Renewable and Sustainable Energy Reviews 68 (2017) 693706

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Thermal energy storage materials and systems for solar energy applications

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Guruprasad Alva, Lingkun Liu, Xiang Huang, Guiyin Fang
School of Physics, Nanjing University, Nanjing 210093, China

A R T I C L E I N F O A BS T RAC T

Keywords: Usage of renewable and clean solar energy is expanding at a rapid pace. Applications of thermal energy storage
Solar energy (TES) facility in solar energy eld enable dispatchability in generation of electricity and home space heating
Thermal energy storage requirements. It helps mitigate the intermittence issue with an energy source like solar energy. TES also helps in
Phase change materials (PCM) smoothing out uctuations in energy demand during dierent time periods of the day. In this paper, a summary
Thermal performance
of various solar thermal energy storage materials and thermal energy storage systems that are currently in use is
presented. The properties of solar thermal energy storage materials are discussed and analyzed. The dynamic
performances of solar thermal energy storage systems in recent investigations are also presented and
summarized.

1. Introduction
Solar energy applications are found in many aspects of our daily
life, such as space heating of houses, hot water supply and cooking. One
major drawback of solar energy is intermittence [1]. To mitigate this
issue, need for energy storage system arises in most of the areas where
solar energy is utilized. There are dierent types of energy storage
solutions [2]. One of the most important elds for solar energy
application is the electrical power generation. Here the best suited
energy storage system depends on the type of technology adopted for
electricity generation. For generating electrical power from solar
energy, there is a choice between Photovoltaic (PV) and Concentrated
Solar Power (CSP) options [3,4]. PV technology usually stores electrical
energy as chemical energy in batteries [5], while CSP utilizes TES to
store solar energy in thermal energy form. Many comparisons have
been done between dierent energy storage technologies [2]. At a large
scale, high temperature TES is found to be more suitable than battery
technology with its higher load capacity and longer storage duration.
There for CSP has a better dispatchability at large scale. But due to
falling prices of the PV cells, there is an increased competition faced by
CSP technology from PV technology [3]. There is a need for CSP to
increase the performance in all aspects like cost, eciency, reliability
etc. Although the overall eciency of the CSP depends on the
performance of all components like collectors, receivers, thermal
energy storage system, heat exchangers, turbines and generators etc.,
but the performance of the TES system is the most crucial factor.
Therefore, progress in the eciency of the TES technologies and
reduction in cost of electricity generation are the need of the hour.
Currently there is a wide range of technologies used for the TES. The
CSP plants operate TES systems at higher temperatures as it improves
the eciency of Rankine cycle of the plant. In other application areas,
such as space heating in buildings, solar hot water supply and heat
sinks of electronic systems like laptops etc, the lower temperature TES
systems are involved. This review summarizes the current aairs of
dierent technologies in the application elds and their performances.
2. The properties of solar thermal energy storage materials
Applications like house space heating require low temperature TES
below 50 C, while applications like electrical power generation require
high temperature TES systems above 175 C [2]. The performances of
the TES systems depend on the properties of the thermal energy
storage materials chosen. The thermophysical properties of thermal
energy storage materials should be presented in the following aspects
according to the given requirements of the application elds.
Melting point: Phase change materials should have a melting point
near the required operational temperature range of the TES system.
Density: High density improves energy storage density which
reduces the volume of the TES system.
Latent heat of fusion: Phase change materials should have very high
latent heat of fusion. High latent heat of fusion improves energy
storage density of the system.
Specic heat (Cp): Sensible heat storage materials should have high
specic heat. High specic heat improves energy storage density of
the system.

Corresponding author.
E-mail address: gyfang@nju.edu.cn (G. Fang).

http://dx.doi.org/10.1016/j.rser.2016.10.021
Received 29 February 2016; Received in revised form 28 August 2016; Accepted 16 October 2016
1364-0321/ 2016 Elsevier Ltd. All rights reserved.
G. Alva et al.
Thermal conductivity: High thermal conductivity increases the
thermal charging and discharging rate which is desired.
Super cooling: For phase change materials, during the freezing
process, super cooling should be minimal. Storage material should
freeze completely at as close as possible to its freezing temperature.
Cost and availability: Cheaper price of storage material reduces
capital and operational costs. They should be abundantly available.
Thermal stability: They should not decompose at high temperatures.
This gives wider operating temperature range and higher energy
storage capacity for the material. Material properties should be
stable even after extended thermal cycles of heating and cooling.
Chemical stability: High chemical stability of storage materials
increases life of energy storage plant.
Volume change: For phase change materials, change in volume
during phase change process should be minimal. Material also
should have low coecient of thermal expansion. Big changes in
volume increase the required size of the container. Large density
dierence between two phases also causes phase segregation issue.
Non-toxic: They should not be harmful to health of operators and
environment.
Non-corrosive: Corrosive thermal energy storage materials bring
down the energy storage plant life drastically due to corrosion of
containers.
Flammability: They should be non-ammable and non-explosive.
Congruent melting: In case of salt hydrates, incongruent melting
aects the reverse process as the salt settles down and the salt is
unavailable during recombination process.
Vapor pressure: They should have low vapor pressure in operational
temperature range. High vapor pressure requires pressure with-
standing containment at high temperatures. It also requires costly
insulation.
2.1. Sensible heat thermal energy storage materials
Sensible heat thermal energy storage materials store heat energy in
their specic heat capacity (Cp). The thermal energy stored by sensible
heat can be expressed as Q = mCpT , where m is the mass (kg), Cp is
the specic heat capacity (kJ kg1 K1) and T is the raise in
temperature during charging process. During the heat energy absorp-
tion process, there is no phase change happening and materials
experience a raise in temperature. The amount of heat stored is
proportional to the density, volume, specic heat and variation of
temperature of the storage material. Some of the most common
sensible heat storage materials are listed below.
2.1.1. Liquid storage medium
Advantage of a liquid storage medium is that it can be circulated
easily and so can transport heat if required. Such a system where
storage medium is circulated is called active system. Also due to density
dierence caused by heating of liquid, the buoyancy helps in creating a
thermal gradient across the storage which is desirable [6]. Hot uid
moves up, and cold uid moves down separating them. Some sensible
heat storage liquids are as follows:
2.1.1.1. Water. Water is one of the best storage media for low
temperature applications. Its operating temperature range is between
2590 C [7]. Its advantages are high specic heat, non-toxicity, cheap
cost and easy availability. But it has few drawbacks like high vapor
pressure and corrosiveness. Water is best used for house space heating
and hot water supply type of applications. Salty water in solar ponds is
used for collecting large amount of solar thermal energy at low
temperatures (5095 C). Heat gets at the dense layer at the bottom
of the pond due to dissolved salt which hinders natural convection.
Salts like NaCl and MgCl2 are used here. Water storage tanks are made
from a wide variety of materials, like steel, aluminum, reinforced
concrete and ber glass. The tanks are insulated with glass wool,
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mineral wool or polyurethane. The sizes of the tanks used vary from a
few hundred liters to a few thousand cubic meters. Large water tanks
require the development of technologies capable of guaranteeing water
tightness, to minimize heat losses caused by steam diusion through
the walls and to optimize stratication within the tank, in order to
preserve the thermal performance and life time of the solar heating
plant. Water can also be used for large scale seasonal heat energy
storage purposes in underground aquifers where water could be found
mixed with sand gravel. Such a system will be very cost eective as we
can avoid expensive water tank construction [8].
2.1.1.2. Mineral oil. Mineral oil is used as a heat transfer uid (HTF)
in CSP plants. It collects the heat at the receiver and then transports the
heat to boiler where steam is generated for driving the turbine. The
same can be also used to store thermal energy in a highly insulated
storage tanks during the night. When the HTF also becomes energy
storage material, it's a direct system. It eliminates need for heat
exchanger reducing the cost. Mineral oil has a lower vapor pressure
than water and is capable of operating at high temperatures in liquid
form up to 400 C. Also unlike molten salts, mineral oil does not freeze
during the night in pipes which creates the need for antifreeze system.
But mineral oil is costly compared to molten salts and recently few
molten salt mixtures with low melting point have been discovered
replacing mineral oil as energy storage material. Recent trend in CSP is
to use indirect systems where mineral oil acts as HTF and molten salt
mixtures act as sensible heat storage materials.
2.1.1.3. Molten salts. Molten salts are currently the most used thermal
energy storage materials in CSP plants. They are cheap (especially the
nitrates). Their density is high compared to other liquid storage
medium, giving them high energy storage density. Molten salts have
a lower vapor pressure than water and are capable of operating at high
temperatures in liquid form up to 400 C. This allows operation of the
plant at high temperatures which improves the eciency of Rankine
cycle. It is desirable to have a lower melting point for molten salts, and
close to ambient temperature so that they remain liquid during
operation and need for antifreeze is minimal during the night when
solar energy is not available. But pure molten salts usually have melting
points above 200 C which is a disadvantage. However, today the
practice is to use salt composites (more salt mixtures) which brings
down the melting point below 100 C and yet have a high maximum
temperature above 500 C [9]. They can also act as HTF but it's safer to
have antifreeze system to deal with any freezing risk. Otherwise
mineral oil will be used as HTF. One of the drawbacks of molten
salts is that they are oxidizing agents and very corrosive and to contain
them at high temperatures is problematic. Also their thermal
conductivity is low and has volume change around 6% during
melting process.
2.1.1.4. Liquid metals and alloys. Pure metals and alloys having low
melting points but above 300 C also have potential as sensible heat
storage media. They have a high thermal conductivity and high
maximum operating temperature. Their vapor pressure is minimal.
But they have drawback like high cost. Also they may require oxygen
and oxide free environment in order to reduce corrosion [7].
2.1.2. Solid storage medium
Solid storage materials have low cost and easily available every-
where. They have no vapor pressure issue. There for the operating
pressure is close to ambient pressure and so no need of pressure
containing vessels and no leak issues. Since they cannot be circulated
G. Alva et al.
easily, they can only do passive heat storage and need a uid, usually
air (HTF) for transporting heat into and out of loosely packed solid
materials in a storage tank. To increase the heat transfer eciency
there is a direct contact between the owing air and solid heat storage
medium during charging and discharging process. One of the issues
with sensible storage is that during discharging process the tempera-
ture of the storage medium decreases, so the HTF temperature also
decreases with time. The low temperature applications like space
heating and industrial waste heat recovery may use some of the solid
sensible heat storage materials.
2.1.2.1. Rocks. They can be used in a packed bed after crushing to
rough sizes of around 5 cm and using a heat transfer uid like air or as
mixture of sand-rock-mineral oil combination. Hot air ows between
the gaps of the packed rocks and heat the rock during charging process
and cold air ows between the gaps of the packed rocks and gets heated
during discharging process. There is a large contact surface area
available for heat transfer between air and rocks which improve heat
transfer eciency. Rocks are poor thermal conductors and there is a
small contact area between rock pieces which minimizes heat loss
during storage. Rocks have advantages like being nontoxic, non
ammable, very cheap and easily available. There are few drawbacks
like it requires large air mass ow rates and higher pressure drops [10].
2.1.2.2. Concrete. Concrete is an easily workable medium. Since it
possesses good mechanical strength, it does not require a container to
hold. One design approach for heat exchanger between concrete and
HTF is to have pipes through the concrete block through which the
HTF ows. One of issue faced at high temperature is crack formation
after repeated cycles of thermal expansion and contraction. Research
work [11,12] is on to develop an appropriate concrete mixing,
optimizing chemicalphysical and durability performances in higher
temperature range.
2.1.2.3. Sand. Locally available small grained materials like gravel or
silica sand can be used for thermal energy storage. Silica sand grains
will be average 0.20.5 mm in size and can be used in packed bed heat
storage systems using air as HTF. Packing density will be high for small
grain materials. Gravel material like basalt gravel will be around
0.4 mm in size. They can be used directly in solar receiver to collect
the solar thermal energy as they fall under gravity from the top in the
solar receiver tower. After absorbing the heat of concentrated solar rays
during their fall inside the tower, the hot sand gets collected in an
insulated storage tank below. Temperature of hot sand can go up to
7001000 C which will then be used for producing steam to drive
Rankine cycle power plant. Schlipf et al. [13] studied the possibility of
using sand in packed bed as heat storage medium for high temperature
thermal energy storage system. The results presented that the sands
have storage potential for temperatures up to 550 C.
2.1.2.4. Bricks. Bricks in building walls can store thermal energy to
minimize space heating electricity costs [7]. They can be heated during
opeak hours during the night with cheaper electricity and store heat.
The stored heat is extracted from the bricks during the day by natural
convection and radiation or by forced convection using an electric fan
[14]. This stored heat keeps the building warm during peak hours
during the day with no electricity consumption.
2.2. Latent heat thermal energy storage materials
Latent heat storage materials also called as phase change materials
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(PCM) absorb heat energy as their latent heat of fusion during the
melting process. During the heat energy absorption process there is a
phase change happening and temperature swing is very small. The
thermal energy stored in phase change material can be expressed
asQ = mL , where m is the mass (kg) and L is the latent heat of fusion
(kJ kg1). Usually it is the solidliquid phase change process that is
used. Transformations from liquid to gas have the highest latent heat of
phase change. However, the enormous changes in the volume of the
storage materials associated with the evaporation make the storage
complex and highly impractical [15]. If solidsolid latent heat storage
materials are used, the lack of liquid material eliminates the risk of
leakage and there is no need for encapsulation. But their latent heat of
transition is about one order of magnitude smaller than that of the
solidliquid latent heat storage material, which is a major drawback
[15]. Latent heat storage materials must have a large latent heat and
high thermal conductivity [14]. They should have a melting tempera-
ture point near the required operational temperature range of the TES
system, and should melt congruently with minimum subcooling [16]
and should be chemically stable, low in cost, nontoxic and non
corrosive. During discharging process, the temperature of the storage
medium is constant, so the HTF temperature also remains stable with
time, which is an advantage over sensible heat storage materials. For
latent heat storage materials, there is a smaller temperature dierence
between storing and releasing heat [14]. The latent heat of fusion of
the material will be very large compared to specic heat. For example,
sodium nitrate salt has a specic heat of 1.1 kJ kg1 K1 but its latent
heat of fusion is around 172 kJ kg1. This kind of large dierence gives
the latent heat storage materials advantage of high energy storage
density. This reduces the volume of the TES vessels, which reduce their
outer wall surface area and minimize the heat loss.
2.2.1. Organic
Organic latent heat storage materials and their eutectic mixtures
have been successfully tested and implemented in many domestic and
commercial applications, such as space heating in buildings, electronic
devices, refrigeration and airconditioning, solar air/water heating,
textiles, automobiles, food and space industries [4]. Organic materials
possess the capability of congruent melting without phase separation
[4]. Organic PCM have inherent characteristic of low thermal con-
ductivity (0.10.35 W/m K), hence, a larger surface area is required to
enhance the heat transfer rate [4]. In addition, because of the low
melting point of organic PCM, they have not yet been explored for high
temperature applications such as in power plants.
2.2.1.1. Paran. Paran waxes consist of straight n-alkanes chain
(CH3(CH2)CH3) [17]. Pure paran waxes are very expensive, and
therefore, only technical grade paran can be used. Commercial
paran waxes are cheap with moderate thermal storage density
(200 kJ/kg or 150 MJ/m3) and a narrow range of melting
temperatures from 10 C to 67 C [14,18]. They undergo a very
little subcooling and are chemically inert and stable with no phase
segregation. They are noncorrosive, odorless, long lasting, inexpensive,
easily available, ecologically harmless and nontoxic. However, they
have low thermal conductivity (0.2 W/m K), which limits their
applications [18]. Commercial grade paran wax is obtained from
distillation of crude oil. Most paran PCM are mixtures of saturated
hydrocarbons with dierent numbers of carbon atoms in the molecules.
The melting temperature and heat of fusion of the parans increase
with the average length of the hydrocarbon chain. This relationship can
be employed to design the PCM properties by mixing physically
dierent paran. Even after 10002000 cycles commercial grade
paran waxes and other pure paran have stable properties and
good thermal reliability. Paran waxes are safe. Since they do not
promote corrosion, they are compatible with metal containers.
However, they interact with some plastic containers which have
chemical similarity to paran. Polymers like polyolen experience
G. Alva et al.
problems like inltrations and softening [18].
2.2.1.2. Fatty acids. They have a general formula of (CH3 (CH2)2n-
COOH) and have ideal thermophysical properties of a low temperature
latent heat storage material. The melting and boiling points of fatty
acids are relatively high compared to that of the parans, and the
saturated fatty acids exhibit low phase transition volume changes. They
have reproducible melting and freezing behavior with very little or no
super cooling. They are more expensive than technical grade parans,
mildly corrosive and possess a disagreeable odor. They are combustible
in nature [17]. Generally, the melting and freezing points, the heat of
melting and the degree of crystallization of fatty acids increase with the
number of carbon atoms in their molecules [18].
2.2.1.3. Easters. Esters are derived from acids in which one hydroxyl
(OH) group is replaced by one alkyl (O) group. Fatty acid Easters
show solidliquid transition over a narrow temperature range. They
can form the eutectics without or little sub cooling. Eutectic mixtures of
Easters have phase transition temperature close to room temperature
with high enthalpy of transition [14]. Fatty acid Easters have a good
availability, due to their commercial applications in polymer, cosmetics
and smart clothing industries in large quantities.
2.2.1.4. Alcohols. Sugar alcohol, also known as polyalcohols, are
considered as medium temperature (90200 C) PCM. They have not
received much attention by researchers. Previous studies revealed that
alcohols such as xylitol, erythritol and mannitol possess a latent heat of
fusion close to 300 kJ/kg, which is much higher value than other
materials in this family. Alcohols have been tested as potential phase
change materials in the last four decades.
2.2.1.5. Glycols. Polyethylene glycol (PEG) has dierent names like
polyoxyethylene (POE) or polyethylene oxide (PEO). PEG is composed
of dimethyl ether chains having the hydroxyl group at the end, with a
formula of HOCH2(CH2OCH2)nCH2OH. They are soluble in
water as well as in organic compounds. PEGs come in various grades
like PEG400, PEG600 etc. Many numerical and experimental studies
are done on these materials in the past. They are chemically and
thermally stable, nonammable, nontoxic, noncorrosive and
inexpensive. The melting point and latent heat of fusion of the PEGs
increase with increasing molecular weight [19]. Like other organic
PCM, the PEG also has low thermal conductivity problem.
2.2.2. Inorganic
These materials have a high volumetric latent heat density of
around 350 MJ/m3. They have stable properties even after a large
number of thermal cycles and have a relatively higher thermal
conductivity of around 0.5 W/m K. However, they melt incongruently
[17]. They are prone to phase segregation and sub cooling. Another
major issue with them is corrosion of salt on metal container.
2.2.2.1. Salt hydrates. Salt hydrates are normally used at low
operating temperatures in the range of 3050 C. They have a
general formula ABnH2 O , which are inorganic salts containing water
of crystallization. During phase transformation, dehydration of the salt
occurs. This can occur in two ways. There could be a salt hydrate that
contains fewer water molecules or there could be anhydrous form of
the salt.
Depending on the melting behavior, the salt hydrates can be
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classied as:
Congruent salt hydrates: Salt is soluble in the hydration water
during melting.
Incongruent salt hydrates: Salt is partially soluble in the hydration
water during melting.
Semi-congruent salt hydrates: After the phase change, the solid and
liquid phases have dierent compositions because of the transforma-
tion of the salt hydrate to a salt hydrate with a lesser amount of
hydration water.
However, a large number of salt hydrates which have the potential
to become PCM with suitable melting temperature and a large latent
heat melt incongruently. The released water during phase transition
does not dissolve the crystalline salt formed during the dehydration
process. Due to density dierence between salt and water phase
separation and sedimentation occurs in containers. This is a serious
technical problem in practical applications. One of the methods used
for preventing segregation and sedimentation of the heavier phase is
adding gelling or thickening agents [18]. The addition of polymeric or
cellulosic gelling material to the salt hinders salt sedimentation, as
thickening agent increases the viscosity of the salt hydrate and helps to
hold the salt hydrate molecules together. Another disadvantage of salt
hydrates is signicant super cooling. This is due to their poor
nucleating ability and so to prevent this problem, nucleating agents
are added. The nucleating agents like borax and carbon [14] etc help to
overcome the sub cooling, but they reduce the heat transfer rate by
lowering the thermal conductivity.
2.2.2.2. Salts. Inorganic salts are already discussed in the molten salt
section above, where salts of relatively lower melting temperatures are
used as sensible liquid storage medium. But they can also act as latent
heat storage materials for high temperature applications above 100 C.
They fall into many subgroups of materials like nitrates, carbonates,
hydroxides and chlorides etc, and have a wide range of melting
temperatures. Few common salts with potential as PCM are listed in
Table 1.
2.2.2.3. Metals and metal alloys. Metals and their alloys have high
thermal conductivity, good thermal stability, reliability and
repeatability [18]. They have largest phase transition heat per unit
volume or unit mass. Therefore, they have very high energy storage
capacity. They have a negligible change in volume during phase change.
They have negligible vapor pressure. However when volume is a
priority, they are capable of competing with salts [15]. Few common
metal alloys with potential as PCM are listed in Table 1.
2.2.3. Eutectic
The eutectic is a composition of two or more components, such as
organicorganic, organicinorganic and inorganicinorganic.
Each of them changes its phase congruently i.e. they have a denite
melting/freezing point and form a mixture of component crystal during
crystallization. Eutectics generally melt and freeze congruently and
leave no chances of separation of components. Eutectic mixtures with a
wide temperature range are listed in Table 1.
2.3. Composite phase change materials
To address the poor thermal conductivity issue, by dispersing high
thermal conductive particles like carbon, graphite or metals into the
PCM, the thermal conductivity of the PCM can be improved. Such a
mixture is called composite phase change material. Composites can be
prepared using both organic and inorganic phase change materials. The
added thermal conductive materials should be compatible with the
PCM. For example, if the PCM is corrosive in case of few inorganic
G. Alva et al. Renewable and Sustainable Energy Reviews 68 (2017) 693706

Table 1
Classification and thermal properties of thermal storage materials.

Type Storage materials Density (kg/m3) Melting Specific Heat of Thermal References
point (C) heat (kJ/ fusion conductivity (W/
Solid Liquid kg K) (kJ/kg) m K)

Sensible heat Water H2O 1000 0 4.184 333.55 0.58

storage Oils Mineral oil 770 1.966 0.12 [6]
materials Therminol VP-1 1068 12 1.546 0.137
Molten Nitrate salts NaNO3 2261 1908 306 1.655 172 0.514 [9,15]
salts KNO3 2109 335 0.953 266 0.5 [9]
LiNO3 250 370 [18]
Hydroxide salts NaOH 2100 318 0.92 165 [9]
KOH 2040 380 1.34 150 0.5 [6,9]
Chloride salts ZnCl2 2907 280 75 0.5 [4]
AlC13 192 280 [18]
Salt composites Solar salt NaNO3 1920 220 100.7 0.56 [4]
KNO3 (5050)
Hitec NaNO3KNO3 120 [6]
NaNO2 (753 40)
Hitec XL NaNO3 130 [6]
KNO3Ca(NO3)2 (7
4548)
Solid Rocks 2560 0.960 0.48 [10]
materials Concrete 2200 0.85 1.5 [6]
Sand 1602 0.83
Cast steel 7800 0.6 40 [6]
Magnesia re bricks 3000 1.15 5 [6]
Silica re bricks 1820 1.0 1.5 [6]
Liquid Al 2707 2375 660 0.89 397 204 [32]
Metals Na 968 850 97 1.3 113 71 [6]
Latent heat Organic Paraffin (CH3- Paraffin wax 916 790 (65 C) 64 173.6 0.167 (liquid, [14]
storage (CH2)n-CH3) (24 C) 63.5 C)
materials 0.346 (solid,
33.6 C)
n-Dodecane (Carbon 10 216 [41]
atoms-12)
n-Tridecane (Carbon 5 160 [41]
atoms-13)
n-Tetradecane (Carbon 6 229 [18]
atoms-14)
n-Pentadecane 10 206 [18]
(Carbon atoms-15)
n-Hexadecane (Carbon 773 20 236 [18]
atoms-16)
n-Heptadecane 778 22.6 214 [18]
(Carbon atoms-17)
n-Octadecane (Carbon 776 28.4 244 [18]
atoms-18)
n-Nonadecane (Carbon 785 32 222 [18]
atoms-19)
n-Eicozane (Carbon 788 36.6 247 [18]
atoms-20)
n-Heneicozane 791 40.2 213 [18]
(Carbon atoms-21)
n-Docozane (Carbon 794 44 249 [18]
atoms-22)
n-Trikozane (Carbon 796 47.5 234 [18]
atoms-23)
n-Tetracozane (Carbon 799 50.6 255 [18]
atoms-24)
n-Pentacozane (Carbon 801 53.5 238 [18]
atoms-25)
n-Hexacozane (Carbon 803 56.3 256 [18]
atoms-26)
n-Heptacozane 779 58.8 235 [18]
(Carbon atoms-27)
n-Oktacozane (Carbon 806 41.2 254 [18]
atoms-28)
n-Nonacozane (Carbon 808 63.4 239 [18]
atoms-29)
n-Triacontane (Carbon 775 65.4 252 [18]
atoms-30)
Fatty acids Caprylic acid (Carbon 981 901 (30 C) 16 148.5 0.149 (liquid, [7,14]
(CH3(CH2) atoms-8) (13 C) 38.6 C)
2nCOOH) Capric acid (Carbon 1004 878 (45 C) 32 152.7 0.153 (liquid, [7,14]
atoms-10) (24 C) 38.5 C)
Lauric acid (Carbon 870 42 171 [7,18]
(continued on next page)

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Table 1 (continued)

Type Storage materials Density (kg/m3) Melting Specific Heat of Thermal References
point (C) heat (kJ/ fusion conductivity (W/
Solid Liquid kg K) (kJ/kg) m K)

atoms-12)
Myristic acid (Carbon 860 54 190 [7,18]
atoms-14)
Palmitic acid (Carbon 989 850 (65 C) 64 185.4 0.162 (liquid, [7,14]
atoms-16) (24 C) 68.4 C)
Stearic acid (Carbon 940 69 2.07 209 [7,18]
atoms-18)
Arachidic acid (Carbon 74 227 [18]
atoms-20)
Undecylenic acid 24.6 141 [18]
(Carbon atoms-22)
Esters Methyl palmitate 27 163.2 [18]
Allyl palmitate 23 173 [18]
Propyl palmitate 20 190 [18]
Methyl stearate 39 160.7 [18]
Isopropyl palmitate 11 100 [18]
Isopropyl stearate 14 142 [18]
Butyl stearate 23 200 [18]
Ethylene glycol 63.2 215.8 [18]
distearate
Dimethyl sebacate 21 135 [18]
Methyl-12- 43 126 [18]
hydroxystearate
Vinyl stearate 27 122 [18]
Glycols (HO CH2 (Poly Ethylene Glycol) 4.2 117.6 [7]
(CH2 O CH2)n PEG400
CH2 OH) PEG600 12.5 129.1 [18]
PEG1000 40 168.6 [18]
PEG3400 63.4 166.8 [18]
PEG10000 65.9 171.6 [18]
PEG20000 67.7 160.2 [18]
PEG35000 68.7 166.9 [18]
PEG100000 67 175.8 [18]
PEG1000000 70 174 [18]
Alcohols Xylitol 93 280
Sorbitol 97 110
Erythritol 117 344
Mannitol 165 341
Inorganic Salt hydrates MgCl26H2O 1569 1450 117 168.6 0.570 (liquid, [14]
(20 C) (120 C) 120 C)
0.694 (solid,
90 C)
Mg(NO3)26H2O 1636 1550 (94 C) 89 162.8 0.490 (liquid, [14]
(25 C) 95 C)
0.611 (solid,
37 C)
Ba(OH)28H2O 2070 1937 (84 C) 78 265.7 0.653 (liquid, [14]
(24 C) 85.7 C)
1.225 (solid,
23 C)
Na2S2O35H2O 1750 48 200 [7,18]
Na2HPO412H2O 1520 36 280 0.476(liquid) 0.514 [7,18]
(solid)
Na2CO310H2O 36 247 [7]
Na2SO410H2O 32 251 [7]
CaCl26H2O 1802 1562 (32 C) 29 190.8 0.540 (liquid, [14]
(24 C) 38.7 C)
1.088 (solid,
23 C)
Nitrate salts Mg (NO3)2 426 [9]
Ca(NO3)2 2113 560 145 [9,15]
Carbonate salts Na2CO3 2533 1972 854 2.0 276 [9,15]
K2CO3 2290 897 2.0 236 [9]
CaCO3 2930 1330 142 [15]
Li2CO3 2110 732 509 [15]
Hydroxide salts LiOH 1460 462 873 [15]
Chloride salts NaCl 2160 802 5.0 420 5 [6,9]
KCl 1980 1527 771 353 [9,15]
MgCl2 2320 1680 714 452 [9,15]
LiCl 2070 1502 610 441 [15]
CaCl2 2150 2085 772 253 [15]
Sulphate salts Na2SO4 2680 884 165 [9,15]
Li2SO4 2220 2003 858 84 [15]
(continued on next page)

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Table 1 (continued)

Type Storage materials Density (kg/m3) Melting Specific Heat of Thermal References
point (C) heat (kJ/ fusion conductivity (W/
Solid Liquid kg K) (kJ/kg) m K)

K2SO4 2660 1069 212 [15]

MgSO4 2660 1130 122 [15]
CaSO4 2320 1460 203 [15]
Fluoride salts LiF 2640 1810 850 1044 [6,15]
NaF 2558 1948 996 794 [15]
KF 2370 1910 858 468 [15]
CaF2 3180 2520 1418 391 [15]
Metals and alloys Zn/Mg (53.7/46.3) 4600 340 185 [15]
Zn/Mg (52/48) 340 180 [15]
Zn/Al (96/4) 6630 381 138 [15]
Al/Mg/Zn (59/33/6) 2380 443 310 [15]
Al/Mg/Zn (60/34/6) 450.3 329.1 [15]
Mg/Cu/Zn (60/25/15) 2800 452 254 [15]
Mg/Cu/Ca (52/25/23) 2000 453 184 [15]
Al/Mg (65.35/34.65) 2155 497 285 [15]
Al/Cu/Mg (60.8/33.2/ 3050 506 365 [15]
6)
Al/Cu/Si/Mg (64.6/ 4400 507 374 [15]
28/5.2/2.2)
Al/Cu/Mg/Zn (54/22/ 3140 520 305 [15]
18/6)
Al/Cu/Si (68.5/26.5/5) 2938 525 364 [15]
Al/Cu/Sb (64.3/34/ 4000 545 331 [15]
1.7)
Al/Cu (66.92/33.08) 3600 548 372 [15]
Al/Si/Mg (83.14/11.7/ 2500 555 485 [15]
5.16)
Al/Si (87.76/12.24) 2540 557 498 [15]
Cu/Al/Si (49.1/46.3/ 5560 571 406 [15]
4.6)
Al/Cu/Si (65/30/5) 2730 571 422 [15]
Al/Si/Sb (86.4/9.6/ 2700 575 471 [15]
4.2)
Si/Al (86/12) 2700 576 560 [15]
Si/Al (80/20) 585 460 [15]
Zn/Cu/Mg (49/45/6) 8670 703 176 [15]
Cu/P (91/9) 5600 715 134 [15]
Cu/Zn/P (69/17/14) 7000 720 368 [15]
Cu/Zn/Si(74/19/7) 7170 765 125 [15]
Cu/Si/Mg (56/27/17) 4150 770 420 [15]
Mg/Ca (84/16) 1380 790 272 [15]
Mg/Si/Zn (47/38/15) 800 314 [15]
Cu/Si (80/20) 6600 803 197 [15]
Cu/P/Si (83/10/7) 6880 840 92 [15]
Si/Mg/Ca (49/30/21) 2250 865 305 [15]
Si/Mg (56/44) 1900 946 757 [15]
Eutectic Organic Lauric acid-capric acid 21 143 [18]
(45/55)
Capric acid-palmitic 21.8 171.2 [18]
Acid (76.5/23.5)
Lauric acid-myristic 34.2 166.8 [18]
acid (66.0/34.0)
Lauric acid-palmitic 35.2 166.3 [18]
acid (69.0/31.0)
Lauric acid-stearic acid 37 182.7 [18]
(75.5/24.5)
Myristic acid-palmitic 42.6 169.7 [18]
acid (58.0/42.0)
Myristic acid-stearic 44.1 182.4 [18]
acid (64.0/36.0)
Myristic acid-stearic 52 162 [18]
acid (65.7/34.3)
Palmitic acid-stearic 52.3 181.7 [18]
acid (64.2/35.8)
Inorganic Na2SO4/H2O/NaCl/ 13 146 [7]
NH4Cl (32.5/41.4/
6.66/6.16)
CaCl26H2O/ 14.7 140 [7]
CaBr2.6H2O (45/55)
Na2SO410H2O/NaCl 18 [18]
(50/50)
CaCl26H2O/ 25 127 [18]
MgCl2.6H2O (66.6/
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Table 1 (continued)

Type Storage materials Density (kg/m3) Melting Specific Heat of Thermal References
point (C) heat (kJ/ fusion conductivity (W/
Solid Liquid kg K) (kJ/kg) m K)

33.3)
CaCl2/MgCl26H2O 25 95 [18]
(50/50)
CaCl2/NaCl/KCl/H2O 27 188 [18]
(48/4.3/0.4/47.3)
Ca(NO3)24H2O/ 30 136 [18]
Mg(NO3)26H2O (47/
53)
CH3COONa3H2O/ 30 200.5 [18]
NH2CONH2 (40/60)
Mg (NO3)6H2O/ 51 131.3 [7]
NH4NO3 (61.5/38.5)
Mg(NO3)6H2O/ 58 106 [7]
MgCl26H2O (58.3/
41.7)
LiOH/KOH (40/60) 314 341 [9]
KNO3/KCl (95.5/4.5) 2100 320 1.21 (solid) 74 0.5(solid) [9]
KNO3/KCl (96/4) 320 150 [9]
KNO3/KBr/KCl (80/ 342 140 [9]
10/10)
NaCl/KCl/LiCl (33/24/ 346 281 [9]
43)
NaOH/NaCl (80/20) 370 370 [9]
MgCl2/KCl/NaCl (60/ 1800 380 0.96(solid) 400 [9]
20.4/19.6)
Li2CO3/K2CO3/ 397 276 [9]
Na2CO3 (32.1/34.5/
33.4)
MgCl2/KCl (39/61) 2110 435 0.8(solid) 351 0.81 (liquid) [9]
0.96(liquid)
MgCl2/NaCl (52/48) 2230 450 0.92(solid) 430 0.95(liquid) [9]
1.00(liquid)
MgCl2/KCl (64/36) 2190 470 0.84(solid) 388 0.83(liquid) [9]
0.96(liquid)
MgCl2/KCl/CaCl2 (48/ 2530 487 0.8(solid) 342 0.88(liquid) [9]
25/27) 0.92(liquid)
CaCl2/NaCl (67/33) 2160 500 0.84(solid) 281 1.02(liquid) [9]
1.00(liquid)
NaCl/KCl/CaCl2 (29/ 2150 504 1.17(solid) 279 1(liquid) [9]
5/66) 1.0(liquid)
BaCl2/KCl/NaCl (53/ 3020 542 0.63(solid) 221 0.86(liquid) [9]
28/19) 0.8(liquid)
BaCl2/KCl/CaCl2 (47/ 2930 551 0.67(solid) 219 0.95(liquid) [9]
24/29) 0.84(liquid)
LiF/MgF2/KF (64/30/ 710 782 [9]
6 mol%)
LiF/CaF2 (80.5/ 767 790 [9]
19.5 mol%)

salts, the added conductive material should be corrosion resistant.
2.3.1. Graphite composites
Graphite can be used in dierent forms as below. Pincemin et al.
[20] tested the performance of the PCM composites composed by the
NaNO3/KNO3 eutectic PCM with thermal conductive graphite by
dispersion of graphite within the molten salt, and found an improve-
ment of the thermal conductivity by 14 times up to an eective
conductivity of 9 Wm1 K1. Sari et al. [21] tested the performance of
the PCM composites composed by the n-docosane paran with
expanded graphite. Thermal conductivities of the composite PCM with
mass fraction of 2%, 4%, 7% and 10% expanded graphite indicated that
the thermal conductivity of the paran (0.22 W/m K) increased as
81.2%, 136.3%, 209.1% and 272.7%, respectively.
2.3.1.1. Graphite akes or natural graphite. They have a well
aligned crystal structure and high thermal conductivity. They have
stacked sheets of carbon, where carbon atoms are held together by
strong covalent bonds and these stacked sheets are held together by
weak van der waals bonds. Hence they have a dense packing and high
density. They require minimum treatment during production and their
cost is very low. A sole particle size is around 400 mm.
2.3.1.2. Expanded natural graphite. This is produced from natural
graphite after undergoing two processes, such as chemical treatment
and thermal exfoliation. In reactions with various acids, the weak
bonds are overcome and molecules of the reactant are incorporated
between the layers of the graphite. The graphite structure has to
expand to accommodate the reactant molecules, but the sheet structure
remains intact. This is called an intercalated compound. After the
graphite intercalated compound is washed in water and dried, it is
heated to cause rapid expansion of the graphite layers. The heat
treatment is done in an air atmosphere at temperatures greater than
500 C. The water is incorporated between the layers of carbon during
the formation of the intercalated compound. The near instantaneous
vaporization of the water during the heat treatment process is
responsible for the expansion. Each natural graphite particle is

700
G. Alva et al.
modied into the form of worm in which the graphene layers are
spread leading to high particle porosity. These worms can be made in
to a bed and then compressed to form a consolidated graphite matrix of
high porosity and thermal conductivity.
2.3.1.3. Expanded graphite powder. This is prepared by grinding
expanded graphite into powder. It has a less compact structure than
natural graphite and tends to build networks even at small
concentrations. Thus compared to natural graphite, smaller amounts
of expanded graphite powder are required to reach a similar thermal
conductivity. Nevertheless, due to the corresponding treatments
needed for their production, it is more expensive than natural
graphite. In the present study, particle sizes vary between 50 and
500 mm.
2.3.2. Nano composites
We can also use dierent nanostructures as thermal enhancement
additives in PCM. Khodadadi et al. [22] explored following types of
nanoparticles as the materials of the thermal conductivity promoters.
Nanoparticles have the advantage being extremely small in size. Hence
they behave like uid and avoid being clogged during ow in pipes.
Generally, the thermal enhancements achieved with carbon based
nanostructures are found better than that with metallic and metal
oxide. Kibria et al. [23] performed a review of current experimental
studies on variations in thermo-physical properties of PCM due to
dispersion of nanoparticles. The types of nanoparticles are as follows:
Carbon-based nanostructure nanobers, nanoplatelets, gra-
phene akes and carbon nanotubes.
Metallic (Ag, Al, C/Cu and Cu) [23].
Metal oxide (Al2O3, CuO, NiO, SiO2, ZnO, MgO and TiO2) [23].
Silver nanowires.
2.3.3. Form-stable composite
A composite is called form-stable composite PCM if it could keep
the same shape in solid state even when the temperature of the
composite is over the melting temperature of the PCM. In a form
stable composite, the PCM can be molded to required shapes with
higher surface area to volume ratio without the aid of an encapsulation
to increase heat transfer rate. Here the main idea is to improve the
contact surface area of the PCM with HTF and increase of thermal
conductivity is not the priority. Sari [24] explored formstable
paran/high density polyethylene composites where paran acts as
latent heat storage material and high density polyethylene acts as
supporting material which gives structural strength to prevent leakage
of melted paran. An improvement of up to 24% in thermal
conductivity was obtained.
2.4. Microencapsulated phase change materials
Microcapsules can be described as particles that contain core
material surrounded by a coating or shell and have diameters in the
11000 m range. Microencapsulation is widely used in commercial
applications including textiles, adhesives, cosmetics, pharmaceuticals
and buildings [17]. The microencapsulated phase change materials
(MEPCM) should have required morphology, uniform diameter, shell
mechanical strength, penetration abilities and thermal stability.
Pouches, tubes, sphere, panels or other receptacles containing
MEPCM directly act as heat exchangers. The MEPCM can also be
incorporated into building materials. The shell holds the liquid PCM
and prevents changes in its composition due to contact with the
environment. It increases the contact surface area for heat transfer.
It also adds the mechanical stability to MEPCM if the shell is
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Renewable and Sustainable Energy Reviews 68 (2017) 693706
suciently rigid. The MEPCM are available in various shapes and
sizes. Microencapsulation is a relatively expensive process. Specialized
techniques are used for microencapsulation with a polymer cover and a
PCM core. Ureaformaldehyde (UF) resin, melamineformaldehyde
(MF) resin and polyurethanes (PU) are the most appropriate micro-
capsule shell material.
2.4.1. Coacervation
When two or more oppositely charged colloids dispersed in an
aqueous solution of the PCM, coacervation happens due to electrostatic
force between oppositely charged colloid particles or macro-ions and
particles separate out to form 2 new phases, one rich and one poor in
colloid concentration. These concentrated colloid particles form sphe-
rical droplets held together by electrostatic forces. For example gelatin
with gum arabic in paran, gelatin and gum arabic form coacervation
providing micron sized locally segregated environments which then
absorb the simple organic molecules like paran from the surrounding
medium. Gelatin and gun arabic form the shell and paran acts as the
PCM core in the microencapsulation.
2.4.2. Suspension polymerization
Microcapsules with a polymer cover and a PCM core can be
obtained by a process based on suspension polymerization. In this
process a monomer or mixture of monomers containing an initiator are
dispersed in an aqueous solution of PCM using mechanical agitation
like strong stirring. The initiator can be decomposed to free radicals by
heating and the free radical then triggers polymerization of monomers.
The droplet size of microcapsules is controlled by chemical parameters
(viscosity, densities and interfacial tension), equipment parameters
(porosity, pore diameter, pipe diameter and stirrer dimension) and the
operating conditions (ow rate, shear rate and pulsation).
2.4.3. Emulsion polymerization
This involves an emulsion where a monomer is emulsied with
surfactants in an aqueous phase. The PCM liquid droplets acting as oil
phase are dispersed in the aqueous solution. The surfactants which
have hydrophobic and hydrophilic sides align themselves around the
interface between monomers in aqueous solution and PCM liquid
droplets. The hydrophilic part contacts the aqueous solution and
hydrophobic part contacts the PCM liquid droplet. This results in the
initiator triggering polymerization of the monomer molecules around
spherical droplet. Such emulsion droplets with polymer shells formed
throughout the aqueous solution result in an emulsion with up to 50%
concentration of suspended microencapsulated PCM [16].
2.4.4. Polycondensation
Using a resin like melamineformaldehyde as coating material by
controlling PCM liquid dropping rate and temperature, microcapsules
with a PCM core can be formed. In a condensation reaction, monomer
1 molecules join together with monomer2 molecules, losing small
molecules as by-products such as water or methanol. Polycondensation
of melamine and formaldehyde shell material with n-hexadecane or n-
octadecane as the PCM core can be used for microencapsulation.
Interfacial polycondensation has advantages like high reaction speed,
mild reaction course and also its products have low penetrability [25].
Interfacial polycondensation can be explained as follows. The core
material is made into droplet. The reactive monomers start forming
oligomers on the surface of the droplets forming capsule shell. When
the initially formed oligomers are insoluble at the interface of the
droplets, they grow, and a thin monolayer membrane forms around the
droplets. The polycondensation leads the monolayer membrane to be a
shell, and leads to the formation of a microscopic shell around the
droplets. Polyurea, polyurethane, polyester, polyamide and amine resin
can be used as the shell monomers in the interfacial polycondensation
process. The PCM such as butyl stearate microencapsulated by inter-
facial polymerization with toluene-2, 4-diisocyanate (TDI) and ethyle-
G. Alva et al.
nediamine (EDA) used as monomers in an emulsion system. Chen et al.
[25] prepared polyurea microcapsules containing PCM using toluene-2,
4-di-isocyanate (TDI) and ethylenediamine (EDA) as monomers, and
butyl stearate as the core PCM material. Zhang and Wang [26]
prepared MEPCM based on a core of n-octadecane and polyurea shells,
which was synthesized by polyaddition of TDI as an oil soluble
monomer and various amines, e.g. EDA, di-ethylene tri-amine, or
polyetheramine as the water-soluble monomers.
2.4.5. Polyaddition
This type of method of forming PCM-lled microcapsules relies on
the interfacial polyaddition reaction between a monomer-1 in the oil
phase and a matching monomer-2 in the aqueous phase. This may
involve dispersing a oil phase solution of the PCM and monomer-1 into
another aqueous phase solution containing mononer-2, then adding an
initiator to start the polyaddition reaction between monomer-1 and
mononer-2. A polyurea membrane forms almost instantly at the
surface of the dispersed oil phase droplets of the PCM.
2.5. Thermochemical heat storage materials
Thermochemical heat storage system [27] uses a reversible chemi-
cal reaction. The heat energy stored is equal to the reaction enthalpy.
During the charging process, a forward endothermic reaction absorbs
heat and the absorbed thermal energy is used to dissociate a chemical
reactant (A) into products (B) and (C). During the discharging process
reactants (B) and (C) undergo backward exothermic reaction producing
(A) and releasing heat. The products of both reactions can be stored
either at ambient temperature or at working temperature. The thermal
energy stored in thermochemical material can be expressed as:
Q = nH , where n is the mol number of the reactant A (mol) and
H is the reaction enthalpy (kJ mol1).
Thermochemical storage technology is still at laboratory stage,
where as sensible and latent heat technologies are matured and are
at industrial stage.
Energy density stored in thermochemical heat storage is higher
compare to both sensible and latent heat storage materials. Sensible,
latent and chemical storages have approximate volumetric energy
storage density of 50, 100 and 500 kW h m3 respectively.
Storage temperature in case of sensible and latent heat storage is at
charging process temperature where as in chemical storage it is the
ambient temperature. Thus heat loss and insulation requirement is
minima for thermochemical storage.
Storage duration is limited in case of sensible and latent heat
storage materials due to thermal losses. In case of chemical storage, it
is theoretically unlimited due to minimal thermal losses.
Complexity of technology of thermochemical storage is complex
where as both sensible and latent heat storage materials have simple
technologies.
The rst step to develop a thermochemical TES system is the
selection of the reaction and the study of its chemical characteristics
such as the reversibility, the rate of reaction, the operating conditions
(pressure and temperature) and the kinetic properties [27]. The
requirements from a suitable thermochemical storage material are as
follows:
The endothermic reaction used for heat storage should occur at a
temperature below 1273 K. The exothermic reaction used for recover
heat should occur at a temperature above 773 K. The large enthalpy of
reaction and small molar volume can maximize thermal energy storage
capacity. Both forward and backward reactions should be completely
reversible with no side reactions and should have high yields in order to
use materials over a long period of time. Both forward and backward
reactions should be fast enough to absorption of solar energy and heat
release can be carried out rapidly. Chemical compounds of both
reactions can be handled easily. Chemical compounds should not react
with the environment.
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Renewable and Sustainable Energy Reviews 68 (2017) 693706
3. The performances of solar thermal energy storage systems
A TES system consists of three parts: storage medium, heat
exchanger and storage tank. Storage medium can be sensible, latent
heat or thermochemical storage material [28]. The purpose of the heat
exchanger is to supply or extract heat from the storage medium. The
storage tank holds the storage medium and insulates the system from
the surroundings. TES systems must be designed to meet certain
criteria, which are dependent on the type, size and design of the
application like CSP plant [28].
Before choosing an appropriate TES system a thorough analysis of
all requirements need to be done. TES system should be compatible
with all the other units in the plant. It should also be conrmed to the
overall operational strategy of the plant like operational temperature
range, number of hours of storage required, charging and discharging
rate, integration with solar collection system etc. It should be ensured
its long-term stability, i.e. the number of cycles that both container and
storage medium can withstand without degradation of their properties.
The long-term stability of the system can be compromised by two
factors, poor stability of the properties of materials under extensive
thermal cycling and/or corrosion and chemical incompatibility be-
tween the PCM and its container. Accordingly the best suited storage
material, heat exchanger between the thermal storage material and
heat transfer uid (HTF) etc should be chosen.
3.1. Sensible heat thermal energy storage systems
Sensible heat storage systems use sensible heat storage materials as
medium. Some of the TES systems of this type are as follows.
3.1.1. Steam accumulators
In this type of system, water is converted to steam at the solar
receiver system, and the excess steam during o-peak hours is stored at
high pressure up to 100 bar in steam accumulators. At this pressure
steam is stored in liquid phase with a high volumetric heat capacity of
water up to 1.2 kW h m3 [29]. This is a simple, low cost system with
all the benets of water as storage medium. But this system has issues
like increased piping cost due to high vapor pressure, instability of two
phase ow inside receiver tubes and a need for auxiliary protective
heating system during start up.
3.1.2. Two tanks direct active system
In this type of system, a HTF like mineral oil acts as both HTF and
thermal storage medium. There for an intermediate heat exchanger is
not required. The HTF does not have the problem of freezing in the
solar receivers during the night. At solar energy generating systems
(SEGS) in the Mojave desert of California this system is operating. A
mineral oil called as Caloria is stored in two separate tanks. One tank is
called as hot tank with a higher temperature at around 307 C and
other tank is called as cold tank where the temperature is around
240 C. The HTF ows from hot tank to power block where it
discharges the heat energy to generate steam and then ows back to
cold tank. During the day time the HTF from cold storage tank ows to
the solar collector system and gets heated and ows back in to the hot
tank. The operation of this type of TES system has limitations in higher
temperature ranges because of high vapor pressure of the HTF.
Alternatively to overcome the limitation on higher operational
temperature molten salts can be used as both HTF and storage medium
too. Molten salt used is composed of a mixture of 60% of sodium
nitrate (NaNO3) and 40% of potassium nitrate (KNO3). This mixture
melted at 207 C, was thermally stable to about 600 C, and oered a
favorable combination of high density, low vapor pressure, moderate
specic heat, low chemical reactivity and low cost. The higher
temperature increases the Rankine cycle eciency. This is used in
Archimede Sicily, Italy solar plant and the temperature here can go up
to 550 C. The storage capacity of 100 MW h for 8 h can be achieved in
G. Alva et al.
this plant [6]. In this case HTF does have the problem of freezing in the
solar receivers during the night. There for an anti-freeze system is
required.
3.1.3. Two tanks indirect active system
In this type of system, a HTF like steam or mineral oil acts as HTF
and molten salt acts as thermal storage medium. This type of TES
system is implemented at Andasol-1 solar power plant located in
Guadix, Granada, Spain. This plant has a solar eld based on parabolic
trough technology. Superheated steam is used as HTF. The super-
heated steam using a heat exchanger, transfers heat to the storage
media, which is a molten salt mixture called solar salt (40% NaNO3 and
60% KNO3, having a melting temperature 221 C). The TES system has
working temperatures of 291 C in the cold tank and 384 C in the hot
tank. The storage capacity of the Andasol-1 solar plant is about
1010 MW h, that means about 7.5 h of full-load production of elec-
tricity [6]. The annual average eciency converting from solar energy
to electricity is 14.7% [29].
3.1.4. Single tank thermocline system
In single tank thermocline system, a thermal gradient is created
within the storage tank due to buoyancy eect and an eective
separation between the hot uid at the top and cold uid at the bottom
is maintained. As the hot storage uid is pumped at the top, it displaces
the cold uid towards down and remains on top. A system where the
whole thermocline tank is lled with liquid storage medium is an active
thermocline system. To reduce the relatively expensive liquid storage
medium requirement, a low cost solid ller material which is compa-
tible with the liquid storage medium is used to ll most of the volume
in the thermocline tank and it acts as primary thermal storage material.
This kind of system where the solid ller is used as primary thermal
storage material is a passive system. The liquid storage medium usually
will be molten salts and solid ller material will be such as quartzite
rock. The molten salt ows through the quartzite ller and exchanges
heat. Zhen and Suresh [30] did a computational modeling of a molten
salt-quartzite rock thermocline system for adiabatic and non-adiabatic
wall boundary scenario and studied the inuence of molten salt ow
rate and wall insulation on discharge eciency of the system. They also
studied the various heat loss conditions at the external wall surface to
analyze the eect of energy loss to environment [31].
3.1.5. Packed bed passive system
This type of storage system is a passive system and used very often
for temperatures up to 100 C in conjunction with solar air heaters. The
system will have loosely packed solid material like quartzite rock and
silica sand, through which the HTF (usually air) is circulated. During
the charging phase, air gets heated at solar collectors and then ows
into a bed of graded particles. While heating the bed air gets cooled.
Cooled air returns to the collectors for reheating and the cycle repeats.
At rst, only the particles near the entrance of the bed are heated while
the temperature near the exit remains unchanged and the air comes out
of the bed almost at room temperature. After many cycles, the exit air
temperature begins to rise. When the bed is fully charged, its
temperature becomes uniform. When energy is needed from storage,
discharge process starts. The airow direction gets reversed. Air at
room temperature enters the bed and gets heated. This heated air is
delivered to the building. After heating the room, cold air from room
ows back to the bed and the cycle is repeated. In order to avoid the
heat losses, the storage system is generally well insulated and installed
close to the solar collectors. The high heat transfer coecient between
the air and solid particles enables fast heat transfer from air to the solid
particles. A packed bed in a solar heating system does not operate
normally with constant temperature. During daytime, dierent condi-
tions like solar radiations, ambient temperature, collector inlet tem-
perature and load requirements result in a variable collector outlet
temperature. A major drawback with packed bed TES systems is
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Renewable and Sustainable Energy Reviews 68 (2017) 693706
thermal ratcheting. Repeated thermal cycles result in the settling of
the aggregate ller at the bottom. During the charging phase the metal
walls expand at higher rate than ller materials and ller materials
settle down to occupy the increased tank volume. During the dischar-
ging phase, the compacted ller material prevents the contraction of
the tank walls, thus generating high lateral stresses on the lower tank
wall. This is process is called as thermal ratcheting and it causes
yielding of the tank walls. Harmeet and Saini [32] did a review on
packed bed solar energy storage systems.
3.1.6. Solid medium passive system
In solid media storage, the heat exchanger for the heat transfer uid
is embedded in a solid matrix. A high cycling stability is important for a
long lifetime of the storage. Ordinary concrete develops cracks after
repeated thermal cycles. There for development of high-temperature
resistant concrete is in progress. Improvements in the solid storage
material's thermophysical properties, cycling stability and economic
factors like availability, cost and production methods is the main focus
area. In Plataforma solar de Almera facility at Spain, a solid material
storage system using concrete as storage medium was tested [12]. Here
storage temperatures up to 325 C have been reached. Emerson et al.
[33] proposed the use of packed concrete bricks in place of the
aggregate ller as the storage medium and using molten (solar) salt
as the heat transfer uid. They estimated that resulting unit cost of
energy stored is $4.50/kW h and $0.88/kW h for molten salt and
concrete respectively. They concluded that signicant reduction in
thermal energy storage cost can be derived from the use of concrete as
a storage medium.
3.2. Latent heat storage systems
In latent heat thermal energy storage systems (LHTESS), once the
latent heat storage material has been decided based on temperature
range and other requirement specications of the applications, a
container has to be designed to house the storage medium. Factors
like daily insolation at the location, geometry of the container and its
thermal parameters aect the melt time, heat transfer characteristics
and performance of the LHTESS [34].
3.2.1. Geometry of the LHTESS
Most commonly seen geometries of a LHTESS are pipe model,
cylinder model, shell and tube model, rectangular slab model. The heat
loss from the shell and tube system is minimal.
3.2.2. Enhancement of heat transfer rate in LHTESS
To address the low thermal conductivity problem with the PCM, the
following heat transfer enhancement methods can be used in the
LHTESS.
3.2.2.1. PCM encapsulation. Heat transfer rate increases with contact
surface area between PCM and HTF. For encapsulating the PCM in
small casings, the contact surface with HTF is increased to compensate
for the poor thermal conductivity of the PCM. Additionally it serves
below two purposes: (1) it prevents the phase segregation and
sedimentation, and (2) it oers a high ratio of area for heat transfer
to volume.
PCM can be packaged and sealed inside casings like cylindrical
tubes, pouches, spherical balls, rectangular panels, bars etc. They are
commercially available with approximate size of 75 mm in diameter.
Encapsulated PCM will be arranged in a packed bed fashion inside the
LHTESS container, through which the HTF can ow for thermal
charging and discharging. Based on chemical compatibility of PCM
and casing materials, for low temperature applications materials like
stainless steel, polypropylene, and polyolen can be used as container
G. Alva et al.
materials [35]. For high temperature applications, metals like stainless
steel, nickel, coatings of sodium silicate, silicon dioxide, calcium
carbonate and titanium dioxide can be used as container materials.
For high temperature applications, selection of the appropriate con-
tainment/shell material is critical as most of the high temperature PCM
is inorganic salts and they are corrosive to common containment
materials.
3.2.2.2. Fins and extended surfaces. Extended surfaces like ns are
used on pipes through which HTF ows in a LHTESS to compensate
for the poor thermal conductivity of the PCM. Fins are the preferred
method of heat transfer enhancement for high temperature LHTESS
[15]. High temperature requires expensive casing materials and ns
require less material compared to encapsulation. The usual materials
for the n are steel, copper, graphite foil or aluminum. Graphite foil has
many advantages like high thermal conductivity, low density and good
corrosion resistance against nitrate salts and nitrite at high
temperatures. Graphite foil occupies less volume for the same
performance compared to steel ns. Hence cost of graphite ns is
much less compared to steel ns. At temperatures below 400 C,
aluminum is also suitable. Both aluminum and graphite sheets do
not show corrosion due to contact with galvanized steel pipes.
3.2.2.3. PCM embedded porous matrices. In this method either a
fabricated structure like metallic matrix made of copper, aluminum etc
or a naturally porous material such as graphite, metal foams etc is
embedded into PCM to enhance the heat transfer rate in a LHTESS.
Performance improvement depends on both porosity and thermal
conductivity of the matrix [36]. Krishnan et al. [37] also arrived at
the same conclusion through a numerical study of the melting process
in a rectangular container lled with metal foam impregnated with
PCM. In a pure PCM as melting is aected by natural convection,
fusion rate is inferior at the lower portion of the container in
comparison with the upper portion. Due to improved eective
thermal conductivity by the presence of a porous matrix, melting rate
at the lower portion can be improved. But presence of the embedded
matrix obstructs the movement of the liquid and dampens the natural
convection. Higher the porosity of the matrix, lesser the dampening
eect and hence better the performance improvement. Expanded
graphite (EG) is a good option, due to its high porosity and high
thermal conductivity. For PCM like paran, melted liquid PCM gets
into the pores of EG resulting in a composite. Carbon bers are
considered as a prospective material that might be used to enhance the
heat conductivity in the heat storage systems [35].
3.2.2.4. Dispersion of heat conductive materials. When the viscosity
of the PCM in liquid phase is high and densities are similar for PCM
and heat conductive additives material such as graphite, then additive
particles could be well dispersed into the PCM in molten state.
PCM-graphite composites can be prepared in this way. Due to the
high viscosity and similarity of density, dispersed particles remain
suspended during the liquid phase. For high melting point salts and
eutectic mixtures, melting is a costly option due to the large heat
required for melting them. Therefore, graphite particles and salts are
mixed together in powdered form and then compressed at room
temperature. This method is called cold compression. Pincemin et al.
[20] used dierent particle size graphite powders for preparing the
composite. Thermal conductivity increases with graphite percentage
but decreases with increase in size at micron level. The presence of
graphite within the PCM induces small reduction in latent heat, no
signicant change in phase change temperature. The decrease in phase
change temperature variation means that composite has a nearly
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Renewable and Sustainable Energy Reviews 68 (2017) 693706
congruent melting point, which is an advantage as it would result in
a nearly isothermal operation. However, cold compressed compounds
are not always reliable since the smallest presence of impurities or
mechanical stresses leads to salt leakage. Other heat conductive
additives that are considered for dispersion are nanoparticles in small
volumetric fractions of CuO, Al2O3, TiO2, SiO2, ZnO, Cu nanowires
(NWs) and Ag nanowires etc [38]. Among them Cu NWs and Ag NWs
are usually used for organic PCM and the oxides are used with
inorganic salts.
3.2.2.5. Multiple PCM method. The heat transfer rate during charging
and discharging depends on the dierence between the temperature of
the HTF and the PCM melting point. When a single PCM is used,
temperature dierence decreases in the ow direction of the HTF. This
results in a decreased heat transfer rate along the ow direction and
poor performance of the unit. In multiple PCM method, LHTESS
contains more than one PCM with dierent melting temperatures. If
multiple PCM with dierent melting temperatures are packaged in the
unit in decreasing order by their melting points in the ow direction of
charging, then there will be an almost constant temperature dierence
during the melting process, even if the HTF temperature decreases.
This leads to a nearly constant heat ow to the PCM. During
discharging process, if the HTF ow direction is reversed, the PCM
remain in the increasing order of their melting points, and almost
constant heat ow is possible from the PCM to the HTF.
3.2.2.6. Heat pipes. Heat pipes have high thermal conductivity and
they can be added to shell and tube storage system with PCM to
increase the performance of the LHTESS. Heat pipes act as thermal
channels between the HTF and the PCM. Within the heat pipes, the
working uid like mercury undergoes evaporation and condensation
process. A heat pipe has two sections that are an evaporator section and
condensation section. The working uid circulates between the sections
to transport heat. Saleh Almsater et al. [39] investigated an approach
for reducing the thermal resistance by utilizing axially nned heat
pipes. A numerical model simulating the phase change material
melting and solidifying processes was developed. The results showed
that by adding four axial ns, the overall thermal performance of the
storage system is enhanced signicantly compared to having bare heat
pipes. After 3 h, a total of 106% increase in energy storage is obtained
during the charging process. The results also show that the combined
eect of incorporating the evaporation/condensation process and
adding the ns lead to a threefold increase in the heat storage during
the rst 3 h. During the discharge process, there was a 79% increase in
energy discharged and also the combined eect of incorporating the
evaporation/condensation as well as adding the ns results in an
almost fourfold increase in the heat extracted within the rst 3 h. Using
heat pipes in low temperature applications has been analyzed
numerically and experimentally by Tardy and Sami [40]. They used
air as the HTF to analyze the heat transfer in the system. Shabgard
et al. [41] investigated heat pipes in PCM using a thermal network
model.
4. Cost evaluations of thermal energy storage technologies
The success of any thermal energy storage technology has a strong
dependence on cost eectiveness of selected technology. For high
temperature application of thermal energy storage, cost evaluation
can be done within the framework of Levelized Cost of Energy (LCOE)
cost models. In case of low temperature thermal energy storage for
applications like space heating or cooling in buildings, Life Cycle
Analysis can be done to estimate the cost over total life span of the
system. U.S. Department of Energy National Renewable Energy
G. Alva et al. Renewable and Sustainable Energy Reviews 68 (2017) 693706

Table 2
Cost per unit mass of different thermal energy storage materials.

Type Storage material Melting point Unit mass Density kg/ Specific heat capacity Latent heat of Thermal conductivity References
C cost $/kg m3 kJ/(kg K) fusion kJ/(kg) W/(m K)

Nitrate salts NaNO3 306 0.4 2261 1.655 172 0.514 [9,15,43]
KNO3 335 0.9 2109 0.953 266 0.5 [9,43]
Hydroxide salts NaOH 318 0.35 2100 0.92 165 [9,43]
KOH 380 1 2040 1.34 150 0.5 [6,9,43]
Chloride salts NaCl 802 0.1 2160 5.0 420 5 [6,9,43]
KCl 771 0.5 1980 353 [9,15,43]
MgCl2 714 0.1 2320 452 [9,15,43]
LiCl 610 10 2070 441 [15,43]
CaCl2 772 0.15 2150 253 [15,43]
Fluoride salts LiF 850 0.5 2640 1044 [6,15,43]
NaF 996 0.9 2558 794 [15,43]
KF 858 0.1 2370 468 [15,43]
CaF2 1418 0.35 3180 391 [15,43]
Solid materials Sand-rock-minerl oil 0.15 1700 1.3 1 [6]
Cast steel 5.0 7800 0.6 40 [6]
Concrete 0.05 2200 0.85 1.5 [6]
Paran Paraffin wax 64 1 916 173.6 0.346 [14,43]
n-Pentadecane 10 0.59 206 [18,43]
n-Hexadecane 20 4 773 236 [18,43]
Fatty acids Caprylic acid 16 5 981 148.5 0.149 [7,14,43]
Capric acid 32 4 1004 152.7 0.153 [7,14,43]
Lauric acid 42 1 870 171 [7,18,43]
Myristic acid 54 1.89 860 190 [7,18,43]
Palmitic acid 64 1 989 185.4 0.162 [7,14,43]
Easters Methyl palmitate 27 100 163.2 [18,43]
Methyl stearate 39 10 160.7 [18,43]
Glycols (Poly Ethylene Glycol) 4.2 2 117.6 [7,43]
PEG400
PEG600 12.5 2 129.1 [18,43]
PEG1000 40 2 168.6 [18,43]

Laboratory has published LCOE models for estimating capital cost and
operational cost of CSP plants with TES. This framework investigates
the impact of geographical, geometrical and operating parameters on
the performance of various CSP technologies with TES. LCOE is
expressed in units like $/MWh. For thermal energy storage system
main sources of cost are storage material cost, container cost,
encapsulation cost and overhead cost. We can refer to Nithyanandam
and Pitchumani [42] for an example cost analysis of CSP plant with
integrated latent thermal energy storage. It can be seen that LCOE
depends on many dierent input parameters specic to a particular
plant design. There for the exact cost estimation needs a detailed cost
analysis for the specic plant designs. One important input parameter
is the cost per unit mass of thermal energy storage material used which
is expressed in $/kg. Table 2 gives cost per unit mass of dierent
thermal energy storage materials along with other material properties
that aect the overall cost. We can use the following rules to under-
stand how material properties aect the overall cost.
Higher density, latent heat of fusion and specic heat of storage
material result in higher energy density which reduces dimensions
of the container. This reduces the container cost part. There for the
capital cost decreases.
Lower thermal conductivity necessitates thermal conductivity en-
hancement through methods like encapsulation etc. This increases
the encapsulation cost, thus increasing the capital cost.
5. Conclusions and outlook
In thermal energy storage, currently the main focus areas are cost
reduction of storage material, cost reduction of operation and im-
provement in the eciency of energy storage. Applications for the TES
can be classied as high, medium and low temperature areas. In high
temperature side, inorganic materials like nitrate salts are the most
used thermal energy storage materials, while on the lower and medium
side organic materials like commercial paran are most used.
Improving thermal conductivity of thermal energy storage materials
is a major focus area. Cost eective manufacturing technologies for
microencapsulated PCM and composite materials are being explored.
Optimizing the thermophysical properties like melting point of thermal
energy storage materials to suite a given requirement is also explored
with techniques like eutectic mixtures and hydrocarbon chain length
etc. For sensible and latent heat storage materials, the technologies are
quite mature and are already commercialized, but thermochemical
materials are still at lab stage. Thermochemical materials have great
potential as thermal energy storage materials in the future due to their
highest volumetric energy storage capacity.
Acknowledgement
This work was supported by the National Natural Science
Foundation of China (Grant nos. 51376087 and 51676095) and the
Priority Academic Program Development of Jiangsu Higher Education
Institutions. The authors also wish to thank the reviewers and editor
for kindly giving revising suggestions.
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