Renewable and Sustainable Energy Reviews 82 (2018) 2730–2742

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Review on thermal conductivity enhancement, thermal properties and T

applications of phase change materials in thermal energy storage
⁎
Yaxue Lin, Yuting Jia, Guruprasad Alva, Guiyin Fang
School of Physics, Nanjing University, Nanjing 210093, China

A R T I C L E I N F O A B S T R A C T

Keywords: In recent years, energy conservation and environmental protection have become most important issues for
Thermal energy storage humanity. Phase change materials (PCMs) for thermal energy storage can solve the issues of energy and en-
Phase change materials (PCMs) vironment to a certain extent, as PCMs can increase the efficiency and sustainability of energy. PCMs possess
Thermal conductivity enhancement large latent heat, and they store and release energy at a constant temperature during the phase change process.
Thermal properties
Thereby PCMs have gained a wide range of applications in various fields, such as buildings, solar energy systems,
PCMs applications
power systems and military industry. However, low thermal conductivity of PCMs leads to low heat transfer rate,
thus, numerous studies have been carried out to improve thermal conductivity of PCMs. The main purpose of this
paper is to review the methods for enhancing thermal conductivity of PCMs, which include adding additives with
high thermal conductivity and encapsulating phase change materials. It is found that addition of thermal con-
ductivity enhancement fillers is a more effective method to improve thermal conductivity of PCMs, where
carbon-based material additives possess a more promising application prospect. Finally, the applications of PCMs
in solar energy system, buildings, cooling system, textiles and heat recovery system are also analyzed.

1. Introduction buildings, electric peak–shaving, solar energy systems, etc. [6–8]. In

There are many forms of energy in nature. Among these forms,
thermal energy is extensively distributed in solar radiation, geothermal
energy, etc. Thermal energy is regarded as a low–grade type of energy
and treated as waste in industrial production in general [1]. On the
other hand, solar radiation continues to supply abundant solar energy
during day time. However, large quantity of energy is often wasted. If
large amount of thermal energy can be stored and released when it is
supplied and demanded, fossil fuels consumption will be reduced,
which plays an important role in overcoming the troubles of energy
crisis and environmental pollution. Hence, thermal energy storage has
been gaining great attention and undergoing rapid development.
There are three types of thermal energy storage: latent heat, sensible
heat and reversible thermochemical reaction [2]. Among different types
of thermal energy storage, latent heat storage type plays a vital role.
Particularly, phase change materials (PCMs) absorb or release heat
from the environment by changes in phase or structure, so as to realize
the storage and release of thermal energy. Some studies [3–5] have
pointed out that the advantages of PCMs are high heat storage density,
huge latent heat storage capacity, low cost, excellent chemical stability,
etc. PCMs have a wide range applications due to continuous research,
such as industrial waste heat recovery, comfort applications in
addition, PCMs have a prominent feature that the temperature nearly
remains constant during phase change process, which can be used in
temperature control system [9].
There are many kinds of PCMs and they can be classified according
to different criteria. According to the state of substances before and
after phase change, PCMs can be divided into solid–solid PCMs, so-
lid–liquid PCMs, solid–gas PCMs and liquid–gas PCMs. At present, the
most commonly used is solid–liquid PCMs, because of their high latent
heat capacity and low volume change during phase change process as
compared with the others [3,9]. Temperature of solid–liquid PCMs rises
until the temperature reaches phase change temperature, then PCMs
absorb massive heat as latent heat storage while phase change occurs
from solid to liquid [10]. On the basis of their chemical nature, they are
classified into organic PCMs, inorganic PCMs and eutectic PCMs. Or-
ganic PCMs can be further divided into paraffin and non–paraffin [11],
where non-paraffin contains fatty acid, polybasic alcohol etc. Non-
corrosive, non-toxic, congruent melting, chemical stability, almost no
supercooling and so on are the advantages of the organic PCMs
[5,11,12]. Inorganic PCMs, which commonly refer to water, hydrated
salt, molten salt and metal or alloy [13], possess the merits of high
latent heat per unit mass, non-flammable and low cost with the same
volume as compared with organic PCMs. Eutectics are two or more

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

http://dx.doi.org/10.1016/j.rser.2017.10.002
Received 29 May 2017; Received in revised form 5 September 2017; Accepted 2 October 2017
Available online 09 October 2017
1364-0321/ © 2017 Elsevier Ltd. All rights reserved.
Y. Lin et al.
soluble ingredients mixed together, which have the feature of si-
multaneous melting and solidification without material's separation
[14]. Fig. 1 shows the classification of PCMs.
Not all PCMs can be used in practical application. The selection of
PCMs has the following requirements [9,15–17]: (1) Phase transition
temperature is within the range of practical operation. (2) High latent
heat storage capacity. (3) High thermal conductivity. (4) Stable che-
mical and thermal properties. (5) Non–toxic, non–corrosive and
harmless to environment. (6) Low cost and easily available. (7) Small
volume change. (8) No or little supercooling.
No PCMs can fully meet the above requirements. Always there are
few defects, like supercooling, phase separation, low heat transfer rate,
leakage in the molten state, instability of performance [8,18,19].
However except metallic-based PCMs, all other kinds of pure PCMs
have a common defect of low thermal conductivity. Organic PCMs have
the lowest thermal conductivity and thermal conductivity of inorganic
PCMs is slightly higher than that of organic PCMs [20]. Hence, im-
proving thermal conductivity is one of the focuses in the field of PCMs.
This paper reviews the reported studies in recent years about thermal
conductivity enhancement of PCMs by adding fillers with high thermal
conductivity and encapsulating PCMs, where the fillers mainly include
carbon-based materials and metal-based materials. Fig. 2 shows the
approaches of thermal conductivity enhancement. Furthermore, the
advantages and disadvantages of each method for improving the
thermal conductivity of PCMs are summarized and compared, with the
aim of providing the reader with a relatively systematic and detailed
awareness of them.
PCMs are applied in various fields, Khan et al. [21] reviewed PCMs
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Renewable and Sustainable Energy Reviews 82 (2018) 2730–2742
Fig. 1. The classification of PCMs.
used in solar absorption refrigeration systems, Kenisarin and Mah-
kamov [22] reviewed PCMs employed in residential buildings with
passive thermal control. As PCMs can maintain constant temperature
and store (or release) massive latent heat during the phase transition
process, they are widely employed in the field of solar energy system,
buildings, cooling system, textile and heat recovery, and the applica-
tions with PCMs in recent years will be summarized in this paper.
2. Thermal conductivity enhancement and thermal properties of
phase change materials in thermal energy storage
Thermal conductivity enhancement can increase the rate of char-
ging and discharging heat, thereby improving the efficiency of thermal
energy storage systems [23]. The ways of enhancing thermal con-
ductivity are roughly divided into two types: adding substances with
high thermal conductivity and encapsulated phase change materials,
which will be discussed in the following sections.
2.1. Adding substances with high thermal conductivity
As we know, pure PCMs suffer from deficiency of low thermal
conductivity. Therefore, there are numerous researches about adding
additives with high thermal conductivity to improve thermal con-
ductivity of PCMs. This review paper focuses on the additives of car-
bon–based materials and metal-based materials, and their thermal
conductivity parameters are listed and compared with each other.
Y. Lin et al.
2.1.1. Carbon-based materials
Carbon based materials are one of the most popular additives due to
their high thermal conductivity, stable chemical nature, extensive us-
ability and low density [24]. They have been extensively studied and
applied. Carbon based materials have a variety of morphological
structure, such as expended graphite (EG), carbon fiber (CF), graphene,
carbon nanotube (CNT) [4].
Expended graphite (EG) possesses a porous structure. Ling et al.
[25] used RT44HC and EG to formulate RT44HC/EG composite, where
RT44HC as organic PCM has phase transition temperature at 44 °C and
good latent heat capacity (above 200 kJ/kg). The composites were
formulated with 25% and 35% content of EG (mass fraction), respec-
tively. Experimental results revealed that the factors affecting thermal
conductivity include the mass fraction of EG and packing density of
composites. For the same density, the thermal conductivity of 35% EG
loading in composites is 30% greater comparing with 25% EG loading.
On the other hand, for the same mass fraction, the thermal conductivity
of composites increases with density, and is 20–60 times the thermal
conductivity of pure RT44HC corresponding to a lower density. Like-
wise, they created a model with the function that can forecast the ef-
fective thermal conductivity of EG based compound material according
to packing density and EG mass fraction at room temperature. D-
mannitol (organic material)/EG composite PCM was manufactured by
Xu et al. [26], which is dedicated to applications like solar heat storage
system or waste heat recovery system. EG plays two significant roles in
composite PCM. It is used as supporting material to prevent D-mannitol
from leaking and is also used as an additive to enhance the thermal
conductivity of composite PCM. It indicated that the D-mannitol/EG
composite PCM with a loading of 15 wt% EG and with a best
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Fig. 2. The approaches of thermal conductivity en-
hancement.
compression density of 1.83 g/cm3 has a thermal conductivity of
7.31 W/m. K, which increased by approximately 12 times compared
with the thermal conductivity of pure D-Mannitol (0.60 W/m. K). Tang
et al. [27] blended together the palmitic acid and capric acid to for-
mulate eutectic mixtures as PCM, and utilized the diatomite as sup-
porting material, further more added EG to improve the thermal con-
ductivity of composite PCM. The results showed that the thermal
conductivity of the composite PCM without EG is 0.119 W/m. K in
freezing state and 0.190 W/m. K in melting state. The thermal con-
ductivity of the composite PCM with 3 wt% and 5 wt% EG was im-
proved by 15.1% and 25.2% in freezing state, and the thermal con-
ductivity of the composite PCM with 3 wt% and 5 wt% EG was
improved by 26.3% and 53.7% in the melting state. As the latent heat of
the composite PCM reduces slightly with the increase in mass fraction
of EG, the composite PCM with 5 wt% EG is selected as the optimal one.
Carbon fiber (CF) is an inorganic fibrous carbon compound pos-
sessing thermal conductivity of 900 W/m. K along the in-plane direc-
tion [28]. Besides, features like excellent corrosion resistance and
chemical attack resistance etc., make CF compatible with a great
variety of PCMs. Nomura et al. [29] used two methods, routine
melt–dispersion and novel hot-press, to prepare a good thermally con-
ductive composite PCM and utilized the laser flash method to measure
the effective thermal conductivity of the composite PCM. Erythritol and
CF were PCM and thermal conductivity enhancement additive, re-
spectively. Experimental results indicated that the effective thermal
conductivity of composite PCM prepared by novel hot-press method is
better than that of composite PCM prepared by routine melt-dispersion
method, what is more, the novel hot-press method need less additive as
compared with melt-dispersion method. The measurement results
Y. Lin et al.
showed that the effective thermal conductivity of erythritol is 0.73 W/
m. K, and the thermal conductivity of composite PCM with approxi-
mately 25 vol% CF has a tremendous enhancement, which is approxi-
mately 30 W/m.K. In other words, the composite PCM with CF ad-
ditives for improving thermal conductivity is effective. Zhang et al. [30]
chose two types of short carbon fibers (SCFs) with diverse lengths as
fillers and erythritol as PCM, and prepared a series of composite PCMs
with different mass fraction of two types of SCFs, respectively. As the
aspect ratio of longer SCF is 25 and that of another one is 5, for the
convenience of narration, longer SCF and another one are named C25
and C5. X–ray diffractometer results showed that both types of SCFs
have almost the same structure. Furthermore, the thermal conductivity
of composite PCMs can be promoted by SCFs, and the C25 for thermal
conductivity enhancement is better than that of C5, which is proved by
experimental result: 3.91 W/m. K of 10 wt% C25 and 2.46 W/m. K of
10 wt% C5. It indicated that the geometry of SCFs have an effect on the
thermal conductivity, which have been explained by thermal resistance
theory and percolation theory in detail. Tian et al. [31] used EG and CF
with different mass ratio as thermal conductivity enhancement fillers.
The fillers were added to the form–stable phase change materials,
where paraffin was used as PCM and ethylene–vinyl acetate (EVA) was
used as supporting material. According to experimental results, the
application of EG and CF has a synergistic effect on thermal con-
ductivity improvement, and the thermal conductivity of longitudinal
orientation is lower compared to horizontal orientation.
Graphene with a single layer two-dimensional structure has gained
great attention because of its distinctive chemical and physical nature,
large aspect ratio, and outstanding thermal conductivity [32,33].
Mehrali et al. [34] used impregnation method to prepare palmitic acid
(PA)/graphene nanoplatelets (GNPs) form–stable PCM, where three
kinds of GNPs with specific surface areas of 300, 500 and 750 m2/g
were added to composite PCM samples S1,S2 and S3, respectively. In
this form–stable PCM, GNPs are not only fillers to enhance thermal
conductivity but also supporting materials to prevent PCM leakage. It
indicated that the amount of PCM absorbed by GNPs is greatly increases
with the increase in specific surface area of GNPs. Thermal conductivity
of form–stable PCM is much higher than that of pure PA, and that of S1,
S2 and S3 are 2.75/2.54, 2.43/2.17 and 2.11/1.84 W/m. K in solid/
molten state respectively, which shows that the smaller specific surface
area of GNPs is more effective on thermal conductivity compared to
bigger ones. Hence, according to the specific needs of practical appli-
cations, suitable specific surface area of GNPs can be selected. Amin
et al. [35] prepared beeswax/graphene composite PCM for thermal
energy storage in building applications. Experimental results indicated
that both thermal conductivity and latent heat are significantly en-
hanced. Initially the thermal conductivity of composite PCM rises as the
mass fraction of graphene rises, which reveals that the thermal con-
ductivity increases linearly with the mass fraction of graphene.
Nevertheless, after reaching an optimum value if the filler is added
further, because of the agglomeration of nanoparticles, the thermal
conductivity does not increase linearly. The value of thermal con-
ductivity of the composite PCM with 0.3 wt% graphene is 2.89 W/m. K,
which is about 11 times that of pure beeswax. Liu and Rao [36] com-
pared the ability of thermal conductivity enhancement of graphene
with that of exfoliated graphite sheet by preparing paraffin/graphene
and paraffin/exfoliated graphite sheet composite PCMs. According to
the experimental results, as compared with paraffin, the thermal con-
ductivity of the composite PCM with graphene of 2.0 wt% increases by
58.6% and that of with exfoliated graphite sheet of 2.0 wt% increases
by 41.4%. Thereby, it illustrates that graphene in thermal conductivity
enhancement is more effective compared with exfoliated graphite
sheet. In addition, other kinds of graphene used as thermal conductivity
enhancement additives are researched, too. Spongy graphene with a
low concentration was added into docosane by Li et al. [37], and it
indicated that both latent heat and thermal conductivity are promoted
greatly. Yang et al. [38] synthesized polyethylene/hybrid graphene
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aerogels composite PCM, which increases the thermal conductivity
from 0.31 W/m. K of pure polyethylene to 1.43 W/m. K of the com-
posite PCM, and the enhancement of thermal conductivity is about
361%. Mehrali et al. [39] used nitrogen–doped graphene as additive to
mix with palmitic acid, and found that the thermal conductivity im-
provement is over 500% at 35 °C when the mass fraction of ni-
trogen–doped graphene is 5%.
Carbon nanotubes (CNTs) have the merits of high thermal con-
ductivity, low density and large surface area–to–volume ratios, mean-
while they are composed of carbon atoms and the density is close to the
density of organic matter, which is easy to form stable mixture with
organic–based matrix [40,41]. At present, CNTs include two primary
kinds, which are single–walled carbon nanotubes (SWCNTs) and mul-
ti–walled carbon nanotubes (MWCNTs) [42,43], where MWCNT is re-
latively more frequently used. Ye et al. [44] used Na2CO3, MgO and
MWCNTs as raw materials of the composite PCMs, where Na2CO3 and
MgO were treated as PCM and supporting material, respectively. A
series of composite PCMs were prepared with the mass fraction of
MWCNTs of 0.1%, 0.2%, 0.3% and 0.5%, and their thermal con-
ductivity were determined by the thermal property analyzer. It reveals
that the thermal conductivity increases with the increase of the mass
fraction of MWCNTs, and that thermal conductivity also increases with
the increase in test temperature. From the experimental values, the
thermal conductivity of composite PCM with 0.5 wt% MWCNTs in-
creases by 69% compared with the composite PCM without MWCNTs at
120 °C. There is a similar case, Xu and Li [45] also utilized MWCTs as
additive in order to enhance thermal conductivity. Compared to par-
affin/diatomite mixtures, the thermal conductivity of paraffin/diato-
mite/MWCNTs composite PCM is greatly enhanced by MWCNTs, which
improves by 42.45%. Tao et al. [43] utilized four types of carbon na-
nomaterials as fillers in order to improve the properties of high tem-
perature salt PCM, where carbon nanomaterials were SWCNT, MWCNT,
graphene and C60. The ability to improve thermal conductivity is
sorted from large to small, which in descending order is SWCNT,
MWCNT and grapheme. However, the thermal conductivity of com-
posite PCM with C60 decreases. It reveals that the columnar structure
facilitates the effective connection of heat conduction route, hence
SWCNT and MWCNT are more beneficial on thermal conductivity im-
provement. For SWCNT and MWCNT, the thermal conductivity of the
composite PCM with the loading of 1.5 wt% improved by approxi-
mately 56.98% and 50.05%, respectively. Besides, other types of CNTs
are researched, such as grafted CNTs. Li et al. [46] grated the acidified
CNTs with three kinds of polyalcohol, then obtained three kinds of
grated CNTs with octanol, tetradecyl alcohol and stearyl alcohol re-
spectively, and the corresponding graft ratio is 11%, 32% and 38%. It is
found that CNTs grafted with polyhydric alcohols possess greater dis-
persibility than pristine CNTs. The grafted CNTs are more beneficial for
improving the thermal conductivity of paraffin than pristine CNTs, and
among three kinds of grafted CNTs, CNTs grafted with stearyl alcohol
for the thermal conductivity enhancement of paraffin is the best. Li
et al. [47] grafted CNTs with stearyl alcohol for improving the thermal
conductivity of microcapsule PCMs. It indicated that the grated CNTs
possess great dispersibility and heat conductivity in microcapsule
PCMs. The thermal conductivity of microcapsule PCM with 4 wt% CNTs
increased by 79.2%. Xiao et al. [48] prepared CNTs, oxidized CNTs and
grafted CNTs as fillers to add into palmitic acid (PA), where the grafted
CNTs was grafted on the γ –propyltrimethoxysilane on the basis of
oxidized CNTs. The thermal conductivity of composite PCMs with
CNTs, oxidized CNTs and grafted CNTs increase by 36.4%, 39.3% and
34.1% respectively compared with that of PA. Nevertheless, it should
be pointed out that the latent heat of PA/grafted CNTs is higher than
that of PA, while the latent heat of PA/CNTs and PA/oxidized CNTs are
reduced compared with that of PA.
In addition to the carbon–based additives mentioned above, there
are some other forms of carbon–based additives. Nano–graphite (NG)
was used as filler to enhance the thermal conductivity of paraffin by Li
Y. Lin et al.
[49]. The experimental results showed that NG is randomly dispersed in
paraffin and thermal conductivity of composite PCM increases with the
increase of the NG loading. The NG (10 wt%) promotes thermal con-
ductivity of paraffin from 0.1264 W/m. K to 0.9362 W/m. K, and the
latter is 7.41 times the former. Seki et al. [50] formulated binary eu-
tectic mixture containing adipic acid and sebacic acid as PCM, and
prepared the eutectics/graphite nanoplates composite PCM. It is found
that supercooling degree of eutectics can be effectively reduced and the
thermal conductivity of eutectics can be improved by graphite nano-
plates. When the content of graphite nanoplates is 0.5 wt%, the thermal
conductivity of composite PCM is 0.131 W/m. K, which increases by
19% compared with eutectics. Wang et al. [51] dispersed graphite na-
noparticles into stable OP10E/water emulsion in order to remove su-
percooling degree and enhance thermal conductivity. The results in-
dicated that supercooling is almost eliminated and the thermal
conductivity is improved by 88.9% in graphite nanoparticles–dispersed
OP10E/water emulsions with the graphite loading of 2 wt%, compared
with emulsions without graphite.
In summary, carbon based materials as additives possess the ad-
vantages of high thermal conductivity, stable chemical property and
low density, etc. There is no doubt that, the high thermal conductivity
of additives is beneficial to improve the thermal conductivity of PCMs,
however, the most important factor is the aspect ratio, large aspect ratio
of additives results in good thermal conductivity enhancement. CFs,
graphene and CNTs have large aspect ratio, where CFs possess corrosion
resistance and chemical attack resistance, graphene with a special
structure of a single layer structure of two–dimension shows distinctive
chemical and physical properties. Secondly, geometry of additives also
has influence on the thermal conductivity enhancement. What is more,
different preparation techniques have influence on thermal con-
ductivity enhancement. The densities of carbon–based additives are low
(commonly less than 2.26 g/cm3) [30], which provide a great con-
venience for the practical applications that have a greater limit to the
mass of system. Various carbon–based additives for thermal con-
ductivity enhancement are listed in Table 1.
2.1.2. Metal-based materials
It is known that high thermal conductivity is a remarkable char-
acteristic of metals, and they have a strong mixing ability. Thereby,
several types of metals are also commonly used as additives for thermal
conductivity enhancement of thermal energy storage system.
Metal foam with a porous structure is composed of a metal, which
includes a great volume fraction of gas–charged pores [52]. Xiao et al.
[53] used the way of vacuum impregnation to formulate paraffin/metal
foam composite PCM, where metal foam include nickel foam and
copper foam. Measurement results revealed that the thermal con-
ductivity of paraffin with nickel foam (1.2 W/m. K) increases approxi-
mately three times compared with that of pure paraffin (0.305 W/m.
K). And 5PPI (pore per inch) copper foam promotes the thermal con-
ductivity of paraffin from 0.305 W/m. K to 4.9 W/m. K, which improves
about 15 times. Xiao et al. [54] continued to study the thermal con-
ductivity enhancement of paraffin/metal foam. They utilized pure
paraffin, nickel foam and copper foam with a variety of pore sizes and
porosities to formulate composite PCMs. Compared with pure paraffin,
thermal conductivity of paraffin/copper foam composite PCM with
porosities of 96.95%, 92.31%, 88.89% and pore size of 25PPI increases
by about 13, 31 and 44 times, respectively. While nickel foam is weaker
on thermal conductivity enhancement than copper foam, they can en-
hance thermal conductivity of pure paraffin 3, 4 and 5 times corre-
sponding to the foam porosities of 97.45%, 94.24%, 90.61% and pore
size of 25 PPI of nickel foam. It can be concluded that reducing the foam
porosity leads to an increase in thermal conductivity, and for the same
porosity, changing the size of the pore does not have any significant
influence on thermal conductivity. Thapa et al. [55] used copper foam
as filler and icosane wax as PCM to prepare composite PCM for
small–scale thermal energy storage. The thermal conductivity of
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icosane wax/copper foam composite PCM is 3.78 W/m. K, which is
much higher than that of pure icosane wax. Chen et al. [56] used
aluminum foams to increase heat transfer of paraffin wax. They studied
the temperature field and melting evolution to obtain a conclusion that
aluminum foams are able to improve heat transfer of solid–liquid PCM.
Furthermore, they found that influence of the metal foam structure on
the heat transfer in the molten state is particularly pronounced. Like-
wise, Wang et al. [57] also proved that aluminum foams are able to
enhance the heat transfer rate of paraffin by experimental study.
Metal particles are a type of metal additives which are commonly
used to promote the thermal conductivity of PCMs. Ghossein et al. [58]
took three kinds of solidification approaches (ice–water bath, room
temperature and oven solidification) to prepare three types of eicosane/
silver nanoparticles composite PCMs with various mass fraction of
silver nanoparticles. Thermal conductivities of composite PCMs are all
increased, regardless of the solidification approaches, where oven so-
lidification approach showed the highest improvement and the ice–-
water bath approach showed the lowest improvement. Likewise, the
thermal conductivity increases as the temperature rises, and when ap-
proaches the melting temperature, a sharp increase in thermal con-
ductivity appears. On the other hand, when the loading of silver na-
noparticles is more than 2 wt%, thermal conductivity of composite PCM
would firstly decrease and then rise until the loading of silver is in-
creased to 10 wt% achieving the highest value. For the same loading of
additives (10 wt%), thermal conductivity of composite PCMs obtained
by three solidification approaches is 0.8319, 0.8534 and 0.8754 W/m.
K, respectively. Oya et al. [59] observed the SEM–EDS pictures of er-
ythritol/nickel particles (NPs) composite PCM with the loading of NPs
of 14 vol%, 24 vol% and 34 vol%. It was found that 14 vol% NPs pro-
duce a few clusters and do not spread throughout the composite PCM,
while 24 vol% NPs produce a lot of clusters, 34 vol% NPs produce
bigger clusters and percolation clusters, which revealed that the for-
mation of percolation clusters is attributed to thermal conductivity
enhancement of the composite PCM. As the loading of NPs is 17 vol%,
thermal conductivity of composite PCM is 290% higher than that of
pure erythritol, whose values were similar to that of spherical graphite.
There are other metal particles used as additives, like copper particles.
Cui et al. [60] found that the content of copper nanoparticles of 0.5 wt
% added into sodium acetate trihydrate would increase the thermal
conductivity from 0.777 to 0.936 W/m. K, which is increased by 20.5%.
Meanwhile, the heat transfer rate was improved by 20%.
It is known that metals are easily oxidized into metal oxides.
Thermal conductivity of metal oxide is lower than that of metal, but
much higher than that of most PCMs, thereby, metal oxides are also
used as thermal conductivity enhancement additives. Sahan et al. [61]
formulated paraffin–nanomagnetite composites consisted of paraffin
and Fe3O4 by a dispersion technique. The thermal conductivity was
measured by “DICO” approach, whose results indicated that the
thermal conductivity of paraffin–nanomagnetite composites with 10 wt
% and 20 wt% Fe3O4 content is improved by 48% and 60%, respec-
tively. SiO2, Al2O3, Fe2O3, ZnO and their mixtures were incorporated
into paraffin by direct–synthesis approach [62] to enhance thermal
conductivity of PCM. All kinds of additives are able to enhance thermal
conductivity of paraffin. Thermal conductivity can be improved sig-
nificantly when the content of additives increases. For the loading of
2 wt%, the composite PCM with the mixtures of additives showed the
highest thermal conductivity (0.724 W/m. K). For the loading of 4 and
6 wt%, the composite PCM with Al2O3 showed the greatest thermal
conductivity (0.919 W/m. K). And for the loading of 8 wt%, the com-
posite PCM with Fe2O3 in thermal conductivity is slightly higher than
that with Al2O3. It can be said that Al2O3 is the optimal nanoparticle in
this research. Other studies on Al2O3 are listed here: Al2O3 were added
into paraffin (10 wt%), lauric–myristic–stearic acid eutectics/expanded
vermiculite composites, PEG/SiO2 (12.6 wt%) and myristic acid/high
density polyethylene composites, and they possess thermal conductivity
of 0.259, 0.671, 0.435 and 0.3972 W/m. K, respectively, which is
Y. Lin et al. Renewable and Sustainable Energy Reviews 82 (2018) 2730–2742

Table 1
Comparison of thermal conductivity with different carbon material additives.

PCM Thermal conductivity of Carbon material Thermal conductivity of Fraction of Thermal conductivity of Magnification
PCM kp (W/m. K) additive additive ka (W/m. K) additive composite PCM kc (W/m.
K)

RT44HC [25] 0.22 Expended graphite 129 25 wt% – 20–60 times (depend on
its packing density)
D–Mannitol [26] 0.60 Expended graphite – 15 wt% 7.31 (1.83 g/cm )3
12 times
Fatty acid eutectics [27] 0.119/0.190 (solid/ Expended graphite – 5 wt% 0.149/0.292 (solid/liquid) 1.25/1.54 times (solid/
liquid) liquid)
Erythritol [29] 0.73 Carbon fiber 900 About 25 vol 30 41times
%
Erythritol [30] 0.77 Short carbon fiber 900 10 wt% 3.92/2.46 (long SCF/ SCF) 5.1/3.2 times (long SCF/
(SCF) SCF)
Palmitic acid [34] 0.29/0.21 (solid/liquid) Graphene Parallel to surface: 3000 5 wt% 2.75/2.54 (solid/liquid) 10 times
nanoplatelets Perpendicular to surface:6 (300 m2/g)
Beeswax [35] 0.25 Graphene Parallel to surface: 3000 0.3 wt% 2.89 11.56 times
nanoplatelets Perpendicular to surface:6
Paraffin [36] – Graphene 3000–5000 2.0 wt% 0.46 58.6%
Paraffin [36] – Exfoliated graphite 300–400 2.0 wt% 0.41 41.4%
sheet
N-eicosane [23] 0.22 Cabon nanotube 2000–6000 1 wt% 0.32 1.45 times
Binary carbonate eutectic – SWCNT – 1.5 wt% – 56.98%
salts [43]
Binary carbonate eutectic – MWCNT – 1.5 wt% – 50.05%
salts [43]
Binary carbonate eutectic – Graphene – 1.5 wt% – 26.11%
salts [43]
Na2CO3/MgO [44] 0.881 MWCNTs – 0.5 wt% 1.489 (120 °C) 1.69 times
Paraffin [46] 0.2312 Grafted CNTs – 4 wt% 0.7903 3.42 times
Palmitic acid [48] 0.214 CNTs – 1 wt% 0.292 1.36 times
Palmitic acid [48] 0.214 Oxidized CNTs – 1 wt% 0.298 1.39 times
Palmitic acid [48] 0.214 Grafted CNTs – 1 wt% 0.287 1.34 times
Paraffin [49] 0.1264 Nano-graphite – 10 wt% 0.9362 7.41 times
Eutectic mixture (adipic 0.110 Graphite – 0.5 wt% 0.131 1.19 times
acid and sebacic acid) nanoplates
[50]
OP10E/water emulsions 0.306 Graphite – 4 wt% 0.648 2.12 times
[51] nanoparticles

31.47%, 37.5%, 20.80% and 94.90% higher than that of composite porous structure and large aspect ratio, and metal foam has a smaller
PCM without Al2O3 [63–66]. density, hence, it has a better prospect employed as additive. However,
There are other forms of metal–based material additives. For in- common defects of metal–based materials, like high density, inferior
stance, silver nanowire was used as thermal conductivity improvement chemical stability and thermal stability, also need to be considered.
additive to formulate the form–stable composite PCMs consisting of Besides, when metal particles are used as additives, it is also necessary
polyethylene glycol (PEG), expanded vermiculite (EVM) and silver to consider whether their dispersion is uniform.
nanowire (Ag NW) [67]. When the composite PCMs contain the Ag NW
of 7.1 wt%, 13.7 wt% and 19.3 wt%, thermal conductivity is 0.36, 0.51
2.1.3. Other materials
and 0.68 W/m. K, which is 6.0 times, 8.5 times and 11.3 times that of
In addition to carbon-based material and metal–based material ad-
pure PEG (0.06 W/m. K) and is 1.44 times, 2.04 times and 2.71 times
ditives, some other additives such as boron nitride and silica are em-
that of PEG/EVM composite PCMs (0.25 W/m. K). It indicated that both
ployed to improve thermal conductivity of PCMs as well. Hexagonal
EVM and Ag NW are beneficial for enhancing the thermal conductivity
boron nitride (HBN) was employed to promote thermal conductivity of
of PEG. Reyes et al. [68] made 8% w/w of aluminum foils mixed with
n-octadecane and stearic acid eutectics PCM by Su et al. [70]. The
paraffin wax, where aluminum foil consists of three configurations.
measurement results revealed that HBN improves thermal conductivity
Experimental results showed that all configurations of aluminum foils
of eutectics. By analyzing the results, the composite PCM with 10 wt%
have positive effects on thermal conductivity enhancement, where
HBN was identified as the optimal one and thermal conductivity of
paraffin wax with aluminum in horizontal perforated disks configura-
composite PCM was 0.3220 W/m. K in solid state and 0.1764 W/m. K in
tion possesses the highest thermal conductivity (0.63 W/m. K), which is
liquid state. That is to say, compared with pristine eutectics (0.2982
about two times that of pure paraffin wax (0.31 W/m. K). Li et al. [69]
and 0.1512 W/m. K in solid and liquid state respectively), the thermal
researched the PCM with aluminum powder inside a sphere. By ob-
conductivity is increased by 8.0% and 16.7% in solid and liquid state
serving the shortening of the melting and solidification time, it can be
respectively. This reveals that the HBN is more effective in enhancing
proved that the aluminum powder can improve thermal conductivity of
the thermal conductivity of the molten state. Fang et al. [71] prepared
PCM. Furthermore, as compared with uniformly diffused aluminum
the paraffin/hexagonal boron nitride (h–BN) nanosheets composite
powder, deposition of aluminum powder is more effective on the
PCM, where the h–BN nanosheets was used as fillers with loadings of 0,
thermal conductivity enhancement of the sphere during melting.
1, 2, 5 and 10 wt%. It can be determined by experimental results that
Thermal conductivity enhancement of multiform metal–based ad-
temperature has a significant effect on thermal conductivity in solid
ditives is listed in Table 2, which indicates that metal–based materials
state and has little effect on that in liquid state. The more h–BN is
are excellent additives in term of improving thermal conductivity of
added, the higher thermal conductivity will be achieved, and the op-
PCMs. Compared with other metal–based materials, metal foam has a
timum enhancement is approximately 60% when the composite PCM
better effect on improving thermal conductivity of PCMs due to its
contains the largest loading of h–BN nanosheets of 10 wt%. And the

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Table 2
Comparison of thermal conductivity with different metal material additives.

PCM Thermal conductivity of Metal material additive Thermal conductivity of Fraction of Thermal conductivity of Magnification
PCM kp (W/m. K) additive ka (W/m. K) additive composite PCM kc (W/m. K)

Paraffin [53] 0.305 Nickel foam (foam 91.4 – 1.2 3.93 times
porosities > 95%)
Paraffin [53] 0.305 Copper foam (foam 398.0 – 4.9 16.06 times
porosities > 95%)
Paraffin [54] 0.354 Nickel foam (foam porosities: 91.4 – 2.33 6.58 times
90.61%)
Paraffin [54] 0.354 Copper foam (foam 398.0 – 16.01 45.23 times
porosities: 88.89%)
Icosane wax [55] 0.20 Copper foam – 7 vol% 3.78 18.9 times
Paraffin [57] 0.21/0.29 (liquid/solid) Aluminum foam 218 – 46.04/46.12 (liquid/solid) 218 times
Sodium acetate 0.777 (30 ℃ ) Copper nanoparticles – 0.5 wt% 0.936 1.20 times
trihydrate [60]
Paraffin [61] 0.25 Fe3O4 9.7 20 wt% 0.40 1.6 times
Paraffin [62] 0.418 Al2O3 41.1 4 wt% 0.919 2.199 times
Paraffin [62] 0.418 Fe2O3 6.4 8 wt% 1.020 2.44 times
Polyethylene glycol 0.06 Silver nanowire 429 19.3 wt% 0.68 11.3 times
[67]

value of the highest thermal conductivity of composite PCM with 10 wt
% fillers is 0.53 W/m. K at 50 °C. What is more, the phase transition rate
is accelerated due to thermal conductivity enhancement. Motahar et al.
[72] dispersed the mesoporous silica (MPSiO2) into n-octadecane,
aiming to formulate a kind of new composite PCM, whose content of
MPSiO2 is 1 wt%, 3 wt% and 5 wt%, respectively. Both in solidifying
and melting state, thermal conductivity of composite PCM was de-
termined via transient plane source technique between 5–55 °C. In so-
lidifying state, thermal conductivity of composite PCM drops from 5 to
20 °C, and the thermal conductivity increases by 5.1% at 5 °C compared
with pure PCM when the loading of MPSiO2 is 3 wt%. In melting state,
thermal conductivity is inversely proportional to the temperature and is
proportional to the MPSiO2 content, moreover, at 55 °C and MPSiO2
loading of 5 wt%, the thermal conductivity enhances by 5.5%.
2.1.4. Comparison of the additives with different materials
Carbon–based and metal–based additives are two main additives
used to enhance the thermal conductivity of PCMs. For carbon–based
additives, they are characterized by manifold allotropes with high
thermal conductivity, stable thermal and chemical properties, low
density and good compatibility. However, in case of some carbon–based
additives like carbon fibers, preparation and processing have a few
challenges. Metal–based additives are very beneficial for thermal con-
ductivity enhancement. Nevertheless, they are subject to many re-
strictions in practical applications such as: (1) most of them have high
density, (2) they cannot be easily dispersed uniformly which results in
unstable heat transfer, (3) their chemical natures are lively, leading
them to being highly reactive with other substances. Hence, carbon–-
based additives possess better application prospects. For other material
additives, the current researches are still relatively less, and the more
materials and their properties are expected to be further developed.
2.2. Encapsulated phase change material
The encapsulated phase change material (EPCM) is also referred to
as microencapsulated phase change material (MPCM), and is made up
of core and shell by emulsion polymerization, interfacial polymeriza-
tion, mini-emulsion polymerization and other methods. The PCM and
the polymer (or inorganic material) is utilized as core and shell, re-
spectively. EPCM has a remarkable ability to enhance thermal con-
ductivity of PCM [9,73]. Thermal conductivity enhancement of various
encapsulated phase change materials is listed in Table 3.
Possessing a relatively high thermal conductivity is one of the rea-
sons why inorganic materials are often employed as shells for EPCMs.
Yu et al. [74] utilized a self–assembly method to fabricate the EPCM
consisting n-octadecane core and calcium carbonate (CaCO3) shell. The
CaCl2 is a CaCO3 precursor used to form a CaCO3 shell. The CaCO3 is
used as the shell to enhance thermal conductivity and increase the
servicing life. The experimental results showed that thermal con-
ductivity of EPCM increases as the mass fraction of CaCO3 shell in-
creases, where the smallest value of thermal conductivity of EPCM
(1.264 W/m. K) is much higher than that of pure n-cotadecane
(0.153 W/m. K). It is indicated that the n-cotadecane encapsulated with
a thicker CaCO3 shell reaches a better thermal conductivity, due to
continuous phase acting like a fictitious thermal transfer meshwork
created by CaCO3, increasing the thermal transfer rate of the entire
microcapsules. Similarly, Wang et al. [75] also employed CaCO3 as
shell, while paraffin–based binary mixtures (RT 28 and RT 42) were
used as core. For the binary cores weight ratios of RT 28 to RT 42 of
10:0, 5:5 and 0:10, thermal conductivity of the EPCM is 0.759, 0.739
and 0.936 W/m. K respectively when the CaCl2/paraffin weight ratio is
1/1, and thermal conductivity of the EPCM is 0.714, 0.701 and
0.817 W/m. K when the CaCl2/paraffin weight ratio is 1/2, where the
CaCl2 is a CaCO3 precursor used to form a CaCO3 shell. Thermal con-
ductivity of the EPCM are about 2–3 times that of pure RT 28 (0.289 W/
m. K) and RT 42 (0.388 W/m. K), which indicated that CaCO3 shell has
an outstanding effect on thermal conductivity enhancement. Mean-
while, it is found that the more content of CaCO3 results in the better
enhancement of thermal conductivity. A kind of EPCM consisting of n-
octadecane core and inorganic silica shell was fabricated by using a
sol–gel method [76]. Thermal conductivity was determined by thermal
conductivity apparatus at an ordinary temperature. It is found that the
mass fraction increase of silica leads to the improvement of thermal
conductivity of EPCM. When noctadecane/TEOS weight ratio increases
from 50/50 to 70/30, thermal conductivity of EPCM corresponds to
0.6213 and 0.4568 W/m. K at pH 2.45 and room temperature, where
the TEOS is the precursor of silica. Nevertheless, no matter which
EPCM, their thermal conductivity are higher than that of pure n–octa-
decane (0.1505 W/m. K). Zirconia was employed as shell by Zhang
et al. [77] to encapsulate n–dodecane core, and the in–situ poly-
condensation method was utilized to synthesize the EPCM. The zirconia
shell plays an outstanding role in promoting thermal conductivity, and
thermal conductivity of pristine n–dodecane is enhanced from
0.152 W/m. K to 0.906 W/m. K, which is increased by about 5 times.
Furthermore, thermal conductivity improvement of n–dodecane has an
inhibitory effect on supercooling degree. Peng et al. [78] synthesized
EPCM with montmorillonite as shell and stearic acid as core. It can be
confirmed that the montmorillonite shell has the capacity to promote
thermal conductivity by measuring heat storage rate.
In order to further increase thermal conductivity, the EPCMs with

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Table 3
Comparison of thermal conductivity with various encapsulated phase change materials.
Core (PCM) Thermal conductivity of Shell
PCM kp (W/m. K)
n–octadecane [71] 0.153 (solid) CaCO3
n–octadecane [73] 0.1505 Silica
n–octadecane [74] 0.152 Zirconia
RT 42 [76] 0.369 CaCO3
Paraffin [77] About 0.265 Silica
RT 21 [78] 0.15 Polymethyl
methacrylate
inorganic material shells are further optimized. Wang et al. [79] pre-
pared EPCM used paraffin (RT42) as core and CaCO3 as shell, which
was blended with EG, and then the mixtures were pressed by 10 kN. It
should be illustrated that surface tension and pressure occur between
EPCM and EG instead of any chemical reaction. The porosity of mixture
blocks, the loading and the connection state of EG have direct influ-
ences on thermal conductivity of the mixtures consisted of EPCM and
EG. According to the experimental results, it is observed that when the
mixture contains EG loading of 24 wt%, it will build a more compact
carbon network structure, and thermal conductivity of the mixture with
24 wt% EG is 24 times that of RT42. Graphene oxide (GO) was grafted
on the EPCM with paraffin core and silica shell [80]. The values of the
experiment revealed that thermal conductivity of EPCM is 1.031 W/m.
K which is much higher than that of pure paraffin, and thermal con-
ductivity has been further improved as the EPCM is grafted with GO,
the value is 1.162 W/m.K.
Polymers are also common materials employed as shells of EPCMs,
however, due to their low thermal conductivity, polymers are usually
modified to improve thermal conductivity. Al–Shannaq et al. [81] used
RT21 as core and polymethyl methacrylate (PMMA) as shell to syn-
thesize EPCM, then the EPCM was coated with silver, aiming to pro-
mote thermal conductivity. It is focused on the impact of two aspects on
improving thermal conductivity, diverse particle size and diverse silver
coating coverage of coated EPCM. The conclusions are as follows: (1)
the apparent thermal conductivity will reduce when the size of non–-
coated EPCM decreases, (2) the apparent thermal conductivity of
coated EPCM increase with the increase of particle size, especially when
the diameter is more than 9.4 µm, the apparent thermal conductivity
improvement of coated EPCM is outstanding, (3) the apparent thermal
conductivity of all EPCM increases with the increase in the concentra-
tion of silver nitrate, but the degree of the increase is different. For the
EPCM with different diameter, the larger the diameter is, the more
obvious the thermal conductivity increases with the concentration of
silver nitrate. For the EPCM with the same diameter, thermal con-
ductivity increases rapidly when the concentration of silver nitrate in-
creases from 10 g/L to 20 g/L, and the enhancement rate of thermal
conductivity is greatly reduced when concentration increases from
20 g/L to 30 g/L, which is related to the coverage of the silver coating
on the EPCM surface. Jiang et al. [82] used emulsion polymerization
method to prepare EPCM with paraffin wax core and poly (methyl
methacrylate–co–methyl acrylate) shell and modified it by embedding
nano alumina in the shell. As expected, thermal conductivity of EPCM
increases with the increase of nano alumina content, however, adding
too much nano alumina will result in a significant reduction in phase
change enthalpy. Finally, the EPCM with 16% mass ratio of nano alu-
mina was selected as the optimal one, whose thermal conductivity is
0.3104 W/m. K, and is 1.271 times that of EPCM without nano alumina.
Fu et al. [83] synthesized a kind of nano EPCM (NEPCM), where core is
n–tetradecane and shell is polystyrene grafted with silica. The NEPCM
was dispersed into base fluid and a new kind of NEPCM slurry was
synthetized in order to store cold energy. It is found that thermal
Renewable and Sustainable Energy Reviews 82 (2018) 2730–2742
Thermal conductivity of Encapsulation Thermal conductivity of Magnification
shell ka (W/m. K) efficiency (%) encapsulated PCM kc (W/m. K)
2.467 40.04 1.264 8.26 times
1.296 57.7 0.6213 4.13 times
2.560 64.52 0.906 5.96 times
– – 0.814 2.21 times
8.855 (with 24 wt% EG) 24 times
– 50.8 1.031 3.89 times
49.6 1.162 (graft with graphene 4.38 times
oxide)
0.192 – 0.189 1.26 times
2.41 (coated with silver) 16 times
conductivity of slurry enhances as the temperature rises and the re-
quired mass fraction of NEPCM reduces. Thermal conductivity values of
1 wt%, 3 wt%, 5 wt% NEPCM slurry with silica and 5 wt% NEPCM
slurry without silica is 0.4341, 0.4128, 0.4035 and 0.3721 W/m. K,
respectively, at 5 °C. It is revealed that the shell of NEPCM grafted with
silica helps to increase thermal conductivity of the slurry. A type of
EPCM with n–octadecane core and polymethylmethacrylate shell added
into silicon nitride powders was fabricated by Yang et al. [84]. It is
found that adding silicon nitride powders has an excellent effect on
increasing thermal conductivity and has little effect on latent heat. The
thermal conductivity of EPCM with 10 g silicon nitride is 0.3630 W/m.
K, increasing by 56.8% compared with the pure EPCM.
2.3. Comparison of two ways for improving thermal conductivity of PCMs
Adding additives with high thermal conductivity into PCM for en-
hancing thermal conductivity is an effective method. Generally
speaking, supporting materials like high–density polyethylene were
employed to improve the stability of the PCM and prevent leakage
during melting process, but for the additives of pore structure, such as
expended graphite and metal foam, they enable to adsorb PCM well, in
other words, they can also play a supporting role in composite PCM.
There are many types of additives to improve thermal conductivity of
PCMs, and most of them are carbon–based and metal–based materials,
where the carbon–based additives possess outstanding properties like
low density, excellent stability and so on, thereby they are applied
extensively. Moreover, with the development of nanotechnology, na-
no–additives have a considerable application prospects. Nevertheless,
there are some problems brought about by additives, which cannot be
ignored. Firstly, it is difficult to ensure that the additive is uniformly
distributed in the PCM, and long–term operation results in undesirable
consequences such as aggregation and precipitation, so as to reduce the
thermal conductivity and deteriorate the temperature uniformity of the
thermal energy storage system. Secondly, the additives increase the
weight of the PCM, especially certain denser additives, which are lim-
ited in applications. What is more, additives will decrease the latent
heat storage capacity in general.
The PCM is encapsulated in a spherical capsule, which separates the
PCM from the external environment, and solves the problems of
leakage, phase separation and corrosiveness. That not only prolongs the
use period of the PCM, but also increases the thermal contact area of the
PCM, improving heat transfer rate of thermal energy storage system. In
addition, the capsule shell is able to control the volume change of PCM
greatly during the phase transition process, greatly improving appli-
cation performance of EPCM.
Besides, some shell materials like organic polymer shells, suffer
from low thermal conductivity, so it needs to be modified with ad-
ditives of high thermal conductivity, such as grafted with graphene
oxide [80], and coated with metal silver [81], in order to further pro-
mote thermal conductivity of EPCM. In other words, the two methods of
improving thermal conductivity can also be combined to achieve the
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goal of thermal conductivity enhancement.
3. Applications of PCMs in thermal energy storage
For the goal of environmental protection and energy conservation,
new renewable energy sources have been developed and utilized, such
as solar energy, wind energy. However, these renewable energy sources
are intermittent and fluctuant. PCMs can bridge the gap between en-
ergy supply and demand, thus the shortcomings of renewable energy
can be overcome. In addition, PCMs can maintain constant temperature
during the phase transition process, making them widely employed in
the field of solar energy, building, textile, industrial heat recovery, etc.
3.1. PCMs in solar energy system
Solar radiation is regarded as being rich in renewable energy, but it
only exists during clear days. PCMs can store solar energy during day
and supply at night, overcast and rainy days, so they are utilized ex-
tensively in solar energy system [85]. There are two popular types of
solar energy system, namely solar water heating system and solar
thermal power generation system, respectively.
3.1.1. Solar water heating system
Solar water heating (SWH) system is a kind of environmental pro-
tection and energy saving facility. Nevertheless, the conventional SWH
suffers from inefficiency in cold weather, severe heat losses at night and
inability to efficiently capture solar energy, leading to the low utiliza-
tion rate, etc. The PCMs can solve these problems to a certain extent
[86].
Narayanan et al. [87] prepared nanocomposite PCM with eutectic
gel PCM (paraffin and oleic acid) and 0.5 wt% nanographite supporting
material, which is applied to SWH. The SWH system mainly contains
three parts: a solar collector unit, a thermal energy storage unit with
nanocomposite PCM and a water storage tank with heat insulation. The
consequences of the solar illumination experiment indicated that the
melting of nanocomposite PCM with 0.5 wt% nanographite needs only
3 min, which decreases by 93% compared with that of eutectic gel PCM
(45 min). Furthermore, compared with the melting rate of conventional
heating route, melting rate of solar illumination is much faster. The
merits of nanocomposite PCM that can be listed are significant solar
energy capture capability, efficient light to heat conversion, high
thermal conductivity, ultra–fast thermal storage and high heat transfer
rate, which result in improving the overall efficiency of SWH system. Su
et al. [88] formulated microencapsulated PCM (MPCM) for SHW sto-
rage system, where the core is paraffin wax and the shell is melami-
ne–formaldehyde resins. It is found that the type of emulsifier employed
for formulating MPCM has an influence on the morphology of MPCM,
and a high enthalpy of 126 kJ/kg can be achieved. The thermal prop-
erties of MPCM with the highest enthalpy were assessed by theoretical
evaluation in an integrated compacted bed unit. And the results re-
vealed that the SWH system with MPCM has larger thermal energy
storage density and correspondingly less physical storage dimension
than water–based system. Compared with the water–based system, the
thermal conductivity of the MPCM is a little lower, but it still is about
two times that of most common PCM storage units. Khalifa et al. [89]
studied a storage solar energy collector for SHW, which is made up of
the paraffin wax as PCM heat storage media and six copper pipes with
80 mm diameter linked to a string. Clear and semi–cloudy days in
January, February and March were chosen to carry out outdoor ex-
periments. It is noticed that the change of the temperature between the
system with PCM and the system without PCM is different, where the
temperature of the system with PCM increases from the entrance to
2.5 m length, and that of remaining 7.6 m length almost remains con-
stant. During the absence or lack of sunshine, the system is cooled down
and the liquid PCM becomes a heat source to transfer heat to circulating
water until it is completely frozen.
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Renewable and Sustainable Energy Reviews 82 (2018) 2730–2742
3.1.2. Solar thermal power generation system
In a solar power tower, linear Fresnel reflectors or parabolic trough
collectors of a concentrated solar thermal power (CSP) can be utilized
to collect sunlight and produce strong heat, and then the heat transfer
fluid will transport it to thermal power plant aiming at power genera-
tion [90]. Due to the large latent heat storage capacity of PCMs, the CPS
which combines with PCMs is the most effective approach to provide
flexible power to the grid and provide large–scale power services [91].
A solar thermal power plant located in Shiraz, Iran, whose ther-
modynamic properties including energy and exergy were studied by
Mahfuz et al. [92]. The properties of the solar thermal power plant with
PCM storage were analyzed based on second law of thermodynamics.
The performances of PCM storage system integrated with solar power
plant were investigated [93]. The results of analysis indicated that the
overall efficiency of energy and exergy of the system without PCM is
30% and 10% respectively, however, after adding PCM into solar col-
lector, the overall efficiency of exergy increased to 30%, due to the high
latent heat storage capacity of the PCM. What is more, the higher
melting point temperature of the PCM leads to higher efficiency of
exergy. Bhagat and Saha [94] investigated an organic Rankine cycle–-
based solar thermal power plant with the packed bed containing EPCM.
Five factors were studied, which were mass flow rate, entrance charging
temperature, storage system size, EPCM shell diameter and porosity.
The results of analysis indicated that the increases in mass flow rate and
entrance charging temperature lead to the improvement in the thermal
property during storage and recovery process. And the fluctuation in
heat transfer fluid (HTF) temperature at the storage exit decreases as
the EPCM shell diameter decreases. The storage system size and por-
osity have little influence on the efficiency of the system, however they
will enlarge the fluctuation in HTF temperature.
3.2. PCMs in buildings
With the continuous improvement of living standards, the demand
for thermal comfort inside buildings is increasing, resulting in more and
more energy consumption, especially in the summer and winter.
Integrating PCM into buildings not only decreases energy consumption,
but also improves the thermal comfort of buildings. Thereby, wall-
boards, floors, concrete, gypsum and other parts are integrated with
PCMs in order to improve their performance [85,95].
Sharifi et al. [96] assessed the efficiency of the gypsum boards in-
tegrated with PCMs for increasing the thermal properties of buildings.
They investigated the properties of the gypsum boards with PCMs by
utilizing computational simulation of real temperature distribution in
diverse cities. It is found that the efficiency of PCMs is directly related
to the external temperature and the large temperature fluctuation
brings about low efficiency of PCMs. It can be confirmed that the
gypsum boards with PCMs have an excellent effect on energy con-
servation, and the gypsum boards can be used in both new buildings
and old buildings. It is worth noting that the efficiency is not propor-
tional to the number of PCMs. Ye et al. [97] prepared the PCM panels
consisting of CaCl2·6H2O/expanded graphite composite PCM for ap-
plication in buildings. The thermal properties of the test room with
PCM panels were compared with the reference room without PCM
panels, and they were placed in the simulated climate chamber. The
experimental results revealed that PCM panels are able to reduce the
temperature fluctuation of the test room, showing smaller range of
temperature compared with the conventional room. In addition, the
thermal performance of the test room is related to the position of PCM
panels. The simulation results are similar to the experimental one and
indicate that the best thickness of the PCM panels is between 8 mm and
10 mm. Xia and Zhang [98] developed a novel double-layer radiant
floor consisting of PCMs, which is propitious to electric peak–shaving,
due to the fact that PCMs possess the ability of storing heat or cold
energy during low–peak period. Two experimental setups were estab-
lished to study the temperature field of the double–layer radiant floor
Y. Lin et al.
system. Compared with box B in the same circumstances, the tem-
perature and temperature fluctuation of box A are lower, and the range
of temperature of box A is only 2 °C in the whole process of heat dis-
sipation. It indicated that the double-layer radiant floor can meet the
heat demand and the energy consumption reduces as the temperature
of thermal storage PCM rises during storage process. Johra and Hei-
selberg [99] pointed out in a review article that furniture has a sig-
nificant impact on the thermal performance of PCMs in building ap-
plications, but there are still too few investigations on them.
3.3. PCMs in cooling system
Cooling system is widely utilized in many fields, such as cooling
electronic equipment, food preservation and cooling buildings. The
cooling system integration with PCMs can effectively improve its per-
formance.
Krishna et al. [100] integrated heat pipe with nano enhanced PCM,
with target application in electronic cooling system. And the PCM stores
or releases thermal energy according to the input power of the eva-
porator and the fan speeds of the condenser. Three types of energy
storage materials, such as water, PCM (Tricosane) and nano enhanced
PCM (Tricosane) with nano alumina particles, were used to verify the
performance of the nano enhanced PCM. The experimental results re-
vealed that thermal conductivity of nano enhanced PCM is higher than
the pure PCM and the maximum increment is 32%. What is more,
compared with the conventional heat pipe, the heat pipe integrated
with nano enhanced PCM reduces the evaporator temperature by ap-
proximately 25.75%, leading to cutting down on 53% fan power con-
sumption. Besides, 30% energy from evaporator will be absorbed by
nano enhanced PCM, which can reduce fan power consumption as well.
For improving the comfort of human body in hot weather, Itani et al.
[101] studied a type of cooling vest with PCM. The main target is to
find the best position and number of the PCM packets in the vest, so as
to achieve the optimal cooling effect and maximize the comfort of the
human body, and the effect is determined by a synthetic fabric–PCM
and bio–heat simulation model. It indicated that the number of PCM
packets are needed by cooling vest were 8, 18 and 20 when the en-
vironmental temperature is 28 °C, 35 °C and 45 °C, respectively, which
can provide comfortable cooling for workers who work outside. In other
words, different environmental conditions require different amounts of
PCM packets. Food preservation and storage cannot be separated from
the refrigerator in daily life, Yusufoglu et al. [102] integrated PCMs into
the domestic refrigerator aiming at improving the performance. Two
types of refrigerator were employed to test the performance of four
kinds of PCMs. The results revealed that the opening and closing time of
compressor is optimized and just 0.95 kg PCMs can save up to 9.4%
energy, besides, the effect of PCM can be enhanced by enlarging the
surface area of condenser. In order to respond to the requirement of
energy saving and emission reduction, cooling systems incorporated
with PCMs have also played a great role in the field of buildings, and
Akeiber et al. [103] and Souayfane et al. [104] made reviews on it in
detail.
3.4. PCMs in textiles
The basic function of the textiles is to provide a relatively stable
ambient temperature to human body. If PCMs are integrated into the
textiles, the insulation capacity of the textiles can be greatly improved,
due to large thermal storage capacity and almost constant phase change
temperature of PCMs. Currently, the main methods of fabricating
thermally stable textiles with PCMs are infiltration of micro-
encapsulated PCMs to fibers, fabrics and foams [105]. Besides, the
PCMs with a phase change temperature range from 18 °C to 35 °C are
the most suitable for application in clothing [105].
Shaid et al. [106] prepared eicosane/aerogel microparticles as
coating additive on textiles to regulate body temperature. The test
2739
Renewable and Sustainable Energy Reviews 82 (2018) 2730–2742
results show that the textiles coated with microparticles have an ex-
cellent thermal comfort property. What is more, the microparticles
possess outstanding thermal stability, eicosane does not leak even at the
temperature that is two times higher than melting point of pure eico-
sane, hence, textiles coated with the microparticles can be employed as
high temperature exposure suits. Nejman et al. [107] investigated the
influence of different integration methods of microcapsule PCMs on the
thermal properties and air permeability of knitted fabric, where three
integration methods, printing, coating and padding were studied. It was
found that among three types of improved knitted fabrics, printed
fabrics have the strongest thermal conditioning ability and weakest air
permeability, while the case of padded fabrics is just the opposite.
Kazemi and Mortazavi [108] developed a new method to prepare PCM
without microencapsulation for textiles, where Na2SO4·10H2O was used
as PCM. Besides, nano montmorillonite as thickening and sodium tetra
borate as nucleating agent were added to maintain the thermodynamic
stability of PCM and to ensure that the thermal storage capacity does
not decrease after diverse thermal cycles. Silicone rubber with elasto-
meric structure was also added to maintain the thickness and bending
properties of the modified textiles. Nevertheless, the modified textiles
have weaker air transfer and water vapor permeability, which can be
improved by using screen printing technique. Carreira et al. [109] used
octadecane as PCM to fabricated acrylic based microcapsules by sus-
pension polymerization. It was found that the microcapsules exhibit
excellent potential for combining with the textiles, making the textiles
with heat regulating function.
3.5. PCMs in heat recovery system
Heat recovery is of great importance for energy saving and emission
reduction, however, in general there is a time–gap and geography–gap
between heat release and heat demand points. This problem can be
solved significantly by heat recovery system with PCMs, as PCMs pos-
sess an outstanding latent heat storage capacity.
Xia et al. [110] designed a heat recovery system with PCM to re-
cover heat from refrigerator condensation heat and release heat for
preparation of household or industrial hot water. The experimental
results indicated that the composite PCM containing carnauba wax
(melting point: 81.98 °C and latent heat: 150.9 J/g) and expanded
graphite (mass ratio of 10:1) possesses great potential as thermal sto-
rage medium in the heat recovery system. Jia et al. [111] compared the
performances of storage–enhanced heat recovery room air–conditioner
(SEHRAC) with PCM and without PCM, which was carried out by
control variable experiment. The results indicated that the space
cooling and water heating abilities of SEHRAC with PCM increase by
5.4% and 16.1%, respectively, compared with those of SEHRAC
without PCM, what is more, PCM greatly improves the insulation ability
of water tank of SEHRAC, the insulation time is extended by 21.1%. In
other words, the performance of SEHRAC is improved by PCM. Ber-
trand et al. [112] pointed out that the household hot water energy
consumption accounted for 16% of household heating energy con-
sumption at EU in 2013, and the proportion would be further increased.
Hence, it is vital to establish waste water heat recovery systems in
buildings, in order to reduce energy consumption. So a way was pre-
sented for determining building energy consumption and energy saving
potentials, which was based on pinch analysis, and was based on
building waste water heat recovery system of a city scale. Building
energy–saving technology for environmental protection and energy
conservation is of great significance, so heat recovery technology in
buildings has been gaining more and more attentions. Cuce and Riffat
[113] considered that heat recovery systems have great potentials to
reduce the fossil fuel consumption of buildings, resulting in saving
energy and decreasing greenhouse gas discharges in the air. Besides,
Mardiana–Idayu and Riffat [114] summarized and analyzed the tech-
nologies of heat recovery for buildings and found that the forms of heat
recovery include fixed plate, heat pipe, rotary wheel, etc.
Y. Lin et al.
PCMs are widely applied in various fields, as they possess remark-
able features, such as large latent heat, almost constant temperature
during phase change process and so on. It is worth noting that in order
to maximize the effect of the PCMs, it is necessary to select a PCM with
a suitable phase transition temperature. PCMs in solar energy systems,
recovery heat systems are mainly used for their large latent heat storage
capacity to adjust the imbalance between heat supply and demand.
PCMs in buildings, textiles and cooling systems are mainly used for
their constant phase change temperature to maintain an optimal en-
vironmental temperature. In summary, PCMs have a prominent role in
protecting environment and saving resources. They are indispensable
materials in the future trend of energy development.
4. Conclusions and outlook
Heat transfer rate is a vital factor to determine the efficiency of
thermal energy storage system, and enhancing thermal conductivity is
an effective approach to improve it. Hence, this review focuses on two
methods for improving thermal conductivity of PCMs, which include
adding fillers with high thermal conductivity and encapsulated PCMs.
The fillers mainly include carbon–based additives and metal–based
additives, namely expended graphite, carbon fiber, graphene, carbon
nanotube, metal foam, metal particles and metal oxides, etc. Both
carbon-based additives and metal–based ones possess excellent thermal
conductivity, however, carbon-based additives are better than metal-
based additives in terms of density and stability. For encapsulated
PCMs, shells prevent the PCM from damage and leakage, and also im-
prove the thermal conductivity. The applications of PCMs in solar en-
ergy system, buildings, cooling system, textiles and heat recovery
system are introduced as well. In addition to the above mentioned
methods to improve thermal conductivity of PCMs, new methods and
new materials need to be developed and investigated for meeting the
requirements of thermal energy storage applications.
Acknowledgements
This project is supported by the National Natural Science
Foundation of China (Grant no. 51376087, 51676095). The authors
also wish to thank the reviewers and editor for kindly giving revising
suggestions.
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