42 The Open Renewable Energy Journal, 2011, 4, 42-46

Open Access

A Critical Review of Thermochemical Energy Storage Systems

Ali H. Abedin and Marc A. Rosen1,*

Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, Oshawa, Ontario,
L1H 7K4, Canada

Abstract: Thermal energy storage (TES) is an advanced technology for storing thermal energy that can mitigate
environmental impacts and facilitate more efficient and clean energy systems. Thermochemical TES is an emerging
method with the potential for high energy density storage. Where space is limited, therefore, thermochemical TES has the
highest potential to achieve the required compact thermal energy storage. Thermochemical TES is presently undergoing
research and experimentation. In order to develop an understanding of thermochemical TES systems and to improve their
implementation, comprehensive analyses and investigations are required. Here, principles of thermochemical TES
are presented and thermochemical TES is critically assessed and compared with other TES types. Recent advances
are discussed.

Keywords: Thermal energy storage, thermochemical energy storage, compact TES.

1. INTRODUCTION energy [4]. Thus, TES plays an important role in increasing

the contribution of various types of renewable energy in the
Societal energy demands are presently increasing while
energy mix of regions and countries.
fossil fuel resources, which dominate most national energy
systems, are limited and predicted to become scarcer and Various TES technologies and applications exist. The se-
more expensive in coming years [1, 2]. Furthermore, many lection of a TES system for a particular application depends
concerns exist regarding the environmental impacts associ- on many factors, including storage duration, economics,
ated with increasing energy consumption, such as climate supply and utilization temperature requirements, storage
change and atmospheric pollution. Greenhouse gas (GHG) capacity, heat losses and available space.
emissions are considered the main cause of climate change, The main types of TES are sensible and latent. Sensible
and agreements to limit them, such as the Kyoto Protocol, TES systems store energy by changing the temperature of
have been developed [3]. the storage medium, which can be water, brine, rock, soil,
Changes are required in energy systems, partly through etc. Latent TES systems store energy through phase change,
the adoption of advanced energy technologies and systems e.g., cold storage water/ice and heat storage by melting par-
where advantageous, to address serious environmental con- affin waxes. Latent TES units are generally smaller than sen-
cerns. The anticipated worldwide increase in energy demand sible storage units. More compact TES can be achieved
and concern regarding environmental problems is fostering based on storages that utilize chemical reactions. Such ther-
the utilization of more efficient and cleaner energy technolo- mochemical storage systems, which constitute the focus of
gies, in relevant applications. Examples include advanced this article, have recently been the subject of increased atten-
systems for waste energy recovery and energy integration. tion and could be especially beneficial where space is lim-
ited.
An important technology that can contribute to avoiding
environmental problems and increasing the efficiency of Thermochemical TES systems are not yet commercial
energy consumption and that has widespread applications is and research and development is required to better under-
thermal energy storage (TES). stand and design these technologies and to resolve other
practical aspects before commercial implementation can oc-
Thermal energy storage is defined as the temporary hold-
cur [5]. In particular, a better understanding of their efficien-
ing of thermal energy in the form of hot or cold substances cies is required. In this article, principles of thermochemical
for later utilization. TES is a significant technology in sys-
TES and recent advances are presented, and thermochemical
tems involving renewable energies as well as other energy
TES is critically assessed and compared with other TES
resources as it can make their operation more efficient, par-
types. Also, advantages and disadvantages of thermochemi-
ticularly by bridging the period between periods when en-
cal TES are considered as they relate to other TES types. The
ergy is harvested and periods when it is needed. That is, TES
objective is to improve understanding and thereby support
is helpful for balancing between the supply and demand of development and ultimate implementation of the thermo-
chemical TES technology.
*Address correspondence to this author at the Faculty of Engineering and 2. THERMAL ENERGY STORAGE
Applied Science, University of Ontario Institute of Technology; Canada;
Tel: 905/721-8668; Fax: 905/721-3370; The importance of thermal energy storage has motivated
E-mail: [email protected]. many researchers to study various aspects of the technology

1876-3871/11 2011 Bentham Open

A Critical Review of Thermochemical Energy Storage Systems The Open Renewable Energy Journal, 2011, Volume 4 43

and the formation of a related task at the International En- ing small amounts of storage substances. Energy storage
ergy Agency [5]. Of the different types of thermal energy based on chemical reactions is particularly appropriate for
storage, sensible heat storages usually are applied for large long-term storage applications, e.g., seasonal storage of solar
plants, e.g. aquifer TES [6], while latent heat storage is typi- heat, because the process involves almost no energy losses
cally appropriate for low-temperature heat sources and nar- during the storing period. Storage is usually done at ambient
row temperature intervals [7]. temperatures.
There are three main types of TES systems [5]: Sorption systems (adsorption and absorption) are based
• Sensible on a chemical processes and thus are also considered chemi-
cal heat storage. Adsorption occurs when an adsorptive ac-
• Latent cumulates on the surface of an adsorbent and shapes a mo-
• Chemical (sorption and thermochemical) lecular or atomic layer. The adsorptive can be a liquid or gas
while the adsorbent can be a solid or liquid. Absorption is a
2.1. Sensible TES process that occurs when a substance is distributed into a
In sensible TES systems, energy (or heat) is liquid or solid and forms a solution.
stored/released by heating/cooling a liquid or solid storage
material through a heat transfer interaction. The amount of 3. THERMOCHEMICAL TES
energy input to a TES in a sensible heat system is related to The principles of thermochemical energy storage sys-
the mass of storage material and its heat capacity as well as tems, as well as the relevant components and processes, are
the temperature difference of the storage medium between its described.
initial and final states. This heat transfer Q can be expressed
as: 3.1. Principles of Thermochemical Energy Storage
The main principle of thermochemical TES is based on a
Q = mCp
T
reaction that can be reversed:
where m and Cp are denote the mass and specific heat of the
C + heat
A + B
storage material and
T is the temperature difference before
and after the storage operation. Examples of materials typi- In this reaction, a thermochemical material (C) absorbs
cally used as a storage medium are water, air, oil, rocks, energy and is converted chemically into two components (A
brine, concrete, sand and soil. and B), which can be stored separately. The reverse reaction
occurs when materials A and B are combined together and C
2.2. Latent TES is formed. Energy is released during this reaction and consti-
tutes the recovered thermal energy from the TES. The stor-
Latent heat involves the change of a substance from one
age capacity of this system is the heat of reaction when ma-
phase to another at a fixed temperature. In latent TES sys-
terial C is formed.
tems, energy is stored during the phase change (e.g. melting,
evaporating and crystallization). Due to the specific heat of a 3.2. Thermochemical Energy Storage Components and
typical medium and the high enthalpy change during phase Processes
change, the latent heat change is usually greater than the
sensible heat change for a given system size. Latent heat During the thermochemical storage reaction, expressible
storage materials are usually useful over a small temperature as C + heat
A + B, C is the thermochemical material
range [5]. (TCM) for the reaction, while materials A and B are reac-
tants. Substance A can be a hydroxide, hydrate, carbonate,
The stored energy during a latent storage process can be
evaluated as: ammoniate, etc. and B can be water, CO, ammonia, hydro-
gen, etc. There is no restriction on phases, but usually C is a
Q = mL solid or a liquid and A and B can be any phase. In general, a
TES cycle includes three main processes:
where m denotes the mass and L is the specific latent heat of
the phase change material (PCM). Examples of PCMs are • Charging
water/ice, paraffin and eutectic salts. An example of an in- • Storing
dustrial PCM is the hand warmer (sodium acetate trihydrate).
PCMs are usually packed in tubes, plastic capsules, wall • Discharging
board and ceilings and they are supplied mainly in three These three processes are illustrated for thermochemical
shapes: powder, granulate and board. energy storage in Fig. (1), and are described individually
below:
2.3. Chemical Energy Storage
Charging: The charging process is endothermic. Ther-
The chemical TES category includes sorption and ther- mal energy is absorbed from an energy resource, which
mochemical reactions. In thermochemical energy storage, could be a renewable energy resource and/or conventional
energy is stored after a dissociation reaction and then recov- energy sources like fossil fuels. This energy is used for dis-
ered in a chemically reverse reaction. Thermochemical en- sociation of the thermochemical material, and is equivalent
ergy storage has a higher storage density than the other types to the heat of reaction or enthalpy of formation. After this
of TES, allowing large quantities of energy to be stored us- process, two materials (A and B) with different properties
44 The Open Renewable Energy Journal, 2011, Volume 4 Abedin and Rosen

many to be promising for residential and commercial build-

ings. Heat storage based on chemical reactions can be ap-
plied to heating and cooling in small and large buildings as
well. Further, thermochemical TES is useful for short dura-
tions as well as longer periods, as used in seasonal thermal
storage.
Several investigations of thermochemical TES have been
reported. Weber and Dorer analyzed long-term heat storage
using a closed sorption system with NaOH and water as the
working pair and compared the results with a conventional
storage system, focusing on system volume [9]. An investi-
gation based on bromide strontium as the reactant and water
as the working fluid [10], in a system using flat plate solar
collectors and applied to direct floor heating, demonstrated
the relations between the attained power levels and the heat-
ing storage capacities of reactive composites. Mauran et al.
[11] analyzed experimentally the same working pair for heat-
ing and cooling purposes (heating in winter or mid-season
Fig. (1). Processes involved in a thermochemical energy storage cycle: and cooling in summer). Zondag et al. [12] characterized
charging, storing and discharging. magnesium sulphate as a storage media and examined the
cycling behavior of MgSO4 and the dehydration temperature
are formed that can be stored. The reaction during charging of the reactant. Thermal energy storage based on the
can be written as: Ca(OH)2 and CaO cycle is another example of thermochemi-
C + heat
A + B cal energy storage, and the reversibility and efficiency of this
system was investigated in Azpiazu et al. [13]. Thermo-
Storing: After the charging process, components A and chemical energy storage based on the chemical pair ammo-
B are separately stored with little or no energy losses. The nia and water has been investigated in conjunction with a
materials are usually stored at ambient temperatures, leading solar thermal plant. General characteristics of this working
to no thermal losses (except during the initial cooling of pair as well as the dissociation and synthesis reactor were
components A and B after charging). Any other energy studied in [14] and the optimization of a related heat recov-
losses are due to degradation of the materials. ery device has been reported [15].
Discharging: During this process, A and B are combined 4. CRITICAL ASSESSMENT AND COMPARISON OF
in an exothermic reaction. The energy released from this THERMOCHEMICAL TES SYSTEMS
reaction permits the stored energy to be recovered. After
discharging, component C is regenerated and can be used Thermochemical TES is assessed and compared to other
again in the cycle. The discharging reaction can be written types of TES, considering thermochemical material candi-
as: dates, factors affecting their selection and primary advan-
tages.
A + B
C + heat
4.1. Advantages of Thermochemical Energy Storage
3.3. Recent Developments in Thermochemical TES
Thermochemical TES systems have several advantages
A comprehensive review of thermochemical energy stor- over other types of TES:
age [8] describes the main concepts, criteria for choosing
appropriate storage media and candidate reaction pairs. Due • Components (A and B) can usually be stored sepa-
to the high energy density and compact nature of thermo- rately at ambient temperature, after cooling to ambient
chemical energy storage, this type of TES is considered by conditions subsequent to their formation. Therefore,

Table 1. Promising Materials for Thermochemical Energy Storage [8, 16]

Energy Storage Density of Ther- Charging Reaction

Thermochemical Material (C) Solid Reactant (A) Working Fluid (B)
mochemical Material (GJ/m3) Temperature (°C)

MgSO4 ·7H2O MgSO4 7H2O 2.8 122

FeCO3 FeO CO2 2.6 180

Ca(OH)2 CaO H 2O 1.9 479

Fe(OH)2 FeO H 2O 2.2 150

CaCO3 CaO CO2 3.3 837

CaSO4·2H 2O CaSO4 2H2O 1.4 89

A Critical Review of Thermochemical Energy Storage Systems The Open Renewable Energy Journal, 2011, Volume 4 45

there is little or no heat loss during the storing period tems. The relevant factors include:
and, as a consequence, insulation is not needed. • Cost
• As a result of the low heat losses, thermochemical • Cycling behavior (reversibility and degradation over
TES systems are especially suitable for long-term en- large numbers of cycles)
ergy storage (e.g., seasonal storage).
• Availability
• Thermochemical materials have higher energy densi-
ties relative to PCMs and sensible storage media. Be- • Toxicity and safety
cause of higher energy density, thermochemical TES • Corrosiveness
systems can provide more compact energy storage
relative to latent and sensible TES. This attribute is • Energy storage density
particularly beneficial where space for the TES is lim- • Reaction temperature
ited or valuable.
• Reaction rate
4.2. Thermochemical Storage Material Candidates
• Ability to be engineered into a practical system (e.g.,
Some promising thermochemical storage material candi- heat transfer characteristics and flow properties)
dates that have been recently identified are listed in Table 1,
along with values of energy density and reaction tempera- 5. COMPARISON OF THERMOCHEMICAL TES AND
ture. Energy density and reaction temperature are two impor- OTHER TES TYPES
tant factors, among others, for a thermochemical material for
application in thermochemical TES systems. The different types of thermal energy storage systems are
quantitatively contrasted and compared in Table 2, consider-
4.3. Factors Affecting the Choice of Thermochemical ing a range of relevant performance parameters and factors.
Material It is evident that each has different operating characteristics,
advantages and disadvantages. For different applications,
Several parameters should be examined in selecting a different TESs can be the most appropriate choice.
thermochemical material, as they affect its use in TES sys-

Table 2. Comparison of Different Types of TES Based on Various Performance Factors*

Type of Thermal Energy Storage

Performance Parameter
Chemical TES (Sorption and Thermo-
Sensible TES Latent TES
chemical)

Temperature range Up to: 20-40 °C (paraffins) 20-200 °C

110 °C (water tanks) 30-80 °C (salt hydrates)
50 °C (aquifers and ground storage)
400 °C (concrete)

Storage density Low (with high temperature inter- Moderate (with low temperature Normally high:
val): interval): 0.5-3 GJ/m3
3 3
0.2 GJ/m (for typical water tanks) 0.3-0.5 GJ/m

Lifetime Long Often limited due to storage mate- Depends on reactant degradation and side
rial cycling reactions

Technology status Available commercially Available commercially for some Generally not available, but undergoing
temperatures and materials research and pilot project tests

Advantages Low cost Medium storage density High storage density

Reliable Small volumes Low heat losses (storage at ambient tem-
Simple application with available Short distance transport possibility peratures)
materials Long storage period
Long distance transport possibility
Highly compact energy storage

Disadvantages Significant heat loss over time (de- Low heat conductivity High capital costs
pending on level of insulation) Corrosivity of materials Technically complex
Large volume needed Significant heat losses (depending
on level of insulation)
* Adapted from several sources including http://www.preheat.org/technology/ and [8].
46 The Open Renewable Energy Journal, 2011, Volume 4 Abedin and Rosen

CONCLUSIONS [3] Fuglestvedt, J.S.; Hailemariam, K.; Stuber, N. Alternatives to the

global warming potential for comparing climate impacts of emis-
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systems, little energy losses during the storing operation and (draft), Task 42, Annex 28, Solar Heating and Cooling Programme,
higher energy densities compared to other types of TES are 2008.
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the scientific and engineering characteristics of thermo- [7] Shilei, L., Guohui, F.; Neng, Z.; Li, D. Experimental study and
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Received: April 21, 2011 Revised: May 18, 2011 Accepted: May 24, 2011
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