Thermal Energy Storage Materials

Sufyan Ali Raza, Muhammad shahid, Dr. Salman Amin

Department of Electrical Engineering

University of Engineering and Technology, Taxila, Pakistan

Abstract: Thermal Energy storage is a technology that reserves thermal energy as a result of cooling or
heating of the medium used for energy storage which is used after heating and cooling application and
power generation in buildings and industries. Recently, Thermal energy storage (TES) has gain a lot of
importance to fulfill the increasing demand of energy, air conditioning and refrigeration with zero
pollution with boosting use of renewable energy source. By using energy of TES during peak hour one
can reduce the peak load, peak to average ratio and thus cost of electricity. This paper accentuates the
enhancing value of thermal energy storage methodologies and their storage capacities based on their
types. This paper mainly focuses thermal and chemical storage materials including sensible heat either
liquid or solid and latent heat (phase-change-materials). An effective comparison of different T.E.S
materials has been made based on their capacity, power, efficiency, storage and cost.

Keywords: storage system; phase-change materials; chemical storage; cold storage; performance
_____________________________________________________________________________________

1. Introduction most importantly it is environment friendly that

According to a prediction, in 2040 the is no emission of carbon dioxide . Solar T.E.S
consumption of energy will increase up to 40 systems, in spite of PV system having better
percent. Due to environmental greenhouse effect efficiency are mostly used in industry and during
increasing pollution fossil fuel energy resources the day use a vital part of thermal energy of the
have replaced sustainable energy resources. sun. Although this system has no backup option
Today increasing energy demand has been full in case of no solar hour. TES has gained more
filled by renewable energy resources such as importance to store using SPP (solar power
wind power, solar, hydro, hydrogen and fuel cell plants) where solar energy is used to produce
geothermal, biomass and others forms of the electricity in the absence of sun light.
energy. So due to unpredictable climatic changes Characterization and selection of new materials,
it is severely important to store this type of with enhancing their thermal and physical
energy to cover up the increasing demand of properties has offered a 24 hour operation of a
energy [1]. This requires most efficient energy better T.E.S system. According to estimation in
storage methods and cost effective energy Europe that emission of 400 million tons of
storage materials. corban dioxide can be avoided and 1.40 million
In renewable energy production, energy GWH/year can be produced.
storage has become a vital part. T.E.S is referred Storage density is very important for
as a technology to store thermal energy by optimization of solar energy ratio, efficiency of
cooling or heating a storage material or a the appliances (absorption chillers) and due to
medium, so that this energy later on can be this fact P.C.Ms has gained more importance in
utilized either for heating or cooling purposes solar system. PCMs may increase the energy
and also to generate electricity. Not only in density of small sized WST(H2o storage tank),
industry but also in buildings the T.E.S system to reduce volume of solar storage or to increase
has gained a vital importance. In energy system the solar fraction of available volume[2].
utilization of T.E.S has many advantages such as .
reliability, low maintenance and running cost
with better economics, reduced investment and
2. Classification and Characteristics of optimal TES systems is very importance.
Storage Systems Although some solar plants in the world have
utilized T.E.S system at a bigger scale, but still
Due to irregularities of availability and the investigation of different T.E.S systems in
variation of solar radiation, TES has gained different domestic application is still continue
popularity in thermodynamic systems as well. [10]. For this optimal operation many
T.E.S not only overcome the supply and demand evolutionary computational based algorithms
of energy, but also enhances the thermal (GA,PSO and others) have been investigated on
reliability and performances of the system. computer [11]. Types of thermal energy are
That’s why designing of the efficient and presented in Figure 1.

Thermal Energy
storage

Thermal Chemical

Thermo
Head of
Sensible Heat Latent Heat chemical pipe Heat Pump
Reaction
line

Liquids Solids
Solid-Liquid Liquid-Gas Solid-Gas

Figure 1 Types of solar thermal energy storage (TES).

Some parameters of T.E.S systems are given in methods for temperature range of −40 °C to
Table 1 [12], storage period, capacity, cost, more than 400 °C: latent heat also known as
efficiency and power. Power capacity for P.C.Ms, sensible heat and thermo chemical
discharging and charging and energy storage energy storage materials based on different
density are desirable and significant properties chemical reactions.[13]
for any storage system. T.E.S system has three

Table 1 Typical parameters of TES system [14]

TES System Capacity Power (MW) Efficiency (%) Storage Cost (€)/KWh
(KWh/t) Period
Sensible hot 10-50 0.001-10.0 50-90 Days/months 0.1-10
water
Phase change 50-150 0.001-1.0 75-90 Hours/months 10-50
material
(PCM)
 Chemical 120-250 0.01-1.0 75-100 Hours/days 8-100
reactions

The process nature defines the energy storage in latent or sensible heat observed, for
storage medium has to be used. For example example sensible heat in a heat exchanger
sensible energy storage is best suitable for water pebble bed. In passive heating storage is utilized
heating. If air heated collectors are utilized, as a sensible heat in building elements.

Figure 2 Methods of thermal energy storage (a) sensible heat; (b) latent heat; (c) thermo-chemical reactions

3. Sensible Heat Storage Mathematically amount of heat stored is defined

as:
S.H.S is a method which is based on
𝑡
storing the thermal energy by cooling or heating Qs=∫𝑡 𝑓 𝑚𝑐𝑝 𝑑𝑡 = 𝑚𝑐𝑝 (𝑡𝑓 − 𝑡𝑖 )
a solid or a liquid storage media (molten salts, 𝑖

sand, rocks or water). The cheapest option is Qs is total quantity of heat energy stored (joul),
water. The commercial and the most popular m: mass in kg of the storage material, Qs: heat
heat energy storage medium is H2O, which has a quantity, Cp: specific heat, J/kg.K, ti: initial
lot of industrial and applications. For large scale temperature (C°), tf: final temperature (C°), in
application underground storage of sensible heat Table [2] represents the most widely used S.H.S
energy with both solid and liquid medium is also materials with their properties [16]. H2O is the
being utilized. There are two main advantages of most suitable S.H.S liquid available as it is the
S.H.S that it is the cheapest and uses non-toxic cheapest having high value of Cp.but for high
materials. S.H.S system uses the property of temperature more than 100 C° molten salts, oils
temperature change and heat capacity of storage and liquids metals are utilized. Rock bed storage
media during discharging and charging process. materials are used for air heating purpose
Change in temperature, amount of storage application some of the characterizations of
materials and specific heat of the given media solid state S.H.S materials are shown in the
defines the amount of the heat stored. [15]. Table 3. [7].

Table 2 List of selected solid-liquid material for sensible heat storage [16]

Medium Fluid Type Temperature Density (kg/𝒎𝟑 ) Specific Heat

Range ℃ (J(kg.K))
Sand - 20 1555 800
Rock - 20 2560 879
Brick - 20 1600 840
Concrete - 20 2240 880
Granite - 20 2640 820
Aluminum - 20 2707 896
 Cast iron - 20 7900 837
Water - 0-100 1000 4190
Calorie HT43 Oil 12-260 867 2200
Engine oil Oil ≤160 888 1880
Ethanol Organic liquid ≤78 790 2400
Propane Organic liquid ≤97 800 2500
Butane Organic liquid ≤118 809 2400
Isotunaol Organic liquid ≤100 808 3000
Isopentanol Organic liquid ≤148 831 2200
Octane Organic liquid ≤126 704 2400

Table 3 Solid-state sensible heat storage materials[7]

Storage material Working Density (kg/𝒎𝟑 ) Thermal Specific Heat

Temperature ℃ Conductivity (kJ/(kg. ℃))
(W/(m.K))
Sand-rock 200-300 1700 1.0 1.30
minerals
Reinforced 200-400 2200 1.5 0.85
concrete
Cast iron 200-400 7200 37.0 0.56
NaCl 200-500 2160 7.0 0.85
Cast steel 200-700 7800 40.0 0.60
Silica fire bricks 200-700 1820 1.5 1.00
Magnesia fire 200-1200 3000 5.0 1.15
bricks

3.1. Water Tank Storage is very cost effective storage material and
through optimal water stratum in the tank with
H2O is the most commonly used better thermal insulation the efficiency of this
material in S.H.S system. Storing of thermal method can be increased further. Evacuated
energy through hot H2O is the most commonly super thermal insulation with thermal
used technology. [17]. Hot H2O tank serves the conductivity of 0.01 W/m.K and a temperature
purpose for energy storing in H2O heating of 90 °C and 0.1 mbar has gained intention of
system through SE (solar energy) and through the researchers. A typical system in which a
cogeneration energy supply system. State of the water tank is used is shown in Figure 3.
art projects represent that the H2O tank storage
 Figure 3 A typical system using water tank storage[18]

The energy storage capacity of a water (or other and space heating [19]. Solar combisystems
liquid) storage unit at uniform temperature (i.e., including combistores were also the topic of the
fully mixed or no stratified) operating over a European project Combisol, whose goal was the
finite temperature difference is given by promotion and standardization of solar
Equation redefined as combisystems in Europe [20].
High specific heat capacity, wide availability,
Qs = mcp∆ts chemically stability, and low cost make water a
good storage media suitable for low temperature
solar cooling applications (e.g., single stage
A more complex system with tank storage is absorption chillers and desiccant systems). Due
shown in Figure 4; a solar combisystem where to the boiling point constraint (100 ◦C at 1 bar),
water store is the central part. The so-called the use of water as sensible heat storage medium
combistore is charged with solar collectors and a for high temperature application (double effect
second heating source, such as a biofuel or gas and triple effect chillers) requires increasing the
boiler, and heat is extracted to two heat sinks of system pressure [6].
very different characteristics: domestic hot water
 Figure 4 Schematic of a solar combisystem with solar collectors and a boiler charging water storage tank [19]

3.2. Underground Storage heat exchanger extracts low-temperature heat

from the soil. Aquifer storage is closely related
Underground thermal energy storage to ground storage, except that the primary
(UTES) is also a widely used storage storage medium is water, which flows at low
technology, which makes use of the ground rates through the ground. Water is pumped out
(e.g., the soil, sand, rocks, and clay) as a storage of and into the ground to heat it and extract
medium for both heat and cold storage. energy from it. Water flow also provides a
Means must be provided to add energy mechanism for heat exchange with the ground
to and remove it from the medium. This is done itself. As a practical matter, aquifers cannot be
by pumping heat transfer fluids (HTFs) through insulated. Only aquifers that have low natural
pipe arrays in the ground. The pipes may be flow rates through the storage field can be used.
vertical U-tubes inserted in wells (boreholes) A further limitation may be in chemical
that are spaced at appropriate intervals in the reactions of heated water with the ground
storage field or they may be horizontal pipes materials. Aquifers, as with ground storage,
buried in trenches. The rates of charging and operate over smaller temperature ranges than
discharging are limited by the area of the pipe water stores. Most applications deal with the
arrays and the rates of heat transfer through the storage of winter cold to be used for the cooling
ground surrounding the pipes. If the storage of large office buildings and industrial processes
medium is porous, energy transport may occur in the summer. Aquifer storage is discussed by
by evaporation and condensation and by the Novo et al. [21], who mention that the heat
movement of water through the medium, and a capacity for aquifers is in the range of 30–40
complete analysis of such a store must include kWh/m3 and the storage volume for 1 m3 water
consideration of both heat and mass transfer. equivalents is 2–3 m3. It is emphasized that the
These storage systems are usually not insulated, relative heat losses get smaller for larger storage
although insulation may be provided at the volumes, since the area susceptible to heat loss
ground surface. Boreholes (ground heat per volume decreases. A state-of-the-art review
exchangers) are also frequently used in for aquifer storage for heating and cooling of
combination with heat pumps where the ground buildings is presented by Paksoy et al. [22], who
explained that, because of the ground conditions
needed for aquifer storage, it is much less 3.3. Packed-Bed Storage
applicable than borehole storage, though aquifer
storage has many advantages over borehole A packed-bed (pebble-bed) storage unit
storage seasonal storage is described by Bauer et uses the heat capacity of a bed of loosely packed
al. [23], who also discuss the heat losses from particulate material to store energy. A fluid,
certain installations. For example, for seasonal usually air, is circulated through the bed to add
water storage with a volume of 12,000 m3 in or remove energy. A variety of solids may be
Friedrichshafen, the yearly heat losses from the used, rock and pebble being the most widely
store were between 322 and 482 MWh, yielding used materials. A pebble-bed storage unit is
a storage utilization factor of around 60%. The shown in Figure 5. In operation, flow is
solar fraction for this system was lower than maintained through the bed in one direction
expected (between 21 and 33% instead of a during addition of heat (usually downward) and
projected 43%), and the reasons given are a in the opposite direction during removal of heat.
higher heat demand from the buildings and Note that heat cannot be added and removed at
higher return temperatures to the store. For a the same time; this is in contrast to water storage
seasonal borehole storage evaluated by Heier et systems, where simultaneous addition to and
al. [24], the borehole storage itself is shown to removal from storage is possible. A major
have a yearly heat loss of approximately 50% of advantage of a packed-bed storage unit is its
the solar energy that is charged into the store. high degree of stratification. The pebbles near
For high-temperature (i.e., above 100 C°) SHS, the entrance are heated, but the temperature of
the technology of choice is based on the use of the pebbles near the exit remains unchanged and
liquids (e.g., oil or molten salts, the latter for the exit-air temperature remains very close to the
temperatures up to 550 C°). For very high initial bed temperature. As time progresses a
temperatures, solid materials (e.g., ceramics and temperature front passes through the bed. When
concrete) are also taken into consideration. the bed is fully charged, its temperature is
However, most of such high-temperature- uniform.
sensible TES options are still under development
or demonstration.

Figure 5 Pebble-bed storage system [18]

A packed bed in a solar heating system temperature. During the day, the variable solar
does not normally operate with constant inlet radiation, the ambient temperature, the collector
inlet temperature, load requirements, and other . Brick does not emit any harmful gases in high
time-dependent conditions result in a variable temperatures, which is important, as the storage
collector outlet temperature. unit is to be located inside a residential house.
Many studies on the heating and cooling of As demonstrated in [26], a system in which heat
packed beds have been published. The first is stored in a sensible heat storage material, such
analytical study was by Schumann [25], and the as ceramic brick, should be provided with a
basic assumptions leading to this model are a means to control airflow rate in order to
one-dimensional plug flow, no axial conduction maximize the effectiveness of heat storage
or dispersion, constant properties, no mass process, if the heat comes from a source of
transfer, no heat loss to the environment, and no variable intensity, such as a concentrated solar
temperature gradients within the solid particles. air collector.

4. Latent-Heat or Phase-Change Storage PCMs are (1) differential thermal analysis

(DTA) and
L.H.S materials are known as PCM due Morrison and Abdel-Khalik [27] developed a
to their property of releasing or absorbing model applicable to PCMs in small containers,
energy with a change in physical state. The where the length in the flow direction is L, the
energy storage density increases and hence the cross-sectional area of the material is A, and the
volume is reduced, in the case of LHS. The heat wetted perimeter is P. The heat transfer fluid
is mainly stored in the phase-change process (at passes through the storage unit in the x direction
a quite constant temperature) and it is directly at the mass flow rate m and with inlet
connected to the latent heat of the substance. temperature tf,i.
The use of an LHS system using PCMs is an The model is based on three assumptions: (1)
effective way of storing thermal energy and has during flow, axial conduction in the fluid is
the advantages of high-energy storage density negligible; (2) the Biot number is low enough
and the isothermal nature of the storage process. that temperature gradients normal to the flow
The main advantage of using LHS over SHS is can be neglected; and (3) heat losses from the
their capacity of storing heat at almost similar bed are negligible.
temperature range. Initially, these materials act An energy balance on the material gives
like SHS materials in that the temperature rises
linearly with the system enthalpy; however, 𝜕𝑢 𝜆𝑠 𝜕 2 𝑡𝑠 𝑈𝑃
= + (𝑡 − 𝑡𝑠 )
later, heat is absorbed or release at almost 𝜕𝜏 𝜌𝑠 𝜕𝑥 2 𝜌𝑠 𝐴 𝑓
constant temperature with a change in physical
state. LHS is based on the heat absorption or Where u,𝑡𝑠 ,𝜆𝑠 , and 𝜌𝑠 are the specific internal
release when a storage material undergoes a energy, temperature, thermal conductivity, and
phase change from solid to liquid or liquid to gas density
or vice versa. The storage capacity Qs, in J, of of the PCM; 𝑡𝑓 and U are the circulating fluid
the LHS system with a PCM medium [7] is temperature and overall heat transfer coefficient
given by between
𝑡 𝑡 the fluid and PCM; τ is the time.
Qs = ∫𝑡 𝑚 𝑚𝑐𝑝 𝑑𝑡 + 𝑚𝑓∆𝑞 + ∫𝑡 𝑓 𝑚𝑐𝑝 𝑑𝑡 An energy balance on the fluid is
𝑖 𝑚
Qs = m[𝑐𝑝𝑠 (𝑡𝑚 − 𝑡) + 𝑓∆𝑞 + 𝑐𝑝𝑠 (𝑡𝑓 − 𝑡𝑚 )]
𝜕𝑡𝑓 𝑚 𝜕𝑡𝑓 𝑈𝑃
+ = (𝑡 − 𝑡𝑓 )
Where tm is the melting temperature, in ◦C; m is 𝜕𝜏 𝜌𝑓 𝐴𝑓 𝜕𝑥 𝜌𝑓 𝐴𝑓 𝐶𝑝,𝑓 𝑠
the mass of PCM medium, in kg; cps is the
average specific heat of the solid phase between Where 𝜌𝑓, 𝐴𝑓 and 𝐶𝑝,𝑓 are the density, flow area,
ti and tm, in kJ/(kg·K); cpl is the average and specific heat of the fluid.
specific heat of the liquid phase between tm and
tf, in J/(kg·K); f is the melt fraction; ∆q is the
latent heat of fusion, in J/kg.
4.1 PCM (Phase Change Material) 3. A suitable container compatible with the
Application PCM.

PCMs can be used for both short-term 4.2. Characteristics Proprieties of PCMs
(daily) and long-term (seasonal) energy storage,
using a variety of techniques and materials. PCMs have been used in thermal
Possible applications of PCMs are as follows: applications for a few decades. PCMs have
 implementation in gypsum board,  thermo-physical properties (latent heat
plaster, concrete, or other wall covering of transition and thermal conductivity
material being part of the building should be high, and density and volume
structure to enhance the thermal energy variations during phase-transition
storage capacity, with main utilization in should be, respectively, high and low in
peak-load shifting (and shaving) and order to minimize storage volume),
solar energy [28] (in this application,  kinetic and chemical properties (super-
typical operating temperature is 22–25 cooling should be limited to a few
◦C, but it can vary as a function of degrees, and materials should have
climate and heating/cooling loads); long-term chemical stability,
 Cold storage for cooling plants compatibility with materials of
(operating temperature 7–15 ◦C) [17]; construction, no toxicity, and no fire
 Warm storage for heating plants (40–50 hazard), and
◦C) [26];  Economic advantages (low cost and
 Hot storage for solar cooling and large-scale availability of the PCMs are
heating (80–90 ◦C) [17]. also very important).
Any latent heat energy storage system therefore PCMs are classified as different groups
possesses at least following three components: depending on the material nature (paraffin, fatty
1. A suitable PCM with its melting point in acids, salt hydrates, etc.). A few advantages and
the desired temperature range, disadvantages of organic and inorganic PCMs
2. A suitable heat exchange surface and their influence on solar cooling application
are listed in Table 4 [29].

Phase Change Material

Organic Inorganic Eutectic

Paraffin Non Paraffin Organic- Inorganic- Inorganic-

salt hydrate Metallics
Compounds Compounds organic inorganic organic

Other Non
Fatty Acid
Paraffin

Figure 6 Classification of phase change material (PCM) [30]

 Table 4 Comparison of organic and inorganic materials for heat storage [29]

Organic Effect on solar cooling Inorganic Effect on solar cooling

system system
Advantages Advantages
Non corrosives Good Greater phase change Good
enthalpy
Low or no undercooling Crucial
Chemical and thermal Important
stability
Drawbacks Drawbacks
Lower phase change Bad Sub cooling Crucial
enthalpy
Low thermal Crucial Corrosion undesirable
conductivity
Inflammability Undesirable Phase separation Undesirable
Lack of thermal stability Crucial

4.2.1. Organic PCMs conductivity, low flash points, and

instability at high temperatures.
Organic PCMs can melt and solidify many Details of thermal properties, applications, and
times without phase segregation, and because of limitations of fatty acids are discussed in [31]
the degradation of their latent melting heat, they and those of sugar alcohols/polyols are found in
crystallize with little or no super-cooling and are [32,33].
usually non-corrosive. The two main groups are:
 Paraffin waxes consist of a mixture of 4.2.2. Inorganic PCMs
mostly straight chain n-alkenes CH3–
(CH2)–CH3. Inorganic PCMs are (mostly) used in high-
The crystallization of the (CH3) – chain release temperature solar applications and one of the
a large amount of latent heat. Both the melting most reported challenges is their maintenance.
point and latent heat of fusion increase with At lower temperatures, they freeze; at high
chain length. Due to cost consideration, temperatures, they are difficult to handle. These
however, only technical grade paraffin’s may be PCMs do not super-cool appreciably and their
used as PCMs in latent heat storage systems. melting enthalpies do not degrade with cycling.
Paraffin is safe, reliable, predictable, less The two main types are as follows:
expensive, non-corrosive, and available in a  Salt hydrate. This is classified as a
large temperature range (5–80°C) [30]. congruent, incongruent, and semi-
 Non-paraffin organic PCMs are the congruent melting method [11]. They
most numerous of the PCMs with highly are alloys of inorganic salts (AB) and n
varied properties. A number of esters, kmol of water, forming a typical
fatty acids, alcohols, and glycols crystalline solid of general formula
suitable for energy storage have been AB.nH2O, whose solid–liquid transition
identified [41]. Main features of these is actually a dehydration and hydration
organic materials include high heat of of the salt. A salt hydrate usually melts
fusion, inflammability, low thermal either to a salt hydrate with fewer moles
of water, i.e.
 AB.nH2O→ mH2O+(n-m) H2O spontaneity of salt hydrates and lower number of
Or to its anhydrous form water moles during the discharge process.
AB.nH2O→ AB+nH2O Adding chemicals can prevent the nucleation of
lower salt hydrates, which preferentially
At the melting point, the hydrate crystals break- increases the solubility of lower salt hydrates
up into anhydrous salt and water, or into a lower over the original salt hydrates with a higher
hydrate and water. One problem with most salt number of water moles. Several research studies
hydrates is that of incongruent melting caused have shown the suitability of salt hydrates for
by the fact that the released water of thermal energy storage [34].
crystallization is not sufficient to dissolve all the .
solid phase present.Other problems include the

Table 5 Main thermo-physical characteristics of certain salt hydrates [30]

PCM Phase Density Latent Heat Volumetric Specific Heat Thermal

Type Change (kg/m3) Capacity Heat Capacity Conductivity
Temperature (kJ/kg) Capacity (kJ/(kg.K)) (W/(m.K)
(°C) (MJ/m3)
S89 89 1550 151 234 2.480 0.670
S44 44 1584 100 158 1.610 0.430
S7 7 1700 150 255 1.850 0.400

 Metallic. This category includes the low in Table 5. Such materials are used for
melting point metals and their alloys. their ability to help meet the high
They are scarcely used in heat storage demands of large capacity power plants.
applications because of their low
melting enthalpy per unit weight, even if
they have high melting enthalpy per unit
volume and high thermal conductivity
[35. A list of selected metallic is given

Table 6 Melting point and latent heat of fusion for selected metallic [35]

Material Melting Point (°C) Latent Heat (kJ/kg)

Gallium-gallium 29.8 -
antimony eutectic
Gallium 30 80.3
Cerro low eutectic 58 90.9
Bi-Cd-In eutectic 61.0 25.0
Cerro-bend eutectic 70.0 32.6
Bi-Pb-In eutectic 70.0 29.0
Bi-In eutectic 72.0 25.0
Bi-Pb eutectic 125.0 -
An inorganic mixture based on an industrial by- freezing points; eutectics nearly always melt and
product (bischofite) was developed and freeze without segregation and have high
characterized for its application as a PCM for thermal conductivities and densities. The weight
low-temperature thermal energy storage [36].
percentage of each material can be varied to
The most appropriate composition was
established as 40 wt % bischofite and 60 wt % obtain variations in the melting point of the
Mg(NO3)2.6H2O. Thermo-physical properties, resulting eutectic mixture [30]. For this reason
specific heat capacity, cycling, and thermal they are a promising type of PCM, even if they
stability were determined. In addition, it was are actually less diffused than the other groups.
shown that supercoiling may be reduced by However, they have low latent and specific heat
increasing the quantity of material. Organic capacities [37].
PCMs have many advantages over inorganic
In fact, the temperature range is one of the main
PCMs, but they are flammable and have low
thermal conductivity. On the other hand, criteria for the suitability of a PCM in any
inorganic PCMs are cheaper, abundant, and application. There are numerous thermal energy
nonflammable and have high heat storage storage applications that use PCMs, which all fit
capacity and thermal conductivities. a particular range suitable for their optimum
thermal performance [38]. Figure 3 presents a
4.2.3. Eutectics brief classification system based on melting
Eutectic materials are a temperatures that, depending on the application
combination of two or more low melting desired, can help one decide which PCM to use
materials with similar (congruent) melting and [29].
Ice
Low Temperature
PCMs
Water Gel

Hydrated Salts
Medium Temperature
PCM PCMs
Organic
Polymer Material

Molten Salts

High Temperature
Metal Alloy
PCMs

Parffin

Figure 7 Categories of PCM based on melting point [29]

4.2.4. PCM Containment composition by interaction with its

Containment of PCMs helps surroundings, to increase its compatibility with
contain the material in liquid and solid phases to other materials in the storage system, to increase
prevent its possible variation in chemical its handiness, and to provide a suitable surface
for heat transfer. Types of containment studied (diameter less than 1 mm) of PCM encapsulated
are bulk storage in tank heat exchangers, in a very thin and high-molecular-weight
macro-encapsulation, and micro-encapsulation. polymer. The spheres are then incorporated in
[39]. some compatible material.
The two other possibilities are macro and micro- The developed capsules can be used in one-tank
encapsulating [40]. Macro-encapsulating TES systems as shown in Figure 8
consists in including a PCM in a tube, sphere, PCM encapsulation has been used extensively in
panel, cylinder, etc. and is the most widespread. building cooling systems where air is passed
The choice of material (plastic or metallic- through flat containers of PCM [41]. The effect
aluminum or steel) and the geometry affect the of encapsulated PCM has a good scope in
thermal performance of the heat storage. Micro- enhancing the performance of LHS systems [42]
encapsulating consists in a micro-sphere
.

Figure 8 Direct Contact TES System [41]

latent heat absorption, they can substantially

increase the thermal mass of buildings compared
4.2 PCMs Used for Energy Storage in to conventional building materials presented in
Buildings Figure 9 [43]
PCMs are considered to be
potential energy saving materials since, due to
 350
288
300

250

200

150
93
100 79
48
50 18 23
2
0
Storage Energy (Wh/m2)
glass wool wood plaster concrete iron water PCM
Figure 9 the maximum energy storage capacity of different 10-mm-thick building materials operating between 18 and 26 °𝑪
for 24h [37]

Storage concepts applied to the building sector 4.2.1 Passive Technologies

have been classified as active or passive
systems. Passive thermal energy systems can The use of TES as a passive technology
effectively enhance the naturally available heat has the objective of providing thermal comfort
energy sources in order to maintain the comfort with minimal use of HVAC energy. When high
conditions in buildings and minimize the use of
thermal-mass materials are used in buildings,
mechanically assisted heating or cooling
systems. passive sensible storage is the technology that
allows for the storage of a high quantity of
The use of active thermal energy systems energy, providing thermal stability inside the
provides a high degree of control of the indoor building. Materials typically used are rammed
conditions and improves the way of storing heat earth, alveolar bricks, concrete, or stone.
energy. These systems are usually integrated in Standard solar walls, also known as Trombe
buildings to provide free cooling or to shift the walls, and solar water walls also use sensible
thermal load from on-peak to off-peak storage to achieve energy savings in buildings
conditions in several applications, such as DHW [46]. A Trombe wall (Figure 10) (from the name
applications [44] and heating, ventilation, and of the French researcher that first proposed it in
air-conditioning (HVAC) systems [45]. 1979) is a wall with high thermal capacity,
shielded by a glass pane. A greenhouse effect is
created, reducing thermal losses from the wall,
heating the air between wall and glass that can
be introduced into the room with a natural
draught due to the chimney effect of the heated
air.
 Figure 10 Schematics of Storage walls of Trombe [40]

The temperature of the wall increases as energy 𝑑𝑡𝑖 𝜆

= (𝑡 + 𝑡𝑖+1 − 2𝑡𝑖 ), 𝑖
is absorbed, and time-dependent temperature 𝑑𝜏 𝜌𝑐𝑝Δ𝑥 2 𝑖−1
gradients are established in the wall. Energy is = 2, … , 𝑁 − 1
lost through the glazing and is transferred from
the room side of the wall to the room by Where λ is the thermal conductivity of wall; ρ is
radiation and convection. This storage wall can the wall density; 𝑐𝑝 is the specific heat of wall; τ
be considered as a set of N nodes connected is the time.
together by a thermal network, each with a
temperature and capacitance [47]. Heat is . A new approach in PCM-wallboards is the
addition of an aluminum honeycomb in
transferred by radiation across the gap and by
containing a micro-encapsulated PCM wallboard
convection between air flowing in the gap and
(Figure 11) [48]. Similarly, PCM can also be
the absorbing surface and the inner glazing.
impregnated or mixed with concrete or mortar.
Energy balances are written for each node of One of the objectives pursued here is to maintain
thickness ∆x, resulting in a set of ordinary he concrete mechanical properties while
differential equations with terms that represent increasing its specific heat capacity. Another
its time-dependent temperature and energy flows approach to incorporating PCM in building
to all adjacent nodes. The general energy walls is to mix it with insulation materials. In a
balance for any node i in the wall is masonry wall, the PCM incorporation can be, for
example, within clay bricks (Figure 12) [49
4.2.2 Active Technologies implementation of RES in the HVAC for space
heating/cooling, improvement in the
The use of thermal energy storage in performance of the current installations, and the
building active systems is an attractive and possible application of peak load-shifting
versatile solution for several applications for strategies [50].
new or retrofitted buildings, such as the

Figure 11 Microencapsulated PCM honeycomb wallboard [42]

Figure 12 Clay bricks including PCM macro-capsules [43]

The integration of TES in a building can be done cold is discharged when required by the cooling
in the building’s core (core, floor, and walls), demand [51].
external solar façades, suspended ceilings, the
ventilation system, PV systems, and water Furthermore, TES has been used in building
tanks. One of the main applications of TES in solar systems to convert intermittent energy
active building systems is the use of free sources and meet heating and DHW demands.
cooling, when the storage is charged with low The most popular solar TES method has been
night outdoor temperatures, and this stored extended to integrate solar air collectors in
building walls or to use PCM in ventilated .
façades (Figure 13) [52].

Figure 13 Operational mode of the ventilated façade with PCM [46]

The combination of PCMs with the solar great opportunity for the research and for energy
buildings and zero energy buildings will make a management

Table 7 Summary of experimental studies on the applications of nano-enhanced PCMs in buildings[29]

Authors Brief Title Highlights Reference

Constantinescu et al. Nano-composite Providing a Nano- [53]
building materials composite with
appropriate thermo-
physical properties for
energy storage (2010).
Kalaiselvam Nano-enhanced PCM Improving the [54]
for cooling solidification and
melting rate by
increasing the amount
of Nano-particles in the
PCM (2012).
Kumaresan et al. PCM-based Nano-fluids Reducing about 14.0 [55]
for and 20.1% at the
cool storage ambient temperature of
9and 12℃, respectively
(2013).
Sayyar et al. Shape-stable Nano- Reducing the energy [56]
PCM consumption for
maintaining the
interior temperature by
79% (2014).
Parameshwaran et al. Hybrid Nano-composite The freezing time of the [57]
PCM Nano-enhanced PCM
was lower than the pure
PCM (2014).
 Harikrishnan et al. Composite PCMs Providing a new [58]
for heating composite PCM
consisting Lauric acid
(LA) and stearic acid.
Sarı et al. Micro/Nano capsules This Nano PCM with [59]
of PCM melting latent heat of
116.25 J/g
was suitable for free
cooling applications
(2015).
Amin et al. Beeswax/graphene Increasing the thermal [60]
PCM conductivity to 2.8
W/(m·K) and
the latent heat by 22.5%
(2017).
Hussain et al. Activated carbon Improvement in thermal [61]
dispersed PCM conductivity of the pure
PCM by 55% for 0.1 wt
% Nano-dispersed PCM

use in any building system, active or passive.

This can be achieved via direct inclusion in the
wall, by impregnation in a porous material such
4.4 Advantages, Drawbacks, and Selection as gypsum [62], via micro-encapsulation
techniques [63], or by using a shape-stabilization
of PCMs
or slurries of PCM suspended on a thermal fluid
[64]. Encapsulation is a key issue for the
The main advantages of PCM versus water
implementation of these technologies in
SHSs are [5]
buildings and must be designed to avoid leakage
 The possibility of reducing the tank
and corrosion.
volume for a given amount of energy
Material selection is the core and most important
stored, which can be done only if
step in designing LHS. PCM is selected based
storage is operated in a very narrow
upon its melting temperature and heat of fusion.
temperature range around the phase-
The parameters necessary to identify the
transition temperature, and
material include the temperature required for the
 Fewer on–off cycles of auxiliary heaters
application and heat requirements. Thus, the
(for plants with storage on the hot side)
type of PCM is selected for its physical and
and chillers (for plants with storage on
chemical properties, considering the drawbacks.
the cold side).
Heat flux DSC is one of the most reliable
The main drawbacks of PCM versus water SHSs
methods of laboratory thermal analysis for
are [5]
testing heat storage capacity of PCM with a
 Higher investment costs, and
constant heating/cooling rate [65].
 Higher risks due to leaks of stability and A visual combination of important thermal
erosion of material encapsulating PCMs. properties (Figure 14) of a few types of PCM
These materials make use of the latent heat was produced by Li et al. [66].
between the solid- and liquid-phase changes and
must be encapsulated or stabilized for technical
4.5 Thermal Energy Storage for generator) similar to the power block of a
Concentrated Solar Power Plants conventional thermal power plant.

CSP systems use mirrors to concentrate Figure 15 shows a two-tank thermal energy
sunlight from a large area to a small area, where storage system integrated into a parabolic trough
it is absorbed and converted to heat at high power plant [67].
temperatures. The high temperature heat is then
used to drive a power block (usually a steam
turbine connected to an electrical power

Figure 14 Thermal properties of various PCMs [66].

 Figure 15 Schematics of a parabolic tough power plant with two tank molten salt storage [67].

usually small, compared to those of the heat of

reaction.

Thermal decomposition of metal oxides for

Chemical Energy Storage energy storage has been considered [68

TCS uses thermochemical materials (TCM) Energy storage by thermal decomposition of

which store and release heat by a reversible Ca(OH)2 has been extensively studied by Fujii
endothermic/exothermic reaction process et al. [69]. The reaction is Ca (OH)2 ↔ CaO +
(Figure 2c). During the charging process, heat is H2O. The forward reaction will proceed at
applied to the material A, resulting in a temperatures above ~450 ◦C; the rates of
separation of two parts B + C. The resulting reaction can be enhanced by the addition of zinc
reaction products can be easily separated and or aluminum. The product CaO is stored in the
stored until the discharge process is required. absence of water. The reverse exothermic
Then, the two parts B + C are mixed at suitable reaction proceeds easily.
pressure and temperature conditions, and energy
is released. Table 9 lists some of the most interesting
chemical reactions for TES [70]. While sorption
The products B and C can be stored separately, storage can only work at temperatures of up to
and thermal losses from the storage units are ~350 ◦C, temperatures of chemical reactions can
restricted to sensible heat effects, which are go much higher.
 Table 8 Some chemical reactions for thermal energy storage [70]

Reaction Temperature ℃ Energy Density (kJ/kg)

Methane steam reforming 𝐶𝐻4 + 𝐻2 𝑂 = 480-1195 6053
𝐶𝑂 + 3𝐻2
Ammonia dissociation 2𝑁𝐻3 = 𝑁2 +3𝐻2 400-500 3940
Thermal dehydrogenation of metal 200-500 3079 (Heat)
hydrides 𝑀𝑔𝐻2 = 𝑀𝑔 + 𝐻2 9000 (𝐻2 )
Dehydration of metal hydroxides 402-572 1415
𝐶𝐴(𝑂𝐻)2 = 𝐶𝐴𝑂 + 𝐻2 𝑂
1 520-960 1235
Catalytic dissociation 𝑆𝑂3 = 𝑆𝑂2 + 2 𝑂2

6. Cool Thermal Energy Storage thermal energy or waste heat from several
processes can be used to regenerate the
Cool thermal energy storage (CTES) has adsorbent and promote energy storage [71].
recently attracted interest for its industrial
refrigeration applications, such as process The adsorption cycle has already been used in
cooling, food preservation, and building air- several research projects to promote TES. In
conditioning systems. PCMs and their thermal 1990, Kaubek and Maier-Laxhuber [72]
properties suitable for air-conditioning patented an adsorption apparatus to be used for
applications can be found in [64]. For air- electric heating storage, working with the
conditioning and refrigeration (ice storage), zeolite/water pair and reporting 30% savings in
temperatures from −5 to 15 ◦C are optimum for energy consumption. The system can be used as
thermal storage, but at lower temperatures, latent an air-heating device or combined with a hot-
heat storage materials are better than sensible water tank. In the first case, the adsorbent bed is
heated by electric heating rods during desorption
. phase, regenerating the adsorbent and releasing
the condensation heat into the space to be
Typical applications involve adsorption of water
heated. In the latter case, the condensation heat
vapor to silica gel or zeolites (i.e., microporous
is released into a water tank during the
crystalline alumina-silicates). Of special
desorption phase, while the adsorption heat is
importance for use in hot/humid climates or
transferred to the water tank through a specific
confined spaces with high humidity are open
closed circuit in the adsorption stage. Hauer [73]
sorption systems based on lithium-chloride to
presented a seasonal adsorption TES system,
cool water and on zeolites to control humidity.
working with the silica-gel/water pair (Figure
Adsorption TES is a promising technology that
16).
can provide an excellent solution for long-term
TES in a more compact and efficient way. Solar
 Figure 16 Seasonal adsorption thermal storage system [73]

The numerical results from the parametric study Important fields of application for TES
investigated by Shaikh and Lafdi [74] indicated systems are in the building sector (e.g., DHW,
that the total energy charged rate can be space heating, and air-conditioning) and in the
significantly enhanced using composite PCMs as industrial sector (e.g., processes heating and
compared to the single PCM. cooling). TES systems can be installed as either
centralized plants or distributed devices.
Figure 17 shows the different TES technologies: Centralized plants are designed to store waste
sensible heat, latent heat and thermochemical heat from large industrial processes,
with respect to their working temperatures. conventional power plants, combined heat and
power plants, and renewable power plants, such
as CSP. Their power capacity ranges typically
from hundreds of kW to several MW.
Distributed devices are usually buffer storage
7. Performance and cost of TES system systems to accumulate solar heat to be used for
domestic and commercial buildings (e.g., hot
TES includes a number of different water, heating, and appliances). Distributed
technologies, each one with its own specific systems are mostly in the range of few to tens of
performance, application, and cost. kW.
 Figure 17 Storage capacity depending on temperature for TES [4]

calcium–chloride storage system for heat

Cost estimated of TES systems include storage rejected from a thermally driven absorption
materials, technical equipment for charging and chiller includes the cost of calcium chloride,
discharging, and operation costs. Although which is rather inexpensive (0.3 €/kg), and the
economic analyses for conventional systems cost of a container, a heat exchanger, and other
(without thermal storage) [75] and systems with components around 65 €/kWh.
sensible storage (water) tanks are abundant, Materials for TCS are also
comparative cost analyses of using a PCM as a expensive, as they have to be prepared (e.g.,
latent heat thermal storage unit in a solar pelletized or layered over supporting structures).
absorption cooling system are rarely seen. Also expensive are the containers and the
Godarzi et al. [76] designed a PCM storage auxiliary TCS equipment for both heat and mass
system based on exergo-economic analysis and a transfer during energy charging and discharging.
genetic algorithm in a 45.4 kW LiBr/H2O TCS systems can be operated as either open
system. Their analysis showed a payback period systems (i.e., basically packed beds of pellets at
of 0.61 years without PCM storage to 1.13 years ambient pressure) or closed systems. Open
with PCM storage. Calise [77] numerically also systems are often the cheapest option, while
investigated an LiBr/H2O system using thermo- closed systems need sophisticated heat
economic and optimization techniques, and 64% exchangers. The overall economic evaluation of
of primary energy was saved with a payback a TES system depends significantly on the
period of 12 years. specific application and operation needs,
In the case of UTES systems, boreholes and heat including the number and frequency of storage
exchangers to activate the underground storage cycles.
are the most important cost elements. Specific TES technologies face certain
costs range from 0.1 to 10 €/kWh [6] and barriers to market entry, and cost is a key issue.
depend heavily on local conditions. The Other barriers relate to material properties and
difference between the pure PCM and the stability, in particular for TCS. Each storage
complete TES system is even higher for active application needs a specific TES design to fit
PCM installations. As an example, the costs of a specific boundary conditions and requirements.
R&D activities focus on all TES technologies. systems is assumed to be 15%. As far as TES for
TES market development and penetration varies power applications is concerned, a driving sector
considerably, depending on the application is the CSP, where almost all new power plants in
fields and regions. Thus, TES potential for co- operation or under construction are equipped
generation and district heating in Europe is with TES systems, mostly based on molten salt.
associated with building stock. The This is perhaps the most important development
implementation rate of co-generation is 10.2%, filed for large, centralized TES installations.
while the implementation of TES in these

8. Conclusions and Future Trends Melting temperature, latent heat of fusion, and
PCM thermo-physical issues are three basic
SHS is applicable to domestic systems, district factors influencing the selection of PCMs in any
heating, and industrial needs. The most popular application. A high heat of fusion and a precise
and commercial heat storage medium is water, melting/solidification temperature (without sub
which has a number of residential and industrial cooling) are two primary requirements in the
applications. Underground storage of sensible selection approach. Numerous mechanical and
heat in both liquid and solid media is also used nano-level enhancements have been achieved to
for typically large-scale applications. However, increase the heat transfer rate. which is
TES systems based on SHS offer a storage promising. Micro-encapsulation increases the
capacity that is limited by the specific heat of the heat transfer surface area and is also a solution
storage medium. Furthermore, SHS systems for phase segregation in salt hydrates.
require proper design to discharge thermal Most of the literature is focused on
energy at constant temperatures. routine and commercialized PCM materials such
PCMs can offer a higher storage as paraffin. We recommend focusing on special
capacity that is associated with the latent heat of PCMs with a wide temperature range such as
the phase change. PCMs also enable a target- salt hydrates and synthesizing specialized PCMs
oriented discharging temperature that is set by suitable for specific building applications. TCS
the constant temperature of the phase change. can offer even higher storage capacities.

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