Art. 42. A Review of Promising Candidate Reactions For Chemical Heat Storage

Renewable and Sustainable Energy Reviews 43 (2015) 1331
Contents lists available at ScienceDirect
Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser
A review of promising candidate reactions for chemical heat storage

T. Yan a,b, R.Z. Wang a,b,n, T.X. Li a,b, L.W. Wang a,b, Ishugah T. Fred a,b
a
b
Institute of Refrigeration and Cryogenics, Shanghai Jiao Tong University, Shanghai 200240, China
Key Laboratory of Power Mechanical Engineering, MOE, Shanghai, China
art ic l e i nf o
a b s t r a c t
Article history:
Received 8 May 2013
Received in revised form
10 May 2014
Accepted 2 November 2014
Thermal energy storage is a necessary technology for the application of renewable energy and low-grade
thermal energy. Chemical heat storage has been proved to be a feasible and promising method to store
thermal energy. As compared to other thermal energy storage methods, chemical heat storage exhibits
high energy storage density as well as feasibility for long-duration energy storage. In this paper, the basic
principle of the chemical heat storage is rstly elaborated. Then the selection criteria of the chemical
reaction are given. The aim of this review is to provide an insight into the promising candidate reactions
for chemical heat storage application. The associated reversible chemical reactions available for thermal
energy storage systems are summarized. Ongoing research and development studies illustrate that
chemical heat storage is a very favorable option for the different application when diverse promising
candidate reactions are selected. As working temperature is one of the key parameters for thermal
energy storage systems, emphasis is given to the judgment of application temperature range for
chemical heat storage. The determination of applicative temperature range of reversible chemical
reactions is discussed. Besides, the challenge and prospect of the chemical heat storage technology are
analyzed in the paper.
& 2014 Elsevier Ltd. All rights reserved.
Keywords:
Thermal energy storage
Chemical heat storage
Candidate reactions
Chemical reaction heat storage
Chemical sorption heat storage
Contents
1.
2.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Technology status . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.1.
Chemical reaction heat storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.1.1.
Chemical reaction heat storage using gasgas reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.1.2.
Chemical reaction heat storage using liquidgas reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1.3.
Chemical reaction heat storage using solidgas reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.
Chemical sorption heat storage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.2.1.
Ammoniated salt pairs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.2.2.
Hydrated salt pairs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.3.
Metal hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.2.4.
Concentration-dilution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3. The judgment of application temperature range for chemical heat storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4. Perspective and conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1. Introduction
Corresponding author. Tel./fax: 86 21 34206548.

E-mail address: rzwang@sjtu.edu.cn (R.Z. Wang).
http://dx.doi.org/10.1016/j.rser.2014.11.015
1364-0321/& 2014 Elsevier Ltd. All rights reserved.
Energy is an important element for the economic growth, social

and environmental sustainable development. With the incremental
depletion of conventional primary energy, the new alternative
energy source becomes more and more important for the energy
14
T. Yan et al. / Renewable and Sustainable Energy Reviews 43 (2015) 1331
conservation. However, on the one hand, the renewable energy

source, such as solar energy and wind energy, is intermittent and
time dependent and thus restricts the large-scale utilization. On the
other hand, more rational and efcient utilization of the energy is
confronted with many technical difculties. Energy storage provides
a feasible solution due to improving the efciency of the energy
system and storing the surplus energy.
Energy storage is an indispensible technology for adjusting the
instability and time-discrepancy between supply and demand of
energy. It is mainly utilized for the intermittent occasion, such as solar
energy, variable energy load, and excessive energy that would be
wasted rather than effectively utilized if it cannot be stored. The
energy that can be stored involves mechanical energy, electric energy,
chemical energy and thermal energy. Thermal energy storage is capable of improving the efciency of thermal energy systems. It can be
used to alleviate the mismatch between energy supply and demand.
Furthermore, thermal energy storage facilitates the solar thermal
applications and other low grade heat recovery and utilization.
There are three thermal energy storage ways: sensible heat storage,
latent heat storage and chemical heat storage. For sensible heat
storage, thermal energy is stored or released accompanying with the
temperature change of storage materials. Of all the ways, sensible heat
storage is the simplest and the cheapest method, and thus it obtains
the earliest practical application. This method, however, has low
thermal capacity, making it necessary to use large sized storage device.
Latent heat storage utilizes the enthalpy difference of the phase
transitions of the phase change material (PCM), i.e. heat storage
process is the phase change of the substance by either fusion or
solidication. Compared to the sensible heat storage, latent heat
storage has a distinct advantage of much higher storage density and
the isothermal nature of storage process [1]. However, the properties
of the phase change materials will degrade after the reduplicative
cycling. Chemical heat storage relies on the reversible chemical
reactions, during which the energy is absorbed or released by breaking
or reforming chemical bonds. All the stored heat (or almost all) can be
retrieved for later use, when synthesis reaction occurs.
Chemical heat storage has attracted considerable interest in
recent years. Chemical heat storage has the capacity of high energy
density and long-term storage duration at near ambient temperature among different thermal energy storage methods. The reactant undergoes the decomposition reaction with the aid of heat
input, and therefore the thermal energy is converted into internal
energy and simultaneously stored. The stored heat can be kept for
a long time as long as the reaction products are separately stored.
This makes this energy storage method a viable and effective
technology for long-duration thermal energy storage and transport. This paper focused on the reversible chemical reactions
available for chemical heat storage. A large number of promising
candidate reactions for chemical heat storage are categorically
summarized. In addition, the selection criteria of chemical reactions and the determination of applicative temperature range for
chemical heat storage are addressed. Moreover, a more holistic
view of the current state and the further direction and challenge of
chemical heat storage are also presented and discussed.
2. Technology status
Chemical heat storage system stores thermal energy using stable
chemical substances by converting heat energy into chemical
potential energy. These chemical substances undergo reversible
chemical reactions to store/release heat. Generally, the ideal chemical heat storage materials/reactions should have the following
characteristics:
(1) Moderate reaction temperature and high reaction heat;
(2) Good reversibility without apparent secondary reaction;

(3) Fast enough forward and reverse reaction rate to facilitate the
energy charging and discharging;
(4) Easily separated and stably stored reaction products;
(5) Non-toxic, non-corrosive, non-ammable and non-explosive
reactants and products;
(6) Small volume variation during reaction;
(7) Large-scale availabilities and abundance, cheap price.
Chemical heat storage can be classied into two categories
based on the reaction mechanism: chemical reaction heat storage
(without sorption) and chemical sorption heat storage. Thermal
energy can be stored through the reversible chemical reactions
and sorption processes.
2.1. Chemical reaction heat storage
For chemical reaction heat storage, the heat storage and heat
release process can typically be described as:
A heat 3 B C
The compound A is split into chemical substances B and C

through an endothermic dissociation reaction. The produced
chemical substances, B and C, stores thermal energy in the form
of the chemical potential energy. The reaction products B and C are
stored separately to achieve long period heat storage with little
heat loss. When the reversible reaction occurs for the later heat
utilization, compound A is regenerated resulting from the synthesis reaction between substances B and C. As a result, the stored
thermal energy is retrieved.
2.1.1. Chemical reaction heat storage using gasgas reaction
2.1.1.1. The NH3/N2/H2 chemical reaction heat storage system. Ammoniabased chemical reaction heat storage system uses reversible dissociation of ammonia to store thermal energy. The chemical reaction is:
2NH3 g 3 N2 g 3H2 g
The reaction enthalpy is 66.8 kJ/mol ammonia at 20 MPa and

300 K. This reaction can be faster by introduction of an appropriate
catalyst. The application of ruthenium-on-carbon catalyst in place
of the iron-based catalyst helps to lower the dissociation temperatures to 673 K and below. Carden [2,3] initially investigated
the ammonia reversible reaction. The investigation work continued at the Australian National University (ANU). ANU devoted to
ammonia dissociation and synthesis system for a period of
approximately 40 years. They carried out a great deal of theoretical
and experimental investigations on ammonia-based chemical
reaction heat storage system [412]. Different studies that have
been done reveal that the ammonia-based system for concentrating solar power is technically feasible. A 1500 t/day ammonia
synthesis reactor can supply a 10-MW base-load plant with 400
large 400 m2 dishes arranged in an array. The heat released by
synthesis reaction is used to drive the power cycle to produce
superheated steam at a temperature and pressure of up to 793 K
and 10 MPa. Tower or dish solar collector systems enable the
dissociation reaction to proceed more completely owing to the
comparatively high temperature in the vicinity of 1273 K. In
addition, the increase in the system pressure can greatly accelerate
ammonia synthesis. This makes necessary for ammonia-based
storage systems to operate at high pressures (1030 MPa),
although this will increase the costs due to material restriction
on reactor and storage vessel. Ammonia dissociation and synthesis
reaction has a number of obvious advantages [5,10]. One of the
advantages is that it is easy to control the reactor since this
reversible reaction is very simple with no unwanted side reactions.
In addition, the temperature of this endothermic reaction is

particularly suited for the solar concentrators. Moreover, the phase
separation of ammonia and hydrogen/nitrogen can proceed automatically at ambient temperature due to the condensation of
ammonia fraction. Besides, the ammonia-based chemical reaction
heat storage system can benet from the well-developed experience of the mature ammonia synthesis industry. The basic principle is illustrated in Fig. 1 [3,5,12]. Dunn et al. [13] summarized
the ANUs work of ammonia-based chemical reaction heat storage
for the concentrating solar power.
2.1.1.2. The SO3/O2/SO2 chemical reaction heat storage system. The
sulphur trioxide (SO3) chemical reaction heat storage system bases
on the reversible dissociation of SO3:
2SO3 g 3 2SO2 g O2 g
The decomposed reaction of SO3 gas proceeds in the temperature range of 10731273 K [14]. The dissociation and synthesis
reaction of SO3 has no undesirable side reactions and possess high
15
reactivity under the circumstance of suitable catalysts [15]. Fig. 2

illustrated the schematic diagram of chemical reaction heat
storage system using SO3/O2/SO2/.
In this storage system, the resultant gases of dissociation
reaction, SO2/O2 can be delivered via the pipes, and used for the
heating purposes. SO3 can be generated by recombination of the
SO2/O2 gas mixture in the presence of catalytic at 773873 K and
release the chemical reaction heat. This system can effectively
achieve the transportation and storage of high temperature
thermal energy. Dayan et al. [16] evaluated the technical feasibility
of the SO3/O2/SO2 thermal energy storage system. They integrated
this kind of thermal energy storage system into a solar steam-cycle
power plant. The heat storage efciency of this storage system is
about 58%. The overall conversion efciency from thermal energy
to electric energy is approximately 26%. For a similar steam-cycle
power plant without the storage unit in the solar energy system,
the overall efciency is about 40%.
2.1.1.3. The CH3OH/H2/CO chemical reaction heat storage system. The
decomposition of methanol occurs at a relatively low temperature.
Apart from being very clean and cheap, methanol can be
stored and delivered conveniently. Hence, methanol has been
considered as a potential candidate for thermal energy storage.
The dissociation reaction is endothermic, whereas the reverse
reaction is exothermic, and obeys the following equation:
CH3 OHg 3 2H2 g COg
Fig. 3 shows the thermal energy storage system using the

decomposition and synthesis reaction of methanol. Liu and Yabe
[17] proposed a methanol energy transport system integrating a
two-step liquid-phase methanol synthesis process. The two-step
methanol synthesis reaction, including the intermediate products
methyl formate, is expressed as follows:
CH3 OH CO-HCOOCH3
Fig. 1. Thermochemical storage of solar heat using ammonia.
Fig. 2. Schematic diagram of chemical reaction heat storage system using SO3/O2/SO2 reversible thermochemical reaction.
Fig. 3. Schematic diagram of chemical reaction heat storage system using methanol reversible thermochemical reaction.
16
HCOOCH3 2H2 -2CH3 OH
Compared to present gas phase reaction, the reaction pressure

and temperature of this system decreased because of the employment of the liquid-phase reaction of methanol. The heat transportation efciency augments with the increase of reaction
conversion ratio. The corresponding transportation efciency of
75% can be obtained with the reaction conversion ratio of 90%.
2.1.1.4. The cyclohexane/benzene/hydrogen chemical reaction heat
storage system. The cyclohexane/benzene/hydrogen system involves
the reversible reaction C6 H12 g 3 C6 H6 g 3H2 g at atmospheric
pressure in the temperature range of 478589 K. Both endothermic
dehydrogenation and exothermic hydrogenation reactions are
catalytic reactions. The enthalpy of reaction is very large. Moreover,
the technology for the hydrogenation of benzene has already formed
the industrial scale [18], which will promote the potential application
of the cyclohexane/benzene/hydrogen system for the chemical
reaction heat storage. Therefore, this reversible reaction is considered as a promising candidate for chemical reaction heat storage.
The existence of impurities in reagents may incur the side reaction.
It is important to do pretreatment of reagents to eliminate the
impurities. Cacciola et al. [19] investigated the interrelation between
coefcient of performance (COP) and different inuence factors for
the cyclohexane/benzene/hydrogen system. For dehydrogenation
temperature of 473 K and hydrogenation temperature of 573 K,
both thermal energy storage density and the COP reached the
highest value when reaction conversions of dehydrogenation and
hydrogenation reactions were 30% and 70%, respectively.
2.1.1.5. Methane reforming chemical reaction heat storage
system. Methane reforming reaction is a promising candidate
used for the energy storage of solar heat and industrial waste
heat due to its highly endothermic reaction [2024]. The synthesis
gas produced by reforming reaction can achieve long distance
transportation by pipeline, via reversible exothermic reaction. The
methane reforming reaction can realize energy conversion, storage
and transportation. Consequently, methane reforming reaction
system, also known as thermochemical heat-pipe, is considered
as an important technology for reasonable and effective utilization
of existing energy as well as optimizing the use of renewable
energy.
Methane with water or carbon dioxide is converted to synthesis
gas at comparatively high temperatures. The endothermic catalytic
reaction is reversible. Up to date, the syngas is mainly obtained by
means of the steam or CO2 reforming in the industrial production
[25]. Solar reforming of methane has captured the great interest.
The two methane reforming reactions can be applied to chemical
heat pipe to achieve chemical heat storage and transmission of
solar heat:
CH4 g H2 Og-COg 3H2 g
CH4 g CO2 g-2COg 2H2 g
In theory, endothermic reactions via solar energy for this

process, which produces syngas, can upgrade the caloric value
of methane feedstock by 2228% [20,2628]. The CH4/CO2 reforming reaction takes advantage over the steam reforming [29,30].
Reaction (7), steam reforming of methane, is mainly concomitant
with the side reaction of the water-gas shift [23,25], which is
slightly exothermic:
CO H2 O-CO2 H2
The chemical reaction heat storage technology based on solar

CH4/CO2 reforming has a series of merits [31]. The solar CH4/CO2
reforming reaction can provide a way to store and convey solar
energy into a high-grade energy as well as reduce the CO2
emissions. The CH4/CO2 reforming reaction and its reverse CO/H2
methanation reaction have ever been considered as the foregoers
of thermochemical heat pipe applications in the storage and
transmission of solar energy [29]. Solar reforming of methane
with CO2 has been investigated for more than 20 years [3235].
The reactor is operated under the temperatures of 9731133 K
with a pressure of 0.35 MPa. The absorbed power by the reactor
ranges from 200 and 300 kW. The maximum methane conversions
can be as high as 88%. NiCrAl metallic foam absorber activated
with Ru/-Al2O3 catalyst is employed to measure the CO2 reforming of methane in a small-scale volumetric solar receiver-reactor
[26]. Compared to a SiC foam absorber activated using same
Ru/-Al2O3 catalyst, the metallic foam absorber possesses better
catalytic stability. Moreover, the metallic foam has the superior
plasticity, which can prohibit the emergence of cracks arising from
the mechanical or thermal shock. The solar-driven thermochemical heat-pipe concepts using this reaction are shown in Fig. 4
[29,31].
2.1.2. Chemical reaction heat storage using liquidgas reaction
2.1.2.1. The isopropanol/acetone/hydrogen chemical reaction heat
storage system. Prevost and Bugarel [36] rst proposed the
isopropanol (2-propanol)/acetone/hydrogen chemical heat pump
system in 1980. Up to now, many computational simulations
and experimental research on this system have been performed.
The system involves the reversible reaction with proper catalysts.
The endothermic reaction is dehydrogenation of isopropanol,
producing acetone and hydrogen as shown in the following the
chemical reaction:
CH3 2 CHOHl-CH3 2 COg H2 g
10
This liquidgas endothermic reaction occurs at 353363 K in

presence of an appropriate catalyst. The exothermic reaction is the
hydrogenation of acetone. This reaction occurs at 423483 K with
suitable catalyst [37]. The reaction equation is shown as follows:
CH3 2 COg H2 g-CH3 2 CHOHg
11
Fig. 5 illustrates the basic principle of isopropanol/acetone/

hydrogen chemical reaction heat storage system [37,38]. The
overall system mainly consists of two reactors: an endothermic
reactor and exothermic reactor. In the dehydrogenation process of
isopropanol, it needs to separate isopropanol from the reaction
products. The fractional condensation can easily be achieved at
ambient temperature by equipping a distillation column in the
system [39,40]. Kitikiatsophon and Piumsomboon [41] investigated the dynamic behavior of isopropanol/acetone/hydrogen
system by the steady-state simulation. They found the system
stability hinged on the working pressure in distillation column and
at the outlet of the compressor. The simulation results showed the
corresponding thermal efciency was 0.06 when the reaction
conversions of dehydrogenation and hydrogenation reactions
were 7.9% and 17.9%, respectively. KlinSoda and Piumsomboon
[37] developed an isopropanol/acetone/hydrogen chemical heat
pump system. The conversions in the endothermic and exothermic
reactors were about 8.5% and 11.6%, respectively. As a result, the
uid temperature in the exothermic reactor rose from 368 to
409 K. Theoretically, the exit uid temperature in the exothermic
reactor could be as high as 473 K. Improving the performance
of the exothermic reactor could lift the level of thermal energy
17
Fig. 4. Concepts for (a) closed- and (b) open-loop chemical reaction heat storage system based on solar energy CH4/CO2 reforming.
reaction employs the metal sulfates (M2SO4) for forming intermediate pyrosulfates (M2S2O7). The subsequent endothermic reaction is the decomposition of M2S2O7. The gas products can be also
condensed into liquid for long period storage and transportation at
room temperature. The process is based on the following reaction
equations:
T 1a
NH4 HSO4 l M2 SO4 s-NH3 g H2 Og M2 S2 O7 l

T 1b
M2 S2 O7 l-M2 SO4 s SO3 g
Fig. 5. Isopropanol/acetone/hydrogen chemical reaction heat storage system.
upgrading. The thermal efciency of the system was around 38%

and the exergy efciency was 27%.
2.1.2.2. The ammonium hydrogen sulfate chemical reaction heat
storage system. Wentworth and Chen [42] evaluated many thermal decomposition reactions available for storing solar thermal
energy. Considering the kinetics performance of the chemical
reaction and the physical properties of the substances in the
reaction, they constructed ten criteria of choosing reactions
for solar thermal energy storage. They found the dissociation
reaction of ammonium hydrogen sulfate could meet almost all
the proposed criteria. Furthermore, they concluded that it is a very
promising candidate reaction for stockpiling solar thermal energy.
The decomposition of ammonium hydrogen sulfate (NH4HSO4)
into ammonia (NH3), water (H2O), and sulfur trioxide (SO3) for the
thermal energy storage stage is shown as follows:
14
15
Besides, the use of metal oxides (MO) to form intermediate

sulfates (MSO4) can also realize the desired product separation in
principle. The chemical reactions are described as:
T 1c
NH4 HSO4 l MOs-NH3 g H2 Og MSO4 s

T 1d
MSO4 s-MOs SO3 g
16
17
13
Additionally, the reactions of twenty ve different metal

oxides and metal sulfates with NH4HSO4 have been examined
experimentally by using differential thermal analysis (DTA) and
thermogravimetric analysis (TGA). The results indicated that
only three sulfates (K2SO4, Rb2SO4, Cs2SO4) and six metal oxides
(ZnO, Cu2O, NiO, MnO, PbO, MgO) might react with NH4HSO4 to
achieve aforementioned two-step reaction. Amongst these different reagents, ZnO is the best choice owing to the achievement of
complete product separation. The products can be released step by
step (water vapor at around 436 K, ammonia gas at 638691 K,
and a mixture gas of SO2 and SO3 at about 1173 K) as a result of the
decomposition of NH4HSO4 by adding the ZnO. The product
separation can be achieved easily by controlling the reaction
temperature. Besides, the thermal decomposition reaction of
ZnSO4 progresses rapidly when the reaction temperature exceeds
1123 K.
The actual temperature required for energy storage stage (T1)

and energy release (T2) depends on the reaction conditions. The
thermal energy storage density provided by this process (storage
of H2O, NH3, and SO3 as liquids at ambient temperature) is
between 3.098 GJ/m3 (740 kcal/l) and 4.102 GJ/m3 (980 kcal/l).
For the purpose of the effective separation of SO3 from NH3 and
H2O, Wentworth [43] explored two-step reaction to realize the
function of the reaction Eq. (12). The rst step endothermic
2.1.3. Chemical reaction heat storage using solidgas reaction

2.1.3.1. Thermal dissociation reaction of metal oxides for chemical
reaction heat storage system. The reduction reaction of multivalent metal oxides and reverse oxidation reaction can be used
for storing thermal energy. Using air as reactant in the reverse
exothermic reactions can avoid storing product gases. Furthermore, metal oxides have good stability and thus are considered
as the candidate materials for chemical reaction heat storage.
T1
NH4 HSO4 lNH3 g H2 Og SO3 g
12
The reverse synthesis reaction is:

T2
NH3 g H2 Og SO3 gNH4 HSO4 l
18
The redox reaction can be given by the following equation:

MO2x 1 HeatQ 3 MO xO2
18
Fahim and Ford [44] illuminated the selection criteria of

reversible chemical reaction used for the thermal energy storage.
They studied the reversible reaction system of BaO2/BaO for the
purpose of examining its potential utilization for thermal energy
storage. The activation energy of forward dissociation reaction of
BaO2 and backward oxidation reaction of BaO are 140.6 kJ/mol and
51.9 kJ/mol, respectively. Compared with the other oxides system,
they concluded BaO2/BaO system is a promising candidate reaction
for the thermal energy storage. This system has the energy storage
density of 3.01 GJ/m3 based on the solid product. The corresponding
chemical equation is shown as:
BaO2 3 BaO 1=2O2
19
In addition, the direct solar thermal dissociation of ZnO into its

elements is an alluring process for the solar energy storage [45].
The reversible chemical reaction is:
ZnO 3 Zn 1=2O2
20
The transformation temperature of Fe2O3/Fe3O4 is 1188 K with the

reaction enthalpy of 576 J/g. The conversion temperature of binary
cobalt-oxide/iron-oxide system is similar to pure cobalt-oxide,
whereas the reaction enthalpy decreases with the rise of doped
iron content. Binary cobalt-oxide/iron-oxide system has higher
structural stability and long duration reversibility of the chemical
reaction than the pure cobalt-oxide. Moreover, the binary system
with about 10% iron-oxide has sufcient heat storage capability
because of the appropriate enthalpy.
2.1.3.2. Decarbonation reaction of carbonate for chemical reaction
heat storage system. Kato et al. [50] surveyed the utility of several
chemical reactions available for heat pump system. They mainly
focused on inorganic oxide/carbon dioxide reaction systems owing
to their high chemical reaction heat. They found that the following
inorganic oxides such as PbO, MgO, CuO, MnO, ZnO, NiO and CoO
can be selected as candidates. As for the chemical reaction heat
storage, the lead oxide/carbon dioxide (PbO/CO2) reaction displays
the most outstanding features.
The working principle of PbO/CO2 reaction system is based on
the following chemical equation:
PbCO3 g 3 PbOs CO2 g
Mller and Palumbo [45] developed a solar chemical reactor for

the direct thermal dissociation of zinc oxide using concentrated
sunlight. The thermal decomposition of ZnO into its ingredients
needs a temperature of above 2200 K, and the produced gases
Zn(g) and O2(g) need to be either quenched or separated at high
temperature to avoid their recombination [46]. The utilization of
carbonaceous materials as reducing agents can not only signicantly lower the reduction temperature but also prevent the
recombination.
The direct thermal dissociation of metal oxides requires very
high temperatures. When the temperature is even up to 3000 K,
the dissociation reaction can occur, such as B2O3, SnOx (x equal 1
or 2) [47,48]. This means that the direct thermal dissociation of
metal oxides is difcult to accomplish in practice for the chemical
reaction heat storage of solar energy. Only a few metal oxides with
high reaction enthalpy and suitable reaction temperature can be
applied to chemical reaction heat storage for concentrated solar
power. The mixture of metal oxides can provide a considerable
range of appropriate thermal storage materials. Block et al. [49]
employ the binary cobalt-oxide/iron-oxide system for high temperature heat storage. The cobalt-oxide has a high reaction
enthalpy and relatively low reaction temperature. These properties
make it a very promising material for chemical reaction heat
storage of solar energy. However, cobalt oxide is expensive and
suspected to be carcinogenic. Compared to cobalt-oxide, ironoxide is cheap, nontoxic and has a high reaction enthalpy as
well. The conversion temperature of Fe2O3/Fe3O4 is 1665 K and
has the reaction enthalpy of 599 J/g as well. The reaction temperature is too high for the concentrated solar power applications.
21
The principle of chemical reaction heat storage system using

PbO/CO2 reaction is shown in Fig. 6 [50]. Kyaw et al. [51,52]
investigated calcium oxide/carbon dioxide reaction for chemical
reaction heat storage, the corresponding reversible chemical reaction can be written as:
Carbonation:
CaOs CO2 g-CaCO3 g
22
Decarbonation:
CaCO3 g-CaOs CO2 g
23
The CaO/CO2 reaction system is very attractive for storing high

temperature thermal energy. The characteristics of this system are
as follows [51,53]: (1) CaCO3 decomposes at 1100 K under 101 kPa
of CO2 pressure; (2) the substances involved in this reversible
reaction are non-toxic and non-corrosive; (3) there are no
undesirable side reactions during this reversible reaction;
(4) CaCO3 is an abundant and relatively cheap raw material;
(5) this reaction system has a relatively high energy storage
density (about 3.26 GJ/m3).
The major challenges of CaO/CO2 reaction system are: (1) CO2
is rather difcult to liquefy; (2) the CO2 pressure dominates
the mode of CaO/CO2 thermal energy storage system either
the carbonation (heat release) process or the decarbonation
(heat storage) process. Actually, similar problem also arises in
the PbO/CO2 storage system.
Fig. 6. Principle of PbO/CO2 chemical reaction heat storage system: (a) heat storage mode; (b) heat supply mode.
19
Considering the above-mentioned aspects, CO2 gas resulting

from the decomposition of carbonates must be stored. Storage
of the produced CO2 gas can be generally implemented in the
following ways [51,53]:
high reaction enthalpy and fast kinetics with an equilibrium

temperature of around 773 K depending on H2O partial pressure
[59]. Besides, the price of this material is relatively low. The
CaO/Ca(OH)2 system for thermal energy storage utilizes the
following reversible hydration/dehydration reaction:
(1) The produced CO2 gas is compressed and stored, which is the
CaOCO2-compressor system;
(2) CaOCO2metal oxide system by making CO2 gas reacted with
other metal oxides and stored in the form of the metal
carbonate;
(3) CaOCO2-adsorbent system by adsorbing CO2 gas with a
suitable adsorbent (i.e. zeolite) and storing in the form of the
adsorbed CO2.
CaOH2 s 3 CaOs H2 Og
Kyaw et al. [51] investigated the corresponding operating

efciency and the upgraded temperature of the above three
different methods that are used to store the produced CO2. The
CaOCO2-compressor system is the most suitable for storing and
transporting thermal energy at the same temperature. This system, however, needs to expend mechanical work. The thermal
efciency of CaOCO2zeolite is strongly inuenced by the adsorptivity of the zeolite. With the increase of adsorptivity, the
efciency will enhance. Kyaw et al. [53] point out that the zeolite
13X adsorbent can be used as a CO2 storage medium in a CaOCO2
high temperature thermal energy storage system.
The crucial consideration in the development of an inorganic
oxide/carbon dioxide system using these reversible reactions
is how to handle and store the carbon dioxide gas phase reactant
[54]. Kato et al. [50] constructed a combination system by integrating CaO/CO2 and PbO/CO2 reactions. The principle of combination system is shown in Fig. 7 [50,5456]. The system is composed
of two reactors and the operation form comprises: (a) the heat
storage stage and (b) the heat output stage. The CO2 is transformed
into the corresponding metal carbonates to achieve the storage
of CO2. Due to higher reaction pressure, the temperature Tc1 of
generated heat is higher than Td1. The CaO/PbO/CO2 system is
driven by thermal energy and no mechanical works is required,
enabling ease in design as well as making the operation simple
and stable. This kind of heat pump system is also called the heat
transformer.
2.1.3.3. Dehydration reaction of hydroxide for chemical reaction heat
storage system. Darkwa and OCallaghan [57] evaluated the
potential of inorganic oxides/hydroxides reaction system for
chemical reaction heat storage. Thermal energy storage utilizing
inorganic oxides/hydroxides reaction system can produce high
heat energy and possess much higher thermal energy storage
capacities (about l-3 GJ/m3). CaO/Ca(OH)2 system, as well as CaO/
CaCO3 system, has been claimed to be among the best candidates
for thermal energy storage of high temperature heat [58].
The calcium hydroxide system exhibits good reversibility and
cycling stability. Furthermore, the CaO/Ca(OH)2 system possesses
24
Fig. 8 shows the schematic diagram of the chemical reaction

heat storage system using the CaO/Ca(OH)2 [60]. The CaO/Ca(OH)2
system stores thermal energy through dehydration of calcium
hydroxide, and releases the stored energy on demand by means of
the hydration of calcium oxide. Ogura et al. [60] investigate the
performance of CaO/Ca(OH)2 chemical heat pump. The obtained
thermal energy storage/release density is 1.86 MJ/kg CaO or
1640 MJ/m3. Fujimoto et al. [61] conducted a dynamic simulation
of CaO/Ca(OH)2 chemical heat pump using energy and exergy
analyses. They stated that CaO/Ca(OH)2 chemical heat pump
systems can meet the demands of the heating and cooling.
The energy and exergy efciencies are 58.7% and 61.6% for heating
and 12.7% and 4.5% for cooling, respectively.
Many researches investigate the thermal energy storage using a
reversible magnesium oxide/water reaction [6271]. To test the
possibility of a developing magnesium oxide/water system,
Kato et al. [66] performed the kinetic study of the hydration of
magnesium oxide. The MgO/Mg(OH)2 chemical reaction heat
storage system is based on the following equation:
MgOH2 s 3 MgOs H2 Og
25
Fig. 9 shows the working principle of the chemical reaction

heat storage system using MgO/Mg(OH)2 [65,67,68,70]. This system can be used for the storage of middle temperature heat.
The dehydration temperature is about 523 K. The dehydration
time highly depends on the temperature. Moreover, the reaction
process highly relies on the heat and mass transfer. A relatively
low dehydration temperature is more favorable for practical
utilization. The enhancement of heat conductivity in the reactor
can reduce the dehydration temperature. The dehydration could
occur at below 583 K by enhancing the heat conductivity of the
reactor. The more rapidly the hydration proceeds, the higher is the
vapor pressure. In addition, a higher-pressure hydration reaction is
favorable for improving the heat output performance of the heat
pump. The output heat at a temperature of around 473 K was
produced under the vapor pressure of 203 kPa [67]. The improvement of the thermal conductivity and mass diffusivity in the
reactor are important factors for upgrading the thermal performance of the heat pump. Higher temperature output can be
realized by enhancement of the heat conductivity and mass
diffusivity in the reactor. The presence of water on a reaction
interface will signicantly retard the decomposition reaction.
Splitting the bulk reagents into tiny particles can improve the
Fig. 7. Principle of CaO/PbO/CO2 chemical reaction heat storage system: (a) heat storage mode; (b) heat output mode.
20
Fig. 8. Schematic diagram of CaO/Ca(OH)2 chemical reaction heat storage system.
Fig. 9. Schematic diagram of MgO/Mg(OH)2 chemical reaction heat storage: (a) heat storage mode; (b) heat output mode.
dehydration dynamics. The porous materials, such as expanded

graphite and expanded vermiculite, can be employed for conning
the hydroxide inside the pores that enables the isolation of reagent
particles. The dehydration relies on the heat conduction inside the
reactor. The porous host matrix provides efcient transport of
water vapor and heat as well by accommodating the solid phase
swelling/shrinkage in the process of chemical transformation.
Shkatulov et al. [72] synthesize a new composite material Mg
(OH)2/expanded vermiculite and investigate its properties relevant to the chemical reaction heat storage. The decomposition
temperature of the conned magnesium hydroxide is lower
by about 50 K than that of the bulk reagents. This fact might
ascribe to a signicant acceleration of the dehydration reaction
of magnesium hydroxide conned to the pores inside the
expanded vermiculite pores. In-depth reason of the decomposition
temperature reduction needs further investigation. The maximal

heat storage capacity is 540 kJ per kg of the composite materials
when the magnesium hydroxide content is 67.4%. Ishitobi et al.
[63] investigate the dehydration/hydration behavior of metal-saltmodied materials. They concluded that LiCl-modied Mg(OH)2 is
a new potential material for chemical heat pump. The dehydration
of authentic Mg(OH)2 behaves as a one-step reaction. However,
the dehydration of LiCl-modied Mg(OH)2 proceeds in two steps.
LiCl/Mg(OH)2 ( 0.10) has the fastest dehydration rate compared
to other samples( 0, 0.02, 0.30). The surplus LiCl might increase
the diffusion resistance and therefore reducing the dehydration
rate. The dehydration reaction rate increases due to the effect
of the LiCl modication, whereas the activation energy for the
rst-order dehydration reaction reduces. Meanwhile, the hydration mechanisms for authentic MgO and LiCl/MgO ( 0.10) are
different. Kato et al. [69] proposed chemical reaction heat storage

materials mixed with metal hydroxides. MgNi1 (OH)2, which is
a hybrid hydroxide of magnesium hydroxide, Mg(OH)2, and nickel
hydroxide, Ni(OH)2 on the atomic level, is prepared by a precipitation method. The decomposition of the hybrid hydroxide
Mg0.5Ni0.5(OH)2 and a physical mixture of Ni(OH)2Mg(OH)2 was
investigated. The physical mixture has a two-step dehydration
because the hydroxides decomposes independently. Only a singlestep dehydration reaction occurs in the hybrid hydroxide. Hence,
the hybrid hydroxide forms a new phase exhibiting a unique
characteristic. The hybrid hydroxide can enlarge the operation
heat storage temperature through varying the composition of the
addition of cation in the material. The dehydration temperature of
Mg(OH)2 can be reduced due to the added cation in the hydroxide.
Mg0.5Ni0.5(OH)2 can be well decomposed while only a few Mg
(OH)2 are dehydrated under the temperature of 553 K. Consequently, the hybrid hydroxide is capable of storing thermal energy
at 473573 K, at which pure Mg(OH)2 could hardly be decomposed
and could not store heat. The second dehydration of the hybrid
hydroxide is lower than that of the rst dehydration because it
embraces structural water. The obtained thermal energy storage
density is 165 kJ/kg Mg0.5Ni0.5(OH)2. So, the hybrid hydroxide
materials are promising heat storage material candidate for
chemically storing medium-temperature thermal energy.
Apart from the above-mentioned chemical reaction heat storage using solidgas reaction, Koutinas [73] studied the chemical
reaction heat storage system of carbon dioxide, ammonia and
ammonium carbamate (NH2COONH4). The chemical equation is:
NH2 COONH4 s 3 2NH3 g CO2 g
26
They investigated the kinetics and the thermodynamics of this

reversible reaction, and found that the decomposition of
NH2COONH4 proceeds very rapidly in the range of 353383 K.
This chemical reaction heat storage system can be integrated solar
thermal collector into organic Rankine cycle power plant to
achieve the production of mechanical work and electricity.
2.2. Chemical sorption heat storage

Sorption is such a phenomenon that the certain gas or vapor
(sorbate) is captured or dissolved onto surface of some solid or
inner of liquid (sorbent). The working principle of chemical
sorption heat storage is also relied upon a reversible chemical
reaction, endothermic in one direction and exothermic in the
inverse direction. The process is either exothermic reaction
(adsorption) or endothermic reaction (desorption) according to
the thermodynamic conditions as shown in the following typical
reaction:
MX n p Gs p H 3 MX n Gs p Gg
where p is the equilibrium pressure of the solidgas pair, H and

S are the enthalpy and entropy changes during the reaction,
respectively. R is the universal gas constant and T is the absolute
temperature.
2.2.1. Ammoniated salt pairs

As a kind of reversible solidgas reaction, chemisorption can
be used for chemical heat storage. A simple thermal energy
storage using chemical sorption comprises of four main processes:
desorption, condensation, evaporation and adsorption. The fundamental of chemisorption is the monovariant reversible gassolid
chemical reaction which occurs in a reactor coupled with a
condenser and an evaporator.
Fig. 10 shows the operating principle of chemical sorption
heat storage system [74,77]. The whole cycle is illustrated by a
liquid/vapor equilibrium line (L/V line) and a solid/gas reaction
equilibrium line (S/G line) in the ClausiusClapeyron diagram as
shown in Fig. 10. There are two modes in the operation: heat
storage (desorption/regeneration) and heat release (adsorption/
production).
In the heat storage mode, the reactor receives middle-grade
heat from an external heat source (such as waste heat) at TM2.
When the reactants are heated to regeneration temperature,
desorption will occur. As long as the corresponding pressure of
reactor reaches the pressure of pL, the valve is opened (point 1 in
Fig. 10). The desorbed gas enters the condenser and condenses into
liquid by releasing condensation heat Qc at the ambient temperature TL (point 2) The valve closes when the dissociation reaction
completes as shown in Fig. 11(a). During the heat release phase,
the intermediate temperature heat at TM1 is introduced to the
evaporator where the liquid evaporates with the heating function.
The valve between the evaporator and the reactor is opened when
the pressure of evaporator arrived at pH (point 3). The chemical
reaction between the reactive salt and the high pressure gas from
the evaporator occurs in the reactor and release reaction heat Qs at
TH (point 4). The valve is closed when the synthesis reaction in the
reactor terminates as shown in Fig. 11(b). Obviously, more reactors
are required under the difference state for the purpose of realizing
continuous high-grade heat output.
Despite a series of advantages (such as the wide pressure and
temperature conditions by selecting the appropriate metal chlorides), the primary drawback is the low thermal conductivity of
metallic chlorides. Dellero et al. [78] proposed the use of carbon
bers to enhance the thermal conductivity of reactive salt using
the different mixtures, impregnation and intercalation compounds. Their results showed that the composite can provide the
superior performances when compared with simple mixture.
27
Here, MX is the solid chemical reactant or liquid absorbent.

The representative reaction salts are metallic halides (such as
CaCl2, MnCl2, CoCl2, BaCl2, NiCl2, NaBr, etc.). G is the gas reactant,
(such as NH3, H2O, H2, etc.), and H is the reaction enthalpy. The
common sorption systems mainly include ammoniated salt pairs,
hydrated salts and concentration-dilution. All of these systems are
specied below.
Both the gassolid equilibrium and the vaporliquid equilibrium are monovariant [74]. The equilibrium pressure in association with the constraint temperature is determined by the
following equation [75,76]:
lnp
H S
RT
28
21
Fig. 10. Diagram of ClausiusClapeyron showing operation principle.
22
Fig. 11. Operation modes diagram of chemical sorption heat storage: (a) heat storage phase; (b) heat release phase.
Considering multistep reactions, Wang et al. [79] investigated

solidgas reaction heat transformer system using the MnCl2 and
CaCl2 as the reactive salt and NH3 as the reactive gas. The reaction
between CaCl2 and NH3 is the multistep reaction and form two
compounds. Relatively high driving temperature, large relative gas
volume, and large specic heat transfer area are advantageous
conditions for the simultaneous occurrence of multistep reactions in the systems with the initial state of CaCl2 2NH3 and
CaCl2 4NH3. Low initial charging pressure is helpful for the system
with the initial state of CaCl2 4NH3, whereas high pressure is
conducive for the system with the initial state of CaCl2 2NH3.
The occurrence of the reaction of CaCl2 4/8NH3 for the initial state
of CaCl2 2NH3 can achieve the larger temperature lift, larger
specic power, and larger system coefcient of performance.
Nevertheless, the occurrence of the reaction of CaCl2 2/4NH3 for
the initial state of CaCl2 4NH3 will result in the lower specic
power. The temperature lift and system coefcient of performance
are larger for the initial state of CaCl2 4NH3; while the cycle time
is shorter for the initial state of CaCl2 2NH3. Furthermore, the
proper selection of system structure and operation conditions can
improve the system performance. Trudel et al. [80] investigated
solidgas equilibrium of the NH3CoCl2 chemical heat pump
system. The solidgas equilibrium is more complex than a single
equilibrium line. Pseudo-equilibrium hysteresis behavior is
observed between the synthesis reaction and the decomposition
reaction. The width of the hysteresis loops is related to the heating
rate. The hysteresis might be eliminated by maintaining temperature for sufciently long times and a single equilibrium line would
be obtained. The synthesis and decomposition reactions occur
over a range of temperatures. Both temperature and pressure need
to be specied in order to determine the system condition. The
system is bivariant not the monovariant. The ammonium chloride
salts would become unstable once the operating temperature
deviates markedly from the equilibrium temperature [80,81].
The solidgas equation for the reversible reaction between cobalt
chloride salt and ammonia is:
CoCl2 U 6NH3 s 3 CoCl2 U2NH3 s 4NH3 g
29
Aidoun and Ternan [81] investigate the pseudo-stable transitions and instabilities of NH3CoCl2 system as chemical heat
pump. The CoCl2 is stable in the nitrogen atmosphere up to
573 K, whereas becomes unstable at the temperatures in excess
of 573 K under the pressures up to 0.6 MPa. The CoCl2 2NH3 isnt
stable in the nitrogen atmosphere at any temperature. The
decomposition product is CoCl2 2NH3 rather than CoCl2 at the
temperature of 413 K in the nitrogen atmosphere. At the temperature of 421, 428 and 443 K, the decomposition product is CoCl2.
The transformation from CoCl2 6NH3 to CoCl2 2NH3 involves in
hysteresis, and the hysteresis phenomenon might also occur
during the transition from CoCl2 2NH3 to CoCl2. The synthesis
product is CoCl2 2NH3 at the temperature of 428 and 443 K,
whereas the CoCl2 6NH3 is the synthesis product at the
Pressure-reducing desorption technique

(Lower heat input temperature)
Low-grade
Heat input
PRS reactor
SRS reactor
(a) Energy storage process
Qcond
Temperature-lift adsorption technique

(Upgrade heat output temperature)
Condenser
Upgraded
Heat output
High-temperature
evaporator
PRS reactor
(b) Energy release process
LnP
S/G(PRS)
Energy upgrade
PH
Qcond
S/G(SRS)
L/G
QH-evap
E
Energy storage
Heat output
Pc
C Qdes
T
Energy upgrade
Qads
Energy storage
PL
B
Tc T a Te
Tin
Heat input
To Tout -1/ T
Fig. 12. Schematic diagram of the novel target-oriented solidgas chemical sorption heat transformer for the integrated energy storage and energy upgrade.
(a) Diagram of the physical arrangement of system components of the novel
target-oriented solid-gas chemical sorption heat transformer and (b) Diagram of
Clausius-Clapeyron.
temperature of 413 and 421 K in the presence of ammonia. The

decomposition of the CoCl2 2NH3 undergoes a pseudo-stable
transition at all temperatures, but the pseudo-stable transition
doesnt occur in the process of the CoCl2 2NH3 synthesis. The
synthesis of the CoCl2 6NH3 undergoes a pseudo-stable transition
at the temperatures of 413 and 421 K. However, the pseudo-stable
transition is dependent on the temperature during its decomposition process. The pseudo-stable transition occurs at the temperature of 421 instead of 413 K.
Li et al. [82] proposed target-oriented chemical sorption heat
transformer. The novel heat transformer realized energy storage as
well as energy upgrade. This system is associated with pressurereducing desorption and temperature-lift adsorption technology.
Fig. 12 illustrated the schematic diagram of the novel solidgas
chemical sorption heat transformer combining energy storage
with energy upgrade of low-grade thermal energy [82]. During
the energy storage phase, the application of the resorption
technology gives rise to the decrease of input temperature of the
exterior heat source. It is comprised of two-step regeneration.
During the energy upgrade phase, the liquid refrigerant is heated
from the condensation temperature to the predetermined evaporation temperature. The temperature-lift adsorption technique
is exerted and therefore can avoid the uctuation of the heat
output temperature. The released chemical reaction heat is used to
supply the thermal energy for thermal load. The research group
analyzed theoretically the innovative target-oriented solidgas
chemical sorption heat transformer system. The results showed
that both energy storage and upgrade can be effectively achieved
by the novel target-oriented chemical sorption heat transformer.
The temperature-lift of thermal energy can be achieved from 360
to 444 K when the two-salt sorption working pair MnCl2NaBrNH3
is used.
In addition, Li et al. [83] proposed dual-mode chemical sorption
energy storage method used for seasonal storage of solar thermal
energy. Fig. 13 illustrated the schematic diagram of dual-mode
chemical sorption thermal energy storage system [83]. The overall
system includes two units. Each unit is composed of a reactor and
a refrigerant vessel. Solar thermal energy is stored in summer and
released for use in winter. There are two operating modes
depending on the ambient temperature during the energy release
High-temperature
discharging unit
(HTDU)
23
phase in winter. If the ambient temperature is high enough to

make the solidgas chemical reaction heat between the reactors
and the evaporators satisfy the user heat demand, the generated
reaction heat arising from the exothermic synthesis reaction is
provided for the heat consumer. Each unit forms a chemical
adsorption heat storage system and can supply the thermal energy
to the heat consumer. If the ambient temperature is relatively low
in winter, the heat output temperature of both units can't meet the
user heat demand. The internal heat recovery process is employed
between the two energy storage units. The generated reaction heat
of one of the units is used to heat the evaporator of another unit.
This leads to the temperature-lift effect and therefore elevates the
heat output temperature of the overall system to meet the
requirement of heat consumer. The theoretical analysis suggested
that the proposed energy storage method is feasible for the
seasonal storage of solar thermal energy. The energy density is
1043 kJ/kg salt and 579 kJ/kg salt respectively under the same
conditions when the heat output temperature is 335 K with the
ambient temperatures of 273 K (without internal heat recovery)
and 253 K (with internal heat recovery) in winter.
Fujiwara et al. [84] reported the equilibrium properties of the
liquid phase with respect to the gasliquid system of NH4SCNNH3. Moreover, the enthalpy changes of the ammoniate were
estimated. The enthalpy changes decreases gradually from 28.9 to
23.8 kJ/mol NH3 when the composition n (mol NH3/mol NH4SCN)
ranges from 1.5 to 7. The enthalpy changes of the ammoniate is
2349% larger than average enthalpy changes of pure ammonia
with the temperature range of 283323 K. The investigation
indicates that NH4SCNNH3 system has a good prospect for
thermal energy storage. A process based on the reaction between
ammonium thiocyanate(NH4SCH) and ammonia is described as:
NH4 SCN U n mNH3 l 3 NH4 SCN U nNH3 l mNH3
30
NH4 SCN U nNH3 l 3 NH4 SCNs nNH3 g
31
(b) Energy upgrade phase
Low-temperature
discharging unit
(LTDU)
LnP
Pc
Phe
Ple
2.2.2. Hydrated salt pairs

Hydrated salt working pair is another potential candidate for
chemical sorption heat storage. Hydrated salts become into
anhydrous salts by releasing water during the energy storage
phase when they are heated. These hydrophilic anhydrous salts
can easily react with water to release the stored heat during
energy release phase. Moreover, it is feasible to realize the longterm storage of the thermal energy by separating the anhydrous
salt and water at ambient temperature. Different from the most
chemical heat storage systems, the charging and discharging
processes of hydrated salt pairs usually have almost same temperatures, which are similar to the characteristics of latent heat
storage using PCM. Therefore, many researchers regard the
hydrated salt as one of kinds of inorganic PCM. Strictly speaking,
the hydrated salt should be considered as one type of chemical
storage material.
The hydrated salt can be used to store thermal energy according to the following general chemical reaction:
Salt U nH2 Os Heat 3 Salts nH2 Og
Twt
Tm
Trec Tst Ta
Tout
Tin
-1/ T
Fig. 13. Schematic diagram of the dual-mode solidgas chemical sorption system
for seasonal storage of solar thermal energy. (a) Internal heat recovery process
between reactor in LTDU and evaporator in HTDU and Energy storage process: A-B;
Energy upgrade process of HTDU: E-F; Energy release process of LTDU: C-D;
Internal heat recovery process: M-N (b) Clausius-Clapeyron diagram.
32
During the charging phase, thermal energy is stored by

performing the dehydration reaction of a hydrated salt. During
the discharging phase, the stored heat is released by undergoing
the hydration reaction of the salt. The process is achieved by
addition of water vapor to anhydrous salt. This hydration effect is
exothermic, hence results in the generation of heat. Among
different hydrated salts, sodium sulphide and magnesium sulphate
have been widely discussed and studied.
24
The chemical heat storage system using sodium sulphide is

based on the following chemical equation:
Na2 SU 5H2 Os 3 Na2 Ss 5H2 Og
33
Sodium sulphide (Na2S) has high thermal energy storage

density due to the large sorption capacity and the high heat
of sorption. Furthermore, the Na2S/H2O pair (pentahydrate Na2S
5H2O) has the high thermal power density as well as the
large energy storage density (1980 kW h/m3 for heating and
1300 kW h/m3 for cooling) [85,86]. However, this material is very
corrosive and might give off the efuvial hydrogen sulde (H2S),
and therefore restricts its practical use. A vacuum pump is
required to maintain the vacuum environment in order to extract
unwanted intermediate gases. Fig. 14 illustrates the system
diagram of the chemical heat storage system using sodium
sulphide [87].
This hygroscopic salt releases the sorption heat due to the
hydration when water vapor ows across it. On the contrary, when
the heat is applied to the hydrated salt, crystal water is deprived
because of the deterioration of hydrated salt as soon as the salt
absorbs heat. The anhydrous salt regains the capacity to produce
heat upon the addition of moisture. Ucar et al. [87] investigated
the sorption properties of sodium sulphide (Na2S) for solar
thermal energy storage system. The storage system can be driven
by almost any low-grade heat, such as solar heat and waste heat.
The system has an energy storage density of 3600 kJ/kg Na2S,
which is ten times higher than that of the phase change materials.
Nevertheless, the initial cost of this system is high owing to the
operation of vacuum pump for the purpose of maintaining the
desired vacuum level. The hydrate of Na2S mainly involves
Fig. 14. Diagram of chemical sorption heat storage system based on the hydration
of sodium sulde.
pentahydrate Na2S 5H2O and nonahydrate Na2S 9H2O. Boer

et al. [88] investigated the structure, thermodynamic and phase
properties of a Na2S/H2O system available for the chemical heat
pump. They found out that there exists a new phase Na2S 2H2O
apart from the above known crystalline phases. The transition
temperature from Na2S 9H2O to Na2S 5H2O is 322 K. The transformation temperature from Na2S 5H2O to Na2S 2H2O is 356 K.
Na2S 0.5H2O is not a phase rather than a 3:1 mixture of Na2S and
Na2S 2H2O. The theoretical cold storage capacity of the Na2S/H2O
working pair (pentahydrate Na2S 5H2O) is 2.54 MJ/kg Na2S
according to the evaporation heat of water.
Magnesium sulphate (MgSO4) is considered as another potential storage material, and its reversible reaction is described as:
MgSO4 U 7H2 Os 3 MgSO4 s 7H2 Og
34
This material is very tempting for the seasonal storage of solar

heat. Posern and Kaps [89] demonstrated the working performance of MgSO4/H2O system. The hydration and dehydration of
the chemical material proceed in the reactor. The system can
employ either a separate reactor or an integrated reactor, as shown
in Fig. 15 [90].
A separate reactor requires much smaller heat exchange area.
It only needs to heat up the required quantity of storage material,
making the charging process much more efcient. Similar benets
occur in the discharging process. Bales et al. [91] gave the main
ndings of the studies on the storage material (MgSO4 7H2O), as
reported by ECN and TU Eindhoven. They proposed a prototype
system using such hydration and dehydration reaction in the Task
32 of the IEA SHC program [92]. Dehydration of MgSO4 7H2O falls
into three steps. The MgSO4 6H2O is formed as a result of the loss
of 1 mol water at rst. Thenceforward, the removal of 5.8 water
molecules leads to the generation of MgSO4 0.2H2O. Finally,
MgSO4 is produced with the removal of residual water molecules.
Among these steps the rst and third steps are single step
reactions. The second dehydration step is the most promising for
storing thermal energy. The corresponding energy density is about
420 kW h/m3. The former two dehydration steps are endothermic
processes. Moreover, the second dehydration step contains an
endothermic conversion from crystal MgSO4 6H2O to an amorphous state. The third dehydration step is an exothermic process.
This phenomenon attributes to the transition from amorphous
precursor to crystalline MgSO4, which leads to the heat release.
The dehydration of MgSO4 7H2O can occur at temperatures below
423 K, which can be achieved by solar thermal collectors. MgSO4
was formed when MgSO4 7H2O was heated up to 573 K. MgSO4
absorbs water until MgSO4 6H2O is produced, during which
thermal energy of 200400 kW h/m3 is released.
Fig. 15. Chemical sorption heat storage system using MgSO4/H2O: (a) separate reactor; (b) integrated reactor.
Table 1
Selected salt/water vapor reversible reactions with corresponding energy densities
[96].
Reversible reactions
MgSO4 U 7H2 Os 3 MgSO4 s 7H2 Og

Al2 SO4 3 U 18H2 Os3 Al2 SO4 3 s 18H2 Og
MgCl2 U 6H2 Os 3 MgCl2 U H2 Os 5H2 Og
CaCl2 U 2H2 Os 3 CaCl2 s 2H2 Og
Heating up water (T 60K)
Solid density of
salt hydrate (kg/
m3)
Theoretical
energy
density
(GJ/m3)
1680
1690
1560
1710
2.8
2.75
2.48
1.44
0.25
MgSO4 7H2O is neither toxic nor corrosive. The MgSO4/H2O

pair has a theoretical storage density of 780 kW h/m3 [93]. Essen
et al. [94] investigated the dehydration of MgSO4 7H2O by means
of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). They found out that the hydration strongly
depends on the water vapor pressure and this material can't
release all of the stored heat during dehydration. There exist some
problems that need to be solved for the application of magnesium
sulfate as chemical reaction heat storage material, such as MgSO4
hydrates too slow and the cycle performance of this material
is poor. In addition, there are several hydrates of magnesium
sulfate, so the intermediates from MgSO4 to MgSO4 7H2O cant be
determined during the hydration reactions. Nonetheless, MgSO4
7H2O is still considered a potential solar heat storage material.
Essen et al. [95] investigated the potential of four kinds of
hydrated salts for seasonal heat storage of solar energy. All four
salt hydrates can be dehydrated at 423 K and this temperature can
be obtained through a medium temperature collector. The theoretical study showed that three hydrated salts could be used as
promising materials for compact seasonal heat storage besides
magnesium sulfate (MgSO4 7H2O): aluminum sulfate (Al2(SO4)3
18H2O), magnesium chloride (MgCl2 6H2O) and calcium chloride
(CaCl2 2H2O). The chlorides (MgCl2 6H2O and CaCl2 2H2O) have
a larger temperature lift than the sulfates (MgSO4 7H2O and
Al2(SO4)3 18H2O) under the similar conditions. However, the
hygroscopic chlorides incline to produce a gel-like material. The
dehydration of Al2(SO4)3 18H2O proceeds through three steps.
Even though at the temperature of 573 K, this material is not
entirely dehydrated. First, Al2(SO4)3 17.5H2O is produced, followed by a gradual removal of 2.5 mol water leading to
Al2(SO4)3 15H2O and in the nal step Al2(SO4)3 2H2O is generated
as a result of the loss of 13 mol water. The calcium chloride is
hydrophilic and has already absorbed the water molecules at room
temperature. Hence, it is observed that its hydration begins with
the transformation from CaCl2 2.3H2O to CaCl2 2H2O. Thereafter,
CaCl2 H2O is formed accompanied with the loss of 1 mol water.
At last, full dehydration occurs at 383 K and anhydrous CaCl2 is
produced resulted from the removal of residual water molecules.
This material can be completely dehydrated under the temperature of 423 K. The dehydration of MgCl2 6H2O occurs in four steps.
First, MgCl2 4H2O is produced, corresponding to expelling 2 mol
water. Thenceforth, MgCl2 2H2O is generated, followed by a
gradual removal of 1 mol water resulting in MgCl2 H2O. The
MgOHCl is formed and release the gaseous HCl when the temperature is higher than 411 K. The formation of both HCl and
MgOHCl is undesired. HCl is harmful to metallic reactor, while
MgOHCl is unable to take up water and thus no heat is released.
Table 1 shows the four most promising reversible hydration/
dehydration reactions of hydrated salts with corresponding energy
density as identied in the theoretical study [96]. The formation of
HCl and MgOHCl can be avoided when hydrolysis proceeds at
403 K during the dehydration of MgCl2 6H2O. The largest
25
Table 2
Some potential thermochemical storage materials [101].
A 3
GJ/m3
T (K)
MgSO4 7H2O
MgSO4 7H2O
MgSO4 H2O
CaSO4 2H2O
CaCl2 2H2O
MgSO4
MgSO4 1H2O
MgSO4
CaSO4
CaCl2 1H2O
7H2O
6H2O
H2O
2H2O
H2O
2.8
2.3
1.3
1.4
0.6
395
378
489
362
447
temperature lift can be obtained using MgCl2 6H2O under similar

conditions. In addition, the agglomeration phenomenon occurs
during hydration of the chlorides. Moreover, a hard impermeable
layer is formed during hydration, which will prevent the further
hydration.
Bertsch et al. [97] investigated the hydration reactions of two
different anhydrous salts (MgSO4, CuSO4) for low temperature
chemical heat storage. They found that magnesium sulfate monohydrate and copper sulfate monohydrate are good candidates
for chemical heat storage materials. The theoretical storage
density of magnesium-sulfate-monohydrate and copper-sulfatemonohydrate are 2.3 GJ/m heptahydrate (633 kW h/m3 heptahydrate) and 2.1 GJ/m3 pentahydrate (574 kW h/m3 pentahydrate),
including the condensation heat of water vapor. The thermal
energy storage densities are about 11 times and 10 times higher
than that of the water with the same conditions, respectively.
Hongois et al. [98] developed a new MgSO4zeolite composite for
long-term thermal energy storage. They investigated its characterization by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The ne magnesium sulphate powder
could rapidly form a skin of the hydrated salt on the surface of the
powder when it exposes to humid air. This skin prevents the
further solidgas reaction, which greatly decelerates the reaction
rate. The prepared composite material can offer a high specic
surface for the solidgas reaction by using zeolite with microporous expanded structure as the matrix. This composite material has
the energy densities of 0.541.44 GJ/m3 (150400 kW h/m3) at a
storage temperature of 423 K. This temperature is sufcient for the
release of 6 mol of water from MgSO4 7H2O, whereas the thorough zeolite dehydration occurs at a temperature of above 473 K.
Nonetheless, the temperature of 423 K is achievable for the
evacuated tube solar-thermal collectors. Zondag et al. [99,100]
investigated the application of MgCl2 6H2O for chemical seasonal
solar heat storage. The thermal energy storage density is ten
times higher than that of the water. The research indicated that
MgCl2 6H2O is one of the most promising materials for compact
seasonal solar heat storage. In addition, some hydrated salts have
been selected for chemical heat storage as shown in Table 2 [101].
2.2.3. Metal hydrides
The metal hydrides are widely used for many industrial
purposes, such as hydrogen storage, thermal energy storage, etc.
Many metals, alloys or intermetallic compounds can react reversibly with hydrogen under the certain conditions. This reaction is
exothermic during the adsorption phase, whereas an endothermic
reaction occurs when hydrogen is desorbed from the metal
hydrides during the desorption phase. The universal reaction can
be described as follows:
M x=2H2 3 MHx H
35
The relevant applications of metal hydride have the common

advantages of being environmentally benign, compact and exible
for various operating conditions [102]. Since various alloys exhibit
different properties, the chemical heat storage systems based on
metal hydride can cover a wide and attractive temperature range
for industrial and domestic applications by choosing versatile
26
materials. In addition, the system can be effectively driven by lowgrade thermal energy, such as the solar heat energy and the
industrial waste heat.
Metallic magnesium is a very abundant and low-cost material.
Magnesium hydride (MgH2) plays a unique role among a number
of hydrogen metal compounds and intermetallides [103]. Bogdanovi et al. [104] demonstrated a process steam generator based
on high temperature magnesium hydride/magnesium chemical
heat storage system. Furthermore, the literature provides the
exact temperature corresponding to the respective H2 decomposition pressure (equilibrium pressure) of magnesium hydride.
The theoretical storage density for chemically stored heat is about
37.2 MJ/kg H2 and volume energy storage density is about
2.2464 GJ/m3. The maximum power output is about 14.4 MJ when
the evaporation quantity of water is about 7 kg/h. Felderhoff and
Bogdanovi [105] stressed the H2 decomposition pressure as a
function of temperature is of fundamental importance for the
operation of the MgH2 heat and hydrogen storage system.
Mg-based metal hydrides are the potential high temperature
heat storage media. The ternary hydride Mg2FeH6 is a very
promising material for chemical heat storage in the vicinity of
773 K [106,107]. This hydride is more economical for many
applications compared to other hydrides. This ascribes to its high
volumetric hydrogen density, the abundant availability and low
cost. Borislav et al. [108] reported the thermodynamic properties
and the cyclic stability of the MgFeH system. The reversible
Mg2FeH6 and the mixed Mg2FeH6MgH2 hydride systems proved
to be highly suitable materials for chemical thermal energy storage
at around 773 K. The hydrogen dissociation pressure of Mg2FeH6 is
lower than MgH2 under the same temperature (for example,
6.6 MPa instead of 10 MPa at 773 K). The relatively low hydrogen
dissociation pressure is favorable both in technical and economical
aspect. The volumetric heat storage density of Mg2FeH6 is considerably higher than that of MgH2. Moreover, Mg2FeH6 has
excellent cyclic stability. Herrich et al. [107] investigated the
desorption behavior of Mg2FeH6 based on synthesis conditions
and initial Fe content. The desorption temperatures of Mg2FeH6
decrease owing to the catalytic effect of Fe during the desorption
process.
NaMgH3 is considered one of the potential solar heat storage
materials because of its high thermal stability and relatively low
price [109]. The enthalpy and entropy change of the rst step
reaction are 86.6 kJ/mol and 132.2 J/(mol K), respectively. NaMgH3
has a more advantageous hydrogen dissociation pressure of
1.1 MPa at 773 K compared to 6.6 MPa for Mg2FeH6. Based on
Mg-compounds, Felderhoff and Bogdanovi [105] found out that
metal hydrides have both high heat storage capacities around
673 K and excellent cycling stability for heat storage application.
Reiser et al. [110] discussed the features and possibilities of
thermal energy storage systems, such as Mg/MgH2, MgFe/
Fig. 16. Test device of chemical sorption heat storage system based on the metal
hydride [111] 1.PID Controller; 2.Constant temperature bath; 3.Mass ow meter;
4. Pressure regulator; 5. Reactor; 7.Blower; 8.Energy meter
Mg2FeH6, MgNi/Mg2NiH4 and Mg-Co-H. The theoretical energy

storage density is 2741 kJ/kg and the observed value is 2147 kJ/kg
for the Ni-doped Mg/MgH2 system when the hydrogen content is
6 wt%. The reaction enthalpy change of Mg2NiH4 is 6264 kJ/mol.
Compared to MgH2, Mg2NiH4 is found to be less stable. The energy
storage density is 916 kJ/kg with a hydrogen capacity of 3 wt%.
They concluded that all the materials show cyclic stability and
their thermal energy storage densities can reach up to 2257 kJ/kg
with the thermal output temperature between 523 and 823 K.
Sekhar et al. [111] carried out the performance tests on Mg 30%
MmNi4 based thermal energy storage device at different pressures
(13 MPa) and temperatures (393423 K). The hydrogen storage
capacity increases from 1.88 to 2.5 wt% when the pressure varies
from 1.5 to 2.0 MPa. The thermal energy storage efciency
increases from 0.5 at 1 MPa to 0.74 at the pressure of 3 MPa when
the temperature was 423 K. For the given operating conditions
under the pressure of 2 MPa and temperature of 423 K, the
maximum amount of stored thermal energy is about 0.714 MJ/kg
and the corresponding thermal energy storage coefcient is 0.74.
Fig. 16 shows the test device of the chemical heat storage system
based on the metal hydride [111].
2.2.4. Concentration-dilution
Concentration-dilution heat storage employs the concentration
change of acid and alkali or salt solution to store or release the
thermal energy. Stephan et al. [112] investigated the dynamic
behavior of a heat transformer with NaOHH2O as working
substances employing numerical and experimental methods.
The maximum temperature lift is 45 K when absorber temperatures range from 403 to 428 K and evaporator temperatures are
between 373 and 383 K. The coefcient of performance for this
heat transformer can be as high as 0.49. Weber and Dorer [113]
analyzed sodium hydroxide (NaOH)water-based process for longterm solar heat storage. The required solar heat input temperature
is more than 393 K during the energy storage process. In comparison with the traditional hot water storage, system-volume heat
capacity is about six times higher for low-temperature space
heating with the supply temperature of 313 K. Meanwhile, it is
about three times higher for domestic hot water supply with the
temperature of 338343 K. Fig. 17 shows the charging and discharging process of thermal energy storage with sodium hydroxidewater as the working pair [113]. The NaOHwater reaction
system can be described as follows:
NaOH U n mH2 Ol heatl 3 NaOH U nH2 Ol mH2 Og
36
The system operates at charging mode when solar heat is

available and discharging mode during the heating demand
periods. In the charging mode, solar heat is introduced to the
dilute NaOH solution in the regenerator. The solution is desorbed
and releases some water vapor. This leads to the increase in the
concentration of NaOH lye. The generated water vapor ows into
the condenser where it condenses. The liquid water is stored in
the water tank. In the discharging mode, the high concentrated
NaOH lye in the absorber absorbs the water steam from the
evaporator heated by a low-temperature heat source. The absorption enthalpy of this exothermic process can be supplied to the
heat utilization device. To further improve the thermal energy
storage density, EMPA (Swiss Federal Laboratories for Materials
Testing and Research in Switzerland) proposed a double-stage
closed absorption storage system (Fig. 18) [113]. This storage
system works in a similar principle to the single-stage system.
The tanks and heat exchangers are separated in the proposed
system in order to simplify the control strategy. The NaOH has
strong corrosivity and thus its application needs special care in the
operation. The complexity of this double-stage system increases
because of more tanks and heat exchangers. In addition, the
Fig. 17. Schematic diagram of NaOH storage.
Fig. 18. Double-stage cycle of NaOH storage system. (a) The charging process and (b) The discharging process.
27
28
Fig. 19. Chemical sorption heat storage for sulfuric acid concentration difference.
storage density of the double-stage system is lower than that of

single-stage system.
For long term thermal storage, the NaOH storage system has a
signicant advantage when compared with water. The energy
density of NaOH storage systems is nearly three times that of
water for long-term heat storage [92]. The experimental results of
the NaOH storage system are given by Report B4 of Subtask B-IEA
SHC Task 32 [93]: The charging process proceeds very fast with
higher efciency, whereas the discharging process is slower than
the expectation. Moreover, most of the existing elastomers can be
corroded by the highly concentrated NaOH lye. Because of this
reason, proper consideration on corrosion must be put it place.
Tanaka et al. [114] introduced the utilization of dilution heat
resulted from sulfuric acid and water regarding the thermal
energy storage. The process between sulfuric acid and water can
be described as follows:
H2 SO4 U nH2 Ol 3 H2 SO4 U n mH2 Ol mH2 Og
37
Fig. 19 illustrates the effective utilization of heat of dilution by

sulfuric acid and water mixture in the case of storing solar energy
[115]. The high dissolution heat of sulfuric acid can be applied to
the thermal energy storage.
3. The judgment of application temperature range

for chemical heat storage
Working temperature is one of the key parameters for chemical
heat storage systems. Different reversible chemical reactions at
different temperatures need to be determined in order to achieve
the ultimate application with an appropriate temperature range.
Consequently, it is necessary to select promising candidate reactions for chemical heat storage with wide temperature ranges. It is
well known that chemical heat storage is based on reversible
chemical reaction. The endothermic decomposition reaction
absorbs heat during the charging phase, whereas the exothermic
synthesis reaction releases the stored heat during the discharging
phase. The turning temperature Tn of the reversible chemical
reactions might be employed to determine which chemical reactions might be selected for the chemical heat storage (with the
standard Gibbs free energy change G1(Tn) H1(Tn) TnS1(Tn) of
the reaction equals zero i.e. Tn H1(Tn)/S1(Tn) [42]). The turning
temperature is an important criterion to choose a chemical heat
storage system. It is expected that the materials used for thermal
energy storage have sufciently high energy density and suitable
temperature range to satisfy versatile application occasions. The
turning temperature is the most important selection criteria in
thermodynamic analysis of the chemical heat storage. Reaction
conditions cannot be realized if the reaction temperature is too
high or too low.
Both the reactants and products will exist at the temperature of
Tn. At T 4Tn, the endothermic decomposition reaction for the
thermal energy storage predominates. The exothermic synthesis
reaction prevails when T oTn and the stored heat is retrieved.

For example, thermal energy with the temperature potential Td
can be stored only if Td 4Tn for the chemical reaction employed.
Hence, if we expect to generate heat at Th and store thermal
energy at Td, the turning temperature Tn should be approximately
in the range between Th and Td. To avoid a synchronous reverse
reaction, the resultants should be quickly separated or quenched.
Examination of the ratio H1/S1 is a very effective method to
select the potential chemical reactions for thermal energy storage.
For example, the endothermic reaction used for the thermal
energy storage occurs at the temperature of 1273 K or higher to
rationally utilize solar heat energy. It is easy to achieve this
temperature level for focused collector and solar tower center
receiving apparatus. If the heat is stored at 1273 K and the
temperature of required heat output is 773 K, the ratio H1/
S1Tn should be approximately between 773 and 1273 K. If
H1 is very high, the corresponding S1 must be also very large
to ensure the Tn within the practical application range. The Tn of
SO3 reaction is located in the range of 7731273 K, so this reaction
can be also used for storing the concentrated solar heat energy.
Table 3
T* and H of ammonia, sulphur trioxide, ammonia salts and organic chemical
reaction heat storage systems [42,51,115,116].
Reactions
Enthalpy
change H
(kJ/mol)
Turning
temperature
Tn (K)
Groupa
2NH3 g 3 N2 g 3H2 g
SO3 g 3 SO2 g 1=2O2 g
NH4 Fs3 NH3 g HFg
NH4 Cls3 NH3 g HClg
NH4 Brs 3 NH3 g HBrg
NH4 Is 3 NH3 g HIg
NH4 HSO4 l 3 NH3 g H2 Og SO3 g
CH3 OHg 3 2H2 g COg
CH4 g H2 Og 3 COg 3H2 g
CH4 g CO2 g 3 2COg 2H2 g
C2 H6 g3 C2 H4 g H2 g
C6 H12 g3 C6 H6 g 3H2 g
C7 H14 g3 C7 H8 g 3H2 g
59
98.94
149.3
176
188
182
337
90.18
205
247
138
205
205
468
1040
499
618
677
649
740
420
961
959
1136
568
549
I
I
III
III
III
III
II
I
I
I
I
I
I
a
Group I: gasgas chemical reaction heat storage; group II: liquidgas chemical
reaction heat storage; group III: solidgas chemical reaction heat storage; group IV:
chemical sorption heat storage using ammoniated salt pairs; group V: chemical
sorption heat storage using metal hydrides.
Table 4
T* and H of some metal oxides and peroxides chemical reaction heat storage
systems [42,44].
Reactions
Enthalpy change
H (kJ/mol)
Turning
temperature Tn
(K)
Group
BaO2 s 3 BaOs 1=2O2 g

PbO2 s 3 PbOs 1=2O2 g
2CuOs 3 Cu2 Os 1=2O2 g
MnO2 s 3 MnOs 1=2O2 g
Li2 O2 s 3 Li2 Os 1=2O2 g
Na2 O2 s3 Na2 Os 1=2O2 g
SrO2 s3 SrOs 1=2O2 g
MgOs 3 Mgg 1=2O2 g
CaOs3 Cag 1=2O2 g
SrOs 3 Srg 1=2O2 g
BaOs3 Bag 1=2O2 g
Li2 Os 3 2Lig 1=2O2 g
Na2 Os 3 2Nag 1=2O2 g
K2 Os3 2Kg 1=2O2 g
Rb2 Os 3 2Rbg 1=2O2 g
Cs2 Os3 2Csg 1=2O2 g
80.9
55.1
143.1
133.9
38.4
99.6
48.1
752
828
755
729
906
634
544
502
481
1011
565
1298
1226
460
1200
416
3360
3800
3550
3600
2650
1880
1652
1494
1432
III
III
III
III
III
III
III
III
III
III
III
III
III
III
III
III
Table 5
T* and H of some carbonates and hydroxides chemical reaction heat storage
systems [42,51,115].
Reactions
ZnCO3 s 3 ZnOs CO2 g

MgCO3 s3 MgOs CO2 g
CaCO3 s 3 CaOs CO2 g
SrCO3 s 3 SrOs CO2 g
BaCO3 s 3 BaOs CO2 g
Li2 CO3 s 3 Li2 Os CO2 g
Na2 CO3 s3 Na2 Os CO2 g
K2 CO3 s 3 K2 Os CO2 g
Rb2 CO3 s3 Rb2 Os CO2 g
Cs2 CO3 s 3 Cs2 Os CO2 g
MgOH2 s3 MgOs H2 Og
CaOH2 s 3 CaOs H2 Og
SrOH2 s 3 SrOs H2 Og
Enthalpy change
H (kJ/mol)
Turning
temperature Tn
(K)
Group
67
125
176
234
269
224
322
394
405
408
84
109
126
406
670
1110
1381
1570
1390
2710
2585
2634
2655
531
752
852
III
III
III
III
III
III
III
III
III
III
III
III
III
29
achieved by choosing the various reactive salts, just like the

ammoniated reaction aforementioned in Section 2.2.1.
4. Perspective and conclusion
Table 6
T* and H of some chemical sorption heat storage systems [51,115].
Reactions
Enthalpy
change
H (kJ/
mol)
Turning
temperature
Tn (K)
Group
CaCl2 U 8NH3 s3 CaCl2 U 4NH3 s 4NH3 g

NH4 Cl U 3NH3 l3 NH4 Cls 3NH3 g
MnCl2 U 6NH3 s3 MnCl2 U 2NH3 s 4NH3 g
MgCl2 U 6NH3 s 3 MgCl2 U 2NH3 s 4NH3 g
LiHs3 Lis 1=2H2 g
NaHs 3 Nas 1=2H2 g
41.0
29.4
47.4
55.7
88
88
305
320
364
408
1220
735
IV
IV
IV
IV
V
V
Table 7
T* and H of other thermochemical reaction storage systems [42,51,115].
Reactions
Enthalpy
change H
(kJ/mol)
Turning
temperature
Tn (K)
Group
COCl2 g 3 COg 3H2 g

KBF4 s 3 KFs BF3 g
2NF3 s3 N2 g 3F2 g
MgSO4 s 3 MgOs SO3 g
CaSO4 s3 CaOs SO3 g
SrSO4 s 3 SrOs SO3 g
BaSO4 s3 BaOs SO3 g
Li2 SO4 s 3 Li2 Os SO3 g
Na2 SO4 s 3 Na2 Os SO3 g
K2 SO4 s3 K2 Os SO3 g
Rb2 SO4 s 3 Rb2 Os SO3 g
Cs2 SO4 s3 Cs2 Os SO3 g
CaNO3 2 s3 CaOs 2NO2 g 1=2O2 g
LiNO2 s LiNO3 s3 2LiOs 2NO2 g
108
109
130
280
402
459
517
444
574
676
700
708
109
109
801
978
945
1470
2145
2450
2660
2470
3190
3867
3900
3940
740
1089
I
III
III
III
III
III
III
III
III
III
III
III
III
III
Tables 37 lists the turning temperature Tn and reaction enthalpy

of some chemical reactions available for the chemical heat storage
[42,44,51,
115,116]. These data provide benecial reference for the selection
of available candidate reactions.
As for the reversible chemical reaction, the reaction temperature and pressure are completely dominated by the equilibrium
state of conditions. Theoretically, the gassolid reaction and the
vaporliquid reaction could occur at any desired temperature by
adjusting the reaction pressure according to the corresponding
equilibrium temperaturepressure relationship. In fact, it is difcult to realize in practice for the given reactant. However, the
application of different temperature occasion can be simply
Thermal energy storage is a promising environmentally friendly as

well as an energy saving technology. Among different technologies,
it has been proved that chemical heat storage has a promising
potential owing to its high thermal energy storage density and distinct
advantage for long-term thermal energy storage with negligible heat
loss. In the past decade, it received the great interest for the
applications of renewable energy and low-grade thermal energy. A
lot of theoretical and experimental researches have been carried out so
as to promote the development of chemical heat storage, and many
reversible chemical reactions were proposed for thermal energy
storage.
In this paper, previous research works on the chemical heat
storage are reviewed. The selection criteria of chemical reactants
and the reversible chemical reactions available for thermal energy
storage systems are discussed and summarized. The performance
of a chemical heat storage system is strongly dependent on the
kinetics and thermodynamic properties of the chemical reactions
utilized. Based on the current situation of chemical heat storage
technology, it appears that chemical heat storage might be suitable
for different application by selecting diverse promising candidate
reactions. However, it is necessary to resolve numerous problems
in the research and development stage before extensive application, such as the complexity of reaction process, appropriate
catalyst, special consideration of safety, the large initial investment
and the low efciency. Thus, further works should be conducted to
implement chemical heat storage in practice, such as the development of new composite reactants, chemical reaction kinetics,
optimization designs, control strategy, and so on.
Acknowledgements
This work was supported by the Project of the Natural Science
Foundation of China under the contract no. 51276211, and also the Key
Project of the Natural Science Foundation of China for international
academic exchanges under the contract no. 51020105010.
References
[1] Sharma A, Tyagi VV, Chen CR, Buddhi D. Review on thermal energy storage
with phase change materials and applications. Renewable Sustainable
Energy Rev 2009;13:31845.
[2] Lovegrove K, Luzzi A. Endothermic reactors for an ammonia based thermochemical solar energy storage and transport system. Sol Energy 1996;56:
36171.
[3] Kreetz H, Lovegrove K. Exergy analysis of an ammonia synthesis reactor in a
solar thermochemical power system. Sol Energy 2002;73:18794.
[4] Williams OM. Ammonia thermochemical energy transport in a distributed
collector solar thermal power plant. Sol Energy 1981;27:20514.
[5] Lovegrove K, Luzzi A, Soldiani I, Kreetz H. Developing ammonia based thermochemical energy storage for dish power plants. Sol Energy 2004;76:3317.
[6] Carden PO. Energy corradiation using the reversible ammonia reaction.
Sol Energy 1977;19:36578.
[7] Lovegrove K, Luzzi A, McCann M, Freitag O. Exergy analysis of ammoniabased solar thermochemical power systems. Sol Energy 1999;66:10315.
[8] Lovegrove KM. High pressure ammonia dissociation experiments for solar
energy transport and storage. Int J Energy Res 1996;20:96578.
[9] Luzzi A, Lovegrove K. A solar thermochemical power plant using ammonia as
an attractive option for greenhouse-gas abatement. Energy 1997;22:31725.
[10] Lovegrove K, Luzzi A, Kreetz H. A solar-driven ammonia-based thermochemical energy storage system. Sol Energy 1999;67:30916.
[11] Luzzi A, Lovegrove K, Filippi E, Fricker H, Schmitz-goeb M, Chandapillai M, et al.
Techno-economic analysis of a 10 MWe solar thermal power plant using
ammonia-based thermochemical energy storage. Sol Energy 1999;66:91101.
30
[12] Kreetz H, Lovegrove K. Theoretical analysis and experimental results of a

1 kWchem ammonia synthesis reactor for a solar thermochemical energy
storage system. Sol Energy 1999;67:28796.
[13] Dunn R, Lovegrove K, Burgess G. A review of ammonia-based thermochemical energy storage for concentrating solar power. Proc IEEE 2012.
[14] Mccrary JH, Mccrary GE, Chubb TA, Won YS. An experimental study of SO3
dissociation as a mechanism for converting and transporting solar energy.
Sol Energy 1981;27:43340.
[15] Hasatani M. Highly efcient conversion technologies for energy utilization.
Energy Convers Manage 1997;38:93140.
[16] Dayan J., Lynn S., Foss A. Evaluation of a sulfur oxide chemical heat storage
process for a steam solar electric plant; 2011. Available from: http://
escholarship.org/uc/item/1sr0w2p9.
[17] Liu QS, Yabe A, Kajiyama S, Fukuda K. A review of study on thermal energy
transport system by synthesis and decomposition reactions of methanol.
JSME Int J Ser BFluids Therm Eng 2002;45:47380.
[18] Delancey GB, Kovenklioglu S, Ritter AB, Schneider JC. Cyclohexane dehydrogenation for thermochemical energy conversion. Ind Eng Process Des Dev
1983:63945.
[19] Cacciola G, Aristov YI, Restuccia G, Parmon VN. Inuence of hydrogen-permeable
membranes upon the efciency of the high-temperature chemical heat pumps
based on cyclohexane dehydrogenation-benzene hydrogenation reactions. Int J
Hydrogen Energy 1993;18:67380.
[20] Hatamachi T, Kodama T, Isobe Y. Carbonate composite catalyst with hightemperature thermal storage for use in solar tubular reformers. J Sol Energy
EngTrans ASME 2005;127:396400.
[21] Chang JS, Park SE, Chon H. Catalytic activity and coke resistance in the carbon
dioxide reforming of methane to synthesis gas over zeolite-supported Ni
catalysts. Appl Catal, A: Gen 1996;145:11124.
[22] Gokon N, Inuta S-i, Yamashita S, Hatamachi T, Hatamachi T, Kodama T.
Double-walled reformer tubes using high-temperature thermal storage of
molten-salt/MgO composite for solar cavity-type reformer. Int J Hydrogen
Energy 2009;34:714354.
[23] Berman A, Karn RK, Epstein M. A new catalyst system for high-temperature
solar reforming of methane. Energy Fuels 2006;20:45562.
[24] Kodama T, Isobe Y, Kondoh Y, Yamaguchi S, Shimizu KI. Ni/ceramic/moltensalt composite catalyst with high-temperature thermal storage for use in
solar reforming processes. Energy 2004;29:895903.
[25] Anikeev VI, Bobrin AS, Ortner J, Schmidt S, Funken KH, Kuzin Na. Catalytic
thermochemical reactor/receiver for solar reforming of natural gas: design
and performance. Sol Energy 1998;63:97104.
[26] Gokon N, Osawa Y, Nakazawa D, Kodama T. Kinetics of CO2 reforming of
methane by catalytically activated metallic foam absorber for solar receiverreactors. Int J Hydrogen Energy 2009;34:1787800.
[27] Gokon N, Yamawaki Y, Nakazawa D, Kodama T. Ni/MgOAl2O3 and NiMgO
catalyzed SiC foam absorbers for high temperature solar reforming of
methane. Int J Hydrogen Energy 2010;35:744153.
[28] Gokon N, Yamawaki Y, Nakazawa D, Kodama T. Kinetics of methane
reforming over Ru/-Al2O3-catalyzed metallic foam at 650900 1C for solar
receiver-absorbers. Int J Hydrogen Energy 2011;36:20315.
[29] Edwards JH, Maitra AM. The chemistry of methane reforming with carbon
dioxide and its current and potential applications. Fuel Process Technol
1995;42:26989.
[30] Xu Z, Zhen M, Bi Y. Catalytic properties of Ni modied hexaaluminates
LaNiyAl12 yO19 for CO2 reforming of methane to synthesis gas. Appl Catal,
A: Gen 2000;198:26773.
[31] Edwards JH, Do KT, Maitra AM, Schuck S, Fok W, Stein W. The use of solar-based
CO2/CH4 reforming for reducing greenhouse gas emissions during the generation
of electricity and process heat. Energy Convers Manage 1996;37:133944.
[32] Levy M, Levitan R, Rosin H, Rubin R. Solar energy storage via a closed-loop
chemical heat pipe. Sol Energy 1993;50:17989.
[33] Kodama T, Kiyama A, Shimizu KI. Catalytically activated metal foam absorber
for light-to-chemical energy conversion via solar reforming of methane.
Energy Fuels 2003;17:137.
[34] Kodama T, Koyanagi T, Shimizu T, Kitayama Y. CO2 reforming of methane in a
molten carbonate salt bath for use in solar thermochemical processes.
Energy Fuels 2001;15:605.
[35] Petrasch J, Osch P, Steinfeld A. Dynamics and control of solar thermochemical reactors. Chem Eng J 2009;145:36270.
[36] Prevost M, Bugarel R. Chemical heat pumps: system isopropanol-acetonehydrogen. In:Proceedings of the international conference on energy storage;
1980.
[37] KlinSoda I, Piumsomboon P. Isopropanol-acetone-hydrogen chemical heat
pump: a demonstration unit. Energy Convers Manage 2007;48:12007.
[38] Chung Y, Kim B-J, Yeo Y-K, Song HK. Optimal design of a chemical heat pump
using the 2-propanol/acetone/hydrogen system. Energy 1997;22:52536.
[39] Meng N, Shinoda S, Saito Y. Improvements on thermal efciency of chemical
heat pump involving the reaction couple of 2-propanol dehydrogenation and
acetone hydrogenation. Int J Hydrogen Energy 1997;22:3617.
[40] Mooksuwan W, Kumar S. Study on 2-propanol/acetone/hydrogen chemical
heat pump: endothermic dehydrogenation of 2-propanol. Int J Energy Res
2000;24:110922.
[41] Kitikiatsophon W, Piumsomboon P. Dynamic simulation and control of an
isopropanolacetonehydrogen chemical heat pump. Sci Asia 2004;30:13547.
[42] Wentworth WE, Chen E. Simple thermal decomposition reactions for storage
of solar thermal energy. Sol Energy 1976;18:20514.
[43] Wentworth W.E. Thermochemical cycles for energy storage: thermal decomposition of ZnSO4 systems. NASA STI/Recon technical report N;1992.
[44] Fahim MA, Ford JD. Energy storage using the BaO2BaO reaction cycle. Chem
Eng J 1983;27:218.
[45] Mo ller S, Palumbo R. The development of a solar chemical reactor for
the direct thermal dissociation of zinc oxide. J Sol Energy Eng
2001;123:8390.
[46] Osinga T, Olalde G, Steinfeld A. Solar carbothermal reduction of ZnO:
shrinking packed-bed reactor modeling and experimental validation. Ind
Eng Chem Res 2004;43:79818.
[47] Abu-Hamed T, Karni J, Epstein M. The use of boron for thermochemical
storage and distribution of solar energy. Sol Energy 2007;81:93101.
[48] Forster M. Theoretical investigation of the system SnOx/Sn for the thermochemical storage of solar energy. Energy 2004;29:78999.
[49] Block T, Knoblauch N, Schmcker M. The cobalt-oxide/iron-oxide binary
system for use as high temperature thermochemical energy storage material.
Thermochim Acta 2014;577:2532.
[50] Kato Y, Watanabe Y, Yoshizawa Y. Application of inorganic oxide/carbon
dioxide reaction system to a chemical heat pump. In: Proceedings of the 31st
intersociety energy conversion engineering conference; 1996;2:763-8.
[51] Kyaw K, Matsuda H, Hasatani M. Applicability of carbonation/decarbonation
reactions to high-temperature thermal energy storage and temperature
upgrading. J Chem Eng Jpn 1996;29:11925.
[52] Kyaw K, Kubota M, Watanabe F, Matsuda H, Hasatani M. Study of carbonation of CaO for high temperature thermal energy storage. J Chem Eng Jpn
1998;31:2814.
[53] Kyaw K, Shibata T, Watanabe F, Matsuda H, Hasatani M. Applicability of
zeolite for CO2 storage in a CaOCO2 high temperature energy storage
system. Energy Convers Manage 1997;38:102533.
[54] Kato Y, Yamada M, Kanie T, Yoshizawa Y. Calcium oxide/carbon dioxide
reactivity in a packed bed reactor of a chemical heat pump for hightemperature gas reactors. Nucl Eng Des 2001;210:18.
[55] Kato Y, Saku D, Harada N, Yoshizawa Y. Utilization of high temperature heat
using a calcium oxide/lead oxide/carbon dioxide chemical heat pump. J
Chem Eng Jpn 1997;30:10139.
[56] Kato Y, O-shima T, Yoshizawa Y. Thermal performance of a packed bed
reactor for a high-temperature chemical heat pump. Int J Energy Res
2001;25:57789.
[57] Darkwa K, O'Callaghan PW. Green transport technology(GTT): analytical
studies of a thermochemical store for minimising energy consumption and
air pollution from automobile engines. Appl Therm Eng 1997;17:60314.
[58] Criado JM, Macias M, Machin AM. Analysis of the system CaOCO2H2O for
storage of solar thermal energy. Sol Energy 1992;49:836.
[59] Fujii I, Tsuchiya K, Higano M, Yamada J. Studies of an energy storage system
by use of the reversible chemical reaction: CaO H2O2Ca(OH)2. Sol Energy
1985;34:36777.
[60] Ogura H, Yamamoto T, Kage H. Efciencies of CaO/H2O/Ca(OH)2 chemical
heat pump for heat storing and heating/cooling. Energy 2003;28:147993.
[61] Fujimoto S, Bilgena E, Ogura H. Dynamic simulation of CaO/Ca(OH)2 chemical
heat pump systems. Exergy Int J 2002;2:614.
[62] Kato Y, Yoshizawa Y. Application of a chemical heat pump to a cogeneration
system. Int J Energy Res 2001;25:12940.
[63] Ishitobi H, Uruma K, Takeuchi M, Ryu J, Kato Y. Dehydration and hydration
behavior of metal-salt-modied materials for chemical heat pumps. Appl
Therm Eng 2013;50:163944.
[64] Kato Y, Nakahata J, Yoshizawa Y. Durability characteristics of the hydration of
magnesium oxide under repetitive reaction. J Mater Sci 1999;34:47580.
[65] Kato Y, Kobayashi K, Yoshizawa Y. Durability to repetitive reaction of
magnesium oxide/water reaction system for a heat pump. Appl Therm Eng
1998;18:8592.
[66] Kato Y, Yamashita N, Kobayashi K, Yoshizawa Y. Kinetic study of the
hydration of magnesium oxide for a chemical heat pump. Appl Therm Eng
1996;16:85362.
[67] Kato Y, Sasaki Y, Yoshizawa Y. Magnesium oxide/water chemical heat pump
to enhance energy utilization of a cogeneration system. Energy 2005;30:
214455.
[68] Kato Y, Minakami A, Li G, Yoshizawa Y. Operability of a thermally driven
magnesium oxide/water chemical heat pump. Can J Chem Eng 2001;79:
53641.
[69] Kato Y, Takahashi R, Sekiguchi T, Ryu J. Study on medium-temperature
chemical heat storage using mixed hydroxides. Int J Refrig 2009;32:6616.
[70] Kato Y, Takahashi F-u, Watanabe A, Yoshizawa Y. Thermal analysis of a
magnesium oxide/water chemical heat pump for cogeneration. Appl Therm
Eng 2001;21:106781.
[71] Kato Y, Takahashi F, Watanabe A, Yoshizawa Y. Thermal performance of a
packed bed reactor of a chemical heat pump for cogeneration. Chem Eng Res
Des 2000;78:7458.
[72] Shkatulov A, Ryu J, Kato Y, Aristov Y. Composite material Mg(OH)2/vermiculite: a promising new candidate for storage of middle temperature heat.
Energy 2012;44:102834.
[73] Koutinas AA, Yianoulis P, Lycourghiotis A. Industrial scale modelling of the
thermochemical energy storage system based on CO2 2NH32NH2COONH4
equilibrium. Energy Convers Manage 1983;23:5563.
[74] Huang HJ, Wu GB, Yang J, Dai YC, Yuan WK, Lu HB. Modeling of
gassolid chemisorption in chemical heat pumps. Sep Purif Technol
2004;34:191200.
[75] Zhong Y, Critoph RE, Thorpe RN, Tamainot-Telto Z, Aristov YI. Isothermal
sorption characteristics of the BaCl2NH3 pair in a vermiculite host matrix.
Appl Therm Eng 2007;27:245562.
[76] Sorin M, Spinner B, Stitou D. Thermodynamic techniques for the conceptual
design of thermochemical refrigerators using two salt materials. Chem Eng
Sci 2002;57:424351.
[77] Yu YQ, Zhang P, Wu JY, Wang RZ. Energy upgrading by solidgas reaction
heat transformer: a critical review. Renewable Sustainable Energy Rev
2008;12:130224.
[78] Dellero T, Sarmeo D, Touzain P. A chemical heat pump using carbon bers as
additive. Part I: Enhancement of thermal conduction. Appl Therm Eng
1999;19:9911000.
[79] Wang C, Zhang P, Wang RZ. Investigation of solidgas reaction heat
transformer system with the consideration of multistep reactions. AIChE J
2008;54:246478.
[80] Trudel J, Hosatte S, Ternan M. Solidgas equilibrium in chemical heat pumps:
the NH3CoCl2 system. Appl Therm Eng 1999;19:495511.
[81] Aidoun Z, Ternan M. Pseudo-stable transitions and instability in chemical
heat pumps:the NH3CoCl2 system. Appl Therm Eng 2001;21:101934.
[82] Li TX, Wang RZ, Kiplagat JK. A target-oriented solidgas thermochemical
sorption heat transformer for integrated energy storage and energy upgrade.
AIChE J 2013;59:133447.
[83] Li TX, Wang RZ, Kiplagat JK, Kang YT. Performance analysis of an integrated
energy storage and energy upgrade thermochemical solidgas sorption
system for seasonal storage of solar thermal energy. Energy 2013;50:45467.
[84] Fujiwara I, Sato M, Hiramatsu M, Furusawa Y, Satake H, Ebe M. Equilibrium of
NH4SCNNH3 system for thermal energy storage. Energy Convers Manage
1987;27:15962.
[85] N'Tsoukpoe KE, Liu H, Le Pierrs N, Luo L. A review on long-term sorption
solar energy storage. Renewable Sustainable Energy Rev 2009;13:238596.
[86] Hou Y, Vidu R, Stroeve P. Solar energy storage methods. Ind Eng Chem Res
2011;50:895464.
[87] Ucar M, Pounder B. Heat-of-adsorption solar thermal energy storage. J
Therm Insul 1982;6:4858.
[88] Boer RD, Haije WG, Veldhuis JBJ. Determination of structural, thermodynamic and phase properties in the Na2SH2O system for application in a
chemical heat pump. Thermochim Acta 2002;395:319.
[89] Posern K, Kaps C. Humidity controlled calorimetric investigation of the
hydration of MgSO4 hydrates. J Therm Anal Calorim 2008;92:9059.
[90] Zondag HA, Kalbasenka A, van Essen M, Bleijendaal L, Schuitema R,
van Helden W, et al. First studies in reactor concepts for thermochemical
storage; 2009. Available from: ftp://ftp.ecn.nl/pub/www/library/report/
2009/m09008.pdf.
[91] Bales C, Gantenbein P, Jaenig D, Kerskes H, van Essen M, Weber R. Final
report of Subtask B chemical and sorption storage the overview: a report of
IEA solar heating and cooling programme-Task 32 advanced storage concepts
for solar and low energy buildings; 2008. Report B7 of Subtask B; 2008.
Available from: http://archive.iea-shc.org/publications/downloads/task32b7.
pdf.
[92] Bales C, Gantenbein P, Jaenig D, Weber R. Laboratory prototypes of thermochemical and sorption storage units: a report of IEA solar heating and
cooling programme-Task 32 advanced storage concepts for solar and low
energy buildings; 2007. Report B3 of Subtask B; 2007. Available from: http://
archive.iea-shc.org/publications/downloads/task32-Laboratory_Prototype
s_of_Thermo-Chemical_and_Sorption_Storage_Units.pdf.
[93] Bales C, Gantenbein P, Jaenig D, Kerskes H, Summer K, van Essen M, et al.
Laboratory tests of chemical reactions and prototype sorption storage units:
a report of IEA solar heating and cooling programme-Task 32 advanced
storage concepts for solar and low energy buildings; 2008. Report B4 of
Subtask B; 2008. Available from: http://archive.iea-shc.org/publications/
downloads/task32b4.pdf.
[94] van Essen VM, Zondag HA, Schuitema R, van Helden WGJ, Rindt CCM.
Materials for thermochemical storage: characterization of magnesium sulfate; 2009. Available from: ftp://ftp.ecn.nl/pub/www/library/report/2009/
m09001.pdf.
31
[95] van Essen VM, Cot Gores J, Bleijendaal LPJ, Zondag Ha, Schuitema R, Bakker
M, et al. Characterization of salt hydrates for compact seasonal thermochemical storage. In: Proceedings of the ASME third international conference
of energy sustainability; 2009.
[96] van Essen VM, Bleijendaal LPJ, Kikkert BWJ Zondag HA, Bakker M,
Bach P.W. Development of a compact heat storage system based on salt
hydrates; 2010. Available from: ftp://ftp.ecn.nl/pub/www/library/report/
2010/m10095.pdf.
[97] Bertsch F, Mette B, Asenbeck S, Kerskes H, Mller-Steinhagen H. Low
temperature chemical heat storage-an investigation of hydration reactions;
2009. Available from: https://talon.stockton.edu/eyos/energy_studies/con
tent/docs/effstock09/Session_6_2_Thermochemical_storage/49.pdf.
[98] Hongois S, Kuznik F, Stevens P, Roux J-J. Development and characterisation
of a new MgSO4zeolite composite for long-term thermal energy storage. Sol
Energy Mater Sol Cells 2011;95:18317.
[99] Zondag HA, van Essen VM, Bleijendaal LPJ, Kikkert BWJ, Bakker M. Application of MgCl2 6H2O for thermochemical seasonal solar heat storage; 2010.
Available from: ftp://ftp.ecn.nl/pub/www/library/report/2010/m10094.pdf.
[100] Zondag HA, Kikkert BWJ, Smeding S, Bakker M. Thermochemical seasonal
solar heat storage with MgCl2 6H2O: rst upscaling of the reactor; 2011.
Available from: ftp://ftp.ecn.nl/pub/www/library/report/2011/m11071.pdf.
[101] Zondag HA, van Helden WGJ, Schuitema R, Bakker M. First systems studies
and characterisation studies of MgSO4 as a TCM for compact thermal storage;
2008.
Available
from:
ftp://ftp.ecn.nl/pub/www/library/report/2008/
m08061.pdf.
[102] Yang FS, Wang GX, Zhang ZX, Meng XY, Rudolph V. Design of the metal
hydride reactors-A review on the key technical issues. Int J Hydrogen Energy
2010;35:383240.
[103] Klyamkin SN. Metal hydride compositions on the basis of magnesium as
materials for hydrogen accumulation. Russ J Gen Chem 2007;77:71220.
[104] Bogdanovic B, Ritter A, Spliethoff B, Straburger K. A process steam generator
based on the high temperature magnesium hydride/magnesium heat storage
system. Int J Hydrogen Energy 1995;20:81122.
[105] Felderhoff M, Bogdanovi B. High temperature metal hydrides as heat storage
materials for solar and related applications. Int J Mol Sci 2009;10:32544.
[106] Polanski M, Pociski T, Kunce I, Bystrzycki J. Dynamic synthesis of ternary
Mg2FeH6. Int J Hydrogen Energy 2010;35:125766.
[107] Herrich M, Ismail N, Lyubina J, Handstein A, Pratt A, Guteisch O. Synthesis
and decomposition of Mg2FeH6 prepared by reactive milling. Mater Sci Eng, B
2004;108:2832.
[108] Bogdanovi B, Reiser A, Schlichte K, Spliethoff B, Tesche B. Thermodynamics
and dynamics of the MgFeH system and its potential for thermochemical
thermal energy storage. J Alloys Compd 2002;345:7789.
[109] Sheppard DA, Paskevicius M, Buckley CE. Thermodynamics of hydrogen
desorption from NaMgH3 and its application as a solar heat storage medium.
Chem Mater 2011;23:4298300.
[110] Reiser A, Bogdanovi B, Schlichte K. The application of Mg-based metalhydrides as heat energy storage systems. Int J Hydrogen Energy 2000;25:
42530.
[111] Sekhar BS, Muthukumar P, Saikia R. Tests on a metal hydride based thermal
energy storage system. Int J Hydrogen Energy 2012;37:381824.
[112] Stephan K, Schmitt M, Hebecker D, Bergmann T. Dynamics of a heat
transformer working with the mixture NaOHH2O. Int J Refrig 1997;20:
48395.
[113] Weber R, Dorer V. Long-term heat storage with NaOH. Vacuum 2008;82:
70816.
[114] Tanaka T, Sakuta K, Kamimoto M, Tani T, Sawata S, Horigome T. Solar thermal
energy storage using heat of dilution: analysis of heat generation in multistage mixing column. Energy Convers 1978;18:5765.
[115] Wyman C, Castle J, Kreith F. A review of collector and energy storage
technology for intermediate temperature applications. Sol Energy 1980;24:
51740.
[116] Cacciola G, Giordano N. Chemical processes for energy storage and transmission. Appl Energy 1986;25:31537.

Art. 42. A Review of Promising Candidate Reactions For Chemical Heat Storage

Enviado por

Dados do documento

Título original

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Art. 42. A Review of Promising Candidate Reactions For Chemical Heat Storage

Enviado por

Direitos autorais:

Formatos disponíveis

Renewable and Sustainable Energy Reviews 43 (2015) 1331

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

A review of promising candidate reactions for chemical heat storage

Corresponding author. Tel./fax: 86 21 34206548.

Energy is an important element for the economic growth, social

T. Yan et al. / Renewable and Sustainable Energy Reviews 43 (2015) 1331

conservation. However, on the one hand, the renewable energy

(2) Good reversibility without apparent secondary reaction;

The compound A is split into chemical substances B and C

The reaction enthalpy is 66.8 kJ/mol ammonia at 20 MPa and

T. Yan et al. / Renewable and Sustainable Energy Reviews 43 (2015) 1331

In addition, the temperature of this endothermic reaction is

reactivity under the circumstance of suitable catalysts [15]. Fig. 2

Fig. 3 shows the thermal energy storage system using the

HCOOCH3 2H2 -2CH3 OH

T. Yan et al. / Renewable and Sustainable Energy Reviews 43 (2015) 1331

Compared to present gas phase reaction, the reaction pressure

CH4 g CO2 g-2COg 2H2 g

In theory, endothermic reactions via solar energy for this

The chemical reaction heat storage technology based on solar

This liquidgas endothermic reaction occurs at 353363 K in

Fig. 5 illustrates the basic principle of isopropanol/acetone/

T. Yan et al. / Renewable and Sustainable Energy Reviews 43 (2015) 1331

NH4 HSO4 l M2 SO4 s-NH3 g H2 Og M2 S2 O7 l

M2 S2 O7 l-M2 SO4 s SO3 g

Fig. 5. Isopropanol/acetone/hydrogen chemical reaction heat storage system.

upgrading. The thermal efciency of the system was around 38%

Besides, the use of metal oxides (MO) to form intermediate

NH4 HSO4 l MOs-NH3 g H2 Og MSO4 s

MSO4 s-MOs SO3 g

Additionally, the reactions of twenty ve different metal

The actual temperature required for energy storage stage (T1)

2.1.3. Chemical reaction heat storage using solidgas reaction

NH4 HSO4 lNH3 g H2 Og SO3 g

The reverse synthesis reaction is:

NH3 g H2 Og SO3 gNH4 HSO4 l

T. Yan et al. / Renewable and Sustainable Energy Reviews 43 (2015) 1331

The redox reaction can be given by the following equation:

Fahim and Ford [44] illuminated the selection criteria of

In addition, the direct solar thermal dissociation of ZnO into its

The transformation temperature of Fe2O3/Fe3O4 is 1188 K with the

Mller and Palumbo [45] developed a solar chemical reactor for

The principle of chemical reaction heat storage system using

The CaO/CO2 reaction system is very attractive for storing high

T. Yan et al. / Renewable and Sustainable Energy Reviews 43 (2015) 1331

Considering the above-mentioned aspects, CO2 gas resulting

high reaction enthalpy and fast kinetics with an equilibrium

Kyaw et al. [51] investigated the corresponding operating

Fig. 8 shows the schematic diagram of the chemical reaction

Fig. 9 shows the working principle of the chemical reaction

T. Yan et al. / Renewable and Sustainable Energy Reviews 43 (2015) 1331

Fig. 8. Schematic diagram of CaO/Ca(OH)2 chemical reaction heat storage system.

dehydration dynamics. The porous materials, such as expanded

temperature reduction needs further investigation. The maximal

T. Yan et al. / Renewable and Sustainable Energy Reviews 43 (2015) 1331

different. Kato et al. [69] proposed chemical reaction heat storage

They investigated the kinetics and the thermodynamics of this

2.2. Chemical sorption heat storage

where p is the equilibrium pressure of the solidgas pair, H and

2.2.1. Ammoniated salt pairs

Here, MX is the solid chemical reactant or liquid absorbent.

Fig. 10. Diagram of ClausiusClapeyron showing operation principle.