Received: 2 July 2020 Revised: 11 September 2020 Accepted: 12 September 2020

DOI: 10.1002/est2.212

REVIEW

Inorganic salt hydrate for thermal energy storage

application: A review

B. K. Purohit | V. S. Sistla

Department of Chemical Engineering and

Engineering Sciences, Rajiv Gandhi
Institute of Petroleum Technology, Jais,
Uttar Pradesh, India
Correspondence
V. S. Sistla, Department of Chemical
Engineering and Engineering Sciences,
Rajiv Gandhi Institute of Petroleum
Technology, Jais 229304, Uttar Pradesh,
India.
Email: vsistla@rgipt.ac.in
Abstract
Salt hydrates are one of the most common inorganic compounds that are used
as phase change material (PCM). These are available for a wide range of phase
transition temperature for thermal energy storage (TES) application. They
have some most desired properties for TES applications like high latent heat
value, good thermal conductivity, nonexpensive, and were nonflammable.
Besides these, due to the undesirable properties like phase segregation, super-
cooling, and corrosion to the containers, this PCM not recommended for TES
application. To mitigate these issues and to make salt hydrates suitable in TES
application, much research has been carried out in past years. This main high-
light of this article is to provide a comprehensive overview of the use of salt
hydrates, their applications and summarize the research outcomes reported by
various researchers to every issue for its TES application. This summarized
information will be useful to those who are interested to work on this research
area. Along with this literature focuses on the advantages, disadvantages, and
mechanism of salt hydrates for TES system during its thermal cycle process.

KEYWORDS
application of salt hydrates, inorganic salt hydrates, mechanism of salt hydrates, phase change
material, review, thermal energy storage

1 | INTRODUCTION industrial heat were the main sources of thermal energy

Energy storage techniques have been applied to enhance
the efficiency of renewable energy and to reduce the
usage of fossil fuels.1,2,3 Thermal energy storage (TES)
methods are considered to be one of the widely used
technique for thermal storage in buildings and industrial
applications. Solar thermal energy and excess/waste
Abbreviations: CMC, carboxymethyl cellulose; DSC, differential
scanning calorimetry; EG, expanded graphite; LHS, latent heat storage;
N.A., not available; PAM, polyacrylamide; PCM, phase change material;
PVA, polyvinyl alcohol; PVC, polyvinyl chloride; SAP, superabsorbent
polymer; SAT, sodium acetate trihydrate; SHS, sensible heat storage;
TES, thermal energy storage; TGA, thermogravimetric analyzer; THS,
thermochemical heat storage.
that requires to be stored using the TES system.4,5 These
stored/reserved energies will be useful, during non-
availability of primary energy source. It will shrink the
mismatch between demand and supply of energy and
therefore it is one of the most attractive technologies.6,7
A storage system with high storage density (energy
units per unit volume), superior charging and dis-
charging capability of thermal energy are highly desir-
able.8 Thermochemical, sensible, and latent heat storage
(LHS) techniques are the known methods for TES sys-
tems. The classification of available materials for TES
reported in various literature.7,9,10 Out of these, sensible
heat storage (SHS) and LHS were mostly applied to TES
applications.6,7,11 In thermochemical heat storage (THS)

Energy Storage. 2020;e212. wileyonlinelibrary.com/journal/est2 © 2020 John Wiley & Sons Ltd 1 of 26
https://doi.org/10.1002/est2.212
2 of 26
systems, thermal energy absorbed and then released by
breaking and reforming of molecular bonds, respectively
in a chemical reaction.7 This basic principle for THS
can be explained by the reactions given below. For exam-
ple, a reactant compound “MN” absorbs Q1 amount of
thermal energy (charging step/endothermic reaction)
and then decomposes into components “M” and “N”
(Equation (1)). Due to the reversible nature of this reac-
tion, the components “M” and “N” again combines (dis-
charging step/exothermic reaction) to form “MN” by
releasing a Q2 amount of heat (Equation (2)).
Q1ð#Þ
MN ! M + N
Q2ð"Þ
M + N ! MN
During charging step, the components “M” and “N”
can be kept separately, to avoid an immediate reverse
reaction. Due to the complicacy related to maintaining
reaction parameters, which were much more difficult to
apply for building and other areas of applications, it is
hardly used for TES application.11 Properties of CaCl2,
MgCl2, MgSO4, and Na2S for thermochemical storage sys-
tem were reported.12
In SHS systems thermal energy is generally stored,
within a solid or liquid medium, by raising/decreasing its
temperature (within the interval where no phase change
involves). The amount of heat stored (Q) depends on the
amount of storage material (m), the temperature change
(from initial temperature T1 to a final temperature T2)
and the average specific heat of the medium (Cp,average
from T1 to T2; Equation (3)).11 To store heat energy, SHS
systems require a large volume of the storage medium
and a high-temperature difference. For practical applica-
tions, these storage systems are space constrained. Water
(inexpensive and has a high specific heat) acts as the best
SHS liquid for temperature range below 100 C. Liquid
mediums such as molten salts, oils, liquid metals, and so
on are used for SHS above 100 C. Rock, brick, concrete,
iron, and so on includes some common solid types for
SHS systems.7
ðT2
Q ðSHSÞ = mC p,medium dT = mC p,ðaverageÞ ðT 2 −T 1 Þ ð3Þ
T1
Latent heat thermal energy storage systems (LHS)
among the other techniques related to thermal heat
storage were attractive and mostly in use. LHS medium
undergoes a phase change between solid/liquid, liquid/
gas or vice versa, within the applied temperature range
(from initial temperature T1 to final temperature T2;
PUROHIT AND SISTLA
Equation (4)). The change in volume of the material
during phase change conversions of liquid/gas is very
high and requires high-pressure containers to store
the materials in the gas phase. Thus, liquid/gas conver-
sions of phase change materials (PCMs) are not practi-
cal.8 If no phase change occurs of TES medium, the
storage medium is referred to as sensible-heat storage.
For LHS systems, the storage medium is referred to as
the PCM.
At a fixed or constant phase transition temperature
(Tm), LHS material interchanges phase between two
phases, solid and liquid (melting and freezing). At this
constant temperature (Tm), they store or release more
ð1Þ
thermal energy (latent heat ΔH).7,8,13 Due to this latent
heat, LHS mediums store more heat (Q (LHS) > Q (SHS))
ð2Þ for the same temperature interval (Figure 1) and offers
high-energy storage density.
ðTm ð T2
Q ðLHSÞ = mC p, solid phase dT + ΔH + mC p, liquid phase dT
T1 Tm
ð4Þ
The principle of using PCMs are simple. As the envi-
ronmental temperature increases, the material absorbs
heat and changes its phase from solid to liquid (endother-
mic reaction). The heat energy absorbed within PCM in
the form of both sensible heat and latent heat of fusion
or energy of crystallization. Similarly, PCM desorbs
energy that absorbed, when the temperature of the mate-
rial decreases or changes phase from liquid to solid (exo-
thermic reaction).14 Application of PCMs as latent heat
thermal storage systems found as to maintain buildings
cooling and heating needs during off-peak hours, for
shipping containers to store food products during trans-
portation that needs to maintain the desired temperature
FIGURE 1 Comparison of sensible and latent heat storage
system47,129
PUROHIT AND SISTLA
for a longer period, textiles with PCM for relief from high
heat and low cool environment, within refrigerators and
freezers, to use less energy, to store solar thermal energy,
and so on. PCMs can able to fulfill the demand for
energy-saving and eco-friendly materials.15 A detailed
review on the application of various TES methods using
PCMs applied to various industrial processes (around
50 case study) for recovery and reuse of industrial waste
heat was explained by Cabeza et al16 The application of
PCMs not only reduces the cost, but also decreases the
emission CO2, which leads to better industrial activities.
An ideal PCM should meet some criteria related to the
desired thermophysical, kinetic, and chemical properties
were reported.8,13,17
PCMs were classified mainly into three categories
as organic PCM (fatty acids, paraffin), inorganic PCM
(metallic, salt, and salt hydrate), and eutectics PCM
(mixtures of different PCM having a sharp melting
point). A huge number of potential materials for LHS
application are reported.18,17,19 A comparison of proper-
ties between sensible and latent heat energy storage
systems (both organic and inorganic PCMs) was
summarised.3,18 Organic PCMs (paraffin [CnH2n + 2] and
nonparaffin compounds) are generally chemically stable,
possess congruent melting (melt and freeze repeatedly
without phase segregation), have a high latent heat
of fusion, nontoxic, and noncorrosive. While salts, salt
hydrates, mixtures of salts, metallic, and alloys come
under the categories of inorganic PCM. Inorganic PCMs
have high latent heat values, good thermal conductivity,
nonexpensive, and nonflammable as compared with
organic materials. PCMs were available in a wide range
of phase change temperature and can be applied for dif-
ferent applications.20
Salt hydrates consist of inorganic salts (AB) and
water (H2O), which form a typical crystalline solid with
the general formula (ABnH2O).11 Water has been
tightly bound to the compound in the hydrate crystal
structure, as a separate and unique compound, and called
as the water of hydration. This article review about the
significances of only inorganic salt hydrates as PCM for
TES application. The basics of salt hydrate as PCM with
its advantage/disadvantage was introduced. Then the
detail explanation about the mechanisms for storing and
discharging of heat using the melting/freezing phenom-
ena for molten salt hydrates, saturated salt solution and
eutectic salt hydrates are explained. Thereafter the exper-
imental/numerical outcomes that were performed for the
improvements to every issue of salt hydrate as PCM are
summarized. At last, the research areas where salt
hydrates were used as an application in TES systems
were mentioned followed by a conclusion.
3 of 26
2 | SALT HYDRATES AS PCM
Application of salt hydrates for their use of latent heat
thermal energy systems initiates from the year 1947. A
large amount of resource in the commercial market, with
suitable properties and desired phase change tempera-
ture, are available.13 Salt hydrates for use in TES applica-
tion with their thermal properties were listed in Tables 1
and 2. The advantages of salt hydrates than other PCMs
for TES application include (1) high latent heat of fusion
per unit volume at its melting point (2) higher thermal
conductivity (as much as two times compared to paraffin)
(3) small volume change during phase change process
(4) slightly toxic (5) no or limited risk to fire (6) inexpen-
sive, a wide range of material available in the market
(7) compatible with plastic containers. Main drawbacks
of these materials include (1) supercooling, (2) phase seg-
regation, and (3) corrosiveness to most of metals.7,21,22
Salt hydrates for TES application can be used alone or a
mixture of salt hydrates (eutectic mixtures).23 Eutectics
are the mixtures of different not reacting substances that
freeze and melt congruently at a fixed temperature below
the melting point of individual components.20 Table 3
provides a list of some reported eutectic salt hydrate
PCMs. The mechanism by which salt hydrates transmits
heat energy during the phase change process slightly dif-
fers from organic PCMs and were discussed.
3 | M E C H A N I S M O F HE A T
TRANSITION IN SALT HYDRATES
DU R I N G T H E PH A S E C H A N G E
PRO CES S
The phase change is the foundation for latent heat energy
storage. The phase change process in salt hydrates is simi-
lar to the melting and freezing of the compound. But with
salt hydrates, this can be achieved by hydration and dehy-
dration (Equations (5) and (6)), or with the process of par-
tial hydration and partially dehydration (Equations (7)
and (8)) of the salt hydrates. Here AB represents some
inorganic salt and Q3, Q4 is the heat released/absorbed
during phase change.11
Q3ð#Þ
Dehydration : AB  nH2 O ! AB + nH2 O ð5Þ
Q3ð"Þ
Hydration : AB + nH2 O ! AB  nH2 O ð6Þ
Q4ð#Þ
Partially dehydration : AB  nH2 O ! AB  mH2 O
+ ðn− mÞH2 O ðm < nÞ ð7Þ
4 of 26 PUROHIT AND SISTLA

TABLE 1 List of inorganic salt hydrates used as PCM

Melting Latent Melting Latent

Salt hydrates point ( C) heat (J/g) Salt hydrates point ( C) heat (J/g)
Aluminium nitrate nonahydrate 723,7 1553,7 Ferric chloride hexahydrate 373,7 2233,7
[Al(NO3)29H2O] [FeCl36H2O]
Aluminium sulfate hexadecahydrate 11289,106 N.A. Iron (III) nitrate nonahydrate [Fe 473,7 1553,7
[Al2(SO4)316H2O] (NO3)39H2O]
Aluminium sulfate octadecahydrate 8889,106 21889 Potassium fluoride tetrahydrate 191,13 2311,13
[Al2(SO4)318H2O] [KF4H2O]
Aluminum ammonium sulfate 951,3 2691,3 DiPotassium hydrogen phosphate 483,7 993,7
dodecahydrate trihydrate [K2HPO43H2O]
[(NH4)Al(SO4) 12H2O]
Ammonium chloride sodium sulfate 1189 16389 Potassium aluminum sulfate 913,7 1843,7
decahydrate dodecahydrate [KAl(SO4)212H2O]
[NH4ClNa2SO410H2O]
Barium hydroxide octahydrate 781,3 2661,3 Potassium iron alum dodecahydrate 337 1737
[Ba(OH)28H2O] 28022 [KFe(SO4)212H2O]
Calcium bromide tetrahydrate 11089,106 Tripotassium phosphate tribasic 4589 14589
[CaBr24H2O] heptahydrate [K3PO47H2O]
Calcium bromide hexahydrate 341,3 115.51,3 Lithium bromide dihydrate 343,7 1243,7
[CaBr26H2O] 1387 [LiBr22H2O]
Calcium chloride tetrahydrate 44.244 99.644 Lithium chloride monohydrate 9989 21289
[CaCl24H2O] [LiClH2O]
Calcium chloride hexahydrate 28-301,131 190-200 1 Magnesium nitrate tetrahydrate 477 1427
[CaCl26H2O] 29.83,13 190.83 [Mg(NO3) 4H2O]
17113,131
Calcium iodide hexahydrate 423,7 1623,7 Magnesium nitrate hexahydrate 89.37,131 1501
[CaI26H2O] [Mg(NO3)2 6H2O] 162.83
1677
Calcium nitrate tetrahydrate 473,7,131 1533,7 Magnesium sulfate heptahydrate/ 48.53,7 2023,7
[Ca(NO3)24H2O] 161.9131 Epsom salts [MgSO47H2O]
Calcium nitrate trihydrate 513,7 1043,7 Manganese(II) chloride tetrahydrate 583,7 1513,7
[Ca(NO3)23H2O] [MnCl24H2O]
[CCl3F17H2O] 8.53 2103 Manganese(II) nitrate tetrahydrate [Mn 37.17 1157
(NO3)24H2O]
Cadmium nitrate tetrahydrate 59.5 1,19 9889 Manganese(II) nitrate hexahydrate [Mn 25.31,3,7 125.91
[Cd(NO3)24H2O] (NO3)26H2O] 1487
Cadmium nitrate monohydrate 59.589 10789 Nickel(II) nitrate hexahydrate 573,7 1693,7
[Cd(NO3)2H2O] [Ni(NO3)26H2O]
Cobalt(II) sulfate heptahydrate 40.73,7 1703,7 Strontium hydroxide octahydrate 8989 37089
[CoSO47H2O] [Sr(OH)28H2O]
Cobaltous nitrate hexahydrate 5789 11589 Zinc chloride trihydrate [ZnCl23H2O] 10106,131
[Co(NO3)26H2O]
Copper sulfate heptahydrate 40.789 17189 Zinc nitrate dihydrate [Zn(NO3)22H2O] 541,7 687
[CuSO47H2O]
Dipotassium hydrogen phosphate 1489 10989 Zinc nitrate tetrahydrate 45.53,7 1103,7
hexahydrate [K2HPO46H2O] [Zn(NO3)24H2O]
Iron(III) bromide hexahydrate 213,89 1053,7 Zinc nitrate hexahydrate 367,131 146.91,3
[FeBr36H2O] 277 [Zn(NO3)2.6H2O] 1347,131
Ferric chloride dehydrate 563,7 903,7
[FeCl32H2O]
PUROHIT AND SISTLA 5 of 26

TABLE 2 List of salt hydrates with thermal properties (density, specific heat, and thermal conductivity)

Specific heat capacity (J/gK) Density (kg/m3) Thermal conductivity (W/mK)

Salt hydrates Solid phase Liquid phase Solid phase Liquid phase Solid phase Liquid phase
13 22 17,132 17132 17,132
Barium hydroxide octahydrate 1.17 2.44 2070 1937, 1.255 0.65317,132
[Ba(OH)28H2O] 1.3422
Calcium bromide hexahydrate N.A. N.A. 2190132,133 1956132,133 N.A. N.A.
[CaBr26H2O]
Calcium chloride tetrahydrate 1.2517 2.1317 168017 150017 0.62617 0.4517
[CaCl24H2O]
Calcium chloride hexahydrate 1.4213,133 2.10133 18001,132 156213,132 1.088132,133 0.540132,133
[CaCl26H2O] 171013
Potassium fluoride tetrahydrate 1.8413,133 2.3913,133 14501,13 145013,133 N.A. N.A.
[KF4H2O]
Lithium chlorate trihydrate N.A. N.A. 172089 153089 N.A. N.A.
[LiClO33H2O]
Magnesium chloride 1.7213 2.8213 1569132 1450132 0.694132 0.570132
hexahydrate [MgCl26H2O]
Magnesium nitrate 1.8417 2.5117 163617,132 155017,132 0.61117,132 0.4917,132
hexahydrate [Mg(NO3)2
6H2O]
Manganese(II) nitrate N.A. N.A. 160051 173811 N.A. N.A.
hexahydrate
[Mn(NO3)26H2O]
Sodium acetate trihydrate 1.717 2.917 1451 N.A. 0.4322 0.3422
[CH3COONa3H2O]
Sodium carbonate decahydrate 1.9289 3.2689 144217 N.A. 0.51489 0.22489
[Na2CO310H2O]
Sodium dihydrogen phosphate 1.5517 2.5117 1.9513,133 1520113,133 144013,133 0.51413,133 0.47613,133
dodecahydrate 1.7013,133
[Na2HPO412H2O]
Sodium sulfate decahydrate/ 1.9213,17 3.2617 146017,134 133017,134 0.51413,17 0.58917
Glauber's salt 3.3134 148513
[Na2SO410H2O]
Sodium thiosulfate 1.4613,17 2.3913,17 175013,17 167013,17 0.7622 0.3822
pentahydrate
[Na2S2O35H2O]
Zinc nitrate hexahydrate [Zn 1.3413,17 2.2613,17 195417 206513 1828132 206513 N.A. 0.4641,132
(NO3)2.6H2O]

TABLE 3 Eutectic salt hydrates used as PCM

Eutectic salt hydrate composition Melting point ( C) Latent heat (J/g) References
55% CaCl26H2O + 45% CaBr26H2O 14 140 [135]
45-52% LiNO33H2O + 48-55% Zn(NO3)26H2O 17.2 220 [135]
75% CaCl26H2O + 25% MgCl26H2O 214 1023 [74]
666% CaCl26H2O + 333% MgCl26H2O 25 127 [106,135]
45% Ca(NO3) 26H2O + 55% Zn(NO3) 26H2O 25 130 [131,135]
40% Na2CO310H2O + 60% Na2HPO412H2O 273 2202 [75]
67% Ca(NO3) 24H2O + 33% Mg(NO3) 26H2O 30 136 [131,135]
25% Na2SO410H2O + 75% Na2HPO412H2O 312 2621 [76]
18% Mg(NO3) 26H2O + 82% Zn(NO3)26H2O 32 130.1 [131]
72% Ca(NO3) 24H2O + 28% Al(NO3) 29H2O 35 138.9 [131]
53% Mg(NO3) 26H2O + 47% Al(NO3) 29H2O 61 148 [13]
50% Mg(NO3)26H2O + 50% MgCl26H2O 58-59 132 [22,135]
53% Mg(NO3)6H2O + 47% MgCl26H2O 59.1 144 [13]
80% Mg(NO3)26H2O + 20% MgCl29H2O 60 150 [135]
53% Mg(NO3) 26H2O + 47% Al(NO3) 29H2O 61 148 [13,131]
6 of 26
Q4ð"Þ
Partially hydration : AB + nH2 O ! AB  pH2 O
+ ðn− pÞH2 O ðp < nÞ ð8Þ
During heating, the salt hydrate (ABnH2O) absorbs
the heat of melting (Q3) breaks into solid anhydrous salt
phase (AB), liquid water (Equation (5)). Upon cooling,
the binary phase turns into solid salt hydrate (ABnH2O)
by emitting heat of fusion (Q3) (Equation (6)). Ideally,
during hydration, the water of hydration will not be suffi-
cient to form the salt hydrate (ABnH2O) and forms a
lower hydrate (Equation (8)).11 The causes and possible
solutions for such behavior were discussed in Section 4.
The melting behavior of the salt hydrates can be classi-
fied into below three categories.7
1. Congruent melting behavior: at the melting tempera-
ture of salt hydrate or during hydration, all the anhy-
drous salt was completely soluble within its water of
hydration.
2. Incongruent melting behavior: at the melting temper-
ature of salt hydrate or during hydration, all the anhy-
drous salt was completely not soluble within its water
of hydration.
3. Semi-congruent melting behavior: at the melting tem-
perature of salt hydrate or during hydration, only par-
tial amount anhydrous salt was converted into salt
hydrate or to salt hydrate with lesser water of hydra-
tion happens.
Some of the salt hydrates those shows congruent
melting behavior includes NaOHH2O, LiClO33H2O,
Cd(NO3)24H2O, KF4H2O, Mg(NO3)26H2O, Zn(NO3)2
6H2O, and (NH4)Al(SO4)12H2O.While the salt hydrates
like KF2H2O, CH3COONa3H2O, Na2S2O35H2O, MgCl2
6H2O, CaCl26H2O, Na2HPO47H2O, Ba(OH)28H2O,
Al(NO3)29H2O, Na2SO410H2O, Na2CO310H2O,
Na2B4O710H2O, Na2HPO412H2O, Na3PO412H2O, and
Al2(SO4)318H2O, were reported as having Incongruent
melting behaviour.19,24 During thermal cycles, the den-
sity of the solid and liquid phase for most hydrated salts
is not varied. But the volume change can be as high as
15% for CaCl26H2O,11 13.3% for CH3COONa3H2O,19
and while KF24H2O offers a volume change of only
0.55%.11 Hydration and dehydration of three molten salts
as heat storage materials (CaCl26H2O, MgCl26H2O, and
Ca(OH)2) were investigated by using the instrument
TGA/DSC. The decomposition reaction of CaCl26H2O,
MgCl26H2O, and Ca(OH)2 was reported as three, two,
and one step reactions, respectively (Equations 9-11).4
CaCl2  6H2 O! CaCl2  4H2 O + 2H2 O! CaCl2
 2H2 O + 4H2 O! CaCl2 + 2H2 O ð9Þ
PUROHIT AND SISTLA
MgCl2  6H2 O ! MgCl2  4H2 O + 2H2 O !
MgCl2
 2H2 O + 4H2 O ð10Þ
CaðOHÞ2 ! CaO + H2 O ð11Þ
Apart from molten salt hydrates, a system having a
eutectic composition of salt hydrates or a saturated solu-
tion of salt in water can also be used in TES application.
In these types of storage systems, the state of PCM existed
as a liquid, slurry/magma (a mixture of salt hydrate and
solution), or solid phase, depending on the concentration
of salt in solution and environment temperature. The
heat energy transition with this type of PCM occurred
through the formation/melting of salt hydrate from satu-
rated salt solution and the operation applied is solution
crystallization. Crystallization is a unit operation that
involves the formation of solid phase material from a uni-
form saturated solution. Simultaneously heat and mass
transfer are involved in this operation. Crystal (solid) for-
mation during crystallization from an aqueous saturated
salt solution is an exothermic process. During the phase
change between saturated liquid solution and salt
hydrate, heat releases within the system (exothermic pro-
cess). In reverse, during dissolution of crystal (phase
change from salt hydrate to the liquid solution) heat is
absorbed by the system (endothermic process).
The solubility of a solute (salt) in a given solvent
(water) varies for different temperatures and it forms
the basis for crystallization operation. In a saturated solu-
tion, both the solid and liquid phases are in equilibrium.
Solubility curve represents the equilibrium relationship
between maximum concentrations of the solution that
can be achieved by bringing solute into equilibrium
with the solvent as a function of temperature. For phase
change, the solution must be supersaturated. The super-
saturation state of a solution will be achieved, when the
equilibrium between solid and liquid phase is disturbed
by the decreasing temperature of a concentrated solution
or evaporating part of the solvent. The quantity of solute
present in the solution will be more or less than the quan-
tity of the solute that is in equilibrium with the solution
at that temperature. This extra solid comes out as crystals.
In Figure 2, solid line CD is the equilibrium or solubility
curve.25 The upper broken line AB is the nucleation
curve. Nucleation curve provides a relation between con-
centrations with respect to temperature at which crystals
will spontaneously form in a pure saturated solution.
The solution that is free of any kind of solute or any
foreign substance having the composition and tempera-
ture indicated by point E (unsaturated solution and no
crystal formation) is cooled in the direction shown by the
arrow along EFG. Supersaturation state or beginning of
PUROHIT AND SISTLA
A C
SUPERSOLUBILITY
CURVE
F E
G Binary phase of salt
CONCENTRATION
H
B E
I SOLUBILITY CURVE
D
TEMPERATURE
FIGURE 2 Solubility and nucleation curve for a saturated salt
solution25
crystallization can be expected, when the temperature
first crosses the solubility curve CD. The formation of
crystals observed only when the solution supercooled suf-
ficiently past the curve CD near to point G. After crystal
formation arises, the concentration curve follows roughly
along GHI. Crystals were formed generally at a tempera-
ture gap (FG) to the solubility curve, which is known as
supercooling behavior of crystal formation. This tempera-
ture gap (FG), difference between the true melting point
temperature and the temperature (below true melting
point temperature) at which salt crystals formed, or delta
T is the supercooling temperature.26,27
Eutectic materials are a mixture of two or more mate-
rials having a sharp melting point similar to pure substance
and have higher volumetric storage density.20,28,29 Eutectic
point is often observed at a specific concentration and tem-
perature condition, lower than the melting points of indi-
vidual components, known as eutectic concentration and
eutectic temperature, respectively. With issues like corro-
sion and supercooling, these eutectic solutions have good
thermal conductivity, density, and low flammability and
used as PCM.29 Segment DEF in Figure 3 shows the gen-
eral solubility curve for a salt-water system. Pure water
freezes at 0 C. With the addition of salt to the water, the
freezing point of water will be depressed below 0 C. When
the temperature of the solution, goes below segment DE,
the water only freezes to form ice by keeping all the salts
as a saturated liquid state. The composition of salt in water
at point E, minimum freezing point of the system, is the
eutectic point. All salt and water freeze simultaneously to
the solid phase. So, at eutectic point E, at a single tempera-
ture and specific eutectic composition, the solution freezes
and melts completely from liquid/solid or solid/liquid
phase.29
With increasing salt concentration, in the segment
range EF, the freezing temperature of the solution
7 of 26
Salt solution (Liquid phase)
F
Temperature
solution and ice (solid)
D Binary phase of salt
solution and salt (solid)
T(EU)
Single phase mixture of
(Eutectic point)
ice + solid salt
0 wt% Salt Wt%(EU) 50 wt% Salt 100 wt% Salt
wt% of salt in water
FIGURE 3 Phase diagram for a salt-water system with a
eutectic point29
increases until the freezing point of pure salt. On cooling
the saturated solution, in the segment range EF, anhy-
drous/hydrate salt starts precipitating/crystallizing in
the solution (solution crystallization). To make a clear
understanding of this, melting phase diagram for sodium
sulfate anhydrous in water with respect to the tempera-
ture is shown in Figure 4.13,30,31 In this melting phase
diagram (Figure 4) the liquidous line (segment PQ) can
also be carried as the solubility of salt hydrates in water
that expresses equilibrium line between the formation of
Na2SO410H2O (crystal) and saturated sodium sulfate
solution. All the possible phases of sodium sulfate that
will form, at different temperature and composition of
the solution are shown. Let point A in region 1 be the
temperature and concentration of the initial aqueous
saturated salt solution used in the TES system. During
cooling, as the temperature of the solution decreases
(from point A-B) below the segment PQ (liquidous line).
The solute concentration at point B will be more than
equilibrium and the solution expels excess solutes as salt
hydrate crystal Na2SO410H2O to attain the equilibrium.
Due to the formation of solid crystals, heat releases (exo-
thermic process) from the solution to the surroundings.
With a gradual decrease in crystallization temperature,
more crystal forms and the heat discharge process occurs
continuously till all the solution get frozen (point C).
The temperatures at point A and B represents the opera-
tional temperature range for PCM in the TES system.
Region 2 (Figure 4) will be the binary phase mixture for
the saturated salt solution and salt hydrate. The amount
of each component (crystal and solution) can be calcu-
lated using the lever rule. During heating the PCM (from
point B to A), the phase will be changed from solid to
liquid and heat absorbed (endothermic process) from
the environment. The resulting process is called solution
crystallization.
8 of 26
F I G U R E 4 Partial phase diagram for sodium sulfate and
water system13,30,31
The melting phase diagram for the different salt
hydrate-water system (Ba(OH)2-H2O, CaCl2-H2O,
Ca(NO3)2-H2O, Cd(NO3)2-H2O, CH3COONa-H2O, KF-H2O,
LiClO3-H2O, LiNO3-H2O, MgCl2-H2O, Mg(NO3)2-H2O,
Mn(NO3)2-H2O, Na2CO3-H2O, Na2HPO4-H2O, NaOH-H2O,
Na2SO4-H2O, Na2S2O3-H2O, NH4Al(SO4)2-H2O, and
Zn(NO3)2-H2O) along with their thermophysical properties
(melting temperature, specific heat, thermal conductivity,
density, the heat of fusion, and viscosity) in both phases
were reported.32 Region for all possible formation of
hydrates of CaCl2 and Zn(NO3)2 from its salt solution was
reported from its melting phase diagram of CaCl2-H2O32,33
and Zn(NO3)2-H2O,13,32 respectively. Different concentra-
tions of saturated aqueous salt solutions can be used as
PCM to get a wide phase change temperature range. With
solution crystallization, congruent melting behavior will be
reduced due to extra solution presents in the medium, but
the volumetric heat storage capacity of the TES system
decreases compared to pure PCM. In the solution crystalli-
zation process the amount of solid formation/dissolution
(heat released/absorbed) process purely depends on the sys-
tem temperature. Phase segregation or settling of crystals at
bottom of the system from solution, due to density differ-
ence, and supercooling is the main issue with this method.
But at eutectic point, all the solution melts and recrystallizes
at a single temperature without phase segregation.
4 | P R O B L E M S A N D PO S S IB L E
S O L U T I O N S FO R S A L T H Y D R A TE S
FO R TES SY S TEMS
4.1 | Difficulties in applications of salt
hydrates for TES systems
Literature has described various problems associated with
the use of salt hydrates for TES systems. These include
PUROHIT AND SISTLA
(1) supercooling or spontaneous nucleation of undesired
lower hydrates, due to its weak nucleation properties,
(2) phase segregation, during repeated thermal cycles, and
(3) corrosion to PCM storage container.7,9,11
During cooling (hydration) step for salt hydrates from
the salt solution, generally, the solidification starts at a
much lower temperature than its true melting temperature
(supercooling effect). Most salt hydrates have poor nucleat-
ing properties and the formation of salt hydrates are
influenced by the presence of nucleating agents, the rate of
cooling and stirring rate. The rate of nucleation of salt
hydrate (starting of a phase change to solid) at the melting
temperature is negligible. The solution has to be cooled
below its melting temperature to achieve a reasonable rate
of nucleation. The degree of supercooling is the tempera-
ture gap (delta T) between the true melting point tempera-
ture and the temperature at which nucleation starts.34,35
The total energy discharge will be higher if crystallization
takes place at a much lower nucleating temperature than
salt hydrates true melting temperature.7 At this condition,
much amount of crystal formed suddenly within the sys-
tem to attain equilibrium. Due to the formation of much
crystals at a time leads to extend the SHS process than LHS
and creates difficulties in practical application.34,36
During the heating cycle (dehydration step), the salt
hydrates dehydrate into anhydrous/lower hydrate salts
(solid) and an aqueous salt solution. These denser anhy-
drous salts (solid) are precipitate to the bottom of the
container. Next, upon the cooling cycle, rehydration
starts only at the interface between precipitated salt and
solution, due to the contact barrier between the solution
and deposited anhydrous salt. The remaining anhydrous
salts present in the system will not have enough water to
dissolve completely and will deposit at the bottom due to
its higher density. This causes irreversibility in the pro-
cess. The deposition of salt (phase segregation) or nucle-
ation of lower salt hydrates increases continuously with
increasing thermal cycles and depreciate the efficiency of
the TES system.11,24 Various researchers have suggested
different techniques to minimize these problems of salt
hydrates and are discussed one by one in detail.7,11,18
4.2 | Improvement of salt hydrate
performance
4.2.1 | Addition of excess water to the
TES system
During cooling cycles for molten salt hydrates, the forma-
tion of an anhydrous salt increases due to clogging of the
deposited salts at the bottom of containers. Researchers
reported that some extra water may be added to a salt
hydrate during the cooling cycle to suppress this
PUROHIT AND SISTLA
phenomenon. These extra water will help to dissolute
the extra deposited anhydrous salt in the system and
keep the medium as a saturated salt solution.13 A mixture
of 68.2 wt% of Na2SO410H2O and 31.8 wt% of H2O
(extra added water) suggested using for TES compared to
Na2SO410H2O PCM.31 Due to extra added water, volumet-
ric heat storage capacity decreases compared to pure
PCM. Which leads to an increase of 50% mass and 70%
volume for the TES system to store the same heat as com-
pared to pure PCM.13 For five different incongruently melt-
ing salt hydrates, heat storage capacity of the storage
mediums having an aqueous salt solution or salt hydrates
(33 wt% Na2SO4, 33 wt% Na2CO3, 27 wt% Na2HPO4, 61 wt
% Na2S2O3, 58 wt% NaCH3COO) with additional water
was reported. Within the temperature interval 0-100 C,
these salt solutions have better energy storage capacity
than water. Extra water causes problems like lower ther-
mal conductivity and supercooling problems in the system.
These issues can be mitigated by some of the methods like
stirring the solution during the thermal cycle, adding
nucleating agents or designing a proper heat storage unit.24
4.2.2 | Mechanical stirring of the TES
system
To reduce problems of phase segregation and super-
cooling, the solid PCM formed suggested to be in a sus-
pension state.24 Mechanical stirring24 of PCM and use of
the rolling cylinder device37 during thermal cycling to
keep the solution in motion are suggested. The perfor-
mance of PCM having 33 wt% Na2SO4 and 67 wt% of
water was stabilized by providing soft stirring of the solu-
tion that decreases the contact barrier between the
melted salt hydrates and saturated salt solution.24 A heat
storage system having PCM within a rolling cylinder
(rotation rate of 3 rpm) device was suggested by General
Electric Research and Development Centre. Herrick
et al37 performed experiments using Na2SO410H2O as
PCM within a rolling cylinder heat storage system.
Advantages like complete phase change, the release of
almost theoretical latent heat, stability for over 150 ther-
mal cycles, high internal heat transfer rates, freezing
occurrence uniformly, were reported with the use of the
rolling heat exchanger.37 But for practical application,
this type of storage system cannot be used because of the
difficulties involved in adding stirring to TES systems.
4.2.3 | Addition of nucleating agent to
the TES systems
Supercooling is one of the common issues for most salt
hydrates. Due to supercooling the temperature for
9 of 26
nucleation/starting of formation of salt hydrate crystal
from salt solution gets delayed. For a PCM the degree
of supercooling (delta T) and fluctuation of phase
change temperature (Tm) must be minimized. Nucleation
triggering methods were classified as active (activating
the crystallization) and passive (reduces supercooling
temperature). The factors that generally influence the
degree of supercooling were (1) homogeneous nucleation,
(2) heterogeneous nucleation, (3) rate of cooling, and
(4) roughness of PCM container, and so on. Other
methods such as application of agitation, mechanical
shock, electro freezing, high pressure, or ultrasonic waves
were also reported to be effective. A review on the super-
cooling phenomenon for PCMs with its detail theory and
factors by which these can be eliminated or reduced were
available.27,26 Beaupere et al27 listed various nucleating
agents for salt hydrates (CaCl26H2O, CH3COONa3H2O,
KF4H2O, LiNO33H2O, MgCl26H2O, Mg(NO3)26H2O,
Na2HPO412H2O, Na2SO410H2O, and Na2S2O35H2O)
and summarized their effect on latent heat, supercooling of
PCMs. Ushak et al38 summarized, the effect of various
nanoparticles for improving low thermal conductivity and
high subcooling degree of a wide range of salt hydrates.
Although organic nanoparticles are noncorrosive, the addi-
tion of inorganic nanoparticles provides better results for
the thermophysical properties of PCMs.
During cooling of salt solution, nucleation, or starting
of formation of salt hydrate crystal as embryos of new
phase formed after reaching a certain degree of super-
cooling. These embryos then grow with decreasing tem-
perature to form salt hydrate crystals. Formation of salt
hydrates through this process known as homogeneous
nucleation. But nucleation formation on some suspended
particles, impurities, foreign particles is known as hetero-
geneous nucleation. These foreign particles were referred
to as nucleating agents that help in minimizing the
degree of supercooling.39 To suppress the effect of high
supercooling, different heterogeneous/nucleating mate-
rials, which are similar in atomic arrangement and lattice
spacing, can be added to the supersaturated solutions.40
Nucleating agents also termed as seed crystals or nuclei,
which assist PCM crystals to grow on them during freez-
ing of the PCM. Nucleating materials were generally clas-
sified into three basic categories: (1) isomorphs (have
similar crystal structures and lattice parameters to the
substrate salt), (2) isotopic (have nearly identical crystal
structures and lattice parameters with the substrate salt,
about 15%), and (3) epitaxial (have different crystal struc-
tures and lattice parameters, but the nucleating salt crys-
tals surface should have the preferred positions for
deposition).36 An effective nucleating agent should have
15% similar atomic arrangement and lattice spacing to
that of PCM.41,40 Popular nucleating agents such as
sodium pyrophosphate decahydrate (Na2P2O710H2O),
10 of 26
borax (Na2[B4O5(OH)4]8H2O), strontium sulfate (SrSO4),
Sr(OH)2, and SrCO3 were used to minimize the degree of
supercooling for most of the salt hydrates.
Lane36 studied the effect of quantity (0.01-1 wt%) of
various nucleating agents for the salt hydrates like cal-
cium chloride hexahydrate (CaCl26H2O), magnesium
chloride hexahydrate (MgCl26H2O) and magnesium
nitrate hexahydrate (Mg(NO3)6H2O). For CaCl26H2O
PCM, which has supercooling of about 22.5 C, the addi-
tives like BaI26H2O (0.5 wt%), SrCl26H2O (1 wt%), and
SrBr26H2O (1 wt%) were found effective compared to
nucleating agents like SrI26H2O, CaI26H2O, and
CaBr26H2O. Other nucleation agents like Ba(OH)2, BaO,
BaCO3, BaSO4, BaC122H2O, and Sr(OH)2 were also pro-
posed for CaCl26H2O.36 Sutjahja et al5 reported
SrCl26H2O (1 wt%) that provided the better effect on
nucleation of CaCl26H2O, compared to Ba2CO3 (0.5 wt
%) and K2CO3 (05 wt%) as nucleating agents. The effect
of different nanomaterials like γ-Al2O3, TiO2, Cu, and
SiO2 (50 nm) as nucleating agents were also studied.
Adding γ-Al2O3 nanoparticles to calcium chloride hexa-
hydrate (CaCl26H2O) PCM found to be most effective.
With the addition of 1 wt% of this nanomaterials, the
degree of supercooling reduces between 0.3 and 1.1 C
and complete solidification time for CaCl26H2O was
reduced by 17.84%.42 The stability of CaCl26H2O forma-
tion was improved for more than 1000 heating and
cooling cycles (18-35 C) by adding NaCl salt as nucleat-
ing agent and excess water (mole ration of water/
CaCl2 = 6.11) than the stoichiometric composition.43
Different alkaline salts like LiCl, NaCl, and KCl were
added to CaCl24H2O and the effect on thermodynamic
properties was studied by Ushak et al.44 Addition of 1 wt
% NaCl or 1 wt% LiCl slightly reduced the supercooling
effect (delta T) from 28 C to about 24 and 25 C, respec-
tively. Then, 1 wt% LiCl mixture in CaCl24H2O showed
a slight increase in heat of fusion than pure CaCl24H2O
and CaCl24H2O + 1 wt% NaCl.44 In the report of Li
et al45 stated that PCM composite having calcium chlo-
ride hexahydrate (96 wt% CaCl26H2O), strontium chlo-
ride hexahydrate (3 wt% SrCl26H2O) and oxidation
expandable graphite (1 wt% EG) suppressed supercooling
and gave the latent heat of 172.26 J/g. These expandable
graphites dispersed homogeneously within PCM due to
the existence of oxygen-containing functional groups and
act as nuclei for heterogeneous nucleation.45 Tayler
et al26 studied the nucleation point of two hydrated cal-
cium chloride (PC 25 and PC 29, phase change tempera-
ture between 25 and 30 C) at the different cooling rate
(1-167 C/min). At high cooling rates, supercooling of up
to 10 C was observed and it takes more time for nucle-
ation at lower cooling rate. Cui et al46 studied the thermal
properties of CaCl2 based PCM (water + varying
PUROHIT AND SISTLA
composition of CaCl2 and CaCl22H2O). The PCM com-
position with 66.21 wt% CaCl22H2O as additive observed
to be reducing the supercooling degree by about 96.8%
(from 24.7 to 0.8 C). Also, Nano-SiO2 (0.1-0.5 wt%) as
additive found to reduces the supercooling and found
effective during cooling conditions.
For MgCl26H2O as PCM, Na3AIF6, CaC2O4.H2O,
Sr(OH)2, SrCO3, Ca(OH)2, CaO, Ba(OH)2, BaO, and Mg(OH)2
founded to be effective nucleating additives than CaSO4,
K2CrO4, K2SO4, (NH4)2SO4, AgNO3, Ca(NH4)2(SO4)2H2O,
CaK2(SO4)2H2O, MgBr26H2O, and (NH4)2SO4NH4NO3.36
Pilar et al47 studied the effect on supercooling of MgCl26H2O
by adding different compositions (0.5-3 wt%) of SrCO3,
Sr(OH)2, and Mg(OH)2 as nucleating agents. Then, 1.0 wt% of
SrCO3 or 0.5 wt% of Sr(OH)2 was reported as a better nucleat-
ing agent for MgC126H2O which reduced the supercooling
(delta T) from 36 to 6.4 C and 4.3 C, respectively. While
Mg(OH)2 (0.5-3 wt%) reduced the supercooling (delta T) to
about 19 C for MgC126H2O. Ushak et al35 studied the effect
of the addition of nucleating agents (0.5-3 wt%) like CaO,
SrCO3, Sr(OH)2, LiOH6H2O, and Li2CO3 to bischofite (95%
MgC126H2O). Among these nucleating agents, SrCO3 (3 wt%)
and Sr(OH)2 (3 wt%) reported being more effective than
others. Other nucleating agents such as calcium oxalate mono-
hydrate (0.5 wt% CaC2O43H2O) were reported for
MgC126H2O.48 A PCM having a mixture of organic erythritol
and inorganic MgCl26H2O (20 wt%) suggested by Kubota
et al.49 Erythritol shows no effect on promoting nucleation and
supercooling of the mixture is found up to 50 C. The mixture
was then continuously irradiated using ultrasound that
helps the initiation of the nucleation on the melt surface. Simi-
larly, for Mg(NO3)6H2O PCM, most effective nucleating
agents were MgSO44H2O, CuSO43H2O, NaBO22H2O,
CaSO42H2O, NiSO44H2O, COSO44H2O, Sr(OH)2, SrCO3,
Ca(OH)2, CaO, CaCO3, Mg(OH)2, MgO, BaO, MgCO3,
Mg3(PO4)2, Ba(OH)2, and BaCO3 compared to BaHPO4,
BaSO4, BaCl2, BaF2, Ba(NO3)2, Zn(NO3)2, Fe2O3,
CuNa2(SO4)22H2O, ZnSO44H2O, MgCl22H2O, KF4H2O,
and CaHPO42H2O.36 A quantity between 0.5 and 3 wt% of
nucleating agents like Mg(OH)2, BaO, MgO, and Sr(OH)2 were
reported being a suitable nucleating agent for Mg(NO3)26H2O
and they are capable to reduce supercooling (delta T) from
28 C (without any nucleating agent) to below 5 C for 50 ther-
mal cycles. Other nucleating agents such as Ba(OH)28H2O
and MgCO3 found ineffective for Mg(NO3)6H2O.50
Mn(NO3)26H2O as a PCM, which has melting point
25.8 C and heat of fusion 125.9 J/g, were studied.51 To
study the modulation of melting point and control the
supercooling effect, NaNO3, NaCl, and MnCl24H2O mix-
ture as an additive to Mn(NO3)26H2O. Addition of
NaNO3 showed no effect to the melting point, but the
heat of fusion showed an inverse proportion to the
increase in the concentration of NaNO3. By the addition
PUROHIT AND SISTLA
of 1 and 5 wt% of NaCl to Mn(NO3)26H2O, melting
point, the heat of fusion was decreased to about 20, 4 C,
and about 120 and 100 J/g, respectively. With the addi-
tion of MnCl24H2O (over 10 wt%), no change in melting
point and the heat of fusion was observed. Again the
effect on supercooling of Mn(NO3)26H2O, by adding
0.1 g of other additives like NaCl, NaNO3, NaSO4,
MnCl24H2O, MnSO44-6H2O, and NiSO46H2O, kero-
sene, heptane and carbon black is reported. These addi-
tives bring the average degree of supercooling (delta T) to
below 15 C.51
Na2SO410H2O has a better melting enthalpy of about
241 J/g and melting temperature at about 32 C. Due to
these properties, it is suitable for using as PCM in room
temperature range.19,31 Borax as nucleating agent reduce
supercooling of Na2SO410H2O from about 15 C to about
1 to 2 C19,40,52 and suppresses the formation of
heptahydrates.53 Two inorganic salts Na2SO410H2O
(40 wt%) and Na2CO310H2O (55 wt%) with the nucleat-
ing agent borax (5 wt%) has a reported phase transition
between 21 and 24 C. Excessive supercooling observed
with less than 1 wt% borax and with above 10 wt%
affected melting phase transition stability of the mixture.54
Surface effect of three nanomaterials (aerosol SiO2 (12 nm),
RNS-A SiO2 (40 nm) and liquid phase SiO2 (50 nm))
with PCMs like Na2S2O35H2O, Na2SO410H2O, and
Na2HPO412H2O were reported by Wu et al.55 Aerosol SiO2
among other nano-particles like RNS-A SiO2 and liquid
phase SiO2 provides better results for Na2SO410H2O. 2 wt%
aerosol SiO2 found to be effective in reducing supercooling
for Na2HPO412H2O, and Na2S2O35H2O.55 Degree of
supercooling for sodium acetate trihydrate (SAT;
C2H3NaO23H2O) depresses under 2 C by the addition of
nucleating agents like borax,56 disodium hydrogen phos-
phate dodecahydrate,57,58 AIN nanoparticles59 and mixture
of Na2SO4 + silver nanoparticles (AgNPs).60 Table 4 shows
lists of nucleating agents recommended for different salt
hydrates.
4.2.4 | Addition of thickening agents to
the TES system
The thickener or gelling agents are cross-linked mate-
rials, which create a three-dimensional network that
helps to hold salt hydrates in its position. On addition of
thickener or gelling agent to a salt solution, the viscosity
of the solution increases and the solution becomes non-
moving gel-like structure. They increase the holding
capacity for salt crystals within the solution during the
hydration/dehydration thermal cycle, by ceasing the crys-
tal movement in the TES system thus providing more
chances to contact water for the dehydrated salts.13,41,61
11 of 26
For the PCM SAT (CH3COONa3H2O), three types of
thickeners such as carboxyl methylcellulose (CMC), gela-
tin and polyacrylamide (PAM) along with various nucle-
ating agents like Na2SiO39H2O, Na2CO310H2O,
Na2B4O710H2O, Na2HPO412H2O, and Na3PO412H2O,
were reported. Effective reduction in supercooling and
phase segregation was reported for a mixed composition
(wt%) of PCM, nucleating agent and thickener to be
CH3COONa3H2O:Na2HPO412H2O:CMC as 100:6.2:3.2
(when CMC was used as a gelling agent) and
CH3COONa3H2O:Na2HPO412H2O: gelatine as 100:6:3.5
(when gelatine was used as a gelling agent). The perfor-
mance of PAM as a thickener with nucleating agents
Na2HPO412H2O and Na3PO412H2O found unstable.56
Studies proved that polyacrylic amide, sodium poly-
acrylate, and polyvinyl alcohol (PVA) were not suitable
as thickening materials for the SAT.62 Different thicken-
ing materials (such as starch (20 wt%), methyl-cellulose
(30 wt %), methyl hydroxyethyl-cellulose (30 wt%), and
bentonite (50 wt %)) along with 1 wt% Na2HPO47H2O as
a nucleating agent for the SAT (CH3COONa3H2O) PCM
are reported. The addition of these thickening agents did
not modulate the melting point but decreases the melting
enthalpy to about 20% to 35% of the original. Cellulose as
a thickener gave a better thermal performance as thick-
ener than starch and bentonite till 65 C.62 The effective-
ness of carboxymethyl cellulose (CMC) and silica gel as
polymer blend to avoid phase segregation, silver
nanoparticles as nucleating agent reported60 for SAT that
reduces supercooling, phase separation, and provides
95% of latent heat compared to pure SAT. Mao et al58
reported the effect of the different nucleating agent (dis-
odium phosphate dodecahydrate, borax, sodium carbon-
ate decahydrate, sodium phosphate dodecahydrate,
sodium silicate nonahydrate), different thickener (CMC,
gelatin, PAM), and additive to increase thermal conduc-
tivity (silica, copper powder, granular activated carbon,
expanded graphite (EG) powder) for SAT. In a recent
study,63 thermal heating and cooling cycles for modified
SAT PCMs tested were carried out for 200 cycles. The
SAT PCMs modified by adding 5 wt% disodium hydrogen
phosphate dodecahydrate as nucleating agent and further
3 wt% CMC as a thickener. In the absence of thickener,
the incongruent melting behaviors arise due to the settle-
ment of salt crystals with the increase of the heating and
cooling cycles. But with a thickener, the viscosity of com-
posite PCM increased about 14 times that reduces the salt
settlement about 8 times than the nonthicken sample.
Dannemand et al,64 on a large scale experiment, studied
the effect of the performance of thickening and non-
thicken PCM within stainless steel cylindrical units
(1.5 m high and with internal fins). The thicken PCM
unit (116.3 kg SAT + 0.5% xanthan rubber as a
12 of 26 PUROHIT AND SISTLA

TABLE 4 Different salt hydrates and its nucleating agents

Degree of supercooling ( C)

Without nucleating With nucleating

Salt hydrate PCM Nucleating agent agent agent References
Calcium chloride BaCO3, SrCO3, BaF2, SrF2 10-14 3-5 [13]
hexahydrate BaI26H2O, SrCl26H2O, SrBr26H2O N.A. N.A. [36]
[CaCl26H2O]
3 wt% KNO3 N.A. N.A. [136]
SrCl26H2O N.A. N.A. [5]
γ-Al2O3 (50 nm) N.A. N.A. [42]
NaCl N.A. N.A. [43]
Potassium fluoride Al2O3 25-30 5-8 [13]
dihydrate [KF2H2O]
Potassium fluoride Pumice stone 15-24 9.5 [13]
tetrahydrate
[KF4H2O]
Lithium chlorate KClO4, Na2SiF6, K2SiF6, BaSiF6 2-8 05 [13]
trihydrate
[LiClO33H2O]
Magnesium chloride Na3AIF6, CaC2O4.H2O, Sr(OH)2, SrCO3, N.A. N.A. [36]
hexahydrate BaO, Ca(OH)2, CaO, Ba(OH)2,
[MgCl26H2O] Mg(OH)2
SrCO3, Sr(OH)2 N.A. N.A. [35,47]
Magnesium nitrate MgSO44H2O, CuSO43H2O, N.A. N.A. [36]
hexahydrate NaBO22H2O, CaSO4.2H2O,
[Mg(NO3)26H2O] NiSO44H2O, COSO44H2O, Sr(OH)2,
SrCO3, Ca(OH)2, CaO, CaCO3,
Mg(OH)2, MgO, BaO, MgCO3,
Mg3(PO4)2, Ba(OH)2, BaCO3
Mg(OH)2, BaO, MgO, Sr(OH)2 N.A. N.A. [50]
Manganese(II) nitrate NaCl, NaNO3, NaSO4, MnCl24H2O, 20 8-15 [51]
hexahydrate [Mn MnSO44-6H2O, NiSO46H2O,
(NO3)26H2O] Kerosene, Heptane, Carbon black
Sodium acetate Na2SO4 20 4-6 [41]
trihydrate SrSO4 N.A. 0-2 [41]
[CH3COONa3H2O]
Carbon (15-6.7 μm) N.A. 4-7 [41]
Potassium sulfate (2 wt%) N.A. 2-3 [41]
Na4P2O710H2O, Activated charcoal, N.A. N.A. [19]
Na2CO3, NaWO42H2O
Borax N.A. N.A. [56]
Na2HPO412H2O N.A. N.A. [57,58]
Na2SO4 + Silver nano particles (AgNPs) N.A. N.A. [60]
AIN nano particles N.A. N.A. [59]
Tetrosodium pyrophosphate N.A. N.A. [137]
decahydrate (Na4P2O710H2O)
Nano-Copper (10-30 nm) N.A. N.A. [65]
Sodium dihydrogen Borax 20 6-9 [41]
phosphate Carbon (1.5-6.7 μm) N.A. 0-1 [41]
dodecahydrate
TiO2 (2-200 μm) N.A. 0-1 [41]
[Na2HPO412H2O]
Copper (1.5-2.5 μm) N.A. 05-1 [41]
PUROHIT AND SISTLA
TABLE 4 (Continued)
Salt hydrate PCM Nucleating agent
Aluminium (8.5-20 μm)
Sodium sulfate Borax (Na4B4O710H2O)
decahydrate Aerosol SiO2 (12 nm)
[Na2SO410H2O]
Sodium thiosulfate K2SO4
pentahydrate Na2P2O710H2O
[Na2S2O35H2O]
Zinc nitrate hexahydrate ZnO, Zn(OH)2
[Zn(NO3)2.6H2O]
thickening agent + 4.4% graphite powder) shows lower
heat transfer rate (due to the less convective transfer of
PCM), higher heat release for multiple thermal cycles
compared to nonthicken PCM unit (116 kg SAT + 6%
extra water).
Again, with 5 wt% AlN nanoparticles (95-300 nm) as
a nucleating agent and 4 wt% CMC as a gelling agent, for
up to 50 thermal cycles, no supercooling phenomenon
occurred for SAT and its phase change temperature and
LHS stabilized to 52.5 C and 227.54 J/g, respectively.59
The PCM has Na2SO4 and silver nanoparticles (AgNPs)
as a nucleating agent (2 wt%), a mixture of CMC and sil-
ica gel (3 wt%) as a thickener and SAT (95 wt%) reduced
the supercooling and phase segregation examined up to
10 thermal cyclings.60 Ryu et al41 reported that
CH3COONa3H2O thickened with CMC nucleated with
1 wt% K2SO4 or 1 wt% Na2P2O710H2O, supercooling
(delta T) reduced from 30 to 2 C and 3 C, respectively.
The effect of Nano-Cu (particle size 10-30 nm, 0.4-0.8%)
for a composite PCM of SAT with additives of CMC
(thickening agent) and sodium dodecyl sulfonate
(C12H25NaO3S, dispersant) were studied. Nano-Cu of
0.5% increases the rate of heat transfer by about 20% and
the degree of supercooling for composite PCM reduces to
nearly 0.5 C.65 Leung et al66 tested the use of bio-derived
chitin nanowhiskers (1 wt%) as the nucleating agent for
SAT. Apart from this, the reported composite PCM added
with 3 wt% of CMC, 0.25 wt% of sodium dodecyl sulfate,
and 1 wt% hexagonal boron nitride and graphene
nanoplatelets as additives to PCM.
For Na2SO410H2O, different concentrations of PAM
and gelatin gel as thickener and borax (2 wt%) as a nucle-
ating agent were used to prevent phase segregation and
to stabilize phase transition temperature between 28 and
32 C. Both supercooling and incongruent melting behav-
ior of PCM reduces with the additive like gelatin gel
13 of 26
Degree of supercooling ( C)
Without nucleating With nucleating
agent agent References
N.A. 3-10 [41]
15-18 3-4 [13,40]
N.A. N.A. [55]
30 0-3 [41]
N.A. 0-2 [41]
2-7 1-6 [13]
(10 wt%) with borax, while PAM (10 wt%) with borax
reduced supercooling (delta T) to 4 C.61 Sodium CMC
(2 wt%) and fumed silica (6 wt%) were also used as thick-
ener/suspending media along with nucleating agent
borax (3 wt%) for Na2SO410H2O as PCM. Different addi-
tives like sodium hexametaphosphate (1 wt%) as crystal
habit modifier and NaCl (4 wt%) to suppress the genera-
tion of large crystalline particles and melting point is also
added. For 20 examined thermal cycles, the phase transi-
tion of PCM occurs at about 32 C with less than 2 C sup-
ercooling and the enthalpy decay of about 20% was
observed.52
Marks53 reported attapulgite clay (hydrous magnesium
aluminum silicate) and borax as a thickener and nucleat-
ing agent, respectively, for Na2SO410H2O. One hundred
and fifty gram each of two Na2SO410H2O PCM samples
(thick PCM: 88 wt% Na2SO410H2O + 2.64 wt% borax
+ 9.36 wt% attapulgite clay and nonthickened PCM: 97 wt
% Na2SO410H2O + 3 wt% borax) was taken. Standard
calorimetric techniques were used for the analysis of sam-
ples for 200 thermal cycles (27-38 C). The thermal capac-
ity from about 238 to 63 J/g, after 40 thermal cycles, for
nonthickened sample. After 200 thermal cycles, the
enthalpy of the thickened sample decreased from about
238 to 105 J/g.53 Addition of 2 to 5 wt% of superabsorbent
polymer (SAP) made from acrylic acid copolymer for
Na2CO310H2O, Na2SO410H2O, Na2HPO412H2O, and
2 to 4 wt% CMC for CH3COONa3H2O, Na2S2O35H2O
reported as effective gelling agents up to 150 thermal
cycles.41 Gutierrez et al67 reported the effect of different
samples of poly(ethylene glycol) as a thickening agent for
bischofite (the inorganic PCM with nearly 95%
MgCl26H2O). It has a melting temperature of 98.9 C and
a heat of fusion of 120.2 J/g. Then, 5 wt% of PEG 2000
found to be effective than PEG 500 and PEG 10000 that
reduces phase separation and the cycling stability up to
14 of 26
30 thermal cycles (40-120 C) without affecting its melting
temperature (constant subcooling of about 36 C) and heat
of fusion.67 Thickening agents such as starch, silica
gel, sepiolite, diatomaceous earth,41,54 nano mont-
morillonite,68 polyethylene glycol,67 CMC,69 and SAP41
were used to minimize the separation of phase in TES hav-
ing salt hydrates. Various polymers, bentonite, and silica
gel as gelling materials were also used.17 Table 5 shows dif-
ferent salt hydrates with respective suggested thickening
agents.
Low thermal conductivity of PCM that slower the
heat transfer process that results in low heat storage/
release rate is a major limiting property for PCMs. Thus,
methods like the addition of high thermal conductive
additives (metallic and carbon-based nanoparticles- car-
bon fiber, carbon nanotubes, and graphene), metallic
foams, EG, and encapsulation of PCM were applied for
better thermal performance of PCM.26 The mixed compo-
sition of some of the nucleating agents and thickeners
were also found to enhance the thermal conductivity of
the PCM. On addition of 2.5 wt% EG (as the nucleating
agent) and 5 wt% CMC (as the thickening agent) to SAT,
thermal conductivity increased to 1.85 W/mK. But the
latent heat value decreased with an increase in the con-
centration of EG and CMC.69 Mao et al57 reported that
the addition of 10 wt% of EG increases thermal conduc-
tivity up to five times that of SAT/disodium hydrogen
phosphate dodecahydrate/carboxyl methylcellulose. Li
et al70 prepared a composite having SAT-8 wt% KCl with
1 wt% Al2O3 as a nucleating agent and 4 wt% CMC as a
thickening agent. DSC results show the onset tempera-
ture to be 50.41 C with enthalpy about 232.29 J/g, which
remains constant up to 50 thermal cycles. Hou et al71 pre-
pared a eutectic composite of KCl (0-7 wt%) with
Na2SO410H2O. DSC analysis shows that the increase in
KCl% melting temperature decreases and KCl did not
improve phase separation. A composite having mixtures
of Na2SO410H2O-5 wt% KCl, 5 wt% PAM, 5 wt% sodium
tetraborate decahydrate, and 3 wt% EG was proposed that
showed no phase separation, reduced supercooling to
about 0.4 C and 2.4 times increase in thermal conductiv-
ity than pure Na2SO410H2O. Liu et al72 reviews different
methods to enhances the thermal conductivity of PCM,
that leads to better charging/discharging of PCM. Com-
posite of CaCl26H2O/EG (50 mass% CaCl26H2O) with
surfactant OP-10 (as a coupling agent to improve the
binding energy between CaCl26H2O and EG)) increases
the thermal conductivity up to 14 times than that of pure
CaCl26H2O.73
The eutectic hydrated salt of CaC126H2O and 25 wt%
MgCl26H2O have a phase change temperature of 21.4 C,
and the latent heat 101.5 J/g. Addition of nucleating
agents 3 wt% SrCl26H2O, 1 wt% SrCO3, and thickener
PUROHIT AND SISTLA
0.5 wt% hydroxyethylcellulose stabilize this eutectic PCM
up to 50 cycles.74 A mixture of 40 wt% Na2CO310H2O
and 60 wt% Na2HPO412H2O as novel eutectic hydrate
salt is also reported with phase change temperature of
27.3 C, supercooling degree of 3.6 C and latent heat of
220.2 J/g.75 In another work, they76 studied for the eutec-
tic composition of 27 wt% Na2CO310H2O and 75 wt%
Na2HPO412H2O. 4.5 wt% α-Al2O3 as main nucleating
agent and 1 wt% borax as auxiliary nucleating agent
enhances, the degree of supercooling (delta T) from about
7.8 to 6.2 C, increases the thermal conductivity to about
61.3% and have thermal stability up to 200 cycles. In a
recent study,77 a mixture of two hydrated salts
(Na2HPO412H2O: Na2SO410H2O = 9:1) was reported to
have a crystallization temperature of 28.2 C with about a
supercooling of 4.8 C. Again, with the addition of
Na2SiO39H2O (3.25%), the supercooling of PCM further
improves to 3.4 C, shows less corrosion to aluminum
containers and found suitable up to 200 tested thermal
cycles. An eutectic mixtures of Na2SO410H2O-KCl (5 wt
%), with additives like 5 wt% PAM (thickener), 5 wt%
sodium tetraborate decahydrate (nucleating agent), and
3 wt % EG (high thermal conductivity medium) was pro-
posed.71 The eutectic mixture provides reduced super-
cooling of 0.4 C with almost no phase separation and
improvement in thermal conductivity about 1.35 W/mK
(up to 2.4 times more than pure Na2SO410H2O). Chen
et al78 studied a ternary eutectic salt hydrate mixture
(K2HPO43H2O-NaH2PO42H2O-Na2S2O35H2O) as PCM.
They reported that sodium tetraborate and sodium fluo-
ride were effective as a nucleating agent. Further addition
of 0, 3, and 5 wt% of CMC as thickeners, the solidification
temperature and latent heat observed to be −11.9, −10.6,
and −14.8 C and 127.2, 118.6, and 82.56 J/g, respectively.
Optimized compositions of nucleating agent and thick-
ener that will prevent both supercooling and phase sepa-
ration of PCMs in the temperature range 30 to 60 C are
reported (Table 6).41
4.2.5 | Incorporation of PCM within the
porous material
Phase segregation can be minimized by incorporation of
PCM within a porous medium. The porous nature of
medium holds the salt solution/molten salt hydrate in its
open capillaries and does not allow the phase segregation
phenomenon. Moreover, some porous medium acts as a
nucleating agent for some salt hydrate crystals. Salt
hydrate mixture of 98 wt% CaCl26H2O and 2 wt%
SrCl26H2O (nucleating agent) PCM has a melting point
of 27.38 C, and have a latent heat of 87.44 J/g. This PCM
was incorporated into a porous supporting matrix of
PUROHIT AND SISTLA 15 of 26

TABLE 5 Different salt hydrates and its thickening agent

Salt hydrate Thickening

Salt hydrate PCM Thickening agent References PCM agent References
Calcium chloride Hydroxy ethyl cellulose [13] Sodium carbonate Superabsorbent [41]
hexahydrate decahydrate polymer (SAP)
[CaCl26H2O] [Na2CO310H2O]
Calcium nitrate Polyacrylic acid [18] Polyethylene [13]
tetrahydrate oxide
[Ca(NO3)4H2O]
Magnesium chloride PEG 2000 [67] Sodium dihydrogen Starch [13]
hexahydrate phosphate dodecahydrate
[MgCl26H2O] [Na2HPO412H2O]
Sodium acetate trihydrate Carboxymethyl [41,56] Super absorbent [41]
[CH3COONa3H2O] cellulose (CMC) polymer (SAP)
Gelatin gel [56] Sodium sulfate Bentonite, [13,53]
decahydrate Attapulgite
[Na2SO410H2O] Clay
Methyl-cellulose, [62] Super absorbent [41,52]
Methyl hydroxyethyl- polymer (SAP)
cellulose
CMC, Xanthan Rubber [138] Gelatin gel [61]
Xanthan [137] Sodium thiosulfate Wood pulp [13]
pentahydrate
[Na2S2O35H2O]
CMC [41]

expanded perlite. Expanded perlite enhanced the thermal
insulation by reducing the thermal conductivity to 70%
and suppressed the supercooling to about 1 C. This com-
posite showed stability up to 1000 thermal cycles, good
thermal storage, nonflammability, and better insulation
compared to foam insulation bricks in building
applications.79
Commercially available calcium chloride hexahydrate
also used within the porous structure of copper metal
foam (open cell, with 30 ppi and 18.5% relative density).
Due to the presence of metal foam, the effective thermal
conductivities of the composite increased three times
compared to pure PCM. Metal foams minimized the
phase change duration and suppressed the supercooling
effect of calcium chloride hexahydrate to about 50%.80
Sepiolite (magnesium hydro silicate), having a high sur-
face area, good flame retardance and high chemical,
mechanical stability is also potential material for sustain-
ing salt hydrates. A composite was prepared by vacuum
impregnation of saturated solutions of CaCl26H2O
(as PCM) within sepiolite (as a sustainer). Composite
(70% CaCl26H2O) shows good stability in the tempera-
ture range from 25 to 100 C and have melting enthalpy
87.9 J/g. Sepiolite reduced both phase separation and the
supercooling effect of CaCl26H2O.81
Polyurethane (PU) foam, having honeycomb-like voids
filled with air, has been used as a thermal insulator (low
thermal conductivity, low density, and superior mechanical
properties). The thermal insulation performance of 0.01 m
thick composite (PU-PCM) having saturated inorganic salt
solution of Na2SO410H2O, MgSO47H2O, and its mixture
within the pores of open-cell polyurethane foam sheet was
performed and compared with the thermal insulation per-
formance of dry open-cell PU foam. During the thermal
cooling cycle, the thermal insulation performance of the
composite found to be effective than dry PU foam.82 Wu
et al83 prepared a composite using sol-gel techniques by
impregnation of hydrated salts (a mixture of Na2SO410H2O
and Na2HPO412H2O) into a porous silica matrix. To
improve the thermal heating/cooling performance and
leakage of PCM, this composite was coated with polyvinyl
pyrrolidone. For a mass ratio of hydrated salts to silica
(70:30), a minor change in the supercooling observed. This
composite having melting temperature 30.13 C and melt-
ing enthalpy 106.2 J/g found to be stable for up to 30 ther-
mal cycles.
Pure salt hydrates for sorption TES applications have
issues like swelling, agglomeration and corrosion during
its hydration/dehydration process. A composite having
magnesium sulfate heptahydrate filled within silicone
16 of 26 PUROHIT AND SISTLA

TABLE 6 Optimized composition of nucleating agent and thickener for salt hydrates

Phase transition
Salt hydrate PCM Thickening agent Nucleating agent temperature ( C) Reference

Na2SO410H2O (94 wt%) SAP (3 wt%) Borax (3 wt%) 32 C [41]
Na2SO410H2O (88 wt%) Attapulgite clay (9.36 wt%) Borax (2.64 wt%) 32 C [53]

Na2CO310H2O (93 wt%) SAP (3 wt%) Sr(OH)2 (4 wt%) 32 C [41]

Na2HPO412H2O (928 wt%) SAP (35 wt%) TiO2 (37 wt%) 35 C [41]

Na2S2O35H2O (92 wt%) CMC (3 wt%) SrSO4 (5 wt%) 48 C [41]
CH3COONa3H2O (96 wt%) CMC (3 wt%) K2SO4 (1 wt%) 58 C [41]
CH3COONa3H2O (96 wt%) CMC (3 wt%) Na2P2O710H2O (1 wt%) N.A. [41]
CH3COONa3H2O (91.4 wt%) CMC (3 wt%) Na2HPO4 .12H2O (5.6 wt%) N.A. [56]
CH3COONa3H2O (91.3 wt%) Gelatine gel (3.3 wt%) Na2HPO4 .12H2O (5.4 wt%) N.A. [56]
CH3COONa3H2O (91 wt%) CMC (4 wt%) AlN nanoparticles (5 wt%) 52.5 C [59]
CH3COONa3H2O CMC and silica gel Na2SO4 and silver N.A. [60]
nanoparticles (AgNPs)
CH3COONa3H2O-8 wt% KCl CMC (4 wt%) Al2O3 (1 wt%) N.A. [70]

composite foam was purposed for sorption TES applica-
tions. The salt content in the porous structure was varied
from 40 to 70 wt% and its performance for sorption analy-
sis was studied. All the composites show good hydration/
dehydration capacity and the water/salt reaction for all
composites is not affected by the foaming process.84 Leak-
age, corrosion tendency and solution vaporization may
be an issue to its application. But this can be avoided by
proper packing of the composite. To prevent leakage of
PCM from composite, encapsulation of PCM is favorable.
4.2.6 | Encapsulation techniques for the
salt hydrates
Encapsulation is the process of wrapping or covering the
limited quantities of PCMs as capsule within a non-
permeable substance of various materials, forms and sizes.
The encapsulation of materials leads to greater heat transfer
area, reduced reactivity with the outside environment and
controlled volume changes during the phase transition.18
Encapsulation layer should be mechanically tough, chemi-
cally inert with the PCM.85 In microencapsulation tech-
nique, very small amounts of PCM were enclosed within a
thin and high molecular weight polymeric film. In microen-
capsulation, PCM materials as package incorporated within
containers like tubes, pouches, spheres and panels. Microen-
capsulation of PCM is inexpensive and effective in reducing
supercooling, phase segregation.18 Both high-density poly-
ethylene bottle and druwn steel aerosol cans reported as a
suitable encapsulation material for CaCl26H2O (fusion tem-
perature 27 C) and steel aerosol cans for Mg(NO3)26H2O
(fusion temperature 89 C).85,86
In review literature,87 the synthesis, characterization,
properties, and applications of different microencapsulated
PCMs were reported. Milián et al88 and Su et al89 gave a
detailed review of the methods to encapsulate inorganic
PCMs and its effects on the thermophysical properties of
PCMs. Milián et al88 classified the encapsulated PCMs as
core-shell PCMs and shape stabilized PCMs. The core-shell
PCMs were prepared by electroplating, inverse pickering
emulsification, solvent evaporation-precipitation method,
and mechanical packaging methods. For shape stabilized
PCMs sol-gel process, infiltration and impregnation encap-
sulation methods were suggested. An experiment with
large scale (more than 45 kg) of PCM (CaCl26H2O,
Mg(NO3)26H2O) was conducted by Lane et al85 to get the
effect of encapsulation on PCM. Thermal batteries were
prepared by taking 97 kg of CaCl26H2O and 100 kg of
Mg(NO3)26H2O within high-density polyethylene bottle
and steel aerosol cans, respectively. Hot/cold air at differ-
ent velocity flows through pipes inside these thermal bat-
teries. The outlet air temperature observed, shows better
efficiency in terms of cooling/heating the inlet air within
thermal batteries. Steel cans can produce stress cracking
corrosion after long exposure and can be mitigated by
adding corrosion inhibitors. Alkan et al90 studied the ther-
mal properties of two salt hydrates (Na2SO410H2O and
CaCl26H2O) encapsulated with a hydrophilic polymer
PVA. The PVA polymer and salt hydrates taken in the
ration of 1:10 and then stirred to maintain homogeneity.
Hydrophilic PVA will hold the release of water from salt
hydrates. Their (PVA-salt hydrate PCM) thermal conduc-
tivity observed in the range between 0.16 and 0.19 W/mK.
The thermal conductivity of the PVA-Na2SO410H2O PCM
increases to about 0.35 W/mK with the addition of 3 mL
PUROHIT AND SISTLA
of water and in PVA-CaCl26H2O thermal conductivity
increases to 1 W/m K with the addition of 1 mL of water.
These encapsulations observed to reduce the issues like
phase separation and corrosion. The encapsulation mate-
rials should improve PCMs thermal and physical perfor-
mances like increase thermal conductivity, stabilizing
melting point and enthalpy, reducing supercooling tem-
perature, leak proof. These should survive in the opera-
tional temperature interval and inflammable.
4.2.7 | Direct contact heat exchangers
for salt hydrates
A heat exchanger setup having packing of hydrated salts
inside was designed in such a way that an immiscible
heat transfer liquid ((lower in density and immiscible
with the aqueous salt solution) can pass through them by
directly contacting to a bed of hydrated salts. The PCM
gets heated by passing the hot immiscible liquid through
the bed. When a hot liquid loses heat to PCM and gets its
temperature reduced. Next, when a cold liquid passes
through the bed, PCM discharges accumulated heat, and
cold liquid temperature increases. The agitation caused
by the bubbles during the passing of the immiscible liq-
uid through PCM bed helps increasing heat transfer rate,
reduces phase segregation and supercooling effects.91
In an experiment, two direct contact heat exchanger
setups consist of two storage tanks having hydrated salts
(inside diameter: 0.184 m and total length: 1 m) con-
nected in series. Hot kerosene as a heat transfer fluid first
bubbled through the column containing sodium thiosul-
fate solution (higher enthalpy and melting point) and
then partially cooled kerosene from the first column pas-
ses through sodium carbonate solution. Next, to heat a
solution the flow direction is reversed. A system having
two different PCM of different crystallization tempera-
tures provide better heat storage than a single unit.92
Solutions of disodium hydrogen phosphate (Na2HPO4) as
PCM with Marcol 72 and Therminol 60 as a heat transfer
fluid is reported.91 Na2HPO4 solutions showed no degra-
dation and the average storage efficiency after 12 thermal
cycles were observed to be 77.6% and 74.3% for Marcol
72 and Therminol 60, respectively. Etherington93 used
solutions of disodium phosphate dodecahydrate as a
PCM and light mineral oil as a heat transfer fluid. For
saturated solutions of Na2SO410H2O, Na2S2O35H2O,
CH3COONa3H2O, and MgCl2, kerosene used as heat
transfer fluid.94 Indirect contact heat exchangers, during
heating of immiscible fluid, the produced salt crystals
tend to settle at the bottom of the heat exchanger. But by
changing flow characteristics and temperature of the
immiscible fluid during operation it can be reduced.
17 of 26
4.2.8 | Corrosion issue in TES systems
with salt hydrates
Corrosion related issues affect both safety and economic
application TES systems with most salt hydrates. Tech-
niques such as gravimetric analysis, optical and scanning
electron microscopy techniques, and chemical analysis
were used to calculate the corrosion rate of a metal sur-
face. In gravimetric tests, the testing metal sample dipped
inside the PCM for a defined time and the loss of mass of
metal corrosion rate calculated. For practical application
the metal to be corrosion resistance, the thickness reduc-
tion should be of <0.1 mm/year.13,95 Microscopy tech-
niques were used to study the surface and give the type
of corrosion for example, pitting corrosion, cracks, and
so on.13
Metal specimens like copper (Cu), aluminium (Al),
stainless steel 316, and carbon steel were dipped for
within five different solid salt hydrates (CaCl26H2O,
Na2S5H2O, Ca(OH)2, MgCl26H2O, MgSO47H2O) and
then weight loss after 12 weeks observed. Among
these stainless steel, founded to be more corrosion-
resistant than others.96 Abhat13 reported corrosion
behavior of CaCl26H2O, CH3COONa3H2O, LiClO33H2O,
Mg(NO3)26H2O, Na2SO35H2O, Na2SO410H2O,
Na2HPO412H2O, Zn(NO3)26H2O and eutectic-mixtures
of Mg(NO3)26H2O-Ca(NO3)24H2O, and Mg(NO3)26H2O-
MgCI26H2O. Stainless steel found to be suitable for
almost all these salt hydrates (CaCl26H2O, Na2HPO412H2O,
Na2SO410H2O, Na2SO35H2O, Zn(NO3)26H2O, and
Mg(NO3)26H2O-MgCI26H2O). Tin-plated mild steel is
compatible with CH3COONa3H2O, LiClO33H2O, and
Mg(NO3)26H2O and eutectic-mixture of Mg(NO3)26H2O-
Ca(NO3)24H2O. Mild steel containers as packing mate-
rials did not show good resistance but can be used as
containers for PCMs like CaCl26H2O, Na2HPO412H2O
except for Zn(NO3)26H2O and the Mg(NO3)2-MgCI2
eutectic. Copper as a PCM storage material compatible
with most PCM except sodium thiosulfate pentahydrate
(Na2SO35H2O) and eutectic mixture of Mg(NO3)26H2O-
MgCI26H2O. After 10 days of contact with Na2SO35H2O,
a black layer of CuS started forming on the metal sur-
face. Aluminium (Al 99.5) and aluminium alloy formed
a white layer of aluminium hydroxide (AI(OH)3) when
contacted with PCM Na2HPO412H2O and reported their
nonsuitability for PCMs CaCl26H2O and Zn(NO3)26H2O.
Cabeza et al95 reported that stainless steel can be
considered for storage material for Zn(NO3)26H2O,
Na2HPO412H2O, and CaCl26H2O. For PCM Na2HPO412H2O
brass and stainless steel showed good compatibility. Alumin-
ium indicated aggressive corrosion, whereas, copper and
steel corrode at a slow rate of 5 to 12 and 0 to 50 mg/cm2yr,
respectively for PCM Na2HPO412H2O. CaCl26H2O was
18 of 26
observed to have good compatibility with copper, brass,
and stainless steel but can corrode steel and aluminium at
a moderate rate of 26-37 and 4-11 mg/cm2yr, respectively.
SAT and sodium thiosulfate pentahydrate showed good
compatibility with aluminium, steel, and stainless steel,
however, both salt hydrates were aggressively corrosive
toward brass and copper.97 A small amount of corrosion
inhibitors (0.5 wt%) like sodium chromate (Na2CrO4),
sodium dichromate (Na2Cr2O7), and sodium nitrite
(NaNO2) are suggested.54,98 A PCM having corrosion
inhibitor (0.5 wt%) along with nucleating agent borax
(3 wt%) added to 35 wt% Na2SO4, 61.5 wt% H2O is
reported.98 To avoid corrosion, plastic containers of poly-
propylene, polystyrene, polyethylene terephthalate and
high-density polythylene were suggested for PCM.8
Table 7 reports different salt hydrates (PCM) and its com-
patible containers to prevent corrosion. The results from
various corrosion studies undertaken with PCMs for LHS
applications are reported elsewhere.13,95,96
5 | NUMERICAL AND
SIMULATION STUDIES FOR SALT
HYDRATES AS PCM
Thermal performance of a building wall with three differ-
ent PCM medium (CaC126H2O, paraffin wax, and con-
crete) were numerically simulated by Khalifa et al.99 A
one-dimensional unsteady heat transfer model was
designed and to solve the problem model finite-difference
and Neumann method was used for concrete and PCM
wall, respectively. An 8 cm wall with CaC126H2O PCM
showed fewer fluctuations (18-22 C) in indoor tempera-
ture and was found to be the equal effective compared to
a wall with paraffin wax (5 cm thick) and the traditional
concrete wall (20 cm thick). Ye et al100 reported the ther-
mal performances of a building wall having two PCM
composites of CaCl26H2O/EG and RT27/EG through
numerical modeling. They applied the unsteady energy
equation for common materials and enthalpy-porosity
technique for the solidification/melting process. The
numerical simulation resulted in the optimum thickness
of the PCM panel having CaCl26H2O/EG found to be
8 to 10 mm, and it showed better performance over panel
having RT27/EG. Farid et al101 reported a one-
dimensional model to simulate the underfloor heating
system having CaCl26H2O as PCM. They used the
explicit finite difference method to solve the model for
the concert slab (dimension 0.5 m × 0.5 m × 0.095 m)
having CaCl26H2O as PCM and compared with experi-
mental results. Simulation results showed good agree-
ment with experiment results and wall with PCM
performance was better than a normal wall without
PUROHIT AND SISTLA
PCM. Balasubramanian et al102 designed a mathematical
model to get the TES capacity of MgSO47H2O during its
dehydration into water vapor and anhydrous salt. They
assumed local thermal equilibrium throughout the sys-
tem and negligible convective thermal or mass transport
in the system. In a square box filled with MgSO47H2O as
PCM, a fixed amount of heat flux employed at its top
boundary while other boundaries were assumed partially
insulated. The time to reach dehydration temperature
increased with boundary heat losses. Water vapor formed
during dehydration supplied more energy to store in the
anhydrous salt. Thermal study for a composite having
solution of sodium sulfate within the open cell polyure-
thane foam (PU-PCM composite) was studied using
COMSOL Multiphysics software. A computational solv-
ing approach for phase change of salt solution within the
open cell PU foam was discussed and the model was vali-
dated with experimental results.103
Multiphase model (using computational fluid dynam-
ics CFD simulation) to analyze the stable supercooling,
triggering crystallization, and regular solidification
periods during discharging of a supercooled PCM
(Na2S2O35H2O) is studied by Zhou et al.104 By taking the
source term and the phase transition term in energy
equation and volume fraction equation, respectively, the
parameter such as rate of heat transfer, phase change and
solid fractions in the system monitored. After super-
cooling and during the triggering crystallization period,
the solid fraction increased up to 33% and a quick
increase in PCM temperature was obtained. Varol et al105
experimentally showed that the solar collector system
with sodium carbonate decahydrate (Na2CO310H2O) as
PCM provided good thermal energy collecting efficiency.
Various soft computing techniques like support vector
machines (SVM), adaptive-network-based fuzzy inference
system (ANFIS), and artificial neural networks (ANN)
were adopted for prediction of experimentally obtained
results. Support vector machines computing techniques
found to be more efficient to predict the results than
other soft computing techniques.
6 | A P P L I C A TI O N O F T E S
SY ST E M S WI T H SA L T H Y DR A TES
The major application of salt hydrate as PCMs for TES
include insulation in buildings wallboards, food con-
tainer, textile, shipping industries to maintain inner tem-
perature, to store solar heat energy in domestic solar hot
water tanks, to reduce industrial waste heat, to manufac-
ture thermoregulating fiber and for low-temperature
application in refrigeration, air conditioning sys-
tem.106,107 For buildings insulation from solar radiation,
PUROHIT AND SISTLA 19 of 26

TABLE 7 Different salt hydrates (PCM) and compatible PCM containers to prevent corrosion [Compatible: C; Not Compatible: X;
Caution: O]

PCM containers

Stainless Carbon Mild Tin platted

Salt hydrate PCM steel steel steel Steel mild steel Brass Copper Aluminium
CaCl26H2O C 96,139
O 95,96
C 13
O95
N.A. C 3,95
C 3,13
Al 99.5, Al Mg3 X13
O3 X3 O96,139
Ca(OH)2 C96 X96 N.A. N.A. N.A. N.A. X96 N.A. O96
CH3COONa3H2O C3,97 C3 N.A. C97 C13 O3,97 O3,97 N.A. C3,97
K3PO47H2O C3 C3 N.A. N.A. N.A. N.A. X3 N.A. X3
K2HPO46H2O C 3
X3
N.A. N.A. N.A. N.A. O 3
N.A. X3
LiClO33H2O N.A. N.A. N.A. N.A. C13 N.A. N.A. N.A. N.A.
Mg(NO3)26H2O C 3
X3
N.A. N.A. C 13
X3
X3
N.A. C3
MgSO47H2O C3 X3 N.A. N.A. N.A. N.A. X3 N.A. C3
MgCl26H2O C 96
X96
N.A. N.A. N.A. N.A. O 96
N.A. O96
Na2HPO412H2O C3,13 X3 C13 O95 N.A. C3,95 O95 Al 99.5, Al Mg3 X13
O95 C3,13
Na2SO410H2O C13,139 O139 N.A. N.A. N.A. N.A. C13 Al 1050, Al 3003, C3,13
O139 Al Mg3
Na2S2O35H2O C3,13 C3 C13 C97 N.A. X3,97 X3,13 Al 99.5, Al Mg3 C13
Na2S5H2O C96 O96 N.A. N.A. N.A. N.A. X96 N.A. X96
NaOH15H2O C3 O3 N.A. N.A. N.A. N.A. X3 N.A. X3
NaOH.3H2O C139 O139 N.A. N.A. N.A. N.A. N.A. N.A. N.A.
ZnCl23H2O C 3
X3 N.A. N.A. N.A. N.A. C3 N.A. X3
Zn(NO3)24H2O C3 X3 N.A. N.A. N.A. N.A. X3 N.A. X3
Zn(NO3)26H2O C3,13 X3 X13 X95 N.A. X3,95 X95 Al 99.5, Al Mg3 X13
Mg(NO3)26H2O-MgCI26H2O N.A. X13 N.A. N.A. N.A. N.A. X13 AlSI403 C13
Mg(NO3)26H2O-Ca(NO3)24H2O N.A. N.A. N.A. N.A. C 13
N.A. N.A. N.A. N.A.
3 3 3
CH3OONa + H2O + additives C C N.A. N.A. N.A. N.A. X N.A. C3
Na2S2O35H2O + sepiolite + C3 X3 N.A. N.A. N.A. N.A. X3 N.A. O3
fumed silica
Na2SO4 + NH4Cl + sepiolite C3 X3 N.A. N.A. N.A. N.A. X3 N.A. O3
Na2SO4 + H2O + additives C3 X3 N.A. N.A. N.A. N.A. X3 N.A. C3

PCMs having melting temperature equal to average day
temperature are suggested. During the daytime, these
PCMs will absorb the solar heat energy and changes
phase from solid to liquid (endothermic process). Again,
in the night time, when environmental temperature
drops below the melting point of PCM, these PCMs
change phase from liquid to solid by releasing the latent
heat (exothermic process). The heat released will main-
tain the inner room temperature of buildings (Figure 5).
Zeinelabdein et al108 reviewed the various free cooling
technology for minimizing energy consumption in build-
ings heating, ventilating, and air conditioning systems
(HVAC) using PCMs.
A composite having a combination of PCMs and
building material should have higher heat storage den-
sity, low volume expansion during phase change, chemi-
cally stable, nonflammable, nontoxic, odourless, and
offers human comfort and saving of energy. These PCM
composites can be combined with construction material
either by direct incorporation of PCM or PCMs inserted
by immersion, vacuum or by encapsulating within suit-
able packaging materials. The porous structure inside the
building bricks helps as a good supporting matrix and
minimize the supercooling, phase segregation, during
thermal cycling.109 Porous concrete blocks impregnated
with sodium thiosulfate pentahydrate PCM, as a thermal
20 of 26
wall was reported by Hadjieva et al.110 To prepare the
composite, heated concrete blocks immersed in a bath
filled with molten sodium thiosulfate pentahydrate
(Na2S2O35H2O) PCM for 7 hours at 75 C and observed
about 60% space occupation of PCM in the concrete
block. Due to the formation of the strong hydrogen bond
with porous concrete, this composited showed high sta-
bility during thermal cycles.
Thermal performance of a concrete slab (0.5 m ×
0.5 m × 0.095 m) having encapsulated CaCl26H2O in spher-
ical plastic modules, for an underfloor heating system, was
reported.101 The encapsulated CaCl26H2O (diameter:
75 mm, manufactured by Cristopia Ltd.) have 10% empty
space to accommodate volume expansion during thermal
cycling. This concrete block having PCM stored more heat as
compared to the simple concrete block and maintained less
fluctuation at surface temperature. In an artificial climatic
chamber, the thermal properties of polyvinyl chloride (PVC)
panels were compared with a composite PCM panel
(CaCl26H2O/EG were packed within polyvinyl chloride
(PVC) panel).100 The panel having CaCl26H2O showed bet-
ter performance compared to without PCM and with organic
PCM RT27/EG. Further, the insulation performance of the
PCM board having CaCl26H2O/expanded perlite composite
better resulted than foam insulating bricks.79 Trombe wall is
a passive solar building design were used to maintain indoor
temperature. In winter, Trombe wall is placed, inside the
room, near to the glass window next to the sunny side of a
building. The heat from the sun is absorbed by the Trombe
wall during daytime and discharged during night hour which
maintains the room temperature. Sodium sulfate dec-
ahydrate111 and calcium chloride hexahydrate112 using as
PCM for the Trombe wall were reported. A better thermal
performance was reported by an 8.1 cm wall having calcium
chloride hexahydrate PCM than a 40 cm thick masonry
wall.112 Hexahydrate of CaCl2 as a PCM was also used as a
sun shading system for the windows. Even at higher day and
night time temperature fluctuations, it was found to be very
useful to maintain indoor temperature.113 Use of salt
hydrates like CaCl26H2O,114 Na2SO410H2O115 as PCM has
also been reported to maintain the temperature inside
greenhouses.
Another application of inorganic PCM is heat storage in
hot water tanks where solar energy is stored for a shorter
time. In hot water tanks, water is used as heat storage mate-
rial due to its high storage capacity and less cost.31 To
extend the storage efficiency, PCMs of salt hydrates are
incorporated into the tank walls that provide heat storage
for longer periods even without exterior energy supply. In
domestically used solar hot water systems, salt hydrate
PCMs with a melting temperature of 50 to 60 C can be used.
CaCl26H2O inserted PVC plastic tubes were arranged in
horizontal cylindrical vessels and studied for the domestic
PUROHIT AND SISTLA
solar water-heating system. The performance of PCM was
found to be better than the water and rock-based storage
system.116 Different salt hydrates like DC58, PT58, and
HD60 (transition temperature 50-61 C and latent heat:
120-240 J/g)117 and SAT118 incorporations in walls of hot
water tanks provided promising results. Sodium thiosulfate
pentahydrate as a PCM for an open-loop passive solar water
heating system was also investigated.119 The effect of some
other PCMs like zinc nitrate hexahydrate, disodium hydro-
gen phosphate dodecahydrate, calcium chloride hexahy-
drate, and sodium sulfate decahydrate was also examined
theoretically and realized that the storage time of hot water
can be increased approximately 2.59 to 3.45 times to the
conventional solar water-heating system.
Due to lower melting temperature and high density
compared to water, various eutectic salt hydrates were
applied to freezing and air condition systems. Since the
melting temperature of water depresses on the addition of
salt and have increased melting enthalpy values, these
concentrated salt solutions can be used for energy storage
at low-temperature applications. Different eutectic con-
centrations of salt solutions as PCM for very low-
temperature (−1.6 to −62 C) applications were reported.29
The performance of PCM, having salt solutions of NH4Cl
(phase change temperature −15.4 C)120 and sodium
nitrate (phase change temperature −18 C)121 in water,
connected to interior refrigeration walls of a commercial
freezer were tested. These PCM panels resulted in a lesser
rate of temperature fluctuations in the freezer. Eutectic
salt hydrates in air conditioning systems improved the effi-
ciency of operation by reducing the capacity of coolant
media and the power of refrigeration equipment by 30% to
50%.15 An air conditioning system generally needs the
coolant media which operates between 4 and 20 C. Effect
of different coolant media like chilled water, ice, and
PCMs were compared for the air conditioning system.
Efimova et al122 suggested a ternary mixture PCM having
equal mass fractions of zinc nitrate hexahydrate,
F I G U R E 5 Working principle of PCM for its application as
insulation layer from solar energy or outer environmental
temperature130
PUROHIT AND SISTLA
manganese nitrate tetrahydrate, and potassium nitrate,
which shows a melting point in between 18 and 21 C and
melting enthalpy of about 110 J/g. For these PCM mix-
tures, to reduce supercooling and phase separation issues,
manganese nitrate hexahydrate (2-3 wt%) as nucleation
agent and various thickeners (3 wt% of SiO2 or xanthan or
methylcellulose) were added thus improved the stability of
PCM up to 480 thermal cycles.29 PCMs (LiCl/H2O, LiBr/
H2O, CaCl2/H2O, and NH3/H2O) as coolant media
reduced problems like environmental pollution, low ther-
mal conductivity, large size and high installing and run-
ning cost for air conditioning system.123 Nanoparticles like
TiO2 and Al2O3124,125,126 are often added into PCMs to
increase the melting rate.
Another possible application for inorganic PCMs is a
solar cooker. The heat source for the solar cooker is solar
radiation energy. But at night, due to the nonavailability of
solar energy, the use of solar cookers is restricted. To over-
come such a problem, PCMs having a melting temperature
between 105 and 110 C can be applied.7 During the day-
time, they store heat from the sun and will be discharged
during night hours. A box type solar cooker having
Mg(NO3)26H2O as a heat storage material was reported.127
Some organic PCMs used in solar cookers were reported in
the literature.128 Kazemi et al68 reported a smart
thermoregulating fabric. A mixture having Na2SO410H2O,
a saturated solution of sodium dodecyl sulfate, nano mont-
morillonite was coated on a fabric with the help of silicone
rubber (to hold PCM). Stable crystal formation of
Na2SO410H2O even after 2 months was reported. Textile
physical properties were not changed significantly and this
fabric may serve as a smart thermal insulator.
7 | C ON C L U S I ON
A wide range of salt hydrates, with suitable properties and
desired phase transition temperature, are readily available
in the commercial market. Salt hydrates are economical to
use, have high latent heat of fusion per unit volume, higher
thermal conductivity, nonflammable and have very small
changes in volume during phase change. These can be used
in the form of a melt, eutectic mixtures or in the form of sat-
urated salt solution. Salt hydrates such as calcium chloride
hexahydrate (CaCl26H2O), SAT (CH3COONa3H2O), and
sodium sulfate decahydrate (Na2SO410H2O) were mostly
studied among other salt hydrates for TES applications.
During the thermal cycles, they exchange heat energy dur-
ing dehydration and hydration of the salt hydrates. The
main drawbacks of these materials include phase segrega-
tion, supercooling, incongruent melting, and corrosiveness
to most metal/storage containers. The supercooling
21 of 26
behavior of salt hydrates is due to its weak nucleation prop-
erties. It has been suggested that various nucleation agents
added in small quantity to suppress the supercooling effects
of salt hydrates during freezing. Borax (Na2[B4O5(OH)4]
8H2O) and sodium pyrophosphate decahydrate
(Na2P2O710H2O) were most commonly suggested nucleat-
ing agent. Apart from the addition of nucleating agents,
extra water addition, and soft stirring to PCM were also
suggested. To reduce the phase segregation, the salt crystals
are proposed to be in suspension within the solution. Com-
mon methods used were the addition of thickener, PCM
encapsulation, use of porous material and appropriate
rolling exchanger. Common thickeners used were carboxyl
methyl cellulose, SAP, gelatin, and so on which reduced the
settling of hydrated salts during thermal cycling.
Appropriate salt hydrates to be suggested for PCM must
have an optimized amount of nucleating agent, thickener
within them. Suitable packaging or containers for salt
hydrate PCM are also important to reduce the problem of
leakage and water evaporation. Again, by adding corrosion
inhibitors or using suitable containers, the effect of corro-
sion on PCM containers can be eliminated. Stainless steel
and various plastic containers will be suitable for long term
storage of most salt hydrate PCM. Although many modifi-
cations have been required to make the salt hydrates appli-
cable as PCM, they can be highly economical and provide
more efficiency to TES systems. Applications of salt
hydrates were far lagging behind organic PCMs. The indus-
try is strongly in search of efficient thickening and nucleat-
ing agents to overcome problems faced during hydration/
dehydration of salt hydrates, for enhancement of thermal
conductivity, and heat storage capacity.
ORCID
B. K. Purohit https://orcid.org/0000-0001-8199-0939
NOMENCLATURES
AB  nH2O/ salt hydrate
AB  mH2O/
AB  pH2O
Cp,average/ average/individual specific heat of
Cp,medium the medium
Cp,liquid phase/Cp,- specific heat of the liquid/solid phase
solid phase medium
m mass of the PCM medium
M/N/MN reactant/product
Q (i) heat energy stored/discharged
T1/T2/Tm initial/final/phase transition
temperature
ΔH latent heat of material
22 of 26
A C K N O WL E D G M E N T
The authors are grateful to Rajiv Gandhi Institute of
Petroleum Technology (RGIPT), Jais, Uttar Pradesh,
India.
DATA AVAILABILITY STATEMENT
The resources, for all the data provided in this review
paper, have been allocated with reference numbers and
have available within the reference section of the paper.
ORCID
B. K. Purohit https://orcid.org/0000-0001-8199-0939
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