Energy & Buildings 164 (2018) 239–253

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Energy & Buildings

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Thermochemical seasonal solar energy storage for heating and cooling

of buildings
Gorazd Krese, Rok Koželj, Vincenc Butala, Uroš Stritih∗
Faculty of Mechanical Engineering, University of Ljubljana, Askerčeva 6, 1000 Ljubljana, Slovenia

a r t i c l e i n f o a b s t r a c t

Article history: Actual national and international energy strategies generally encourage the use of renewable energy
Received 12 January 2017 sources. Thermal energy storage (TES) offers various opportunities in the design of renewable en-
Revised 21 December 2017
ergy systems. Thermochemical heat storage has gained popularity among researches because of higher
Accepted 22 December 2017
energy density and lower heat loss compared to sensible and latent heat storage. On the other side solar
Available online 12 January 2018
energy has been recognized as one of the renewable energy sources with the most potential. This pa-
Keywords: per reviews thermochemical heat storage technologies and systems with emphasis on systems involving
Thermochemical heat storage solar energy utilization in buildings. The studies are reviewed based on used storage materials, system
TCM configuration as well as models to predict and optimize system performance.
Adsorption © 2018 Elsevier B.V. All rights reserved.
Solar energy
Heating
Cooling

1. Introduction
The key targets of the European Union (EU) 2030 Energy Strat-
egy is to reduce greenhouse gas (GHG) emissions by at least 30%
compared to 1990 levels, increase the share of renewable energy
sources in final energy use to at least 27% and achieve an energy
efficiency increase of at least 27%. Improving the energy perfor-
mance of buildings is the key to achieve these goals, as buildings
are responsible for 40% of energy use and 36% of CO2 emissions
in the EU [1,2]. The easiest and also the most promising measure
is to increase the utilization of solar energy. Due to the stochas-
tic nature of solar energy the use of heat storage technologies is
necessary to realize its full potential.
Heat storage can be accomplished through physical or chemi-
cal processes. With respect to the form of heat involved we distin-
guish between sensible and latent physical heat storage methods.
Sensible heat storage is achieved through the temperature rise of
the storage material. In this case the density of the stored ther-
mal energy (i.e. stored energy per unit volume or mass) depends
on the temperature lift and thermal capacity of the storage mate-
rial. Latent heat storage involves heat interactions associated with
a phase change of a material (at constant temperature), commonly
from liquid to solid, and vice versa. Latent heat storage generally
allows higher heat densities than sensible heat storage, since ther-
mal energy change during phase change in usually significantly
∗
Corresponding author.
E-mail address: uros.stritih@fs.uni-lj.si (U. Stritih).
higher than the energy change due to temperature rise of a chosen
material. Nevertheless sensible heat storage systems are still the
prevalent technology for seasonal solar energy storage because of
higher thermal stability and significantly lower cost of the involved
storage materials compared to phase change materials (PCMs).
On the other side there are thermochemical TES systems which
are not yet commercially viable. Thermochemical heat storage in-
volves reversible chemical reactions. During the charging process
heat is supplied to the storage material which causes an endother-
mic reaction. The supplied heat can be stored for an arbitrary time
(almost) without heat loss as long as the products of the endother-
mic reaction are separated. This combined with a several times
higher stored thermal energy density compared to sensible and
latent storage (Fig. 1) makes thermochemical materials (TCM) a
promising alternative for mid- and long-term heat storage.
The main objective of this paper is to review thermochemical
heat storage technologies and systems with emphasis on systems
involving solar energy utilization in buildings; hence with focus
only on TCMs with a charging temperature below 140 °C [3]. The
paper is organized as follows: Section 2 sums up the fundamen-
tals of thermochemical heat storage and contains an overview of
TCMs suitable for solar energy storage. Sections 3 presents’ pos-
sible system configurations for thermochemical heat storage and
evaluates applications appropriate for reducing the energy needs
of buildings. An overview of models for predicting and optimizing
the performance of thermochemical storage systems in included in
Section 4. Section 5 concludes the paper.

https://doi.org/10.1016/j.enbuild.2017.12.057
0378-7788/© 2018 Elsevier B.V. All rights reserved.
240 G. Krese et al. / Energy & Buildings 164 (2018) 239–253

Fig. 1. Energy density of thermal storage technologies (adopted from [4]).

Fig. 2. Classification of chemical heat storage.

2. Thermochemical heat storage

2.1. Basics

Thermochemical heat storage is generally classified under

chemical heat storage processes (Fig. 2). Under the term thermo-
chemical heat storage we usually summarize sorption heat storage
processes. Some authors [e.g. [4]] also mention thermochemical
storage without sorption but with no exact definition of the lat-
ter. Sorption can be defined as a phenomenon of fixation of a gas
by a substance in solid or liquid phase [5]. We distinguish between
adsorption and absorption. The term absorption is used when the
molecules of a substance in gas phase enter a liquid (usually) or
solid thereby changing the composition of the liquid or solid [6].
Adsorption is defined as binding of a gas on a surface of a solid or
porous material [4]. Adsorption is further divided in physical ad-
sorption or physisorption and chemical adsorption or chemisorp-
tion. The attraction between the gas and solid in physisorption
is caused by Van der Waals forces. Chemisorption on the other
hand is based on valence forces which form stronger bonds than
Van der Waals forces. Consequently chemisorption processes en-
able to achieve higher thermal energy densities than physisorption
however may also be irreversible and therefore unsuitable for heat
storage applications. In the following sections only reversible sorp-
tion processes are considered.
Reversible sorption heat storage processes can be written in the
following way:
AB + Q ↔ A + B
where AB is a compound of components A and B, Q designates the
heat supplied to dissociate AB into components A and B. Hence
Fig. 3. Thermochemical heat storage cycle.
the dissociation of compound AB represents an endothermic re-
action. When components A and B are put in contact heat is re-
leased (exothermic reaction) during the forming of compound AB.
The supplied heat Q can be stored with negligible heat loss as long
the components A and B are separated. As a result of this the dis-
sociation of compound AB is called charging while the forming of
compound AB represents the discharging process of the thermo-
chemical heat storage cycle (Fig. 3). The component which is des-
orbed during charging is named adsorbate. The material capable
of adsorbing (absorbing) the other component is called adsorbent
(absorbent). The term adsorptive (absorptive) is also used for the
adsorbate in the desorbed state, especially when adsorbate and ad-
sorptive differ in chemical structure (not the case in physisorption).
In heat storage applications mainly water (vapor) is used as adsor-
bate because of its availability (i.e. cheap) and nontoxicity.
The heat needed for desorption can be divided into three parts
(1)
[5]:
Q = Qsens + Qcond + Qbind (2)
 G. Krese et al. / Energy & Buildings 164 (2018) 239–253
Fig. 4. Break down of the required heat for desorption for Zeolite as an example
[5].
Here, Qsens represents the sensible heat needed to heat the ab-
sorbent to the temperature required for desorption. Qcond is the
heat needed to vaporize the adsorbate while Qbind is the heat re-
quired to overcome the sorption forces. The latter is therefore usu-
ally termed as binding heat. As seen from Fig. 4 Qbind decreases
with the increase of sorbate concentration. This means than more
needed at the beginning of the charging process when the sorbate
concentration is low. For heat storage applications the contribution
of Qbind must be as low as possible compared to Qcond since it re-
sults in lower temperatures required for desorption [7].
2.2. Reactants
Knowledge on materials is a prerequisite to design thermal
storage systems and their components. Different sorption work-
ing pairs or reactants have been studied for thermal energy stor-
age applications. In sorption storage systems, low-cost crystalline
or amorphous silica-based porous materials and their composites
with hygroscopic inorganic salt hydrates (e.g., CaCl2 ) have been
considered as the most promising sorbents. Despite many scientific
efforts, none of these materials currently meet the requirements
for large-scale applications. Through the literature [4,7–14] the fol-
lowing requirements have been exposed:
• high energy density;
• low charging temperature;
• high uptake of sorbate;
• thermal and chemical stability;
• high thermal conductivity;
• high heat transfer with the heat transfer fluid;
• moderate operating pressure range;
• non-corrosive;
• environmental safety;
• low cost.
Of these, the sorption properties are the foundations to find-
ing suitable TCM materials for any given application, however the
comprehensive evaluation of sorption properties of available sor-
bents is a time consuming task as it requires precise measure-
ments of a set of sorption isobars, isosters and isotherms under
a wide range of temperatures and pressures. The energy storage
densities and charging / discharging temperatures of some materi-
als suitable for thermochemical heat storage are listed in Table 1.
The most promising materials have low charging temperatures and
high energy storage densities.
For seasonal solar energy storage in buildings water is the pri-
mary sorbate substance of choice since it satisfies the conditions of
environmental friendliness and low cost. Hence, hydrophilic mate-
241
rials are appropriate for the counterpart reactant or the sorbent.
Silica gels are widely studied as hydrophilic compounds due to
their high affinity to water vapor, large water sorption capacity
at low humidity, low cost, and easy regeneration [12]. However,
silica gels have one major drawback, i.e. they provide low mate-
rial energy densities because of the low hydrophilic characteris-
tic within the working window. Therefore the application prospect
of silica gels in solar energy storage is obscure. Zeolites on the
hand are more hydrophilic than silica gel, because the strong inter-
action between their electrostatically charged framework and the
water molecules [59]. Consequently they require a higher desorp-
tion or charging temperature, which can be altered with dealumi-
nation, ion exchange or the variation of the aluminum – silicon
ratio [35,56,59,102]. Another option is to impregnated mesoporous
silicates with hygroscopic salts [103–107] to increase performance
of the sorption reaction and enhance heat and mass transfer. Nev-
ertheless, these composite materials suffer from leakage of salt
species and are also corrosive due to the contained salts [108].
Some authors [3,41,56–60] favor microporous aluminophos-
phates (APO-n) and their modified analogues (SAPO-n and MeAPO-
n) to modified zeolites, because of lower discharging temperatures
and higher energy densities. The main focus in research of ma-
terials suitable for heat storage applications has been to increase
the uptake of sorbate (water) with incorporating silicon or metal
cations in aluminophosphates [3,109,110]. The performance of the
latter substances usually degrades after a few charging/discharging
cycles because of framework structure degradation and dislodge-
ment of incorporated cations from the framework [56,57,109,110].
However, the main limitation of aluminophosphates compared to
zeolites (and silica gels) is their high synthesis cost [12,41,59].
In absorption heat storage studies mostly calcium chloride
(CaCl2 ), lithium chloride (LiCl), lithium bromide (LiBr) and sodium
hydroxide (NaOH) are used as the reactive sorbent with water as
sorbate. Of the listed substances NaOH is a base while the other
compounds are hygroscopic salts and are thus applied in form of
solutions. Strong acids and bases have the advantage of high wa-
ter uptake and low cost but are also corrosive and require a high
charging temperature.
In contrast to sorption processes chemical reactions are char-
acterized by a change in the molecular configuration of the com-
pound involved during the reactions. Though chemical reactions
possess excellent storage potential based on the analysis on the
material level, their performance in actual systems requires fur-
ther research. Due to the deliquescence, swelling and agglomera-
tion phenomena after several incipient cycles, the reaction is very
difficult to continue [7]. Furthermore because chemical reactions
induce volume modification of the solid an obvious hysteresis may
exist.
Since sorption processes demand lower activation energy to
start the reaction than chemical reactions, they are more suitable
for low temperature applications such as seasonal solar energy
storage. Furthermore, because liquid–gas absorption systems are
limited with corrosion and crystallization issues, only heat storage
applications utilizing solid–gas adsorption processes are discussed
in the subsequent sections.
3. Sorption storage systems
According to the system design, sorption thermal storage sys-
tems can be divided into open and closed systems. The key dif-
ference between these system configurations is in the storage of
the gas reactant (sorbate). Closed system are isolated from the at-
mospheric environment, therefore they require an additional vessel
for storing the working fluid. In contrast, the working fluid vapor
is released to the environment in open systems, which means that
only water (vapor) can be used as the sorbate.
242 G. Krese et al. / Energy & Buildings 164 (2018) 239–253

Table 1
Materials used in thermochemical heat storage studies.

Phenomena Sorbent Sorbate Charging temperature (°C) Discharging temperature (°C) Energy density (kWh/m3 ) Reference

Adsorption
silica gel H2 O 88 32 50–125 [15–29]
zeolite 13Xa H2 O 160–230 20–40 97–160.5 [8,25,30–46]
zeolite 4Ab H2 O 180 65 130–148 [39,47–52]
zeolite 5Ac H2 O 80–120 20–30 83 [53–55]
APO-nd H2 O 95–140 40 240 [3,41,56–60]
SAPO-nd H2 O 95–140 40 – [3,41,56–59]
MeAPO-nd H2 O 95–140 40 – [3,56,57,60]
Absorption
CaCl2 H2 O 45–138 21 120–381 [61–66]
LiCl H2 O 66–87 30 253–400 [23,62]
LiCl2 H2 O 46–87 30 253 [8,10,23]
LiBr H2 O 40–90 30 252–313 [62,67–71]
NaOH H2 O 50–95 70 154–250 [23,62,72–79]
SrBr2 H2 O 80 – 60–321 [48,80–84]
Chem. react.
BaCl2 NH3 56–70 40 787 [85–89]
CaCl2 NH3 95–99 – 673 [86,90,91]
CaSO4 H2 O – 89 390 [92]
CuSO4 H2 O 92 – 575 [93]
Li2 SO4 H2 O 103 – 255 [93]
MgCl2 H2 O 130–150 30–50 556–695 [61,64,94]
MgSO4 H2 O 122–150 120 420–924 [12,95]
MnCl2 NH3 152 – 624 [86]
Na2 S H2 O 80–95 80–110 780 [96–100]
a
|(Na+ 2 )29 (H2 O)240 | [Al58 Si134 O384 ] [101].
b
|Na+ 12 (H2 O)27 |8 [Al12 Si12 O48 ]8 [101].
c
|Ca2+ 6 (H2 O)27 |8 [Al12 Si12 O48 ]8 [101].
d
A = Al, S = Si, Me = transition metal, n = structure type

Fig. 5. Operation principle of sorption storage systems: (left) closed, (right) open.

Closed system generally consists of two vessels (Fig. 5).
Namely, a reactor where reactive sorbent is located and a con-
denser/evaporator where liquid water is collected. The vessels are
connected by a conduct as a passage for vapor. The charging pro-
cess consists of a desorption reaction in the reactor and a phase
change reaction in the condenser. When a high temperature heat
source (e.g. from solar collector), is added to the reactor, the sor-
bate starts to escape from the sorbent. Through the duct, the va-
por turns into its liquid state in a condenser at a low temperature
level. The heat of condensation is taken away and released to the
heat sink. After the charging process is finished, the reactor and
the condenser are separated from each other. If heating is needed,
the reactor and the condenser/evaporator are connected again. The
discharging process works in a reverse direction, whereby an ad-
ditional low temperature heat source is needed for water evapora-
tion. Closed systems allow adjusting the operating pressure of the
working fluid and are able to reach higher output temperatures for
heating applications compared to open systems [14]. However, the
regeneration of closed systems usually requires a higher tempera-
ture level. Therefore closed systems are appropriate especially for
small-scale applications.
In open systems (Fig. 5) a dry air stream is guided to a re-
actor filled with sorbent during the charging process. Water ad-
sorbed/absorbed by the sorbent is extracted by the hot air and ex-
its the reactor bed. Hereby the air is adiabatically cooled. During
discharging humid cooler air stream enters into the (desorbed) re-
actor. Part of the water vapor in the air is attracted by the sorbent.
The air temperature decreases, due to the released sorption heat.
Weather conditions are limiting the operation of open systems. The
ambient air humidity must be sufficient for a good discharging
rate. Thus, the air must be additionally humidified when the ambi-
ent moisture content is insufficient. The design of open systems is
much simpler and consequently cheaper compared to closed sys-
tems, since they do not require the use of condensers, evaporators
and working fluid storage reservoirs. However, the main advantage
of using the open system configuration are the better heat and
mass transfer conditions, because the heat transfer fluid (air) is in
direct contact with the solid reactant, while closed systems require
a separate heat transfer loop and hence a heat exchanger in the
reactor (heat transferred mainly by conduction). On the other side
open systems may suffer from high (electric) energy consumption
for overcoming pressure losses through the reactor.
 G. Krese et al. / Energy & Buildings 164 (2018) 239–253
Fig. 6. HYDES seasonal storage system concept [25].
The main objective of this section is to review the available
equipment used for sorption heat storage, especially concerning
gas–solid reactors for solar energy utilization.
3.1. Closed systems
A closed adsorption system with silicagel-H2 O as the working
pair suitable for the long-term storage of low-temperature heat
was developed within the HYDES project [24,25,27]. The developed
storage system consists of multiple storage units combined with
solar collectors (Fig. 6). Each storage unit includes an absorber with
an integrated heat exchanger, which is connected through a valve
to a combined evaporator/condenser unit. Both the high tempera-
ture heat for desorption as well as the low temperature heat for
evaporation heat is provided by the solar collectors. To study the
performance of the proposed design a prototype with two sorp-
tion storage units with a combined volume of 1.25 m3 (1.1 m3 of
silica gel)connected to solar collectors with an area of 20.4 m2 was
installed in a low energy house to provide heating and domes-
tic hot water production. Two heat sink options for condensation
were provided. Namely, a 10 m3 rainwater reservoir for simultane-
ous condensation (with desorption) and water from the solar plant
loop (as in evaporation) for asynchronous condensation. The ex-
perimentally determined storage density of silica gel was around
20% lower from the theoretically expected value (i.e. 123 kWh/m3
compared to 150 kWh/m3 ).
The follow-up project of HYDES was called MODESTORE
[24–27,39]. Within this project a second generation storage mod-
ule prototype was developed (Fig. 7). To improve the performance
the reactor and the condenser/evaporator were combined in a sin-
gle casing, thereby achieving a significantly more compact design.
The reactor contains a spiral heat exchanger containing the silica
gel, whereby a channel in the center is left free for vapor diffu-
sion. In contrast to the HYDES prototype, where the evaporator
was submerged at the bottom of the reservoir for the entire wa-
ter for adsorption, only a small amount of water was pumped into
the evaporator area at the bottom of the storage module, which
significantly improved the heat transfer. The volume of laboratory
tested prototype was approximately 350 l while the reactor con-
tained around 200 kg of silica gel. The experimental performance
of the prototype was unsatisfactory, since the energy storage den-
sity of silica gel on the prototype scale was below that of water
sensible storage (50 kWh/m3 ). The discrepancy between the mate-
rial and system scale energy densities was due to the adsorption
conditions required to guarantee desorption under the tempera-
ture provided by the solar collectors and the heat sinks (i.e. sil-
243
Fig. 7. Scheme of the MODESTORE storage module prototype [39].
ica gel water content between 3% and 13%). The authors therefore
declared the working pair silica gel-H2 O as unsuitable for solar en-
ergy storage systems for building applications. Stritih and Bombač
[29] came to same conclusion with a similarly designed closed
storage unit prototype with silica gel-H2 O working pair, but on a
smaller scale (5.7 kg of silica gel).
Schreiber et al. [31] developed a laboratory-scale closed heat
storage unit with zeolite 13X and water as the adsorption pair
suitable for cogeneration in industrial batch processes (i.e. brew-
ery). The design of the storage unit is similar to that of the MODE-
STORE prototype, since the absorber and evaporator/condenser unit
are integrated into a single container (Fig. 8) without valves in be-
tween. In contrast to the MODESTORE module a lamellae heat ex-
changer is used in the reactor bed while thermal oil was used as
the heat transfer fluid to allow temperatures higher than 100 °C.
For the evaporator/condenser heat exchanger water was used as
the heat transfer fluid. The absorber contained 20 kg of zeolite.
In the experiment the heat supply was provided via an electric
heater while the heat demand was emulated using a water reser-
voir, which was heated during the discharging process. Measure-
ments were conducted with constant power of the electric heater.
The temperature was 120 °C during adsorption while the charg-
ing temperature was up to 200 °C (i.e. too high for solar energy
storage). Three temperature profiles for evaporation/condensation
were tested, namely 60/90 °C, 90/60 °C and 90/ 90 °C. The results
of the study showed a strong dependence between the storage
unit performance and the evaporation/condensation temperatures,
whereby a low evaporation temperature proved to be crucial.
244 G. Krese et al. / Energy & Buildings 164 (2018) 239–253
Fig. 8. Scheme of the closed zeolite-H2 O heat storage unit [31].
Fig. 9. Closed adsorption cold storage system [38].
Lu et al. [38] developed an closed adsorption cold storage sys-
tem also using zeolite 13X and water as a working pair. The sys-
tems has been has been installed in an internal combustion en-
gine locomotive for producing chilled water for air conditioning
the driver’s cab. In contrast to the previously mentioned closed
system with zeolite – H2 O working pair [31] the evaporator and
condenser are separate units, since the evaporator is used to ab-
sorb heat from the cabin (Fig. 9). During charging the adsorbent
bed is heated by the locomotives internal combustion engine ex-
haust gasses while ambient air is used to cool the condenser and
the adsorber during discharging. The prototype system was filled
140 kg of zeolite grains and 185 kg of water. The system reached an
average cooling power of 4.1 kW while a maximum storage capac-
ity of 5.5 kWh was obtained at an adsorption bed temperature of
125 °C. Since the expected maximal storage capacity was 23.3 kWh
the authors concluded that heat and mass transfer of the adsorber
need to be improved for better performance.
Lass-Seyoum et al. [111,112] developed a large scale adsorp-
tion storage system (volume 750 l) with water and an unspecified
porous material as the adsorption pair. The storage systems consist
of two subsystems connected by a valve, i.e. the storage reactor
and the evaporator/condenser unit (Fig. 10). The reactor contains
a copper matrix heat exchanger, which enables to reach a rela-
tively uniform temperature distribution in the reactor (Fig. 10). So-
lar thermal heat pipes with a capacity of 4 kW served as the high
temperature source. Several dynamic performance tests were car-
ried out. The maximum charging temperature varied between 100
and 120 °C while the maximum discharging temperatures lied in
the interval 65–70 °C. The daily average heat output ranged be-
tween 2.5 and 3 kW. The achieved material energy storage den-
sity was 30–40% lower than the values expected from laboratory
tests due to the significantly lower charging temperatures (labora-
tory 220 – 250 °C). For his reason the authors intend to use a stor-
age material more suitable for the available charging temperature
range in the developed storage system.
TNO [53–55] developed and build modular seasonal storage
system, whereby zeolite 5A and water were chosen as the reac-
tants. The system basically consists of two separate cylindrical ves-
sels, i.e. heat storage (reactor) and evaporator/condenser (single)
unit, connected to a high and low temperature heat source. The
reactor is built of parallel arranged finned heat exchangers packed
with zeolite (Fig. 11), placed in a stainless steel vessel. The evap-
orator/condenser unit consists of a combination of a copper fin
connected on one side to a copper spiral and a capillary working
material on the other side with a heat exchange area of 1.4 m2
(Fig. 11). A prototype filled with 41 kg of zeolite corresponding to
a storage capacity of 3 kWh was constructed, consisting of one re-
actor and one evaporator/condenser unit. A 12 kW electrical heater
served as the high temperature source while thermostatic water
bats were used as a low temperature heat source (evaporator)
and/or heat sink (condensation, discharging). Although the test re-
sults were in accordance with expectations, i.e. maximal heat stor-
age 4 kWh, heat output between 0.7 and 1.6 kW, the system energy
density was around 73% lower than the material energy density
(22 versus 83 kWh/m3 ). The authors expect that an approximately
60% performance increase can be achieved by optimizing the sys-
tem.
3.2. Open systems
Within the project MONOSORP [23,50,51] an open adsorption
heat storage with zeolite 4A and water as adsorption pair was de-
veloped. The storage system was designed for the inclusion in a
building ventilation system with heat recovery. During discharg-
ing the exhaust air flow is blown through the sorption material
which leads to a rise in temperature and dehumidification. The
leaving air stream is then guided into an air to air heat exchanger
(Fig. 12) where it releases heat to the fresh air stream. To achieve
a good heat transfer between air flow and sorption material hon-
eycomb monoliths with a numerous straight, small channels (large
contact area) were developed and made by extrusion of zeolite 4A
powder (Fig. 12). Apart from the good heat transfer the main ad-
vantage of these structures is the low pressure loss. The only re-
quired component aside from the monolith container is a water
to air heat exchanger (Fig. 12), which is connected to solar collec-
tors (i.e. high temperature heat source). Since a desorption tem-
perature above 160 °C was required, only evacuated tube collectors
were suitable. A lab scale prototype (Fig. 12) with volume of 100 l
(62 kg of zeolite) was build and connected to 4.4 m2 of collectors
via a finned tube heat exchanger. For air to air heat recovery a
plate heat exchanger was used. Both heat exchangers were com-
mercially available, not specifically designed for adsorption heat
storage. The prototype preformed satisfactory with an energy den-
 G. Krese et al. / Energy & Buildings 164 (2018) 239–253 245

Fig. 10. 750 l closed adsorption heat storage prototype: (left) scheme [111]; (right) temperature distribution inside the reactor [112].

Fig. 11. TNO adsorption storage module: (left) adsorber/desorber unit; (right) evaporator/condenser unit [55].

Fig. 12. MONOSORP prototype: (left) laboratory setup; (right) zeolite monolith [51].

sity of 130 kWh/m3 (without sensible heat) and a heat output be-
tween 1 and 1.5 kW, whereby a maximal temperature lift of 22 °C
was achieved. The charging rate on the other side ranged from 2
to 2.5 kW. Contrariwise, no data is available for the electrical power
consumption of the storage system. The discharging rate could be
increased with additional humidification of the exhaust air. Apart
from this the major drawbacks of the proposed systems are the
high desorption temperature and the high material and production
costs.
The follow-up project of MONOSORP is called SolSpaces
[42,113]. Within SolSpaces a new solar heating system, including
adsorption storage for seasonal energy storage with binderless ze-
olite 13X as adsorbent, has been developed. The system concept is
similar to the MonoSorp project with the difference that air solar
collectors were used (Fig. 13), therewith eliminating the need for a
water to air heat exchanger. The projects also differ in the reactor
design. In contrast to MONOSORP a packed bed of zeolite spheres
is used instead of honeycomb monoliths. The storage has been
further subdivided into smaller segments (Fig. 13) to improve the
thermal performance (i.e. reduced heat capacities and heat losses).
The developed system has been built up in full-scale in a research
building with vacuum tube air collectors for testing and demon-
stration. Although the building has an area of only 43 m2 it is
comparable to larger buildings, since it has a relatively high spe-
246 G. Krese et al. / Energy & Buildings 164 (2018) 239–253
Fig. 13. SolsSpaces project: (left) heating system scheme; (right) vertical cut through the storage systems [42].
Fig. 14. Separate adsorption storage: (left) unit concept; (right) reactor design [116].
cific heat demand due to a large surface-to-volume ratio. The build
storage unit has a total volume of 8 m3 and is filled with 4.3 m3
of zeolite grains (diameter 2 mm) with a heat storage capacity of
around 700 kWh. The unit is divided into four quadrants and each
quadrant itself is subdivided into six segments. The selection of the
segment pairs is realized through the opening and closure of aper-
tures in the outlet ducts, which are the only moving parts within
the reactor. On an exemplary (discharging) operation day the dis-
charging rate varied between 565 and 790 W while a temperature
lift between 22 and 28 °C was achieved. Low pressure drop and
mass flow rate of 90 kg/h contributes to low electrical power con-
sumptions of two fans which is only 20 W. The experiments also
showed that the flow through two segments of a segment pair
is quite homogeneous, meaning that the charging and discharging
process takes place simultaneously in both segments. The authors
plan to further monitor the developed system also during the dis-
charging period. Same as for the MONOSORP prototype the heat
output could be increased with humidifying the exhaust air stream
before it enters the storage unit.
Within the CWS [34,43,44,49,114–117] project a seasonal solar
storage system for a composite material of zeolite and salt was de-
veloped. The system was designed for integration in a solar com-
bisystem, i.e. solar collectors alternatively heat the combined stor-
age tank or supply the heat required for desorbing the storage ma-
terial. The main difference from the previously mentioned projects
lies in the design of the sorption storage unit. In contrast to the
MONOSORP and SolSpaces units, where sorption reactions occur
within the storage vessel, the CWS storage unit consists of an ex-
ternal reactor in which the adsorption/desorption takes place and
a separate storage vessel for hydrated and dehydrated storage ma-
terial as well as a material transport system (Fig. 14). The reactor
consists of two chambers, one chamber to load the material and
one chamber to regenerate it. Both chambers are separated by an
air to HTF (e.g. water, oil) heat exchanger (Fig. 14). During the re-
action the material is filled into the reactor from the top and emp-
tied through the outlet at the bottom, driven only by gravity. The
air enters the reactor from the side. A lab scale prototype reac-
tor with a storage volume of about 20 l was build. A thermostat,
connected to an air to oil heat exchanger in the reactor, was used
alternately as heat source or heat sink. The experiment was car-
ried out with zeolite 13X as the adsorbent. Although the prototype
suffered from significant heat losses (37% of released heat) due to
the uninsulated reactor, the prototype achieved a satisfactory heat
output of 750 W and a 30 °C temperature lift at an electrical power
consumption of 1600 W.
ZAE Bayern designed and installed an adsorption storage sys-
tem with zeolite 13X as adsorbent for providing space heating and
cooling to a school and jazz club connected to district heating sys-
tem [25,36,45]. The build storage system contains 70 0 0 kg of zeo-
lite and consists of three cylindrical storage modules connected in
series, a humidifier, water reservoir (for humidification) and a con-
trol unit. The storage units are connected to the district heating
system via a heat exchanger on the supply side, and a combined
air/radiator/floor heating system on the demand side (Fig. 15). The
storage system is used as a buffer between the district heating sys-
tem and space heating system of the school. The storage is charged
by the district heating system during off-peak periods (desorption
temperatures between 130 and 180 °C) while during peak hours
the building heating system can be powered only by the energy
stored in the zeolite, hereby reducing the peak power demand of
 G. Krese et al. / Energy & Buildings 164 (2018) 239–253
Fig. 15. Large scale open adsorption storage system connected to district heating system: (left) actual setup [36]; (right) schematic representation of the discharging process
[25].
the district heating system. During monitoring the system reached
a 19% lower energy density than the theoretical maximum value,
namely 124 kWh/m3 . In order to use the storage system as a desic-
cant cooling device for the mentioned jazz club the system was
additionally upgraded with a heat recovery device (exhaust air)
to cool the dried supply air exiting the zeolite modules, and a
supply air humidifier to adiabatically cool the air afterwards. The
heat recovery device consisted of an exhaust air humidifier with
an integrated heat exchanger and the supply air heat exchanger,
which were connected by a fluid circuit. Three desorption temper-
atures were tested, namely 130, 100 and 80 °C. The correspond-
ing achieved energy densities (in the same order) are as follows
168, 105 and 100 kWh/m3 . Although, higher energy densities were
achieved at higher desorption temperatures the best overall system
performance (COP) was achieved at the lowest tested desorption
temperature (i.e. 0.87). The payback time of the installed adsorp-
tion storage system was estimated to be 7–8 years. The authors
concluded that the system performance could further be enhanced
with an improvement and simplification of the operation control
strategies.
Zettl et al. developed a revolving drum reactor for open adsorp-
tion heat storage systems [47,52,118,119]. The reactor was designed
as a slowly rotating cylindrical drum to enable a steady mixing of
the storage material in granular form in order to reach homoge-
neous temperatures and to avoid over-hydration of the storage ma-
terial. Air is supplied/extracted from the reactor through pipe-in-
pipe air inlet/outlet construction, whereby the supply air is blown
through the outer part while the extracted air leaves the reactor
through the central pipe (Fig. 16). The main advantage of this de-
sign is that in contrast to fixed bed reactors no reaction front is
formed, since adsorptions takes places throughout the whole stor-
age material volume due to bed rotation. A lab scale reactor with a
maximum design heat output of 1.5 kW was built (Fig. 16). It was
filled with 70 l of a granular storage material, i.e. alternately zeo-
lite 4A (53 kg) and zeolite 13X (NaMSX) (50 kg), covering a volume
fraction of about 80% of the interior. Special care was taken in the
design of the reactor interior to avoid abrasion of the storage ma-
terial (e.g. no sharp edges). Only adsorption was monitored in the
reactor, desorption took place in a conventional drying oven prior
to the adsorption tests. During the adsorption tests the inlet air
was adiabatically humidified. Both materials reached a comparable
maximum temperature lifts of 36 °C. The test with zeolite 4A gen-
erated 10.5 kWh of heat and 11.9 kWh were reached with zeolite
13X, which corresponds to a stored energy density of 148 kWh/m3
for zeolite 4A and 154 kWh/m3 for zeolite 13X. The average heat
output during the tests was 1.2 kW while the combined electric
247
energy use for drum rotation and fan operation was around 100 W.
The authors plan to up-scale the developed reactor, whereby spe-
cial care will be taken on the containment material to guarantee
loss-free storage.
Johannes et al. [46] designed a high powered energy dense zeo-
lite heat storage system with the intention to shave the electricity
peak loads in a house by reducing the heating part of the demand.
A packed bed reactor system was built containing 80 kg of zeo-
lite 13X, which was split into two equal sized reactors, in order to
test serial and parallel configurations of reactors. The whole system
consists of two reactors and ducts to drive the airflow into the re-
actors (Fig. 17). An air treatment system was used to prepare (i.e.
heat and/or humidify) the airflow during the experiments. Several
tests have been carried out both during discharging and charging
at various flow rates, relative humidity and temperatures of hy-
dration. The experiments revealed that serial configuration of reac-
tors is unsuitable because the thermal mass of the second reactor
draws heat from the first one in serial configuration which results
in a unstable maximum heat output during discharging. For paral-
lel configuration the results show that the reactor is able to supply
a constant power of 2.25 kW for more than two hours while the
COP varied between1.7 and 6.8 depending on the air temperature
during charging and air humidity during discharging. For the next
step the authors plan to validate a numerical model of the system
to further optimize the developed storage system as well to nu-
merically asses the performance when coupled to a building.
Within the FlowTCS project [120] an open adsorption storage
system with an external reactor configuration has been developed,
whereby zeolite and salt impregnated zeolite were used as the
sorbent. The storage system consists of a reactor with approxi-
mately 30 l of zeolite and the adsorbent storage reservoir with
a volume of 200 l, thereby achieving a high flexibility regarding
both storage capacity and heat output. The reactor is designed as a
quasi-continuous cross flow reactor, i.e. the adsorbent flows down
through the reactor led by gravity and controlled by a rotary valve
through which it is discharged out of the reactor (Fig. 18). The
heat released during discharging is transported to the heating sys-
tem/buffer store via an air to water heat exchanger. During charg-
ing the air is heated up in the air to water heat exchanger. For
heat recovery an air to air heat exchanger was additionally inte-
grated into the reactor unit. The storage system was experimen-
tally tested by varying the air humidity and the heating demand.
The system performance was in compliance with the theoretically
expected thermal power and temperature lift based on the heat
storage density of the adsorbent. The developers further plan to in-
crease the system compactness, reduce heat losses and lower the
248 G. Krese et al. / Energy & Buildings 164 (2018) 239–253

Fig. 16. Revolving drum reactor: (left) laboratory setup; (right) cross section sketch [119].

4. Numerical modelling

Sorption storage systems can be designed and simulated with

Fig. 17. Experimental setup of an open adsorption storage system with reactors in
parallel configuration [46].
Fig. 18. External reactor concept during discharging [120].
charging temperature and also to test the concept in an in situ
setup.
the use of numerical models based on characteristics of the stor-
age material. In this way one can optimize the design of the stor-
age system and analyze its performance on an application scale
without having to perform costly experiments. Hence, only the
most promising storage systems and materials can be tested in
full scale experiments. There are generally three approaches for
modelling solid–gas adsorption processes, i.e. steady-state models,
lumped-parameter models and spatially resolved models. Steady-
state models disregard the heat and mass transfer kinetics inside
the adsorbent bed. Since these models assume that the adsorbate
and adsorbent are in thermodynamic equilibrium, they are suitable
only to predict the upper performance limit of the storage system.
Lumped-parameter models on the other hand consider the global
heat and mass transfer between the adsorbent bed and the sur-
rounding, but still threat the reactor as a homogenous control vol-
ume with an internally uniform state. Because of the higher accu-
racy compared to steady-state models, lumped-parameter models
can be used to approximately size the reactor or to simulate the
global performance of the reactor at different conditions. However,
for detailed modelling and optimization of processes occurring in-
side the reactor spatially resolved models are needed, as they con-
sider both heat and mass transfer during a process inside the re-
actor, i.e. temporospatial evolution of state variables (e.g. temper-
ature gradient inside the adsorbent bed). The drawback of using
spatially resolved models is that their computation requires solving
transient and spatial coupled heat and mass transfer balance equa-
tions with complicated boundary conditions, which involves the
application of specialized numerical methods. The mostly applied
discretization methods are the finite difference method (FDM), the
finite element method (FEM) and the finite volume method (FVM).
Despite the differences between the mentioned modelling ap-
proaches, all need an equilibrium isotherm to calculate the amount
of vapor uptake by the adsorbent at a given pressure and tem-
perature. The most widely used approaches for describing ad-
sorption equilibria are the Langmuir isotherm [121], BET isotherm
[122], Tòth isotherm [123] and the Dubinin–Polanyi (DP) theory
[124]. The latter is the most popular approach since all isolines
(isotherms, isobars, isosteres etc.) of an adsorption working pair
can be derived (extrapolated) based on one single characteristic
curve. The most celebrated expressions for fitting to an experimen-
tally obtained characteristic curve are the Dubinin-Radushkevich
(DR) equation [125] and its generalization the Dubinin–Astakhov
(DA) equation [126]. A crucial parameter of the Dubinin–Polanyi
 G. Krese et al. / Energy & Buildings 164 (2018) 239–253 249

Table 2
Summary of modelling efforts in adsorption heat storage and transformation studies.

Reference Sorbent Sorbate Aim Parameterization Equilibrium Kinetics Mass transport Numerical method Software

[136] silica gel H2 O system design 1D modified DA LDF Ergun eq. FDM MATLAB
eq.
[137] silica gel H2 O system design 2D Tòth isoth. LDF – FDM –
[21] silica gel H2 O system design 2D empirical eq. LDF Ergun eq. FVM –
[138]
[139] silica gel H2 O system design 2D Freundlich eq. LDF – FDM –
[140] silica gel H2 O system design 3D [141] LDF Darcy’s law FVM –
[19] silica gel H2 O system design 3D Tòth isoth. – – FVM Ansys Fluent
[142,143] silica gel H2 O system analysis lumped Tòth isoth. LDF – – MATLAB
[144] silica gel H2 O system analysis lumped empirical eq. LDF – BDF –
[145]
[146] silica gel H2 O system analysis 1D Tòth isoth. [147] – FDM –
[148] silica gel H2 O system analysis 1D Modified DA – – FDM MATLAB
eq.
[149] silica gel H2 O system analysis 2D empirical eq. NS eq. – FEM COMSOL
Multiphysics
[20] silica gel H2 O process understanding 1D empirical eq. LDF – FDM –
[150]
[150] silica gel H2 O process understanding 1D empirical eq. LDF Darcy’s law FDM –
[15] silica gel H2 O process understanding 2D Tòth isoth. LDF Darcy’s law FVM Ansys Fluent
[151] silica gel H2 O process understanding 2D modified DR derived derived FDM –
eq.
[34] zeolite H2 O system design 1D DA eq. LDF Brinkman eq. FEM COMSOL
Multiphysics
[152] zeolite H2 O system design 1D Langmuir isoth. – Ergun eq. FDM –
[153–155] zeolite H2 O system design 2D DR eq LDF – FEM COMSOL
Multiphysics
[31] zeolite H2 O system analysis lumped DP theory, LDF – – Modelica
Núñez
modification
[156]
[157] zeolite H2 O system analysis 1D empirical eq LDF Darcy’s law FVM Dymola
[158] zeolite H2 O system analysis 1D modified DA LDF – FVM –
eq. [159]
[160] zeolite H2 O system analysis 1D Gorbach model – – – PDEX, TRNSYS
[161]
[162] zeolite H2 O system analysis 1 D empirical eq – Ergun eq. FVM –
[163] zeolite H2 O system analysis 1 D empirical eq LDF Darcy’s law FDM Dymola
[164,165] zeolite H2 O system analysis 1 D empirical eq – Darcy’s law FDM –
[32] zeolite H2 O system analysis 2 D modified LDF Poiseuille, FVM –
Langmuir isoth. Knudsen flow
[166]
[167,168] zeolite H2 O system analysis 2D empirical eq – Ergun eq. FDM –
[169] zeolite H2 O system analysis 2D modified DA LDF Darcy’s law FDM –
eq. [159]
[33] zeolite H2 O process understanding 1D – NS eq. NS eq. FDM –
[44] zeolite H2 O process understanding 2D DA eq LDF Brinkman eq. – –
[170] zeolite H2 O process understanding 2D DR eq. NS eq. Darcy’s law FVM –
[30,129] zeolite H2 O process understanding – DP theory, – – – OpenGeoSys
Núñez
modification
[156]

theory is the adsorbate density function, which describes the
temperature dependence of the adsorbate density, since it is re-
quired to calculate the absorbent loading and the corresponding
adsorption enthalpy. Several density functions were proposed (e.g.
[127,128]), of which none is generally preferred. This dilemma was
addressed in the works of Lehmann et al. [30] and Nagel et al.
[129], in both of which a comparative analysis of different adsor-
bate density models was performed. Lehman et al. [30] concluded
that the choice of adsorbate density function has little effect on
the obtained heat storage densities and hence in view of compu-
tational efficiency simpler density models should be preferred. On
the other hand, Nagel et al. [129] came to the conclusion that for
energy storage applications a sufficiently general mathematical ex-
pression for an accurate fit of the experimentally determined char-
acteristic curve together with a (quasi) linear density model should
be applied.
The mentioned adsorption isotherms only correlate the equilib-
rium vapor uptake to the conditions (temperature, pressure) in the
adsorbent bed. Non-equilibrium states are marked by a difference
between the actual vapor uptake and the maximum vapor uptake
at equilibrium conditions. This difference dictates the rate of ad-
sorption or the so-called adsorption kinetics. The adsorption kinet-
ics can be modeled by Fickian diffusion [130], linear driving force
(LDF) model [131] or its modified form [132]. Among these models
the LDF model is the most widely used for modelling, because of
its accuracy and simplicity. In the LDF model the mass transfer re-
sistance from the fluid phase into the adsorbent pores is reduced
to an overall mass transfer resistance.
The above mentioned adsorption kinetics models account for
mass transfer resistance inside the adsorbent particles, i.e. inter-
nal mass transfer resistance between the solid and the adsorbate
gas. In order to model adsorption processes accurately external
mass transfer resistance, i.e. pressure gradient inside the adsorbent
250 G. Krese et al. / Energy & Buildings 164 (2018) 239–253
bed, must also be considered. The most prevalently used models
for describing gas flow inside the adsorbent bed are Darcy’s law
[133] and Ergun’s equation [134]. The latter model is more gen-
eral, since it includes both viscous and inertial effects. Conversely,
Darcy’s law assumes that inertial effects are negligible with regard
to viscous forces. The application of Navier–Stokes (NS) equations
to describe gas flow though porous solids is rare, because the exact
pore network and topology are unknown and computational com-
plexity.
A summary of solid–gas adsorption processes modelling efforts
in the literature concerning heat storage and transformation is pro-
vided in Table 2, whereby the works are classified based on the
modelled adsorption pair, the aim of modelling, model parameteri-
zation, the applied adsorption equilibria approach, the models used
for internal and external mass transfer resistances and the numer-
ical methods and/or software used to solve the model equations.
For a more comprehensive review concerning numerical modelling
of thermochemical heat storage and transformation processes we
would like to refer the interested reader to the work done by Nagel
et al. [135].
5. Conclusions
Thermochemical heat storage is considered as the only storage
concept with a potential for long-term low-temperature heat stor-
age of high enough storage density to be also economically attrac-
tive. In this paper thermochemical heat storage technologies and
systems were reviewed. The studies were reviewed based on used
storage materials, system configuration as well as on models to
predict and optimize system performance. Emphasis was placed on
systems suitable for solar energy utilization in buildings
An overview of working pairs studied for thermochemical heat
storage and transformation applications was given. None of the
presented materials currently meet the requirements for large-
scale low-temperature heat storage applications due to unsuitable
operating conditions (i.e. too high charging temperature), too low
energy density and discharging temperature, corrosiveness, ther-
mal/chemical instability, environmentally-unfriendly production or
high cost. The most promising are solid materials which participate
in reversible chemical and physical sorption processes with water
vapor as sorbate. The focus of material research has been on zeo-
lites and their composites with hygroscopic inorganic salt hydrates
and on microporous aluminophosphates. Nevertheless, one issue is
common to all sorption storage materials, i.e. the discrepancy be-
tween the material and system energy storage density.
One of the main reasons that the prototypes do not achieve
the storage capacity expected based on the material energy stor-
age density is insufficient heat and mass transfer inside the reac-
tor. In this regard open reactor concepts have an advantage over
closed reactor configuration, since the heat transfer fluid is in di-
rect contact with the solid reactant, while closed systems require
a separate heat transfer loop and hence a heat exchanger in the
reactor. Additionally, the design of open systems is much simpler
and consequently cheaper compared to closed systems, because
they do not require the use of condensers, evaporators and work-
ing fluid storage reservoirs. However, weather conditions are lim-
iting the operation of open system, i.e. supply air must be hu-
midified when the ambient moisture content is insufficient (e.g.
during winter). Another issue limiting the performance of sorption
storage systems is the sensible heat loss during charging and dis-
charging as a consequence of heating up the sorbent material and
consequently the reactor to the charging/discharging temperature.
Therefore, modular, moving beds and fluidized beds reactors are
favorable. Also, attention should be paid on building reactors from
materials with lower thermal mass, yet with comparable thermal
conductivity, than the usually used steel alloys.
Since seasonal storage requires a steady and continuous heat
output when discharging, the reactor bed must be optimized in
such a way that it guarantees a constant flow rate to enable stable
heat output during discharging. In order to achieve this without
sacrificing the heat storage unit compactness numerical modelling
techniques have to be employed in the reactor design phase. The
review of literature indicates that in the majority of solid–gas ad-
sorption processes modelling efforts the Dubinin–Polanyi theory is
applied for describing adsorption equilibria while Darcy’s law and
LDF model are used to predict the pressure gradient inside the ad-
sorbent bed and the adsorption rate.
To conclude, the storage materials represent a bottleneck for
the development of thermochemical heat storage systems. There-
fore, in order to achieve the commercial breakthrough of thermo-
chemical heat storage systems a bottom-up approach of storage
materials engineering is needed, i.e. during material development
the required material characteristics have to redefined according to
the dynamics of the thermochemical process in the particular stor-
age design. Thereby obtaining a better understanding of the rela-
tions between material synthesis procedures, structural properties
and system level properties. In addition, a significant performance
increase can also be expected from the optimization of the storage
systems control strategies.
Acknowledgment
This study was financially supported by the Slovenian Research
Agency through research project L1-7665 and research program
P2-0223.
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