkali carbonate salt capable to dissolve the
amphoteric iron oxides through a basic dissolution mechanism. MAC salts are also optimal media for chemical dissolution reactions of molecular organic functional groups and
structures. Thanks to combined effects of thermal energy and
chemical action, MAC salts have been demonstrated to be
very effective in dissolving and destroying structural integrity
of complex molecular compounds, including polymers and
other many hard-to-burn organic compounds.
a) Thermal and moisture stability
Since MAC salts are compounds with high melting points,
eutectic mixtures of alkali carbonates are more often used in
many practical purposes to significantly lower the melting
point and also to obtain more favorable properties, for instance,
in terms of lower freezing points and minimal undercooling
effects. Melting point and composition of single salts and
common eutectic carbonate mixtures are given in Table 3.
Molten carbonates are much stronger Coulomb liquids
than other high temperature molten salt media, thus resulting
in extremely low vapor pressures, high thermal and chemical
stability through the entire liquid region up to the boiling
points and in a wide range of variable reducing/oxidizing and
moisture gas conditions, respectively. Table 4 reports some
experimental evaporation data taken at 700  C [11], from
which the very low volatilization of carbonate melts even in
comparison with a solid KCl salt can be appreciated. Data also
indicate an evident advantage in using sodium-containing
carbonate eutectic mixtures to further reduce melt volatility.
Carbonate hydrolysis may generate some enhanced volatility
by formation of alkali hydroxide species. Vaporization and
hydrolysis of molten carbonates have been recently
measured. Reported values for vaporization enthalpies of
Li2CO3, Na2CO3 and K2CO3 are 310, 260 and 200 kJ/mol,
respectively, thus confirming the much higher tendency to
evaporate of K2CO3 [25]. Thermal stability of MAC salts has
been studied in much more detail in a very recent study using
a ternary Li2CO3e Na2CO3 eK2CO3 eutectic as system example
[26]. MAC salts are very stable up to nearly 800  C under a CO2
atmosphere. In absence of CO2, massive signs of salt decomposition have been observed at around 700  C in argon and at
670  C in air. This means that a CO2 atmosphere is preferable
for stable and prolonged operations at temperatures higher
than 700  C and below 800  C.
The influence of water vapor on chemical stability of MAC
salts has been widely investigated in the past in relation with
studies on electrochemistry of MCFC fuel cells [11,24]. Hydroxide/oxide ion equilibria may be promptly established in
molten carbonates as a result of acid-base reactions (discussed in more detail in a next paragraph) of water with the
oxide ions dissolved in the melt according to:

Please cite this article in press as: Frangini S, Masi A, Molten carbonates for advanced and sustainable energy applications: Part I.
Revisiting molten carbonate properties from a sustainable viewpoint, International Journal of Hydrogen Energy (2016), http://
dx.doi.org/10.1016/j.ijhydene.2015.12.073

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Table 2 e Physico-chemical properties of a Li2CO3eK2CO3 (62e38 mol %) carbonate eutectic at 650  C and water at 25  C.
Liquid system

Density
(g/cm3)

Viscosity
(cP)

Thermal
conductivity
(W/m-K)

Heat
capacity
(J/g-K)

Surface
tension
(mN/m)

Refractive
index

Specific
conductance
(S/cm)

O2 gas
solubility
(mg/l)

1.94
1.00

5.7
0.91

0.83
0.60

1.60
4.19

216.2
72.1

1.416a
1.332

1.3
0.12b

9.6
8.6

LiK carbonate eutectic@650 ; C

H2O@25 ; C
a
b

Refractive index of molten NaNO3 salt at 300  C [20].

value refers to a 1.0 M KCl solution.

Table 3 e Melting points of single alkali carbonate salts

and common carbonate eutectic mixtures. A mixed
alkali-alkaline earth (KeMg) carbonate eutectic with an
unusual low-melting point has been also included in the
list.
Salt system
Li2CO3
Na2CO3
K2CO3
Li2CO3e Na2CO3 (52e48 mol %)
Li2CO3e K2CO3 (62e38 mol %)
Na2CO3e K2CO3 (56e44 mol %)
Li2CO3e Na2CO3e K2CO3 (43.5e31.5e25 mol %)
K2CO3eMgCO3 (57e43 mol %)

H2 O O2 2OH

Melting point ( C)
723
854
891
501
498
710
397
460

(1)

The hydrolysis constant is very high and its value increases

at increasing temperature [24], indicating that hydroxide is a
strong base and that the oxide ion concentration in the molten
carbonates is buffered by the presence of water vapor.
Although the hydrolysis reaction increases with temperature,
presence of CO2 in the atmosphere promotes high chemical
stability against moisture effects even at relatively high temperatures. For instance, Andersen has estimated that the hydroxide content at 723  C in the ternary Li2CO3e Na2CO3
eK2CO3 eutectic is very small, being about 0.016 mol fractions
under a PCO2/PH2O 1 ratio [24]. These results clearly indicate
that MAC salts can sustain high concentrations of water vapor
in the atmosphere keeping at minimum the formation of
highly corrosive hydroxides if an adequate CO2 blanket protection is provided.
b) Reusability properties
The well known compatibility of carbonate salts with living
systems and their use in medicine also suggests that MAC
salts are safe to handle chemical systems and may also
inherently constitute a versatile medium of benign and sustainable chemistry in operation. Sustainability is also

supported by their known capability to easily decompose or

dissolve large amounts of solid wastes of various nature,
which is at the basis of some recent attempts to use MAC salts
for development of sustainable waste destruction [27] and
waste-to-energy processes (i.e., biomass gasification) [28,29].
As a further sustainable aspect, it should be mentioned
that MAC salts are easy to regenerate as compared to other
molten salt media. Depending on the specific application,
degradation or reaction products of MAC salts may include
different soluble or insoluble anion species like oxides, reactive oxide species (superoxide, peroxide ions), hydroxides,
nitrate or sulphates. In many cases, soluble species can be
easily converted back to the pristine carbonate salt by simple
CO2 gas flowing treatments. For instance, the use of CO2 as
easy regeneration agent has been recently applied by Raharjo
[30], who describe a novel hot gas desulfurization process
utilizing MAC salts (i.e., Na2CO3eK2CO3 eutectic mixture) as
liquid sorbent. In order to improve the overall process efficiency, a regeneration step of the liquid sorbent is included.
Flowing CO2 at temperatures above salt melting point allows
to completely regenerate the pristine carbonate with sulfur
elimination as gaseous COS. In a more recent paper, an
improved regeneration step has been illustrated by the same
authors, which is based on using CO2 steam flue gases as
regeneration agents that allows MAC recovery at temperatures well below salt melting point [31]. On the other hand,
removing insoluble products from a molten salt bath may be a
much more complex and tedious process, requiring filtering
off steps, and sometimes quenching and aqueous purification
treatments before MAC salts could be used again [32].
c) Melt corrosivity
Corrosion compatibility with container or contact metal
materials is a practical aspect of great importance for both
sustainability and economic reasons. In spite of being excellent electrical conductors, it is notorious that MAC salts,
including their vapors, are much less corrosive than other
high temperature molten salts. For instance, halide and sulfate melts are extremely corrosive for most metallic materials

Table 4 e Evaporation rates of various molten alkali carbonate compositions and a solid KCl salt.
Salt system
KCl (solid)
62Li2CO3 38K2CO3
43.5Li2CO3 31.5Na2CO3 25K2CO3
52Li2CO3 48Na2CO3

Gas atmosphere

Temperature
( C)

Evaporation rate (mg/h)

N2
3.5H2O 20CO2 76.5N2
3.5H2O 20CO2 76.5N2
3.5H2O 20CO2 76.5N2

634
700
700
700

0.22
0.013
0.013
0.0025

Please cite this article in press as: Frangini S, Masi A, Molten carbonates for advanced and sustainable energy applications: Part I.
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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

due to easy formation of acid halide and SO3 vapors, respectively. On the contrary, commercial stainless steels like the
310S grade can be safely used in most practical situations
showing an excellent corrosion resistance to liquid and vapor
phases of carbonate salts in a wide temperature range. Presence of lithium in the melt further reduce salt corrosivity
allowing the use of stainless steels cheaper than the 310S
grade. It is also notorious that molten salt corrosion is
amplified under thin-film salt conditions, where acidic or
basic fluxing/dissolution mechanisms may be a dominant
mode of attack. For example, fluxing dissolution of metal oxides is usually a serious and well recognized technological
issue for most metallic alloys being exposed to sulfate-containing thin film melts. However, fluxing attack is rarely
observed in molten carbonate environments on stainless
steels and other commercial high temperature alloys, which is
a clear advantage for sustainable uses. Thin films of molten
carbonates is the normal condition found in MCFC systems
[13]. However, MAC salts have been observed to act as fluxing
agents only under special fuel cell conditions as highly
reducing atmospheres and temperatures above 600  C, where
iron oxide fluxing and carburization processes both impede
the formation of protective oxide scales on stainless steels
[33,34].
d) Acid-base and redox properties
In most cases, environmental benignity of MAC salt
chemistry may also include the advantage of short reaction
times, if appropriate acid-base and redox conditions are chosen. Observation of large variability in chemical reactivity of
MAC salts has been sometimes reported in literature, which
may be possibly due to poor definition of acid-base or redox
salt properties. Acid-base measures the content of free oxide
ion that forms by thermal decomposition of the oxyanion salt
constituent, i.e. the carbonate ion according to eq. (2a):
2
CO2
3 CO2 O

KD

aO2 pCO2
aCO2

(2a)
(2b)

Eq. (2a) is an acid-base reaction involving oxide ion transfer

between a base (carbonate anion) and the CO2 gas that behaves as the acidic component of the system (oxide ion
acceptor). From eq. (2b) it is also evident that the oxobasicity
range is defined by the equilibrium constant KD, which varies
with the temperature and with the nature of alkali cations
present in the melt. Carbonate basicity extends from
PCO2 1 atm, for the most acidic medium, to PCO2 KD, for
the most basic medium (at O2 1 atm). Thermodynamic
considerations show that the accessible basicity range is
limited by a melt saturated with the least soluble among the
alkali oxides Li2O, Na2O and K2O. For example, in lithiumcontaining carbonates, oxobasicity limit is determined by a
melt saturated with Li2O oxide because of its lesser solubility.
Further, many studies indicate the existence of other
important acid-base equilibria in carbonate melts involving
the formation of reactive oxide anions such as O2 2 (peroxide)
and O2  (superoxide) as follows:

0:5O2 O2 O2

2

(3a)

0:75O2 0:5O2 O
2

(3b)

Equilibrium concentration between oxide and reactive

oxide species can be related by the disproportion reaction of
superoxide ion (eq. (4a)), which is obtained as a linear combination of eqs. (3a) and (3b):
2
2O
2 aO O2
2

K3

pO2 aO2
2

aO2

(4a)

(4b)

For instance, K3 is reported to be ca. 0.11 at 723  C, for a

binary lithium-sodium carbonate eutectic salt [24]. This
makes clear that, in general, with presence of appreciable
amounts of oxygen in the supernate, oxide and peroxide ions
are almost fully converted to superoxide, while in oxygen-lean
atmospheres, oxide and peroxide are more important species
than superoxide ions.
The redox power of a carbonate melt is controlled by the
amount of molecular oxygen and reactive oxides species dissolved in the melt. Since chemical stability of reactive oxide
species greatly improves in basic melts, this implies that the
oxidizing power of carbonate salts considerably increases
along with melt basicity. Energetic considerations also indicate that stability of the peroxide compared with that of oxide
and superoxide anions increases with decreasing the size of
the alkali cations [35]. Thus, peroxide is largely predominant
over superoxide concentration in lithium-sodium eutectic
carbonate under basic conditions, namely CO2-lean gases. At
750  C, for instance, its concentration is of the order of
105 mol fractions, which is a value 100 to 1000 times higher
than under acidic conditions [36].
The superoxide anion is the most powerful oxidizing agent
in carbonate media. In this respect, Cassir et al. [36,37]
calculated a series of standard potential (E ) values for the
redox couples involving superoxide and peroxide anions:
2
O
2 3e 2O

(5a)

2
O2
2 2e 2O

(5b)

Calculation of Gibbs free energy changes with respect to an

oxygen electrode taken as zero value reference was used for
standard potential determinations. Thus, for instance, reported values for standard potentials
 in the binary lithium
sodium
eutectic
at 750  C, are: E O2  2 0.443 V and


O
2

0.094 V [36]. These values clearly indicates
E O2
O2
that superoxide anion is much more oxidizing than peroxide
and that there is a clear advantage in using superoxide-rich
carbonates for use in gasification and oxidation reactions.
Since the concentration of reactive oxygen species dissolved in the melt is very small under many practical gas
conditions, MAC salts are usually considered to be neutral or
slightly acidic melts. This may greatly limit their use as
effective dissolving media in most applications.
However, it has been recently demonstrated that small
additions of soluble alkali nitrate salts may dramatically increase the basicity/oxidizing power of MAC salts as a result of

Please cite this article in press as: Frangini S, Masi A, Molten carbonates for advanced and sustainable energy applications: Part I.
Revisiting molten carbonate properties from a sustainable viewpoint, International Journal of Hydrogen Energy (2016), http://
dx.doi.org/10.1016/j.ijhydene.2015.12.073

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

formation of large amounts of stable active superoxide species

[38,39]. Interestingly, thermal decomposition of nitrate salts
and formation of noxious gas species appears to be strongly
suppressed by mixing with carbonate salts, at least at temperatures up to 600  C [39]. Recent studies confirm that nitrate/
carbonate salt mixtures are sufficiently stable without
appreciable formation of noxious NOx species up to 630  C,
under argon atmosphere [26]. These results seem to suggest
that these oxidant mixtures can be acceptable from a sustainable point of view, yet under mild temperature conditions.
Interestingly, possible causes for the observed reduced tendency of nitrates to thermal decomposition in mixed melts
with carbonates have been recently analyzed with Density
Functional Theory (DFT) models. Stable formation of adduct
products between nitrates, nitrites and oxide species due to
attractive electrostatic interactions with carbonate anions has
been given as the most likely explanation [39]. Alkali nitrate
additions are supposed to form a closed nitrate/nitrite cycle
reaction system that maintains the peroxide formed by eq.
(3a) and increases the superoxide concentration as long as air
bubbling is kept active [39]. The entire nitrate/nitrite catalytic
cycle can be schematized as follows:

where M is an alkali cation and the total reaction (7d) is the

well known water gas shift reaction. Presence of water promotes the formation of a mixed M2CO3-MOH molten system,
being the hydroxide a direct participant to the process
through eq. (7c). The catalytic effect of alkali cations is usually
explained on the basis of a vapor cycle mechanism [42]. According to this mechanism, metal vapor formation is required
for reaction (7b) to proceed. Thus, at given experimental
conditions, the higher equilibrium partial pressure of potassium vapor with respect to sodium could explain its observed
greater activity as catalyst. For the same reason, the poor
lithium activity as gasification catalyst should be related to its
negligible vapor partial pressure.
Carbonate salts are also known to catalyze partial oxidation reactions such as the oxidative coupling of methane into
C2-hydrocarbons, which could be potentially a process of great
importance in a sustainable energy future [44e46]. The catalytic efficiency of MAC salts has been reported to increase with
melt oxobasicity. More in detail, peroxide anion in diatomic
O2 2 or monoatomic form (O) is usually proposed to play a
decisive role in the methane coupling catalytic mechanism by
MAC media. The reaction should proceed as follows [46]:

2


2NO
3 O2 2NO2 2O2

(6a)


O2
2 2O

(8a)

2

2
NO
2 O2 NO3 O

(6b)

2CH4 2O 2CH3 2OH

(8b)

2CH3 C2 H6 /C2 H4 H2

(8c)

H2 2OH 2H2 O

(8d)

With the simultaneous presence of stable peroxide and

superoxide anions the mixed carbonate-nitrate salt system
are reported to provide a very strong oxidizing molten salt
medium, although more systematic studies are clearly needed
to confirm the long-term chemical stability of mixed
carbonate-nitrate salts. On the other hand, recent works
report that simultaneous addition of soluble rare earth and
alkaline earth cations dramatically increases the formation of
reactive oxygen species in carbonate melts, thereby providing
an alternative strategy to produce carbonate melts with
powerful basic/oxidizing properties for uses in limited temperature ranges (500e650  C), namely as far as additives
remain soluble in the melt [40].
e) Catalytic properties
Chemical properties of MAC salts may be useful also in
designing environmental benign catalysis reactions. Steam or
CO2 gasification of carbon in molten carbonates is a well
known example of clean catalysis, in which the presence of
the alkali metal ions, potassium and, to a lesser extent, sodium, play also a decisive role in determining the overall salt
catalytic effect [41]. By way of example, the proposed multistep reaction mechanism for steam gasification is as follows
[42,43]:
M2 CO3 2C 2Mg 3CO

(7a)

2Mg 2H2 O 2MOH H2

(7b)

2MOH CO M2 CO3 H2

(7c)

C H2 O CO H2

(7d)

where CH3 is a methyl radical. However, tendency of the

methyl radical to react with oxygen in the gas phase strongly
limits the yields and selectivity of the desired C2-hydrocarbons. Due to these catalyst performance limitations, the
number of studies on oxidative coupling of methane by
molten salts has been largely declined during the last 10e15
years.
f) Washing-off properties
While MAC salts offer several advantages in terms of sustainability criteria, it is also fair to mention that there are some
drawbacks as well. Spent MAC salts are not always easy to
dissolve and remove by simple treatment such as, for instance,
hot water. This is because, as compared to nitrates or halides,
carbonate salts typically solidify to rock-like hardness, making
it difficult their removal by hot water especially if deep salt
layers remain onto solid or reaction product surfaces. In this
respect, it may be of interest observing that improved water
removability can be obtained by addition of chloride salts up to
form mixed carbonate-chloride salt eutectics. An example is
given by the eutectic Na2CO3eNaCl (42e58 mol%) system with
a melting point of 636  C [47]. Once cooled down to room
temperature, this eutectic salt appears as a conglomerate of
randomly dispersed and separated chloride and carbonate salt
particles [47] resulting in a granular coarse consistency, which
allows an easy washing off with hot water. The high water
removability of chloride-carbonate mixtures is exploited, for
instance, in the light metal casting technology [47,48], where

Please cite this article in press as: Frangini S, Masi A, Molten carbonates for advanced and sustainable energy applications: Part I.
Revisiting molten carbonate properties from a sustainable viewpoint, International Journal of Hydrogen Energy (2016), http://
dx.doi.org/10.1016/j.ijhydene.2015.12.073

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

salt cores of mixed chloride-carbonate salts are increasingly

used to replace the more conventional sand cores because of
the ease of removal. Together with metal casting, mixed
chloride-carbonate salts are gaining some interest also for
other applications such as, for instance, synthesis of ceramic
materials [49], secondary smelting processes [50] and municipal waste destruction [51]. However, mixed chloride-carbonate
salts can pose challenging corrosion issues with respect to pure
carbonate systems due to the presence of chloride anions and
this can be a practical limitation for most applications, especially if metallic alloys must be in contact with the salt melt.
Metallic corrosion in chloride-carbonate systems is, in fact,
strongly sensitive to the chloride content, operating temperature and conditions and can be rapidly exacerbated in case of
concomitant presence of moisture and oxygen in the gas atmosphere. This would require special salt handling and protection from wet atmospheres and therefore it is believed that,
although mixed chloride-carbonate eutectics could be an
interesting medium for some demanding applications, these
salts cannot be considered a competitive alternative to MAC
salts in a context of wide sustainable engineering applications.

Conclusions
Molten alkali carbonates have recently attracted increasing
interest for use as an effective functional medium in a broad
range of innovative high temperature applications, mainly in
the field of sustainable energy and advanced energy processes. To explain this renewed interest, some of the most
interesting properties and characteristics of molten carbonate
salts have been here reviewed and discussed from a modern
and sustainability perspective.
Owing to their unique physical and physico-chemical
properties, this analysis suggests that molten carbonates
could be very attractive to design multiple energy applications
in a wide range of operating condition contexts. Main sustainable and interesting characteristics highlighted in this
analysis are related to their high thermal and moisture stability, easy reusability, high electrical conductivity, low corrosivity, benign carbonate chemistry, tunable acid-base and
oxidizing properties. Molten carbonates are best suited for
processes operating at mild-to-moderate temperature range
(500e800  C). It is worth mentioning that addition of soluble
additives such as nitrate salts or rare earth and alkaline earth
elements has been recently demonstrated to promote the
formation of MAC salts with unusual powerful basic/oxidizing
properties. Temperature stability of additives limits the
applicability of oxidizing MAC salts at temperatures below
650  C, in order to avoid decomposition or precipitation of the
additives, which could result in a significant loss in oxidizing
efficacy.
Due to their unique properties, MAC salts appear to be ideal
candidates for combined uses with solar energy sources. According to latest research trends, it is becoming increasingly
apparent that strong reduction of fossil-carbon energy consumption and environmental impact can be expected from
hybrid integration strategies of molten carbonate processes
and solar energy.

Acknowledgments
One of the authors (A. M.) gratefully acknowledges scholarship from University of Tuscia, Italy, to pursue his doctorate
studies.

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Please cite this article in press as: Frangini S, Masi A, Molten carbonates for advanced and sustainable energy applications: Part I.
Revisiting molten carbonate properties from a sustainable viewpoint, International Journal of Hydrogen Energy (2016), http://
dx.doi.org/10.1016/j.ijhydene.2015.12.073