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Thermal conductivity enhancement on phase change materials for thermal energy

storage: A review

Shaofei Wu, Ting Yan, Zihan Kuai, Weiguo Pan

PII: S2405-8297(19)31006-2
DOI: https://doi.org/10.1016/j.ensm.2019.10.010
Reference: ENSM 953

To appear in: Energy Storage Materials

Received Date: 8 April 2019

Revised Date: 29 September 2019
Accepted Date: 10 October 2019

Please cite this article as: S. Wu, T. Yan, Z. Kuai, W. Pan, Thermal conductivity enhancement on
phase change materials for thermal energy storage: A review, Energy Storage Materials, https://
doi.org/10.1016/j.ensm.2019.10.010.

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 Thermal conductivity enhancement on phase change materials for

thermal energy storage: A review

Shaofei Wu, Ting Yan *, Zihan Kuai, Weiguo Pan*

College of Energy and Mechanical Engineering, Shanghai University of Electric Power, Shanghai 200090, China

Institute of Distributed Energy System and Energy Storage, Shanghai 200090, China

Abstract

Phase change energy storage technology, which can solve the contradiction

between the supply and demand of thermal energy and alleviate the energy crisis, has

aroused a lot of interests in recent years. Due to its high energy density, high

temperature and strong stability of energy output, PCM has been widely used in

thermal energy systems. The aim of this review is to provide an insight into the thermal

conduction mechanism of phonons in PCM and the morphology, preparation method as

well as thermal conductivity of composite PCMs. Phonon thermal conduction

mechanism is suggested to cover three forms: phonon-phonon scattering,

phonon-defect scattering and phonon-boundary scattering. Then the microcosmic

factors affecting the thermal conductivity of composite PCMs are analyzed. The

research progress of adding three-dimensional, two-dimensional, one-dimensional and

zero-dimensional structure additives to PCM is reviewed. Besides summarizing the

preparation method and microstructure, the thermal conductivity of the composite

PCMs are also analyzed from the aspect of phonon thermal conductivity mechanism.

Meanwhile, some new materials, including metal organic frameworks (MOFs),

Corresponding authors.
E-mail addresses: [email protected] (Ting Yan), [email protected] (W.G. Pan).

1
titanium dioxide foam (TDF), highly graphitized network carbon, graphene foam and

hexagonal boron nitride (HBN) nanoparticles, are proposed for the additives of heat

storage materials. Ongoing research and development studies indicate that the

challenges of the improving the thermal conductivity of PCM focus on the aspects of

clarifying the phonon scattering mechanism in PCM, increasing the number of thermal

conductivity chains and broadening the thermal transmission channels. Booming

progress illustrates that the exploration of high performance PCM is an extremely

valuable and scalable option for storing industrial waste heat and solar energy,

especially for constant temperature storage and utilization. To bring the phase change

heat storage solution into a broader market, more intensive studies in fields of phonon

thermal conductivity mechanism, development of high performance composite PCMs

and efficient and compact phase change heat storage system are still required.

Keywords: Thermal energy storage; Phase change materials (PCM); Thermal

conductivity enhancement; Morphological characterization; Mechanism analysis

2
 Thermal conductivity enhancement on phase change materials for

thermal energy storage: A review

Abstract

Phase change energy storage technology, which can solve the contradiction

between the supply and demand of thermal energy and alleviate the energy crisis, has

aroused a lot of interests in recent years. Due to its high energy density, high

temperature and strong stability of energy output, PCM has been widely used in

thermal energy systems. The aim of this review is to provide an insight into the

conduction mechanism of phonons in PCM and the morphology, preparation method

well as thermal conductivity of composite PCMs. Phonon thermal conduction

mechanism is suggested to cover three forms: phonon-phonon scattering,

phonon-defect scattering and phonon-boundary scattering. Then the microcosmic

factors affecting the thermal conductivity of composite PCMs are analyzed. The

research progress of adding three-dimensional, two-dimensional, one-dimensional and

zero-dimensional structure additives to PCM is reviewed. Besides summarizing the

preparation method and microstructure, the thermal conductivity of the composite

PCMs are also analyzed from the aspect of phonon thermal conductivity mechanism.

Meanwhile, some new materials, including metal organic frameworks (MOFs), TiO2

foam, highly graphitized network carbon, graphene foam and hexagonal boron nitride

(HBN) nanoparticles, are proposed for the additives of heat storage materials.

research and development studies indicate that the challenges of the improving the

1
thermal conductivity of PCM focus on the aspects of clarifying the phonon scattering

mechanism in PCM, increasing the number of thermal conductivity chains and

broadening the thermal transmission channels. Booming progress illustrates that the

exploration of high performance PCM is an extremely valuable and scalable option

storing industrial waste heat and solar energy, especially for constant temperature

storage and utilization. To bring the phase change heat storage solution into a broader

market, more intensive studies in fields of phonon thermal conductivity mechanism,

development of high performance composite PCMs and efficient and compact phase

change heat storage system are still required.

Keywords: Thermal energy storage; Phase change material (PCM); Thermal

conductivity enhancement; Morphological characterization; Mechanism analysis

2
Contents
1. Introduction ................................................................................................................................. 4
2. Mechanisms of thermal conductivity ........................................................................................ 6
2.1 Lattice vibration and phonon transmission ......................................................................... 7
2.1.1 Phonon–phonon interactions ................................................................................... 9
2.1.2 Phonon–defect scattering ....................................................................................... 11
2.1.3 Phonon-boundary scattering .................................................................................. 12
2.2 Factors influencing effective thermal conductivity of PCM .............................................. 13
2.2.1 Heat capacity Cv..................................................................................................... 13
2.2.2 Phonon group velocity v ......................................................................................... 14
2.2.3 Phonon mean free path l ........................................................................................ 14
3. Approaches to enhancing the thermal conductivity of PCMs and their mechanisms ......... 18
3.1 Chemical modification of matrices ................................................................................... 18
3.1.1 Doping.................................................................................................................... 18
3.1.2 Graft functional groups .......................................................................................... 22
3.2 Fabrication and characterization of composite PCMs ..................................................... 24
3.2.1 Passive composite PCMs using three-dimensional structure additives ................. 25
3.2.2 Passive composite PCMs using two-dimensional structure additives .................... 44
3.2.3 Initiative composite PCMs using one-dimensional structure additives ................. 58
3.2.4 Initiative composite PCMs using zero-dimensional structure additives................. 70
4. Conclusions and perspectives ................................................................................................... 80
Acknowledgments ......................................................................................................................... 83
References ...................................................................................................................................... 83

3
1. Introduction

Latent heat storage has allured great attention because it provides the potential to

achieve energy savings and effective utilization [1, 3]. The latent heat storage is also

known as phase change heat storage, which is accomplished by absorbing and

releasing thermal energy during phase transition. Latent heat storage has the higher

storage density than conventional sensible heat storage due to high enthalpy change in

the phase change process. Compared to the sensible heat storage systems, latent heat

storage systems require a smaller weight and volume, which brings about the

relatively lower costs. In addition, latent heat storage has the capacity to store heat of

fusion nearly isothermally which corresponds to the phase transition temperature of

the phase change material (PCM) [4]. Latent heat storage based on PCM can be

applied in various fields, such as solar heat storage, energy-saving buildings and

wasteThere
heat recycle,
are a variety
etc. of PCM to choose, but not all PCM can be used for latent

heat storage. Generally, the ideal PCM available for the latent heat storage should

have the following features:

(1) Appropriate phase transition temperature to satisfy the practical application;

(2) Large melting enthalpy to provide the high latent heat storage capacity;

(3) High thermal conductivity to achieve the faster charging and discharging

rate; (4) Stable thermal and chemical properties to ensure the persistent thermal

storage capacity;

(5) Non–toxic, non–corrosive, non–flammable and non–explosive to ensure the

safety and harmless to surroundings;

4
 (6) Small enough supercooling;

(7) Subtle volume variation during phase transition;

(8) Abundance and easily available, cheap price to ensure the low cost.

It is hard to find the PCM can fully satisfy the above requirements. There always

exist the diverse defects, such as phase separation, low heat transfer rate, supercooling,

leakage in the molten state, instability of performance. PCM mainly include organic

materials, inorganic materials and eutectic materials. The former is classified into

paraffin, fatty acids and polybasic alcohols, while the latter is divided into hydrated

molten salts and metal or alloy materials. Various PCM, which can be used for the

latent heat storage, are shown in Fig. 1. Almost all pure PCM have a common

shortcoming of low thermal conductivity except for metallic PCM [5]. Hence, thermal

conductivity enhancement is one of the main issues for the PCM in the application

of the latent heat storage. Many efforts have been made to improve the

properties of PCM. Besides, a great deal of theoretical and experimental studies were

carried out to investigate the heat transfer mechanism of various latent heat storage

systems [6]. At present, the main methods to improve the thermal conductivity of

is to add high thermal conductivity matrix and chemically treat the surface of additive.

These include modification of surfaces and grafted functional groups, and addition of

porous carbon-based materials, metal foam, mineral clays, and nanoparticles.

Modification and grafted functional groups can improve the compatibility of materials

and reduce interfacial thermal resistance, but the success rate of modification is lower

and the operation is more complicated. The addition of thermal conduction matrix can

5
form thermal conduction chain, reduce phonon scattering and accelerate heat transfer.

However, high content will significantly reduce the heat storage capacity of PCM.

Therefore, appropriate addition amount and experimental conditions should be

considered when selecting methods to improve thermal conductivity of PCM.

In this review, the microscopic mechanism of enhancing thermal conductivity on

the composite PCMs were systematically analyzed. Further, we introduce preparation,

morphological characterization and microscopic explanation of the composition PCM

added a variety of new substrates. We also emphasize that to enhance the thermal

conductivity of the composite PCMs and to solve the research problems and emphases

for the upcoming wide application are urgently needed. The contents of this review

article are shown in Fig. 2. In conclusion, we need to have a thorough understanding

of the system and apply technical knowledge to decrease the phonon scattering caused

by one or other factors, and employ appropriate techniques to enhance the thermal

conductivity of the system.

2. Mechanisms of thermal conductivity

Although many studies have been carried out in this field, the research on

thermal conductivity in PCM is relatively few from the perspective of micro

mechanism and material morphology. How to improve the thermal conductivity of

PCM is still an important research topic [7, 8]. Many factors affect the thermal

conductivity of composite PCMs, especially for phonon scattering as one important

factor limiting the thermal conductivity of composite PCMs. The study of phonons is

the most fundamental description of heat conduction at the microscopic level. In

6
addition, the phonon is the driving force responsible for transferring heat from one

end to the other. In microscale heat transfer, the key research to improve the thermal

conductivity of composite materials lies in the effective phonon transmission around

the axis point. Of course, pretending the phonon as a heat carrier can be propagated

randomly without any hindrance, it is the best way to transmit phonon, and it is very

likely to reach with desired thermal conductivity in a specific composite material. In

composites, the three main factors controlling phonon transmission are phonon

velocity, specific heat capacity and mean free path. The thermal transfer of composite

PCMs and interfacial phonons is not limited to these factors, because these factors are

also directly or indirectly affected by various factors, such as temperature, atomic

weight, density and binding energy.

The process of heat transfer is shown in Fig. 3. including: (a) heat is first

transmitted to atoms on the surface of the sample; (b) surface atoms gain vibrational

energy; (c) the heat energy of the surface atoms is then transferred to the neighboring

atoms at the same speed; (d) thermal energy is then diffused to the sample in the form

of vibration waves; (e) after diffused by heat energy in a common vibration mode or

phonon throughout the crystal; (f) when heat reaches the back of the sample, it is then

partially transferred to the surrounding environment by conduction or radiation.

2.1 Lattice vibration and phonon transmission

Heat transport can be achieved through electrons and lattice vibrations in the

solids. For the metallic PCM, heat transport is dominated by electrons. While most

inorganic nonmetallic PCM have electrons bound in their ionic crystal lattice, but free

7
electrons are few and cannot be heat conduction carriers [9]. For the nonmetallic PCM,

heat conduction mainly relies on the vibration of the crystal lattice [10]. Lattice

vibration is the main mechanism of heat conduction for these PCM. As a result, the

phonons are the dominant heat carriers in these PCM. Obviously, heat transport by

lattice vibration is addressed in this work [10-12].

The particles in the crystal vibrates near the equilibrium position even at a low

temperature. Hence, the lattice of the PCM can be regarded as a coupled mass and

spring system, as shown in Fig. 4. The vibration will deviate from the equilibrium

position when the crystal is subjected to heat. Afterward the high energy phonons are

generated and diffuses, which forms the temperature gradient. As a result, the heat

will flow from the hot end to the cold end in the presence of the temperature gradient.

Fig. 5 shows the temperature gradient between the hot end and cold end due to the

diffusion of the phonons. Thus, the heat conduction is a nonequilibrium phenomenon

[13].

As above mentioned, phonons play a pivotal role in the heat transfer of

non-metallic materials. Commonly, the stronger is phonon diffusion in a material, the

larger is its ability to heat conduction and the higher thermal conductivity. Conversely,

the phonon diffusion is obstructed in non-metallic materials, it will result in the low

thermal conductivity. Indeed, different phonon scatterings inside the non-metallic

materials is the fundamental reason for the deterioration of phonon diffusion. Phonon

scattering can shift or even reverse the direction of energy transport, and thus is the

dominating reason for the poor heat conduction in the non-metallic materials. In

8
composite materials including the PCM, the phonon scattering is primarily caused by

the mismatch between the filler-matrix and the PCM. Specifically, phonon scattering

mainly contributes to the interfacial thermal resistances and thus degrades the thermal

current. There are three types of phonon scattering: phonon-phonon scattering,

phonon-defect scattering and phonon-interface scattering [14], as shown in Fig. 6.

2.1.1 Phonon–phonon interactions

Phonons arise from lattice vibration and are quanta of lattice vibration. Phonons

have the significantly particle-like vibrational modes of a crystal and therefore can be

treated as quasi-particles. Different waves propagating all the time makes a number of

phonons taken part in the interactions. However, the phonon numbers are not

conserved due to the creation or annihilation of phonon. It is a remarkable fact that

three-phonon scattering is the most important interactions between the waves, which

determines the thermal conductivity. Furthermore, three-phonon scattering has two

fundamentally different kinds of diagrams: either two phonons interact and combine

into the third phonon, or energy is divided from one mode to two other modes.

Phonon-phonon collision can be usually classified into two types: normal process (N

process) and Umklapp process (U process) [15, 16]. Three-phonon processes obey the

following equations [17]:

Case (a):

hω1 + hω2 = hω3 (1a)

hk1 + hk2 = hk3 (1b)

Case (b):

9
 hω1 = hω2 + hω3 (2a)

hk1 = hk2 + hk3 (2b)

Case (c):

hω1 + hω2 = hω3 (3a)

hk1 + hk2 = hk3 + G (3b)

Since ħω is energy of phonon with the angular frequency ω, the first relation of

these cases represents the energy conservation. Where k is the wave vector, and G is

the reciprocal lattice vector. A phonon doesn’t have an ordinary mechanical

momentum, but ħk has some of its attributes and can be perceived as the phonon

quasi-momentum. Therefore, the equations (1b) and (2b) reflect the momentum

conservation. The N processes obey both energy and momentum conservation

whereas the U processes only conforms to the energy conservation. As depicted in Fig.

7, Case (a) and Case (b) are the N processes and Case (c) is the U process.

If there is no interaction between phonons, the thermal energy is propagated

through the perfect crystal without the defects and the thermal conductivity will be

infinite. However, the heat transfer is a random process and this random nature of the

conduction process brings the temperature gradient [18]. The thermal energy does not

simply and directly proceed in a straight path from one end to the other, but diffuses

through the crystal and undergoes the frequent collisions. Among then the average

distance traveled by a phonon between collisions is called the mean free path. At

sufficiently low temperature, lattice vibrations will be frozen at the ground state and it

is hard to be excited for the phonon. Only low frequency phonon (or long wavelength

10
acoustic modes) and small phonon number (or wave number modes) are excited. As

the probability of the collisions between phonons is very small and therefore causes

the long mean free path [19]. Moreover, phonon-boundary scattering is the dominant

mechanism that affects the improvement of thermal conductivity. For the most part,

the temperature dependence of thermal conductivity λ is dependent on the specific

heat capacity and thus is proportional to T3 where T is the absolute temperature [20].

The number of excited phonons increases with the rise of the temperature, and thus

the probability of the collisions between phonons becomes large. Meanwhile, mean

free path becomes shorter and the thermal conductivity is increased. At high

temperature, the number of phonons is proportional to T. The effect of anharmonic

coupling between different phonons limits the mean free path. While the mean free

path is proportional 1/T at high temperatures. As a result, thermal conductivity is

proportional to 1/T.

2.1.2 Phonon–defect scattering

Lattice defects could give rise to the scattering of phonons, such as: phonons are

reflected, diffracted or refracted, all of which have a negative impact on the phonon

transport. Lattice defects mainly include point defects, dislocations, vacancy defects,

impurities, etc. Phonon collisions with the defects or a crystal boundary don’t change

the energy of individual phonons. But the presence of the defects makes the mean free

path shorten and therefore leads to a lower the intrinsic thermal conductivity of the

crystal. Even if there are only small amounts of impurities in the crystal structure,

however, they can have a significant impact on the thermal conductivity. Apparently,

11
the impurities in the crystal inevitably produce the additional thermal resistance, and

thus lead to the decrease of the thermal conductivity.

2.1.3 Phonon-boundary scattering

When phonon travels across the boundaries of crystal of finite size, it gets

scattered and this affects the effective mean free path of phonon. Impact of

phonon-boundary scattering is most significant at low temperature, where the mean

free path of phonon is the longest. At room temperature and above, it can also

contribute to scattering especially in materials like very thin silicon layers [21]. In

nanostructures, when the mean free path of phonon approaches to the characteristic

scale of materials, thermal transport deviates from the Fourier law [22, 23]. Phonon

transport greatly varies when characteristic length of materials is smaller than the

mean free path of the phonon. In simpler terms, heat transfer is also a function of the

characteristic length of materials especially in nano-structures or low dimension

materials [23-25]. When phonon approaches boundary, it can lead to two types of

boundary scattering. One is specular phonon–boundary scattering where the reflection

of phonon from the boundary is specular in nature [26]. The other is diffuse and

phonon is scattered at various angles. Both of these scattering modes pose serious

bottlenecks in heat transport across interfaces. In composite PCMs, phonon scattering

is mainly attributed to the interfacial thermal resistances which arise from acoustic

mismatch at filler-matrix interface [27].

Three kinds of phonon scattering mechanisms will inevitably generate thermal

resistance in the heat transfer process of composite PCMs, but the existence of

12
scattering phenomenon leads to a significant reduction in thermal conductivity, such

as phonon-phonon scattering, phonon-impurity scattering and phonon-boundary

scattering, etc.

2.2 Factors influencing effective thermal conductivity of PCM

The heat conduction inside materials is caused by the collision of various

microscopic particles. As a result, the variation of crystal structure or any

microstructure of the material will change the thermal conductivity of materials. The

complexity of the heat conduction mechanism through composites also arises from the

many factors. For the crystalline materials, the lattice thermal conductivity can also be

theoretically estimated through Debye formulation Eq. (5) [12, 28-30]:

1
λ= Cv ( ω ) × v (ω ) × l (ω ) dω
3∫
(5)

Where Cv is the heat capacity of the phonons per unit volume, v is the phonon

group velocity, l is the phonon mean free path.

According to the calculation expression of thermal conductivity, the direct

factors affecting the composites thermal conductivity are the specific heat capacity

(Cv), phonon group velocity (v) and phonon mean free path l. The individual

parameter of analyzing the effect of phonon thermal conductivity by phonon

scattering mechanism from the microscopic perspective is shown in Fig. 8.

2.2.1 Heat capacity Cv

For the nonmetallic PCM, heat capacity Cv is temperature-dependent. At an

extremely low temperature, the specific heat capacity of the phonon is proportional to

T3 [29]. At relatively high temperature, the heat capacity becomes basically constant,

13
which approximates to 3R (R is the gas constant).

2.2.2 Phonon group velocity v

Phonon group velocity is a vital factor in the microscopic theory influencing the

thermal conductivity of composites. Phonon group velocity, which is the transmission

velocity of a wave packet, can be obtained from the dispersion relation. In addition,

the phonon scattering is intimately related to the frequency. The higher is the

frequency of phonon, the stronger is the phonon scattering. The continuous

low-frequency modes associated with the acoustic phonons. The group velocity the

acoustic phonons is large. However, the phonon group velocity is so small that it can

be negligible for the short wavelength optical modes near the edge of the Brillouin

zone. The optical phonons contribute to the specific heat, but only a little bit to the

heat flux. Hence, the long wavelength acoustic phonon branch accounts for the

thermal transport [31, 32]. At the long wavelength limit or continuum limit, the group

velocity reaches the acoustic velocity Cs in a crystal, which is associated with the

elastic stiffness E, and mass density in the long wave-length region [14, 33].

dω E
lim v = lim = Cs = (6)
q ph →0 q ph →0 dq
ph ρ

2.2.3 Phonon mean free path l

There are three main factors: inelastic phonon–phonon scattering resulted from

the anharmonicity effect, phonon–defect scattering and phonon–boundary scattering,

all of which can impact on the mean free path. In the preparation of composites, the

large phonon mean free path is expected and the effective phonon mean free path Leff

can be described by the following Matthiessen’s rule [29, 30]:

14
 1 1 1 1
= + + (7)
Leff Lph Ld Lb

Where Lph, Ld, and Lb are the mean free path arisen from the phonon-phonon,

phonon-defect, and phonon-boundary scattering, respectively. Three phonons mean

free paths deriving from the different scattering patterns can be shown in Fig. 9. All

phonon scattering processes can make the mean free path reduce. Only one of the

factors among which brings about the shortest mean free path, will have a prominent

influence. Here, we will analyze the dominant factors.

Phonon–phonon scattering mean free path, Lph

As above mentioned, the lattice vibration can be analogous to the spring mass

system. Two lattice waves haven’t interactions and a single wave doesn’t decay for

the harmonic theory. Moreover, the elastic coefficients don’t vary. The heat transport

could proceed with no obstruction and therefore cause an infinitely large thermal

conductivity. In a real crystal, the elastic coefficients may be changed because of the

distortions of the lattice arisen from the atomic displacements. When the phonon

propagates, the change of the elastic coefficients will influence the heat transfer. If the

temperature is low enough for the number of phonons to be so small that even N

processes can be neglected [34]. However, the phonon excitation and three-phonon

scattering rate augments with the increase of the temperature. The N processes

become the dominant. At the higher temperature, all phonon vibrational modes are

thermally excited. The main mechanism of thermal resistivity is phonon–phonon

umklapp scattering with the attendant large momentum change in the collision. The U

processes are more prominent and account for the decrease of the thermal

15
conductivity at a relatively high temperature [35].

Defect scattering mean free path, Ld

Phonons can be regarded as pseudo-particles. In this sense, kinetic theory can be

used to explain phonon impurity scattering. According to kinetic theory, the mean free

path due to an impurity is

1
Lim =
σ sct ( χ ) ×η
(8)

Here, η denotes the impurity concentration. σsct is the scattering cross-section,

which is a function of the size parameter χ. The size parameter χ is defined as the

wave-vector q of an incoming phonon multiplied by the radius of the scatter r, i.e., χ

= qr. The important parameter in impurity scattering is the scattering cross-section.

When the size parameter approaches zero, the scattering cross-section forms

according to the Rayleigh law. In the Rayleigh scattering regime, the scattering

cross-section varies as ~ , where d is the size of the scattering particle, and w is

the phonon frequency. For atomic substitutions in alloys, d~1 angstrom. The above

relation suggests that short wavelength or Brillouin zone edge phonons are scattered

much more effectively than mid- and long-wavelength phonons. At the other limit,

where the size parameter approaches infinity, the scattering cross-section is

independent of frequency.

In porous matrix materials, impurities are usually defects, vacancies, dislocations,

etc., which are on the order of the atomistic scale. Therefore, in porous matrix

materials, the scattering cross-section follows the Rayleigh law, i.e. Lim~w-4. Although

short-wavelength phonons can be scattered by porous matrix atoms or empty space,

16
long- to mid-wavelength phonons are not affected by the scattering of porous matrix

and still have strong thermal conductivity. Therefore, by decreasing the width of grain

boundary and increasing the grain size to reduce the volume percentage of grain

boundary in the crystal, and transforming the amorphous state of grain boundary into

grain state, the scattering of short-wavelength phonons can be significantly reduced,

and the total thermal conductivity of crystal composites can be increased [36].

Boundary scattering mean free path (Lb)

Phonon often suffers strong scattering at the boundary or interface of the

crystal when it propagates. For the PCM working at room temperature or above,

boundary scattering is often important in practice. In the composites PCMs, the

interface between the filler-matrix and the PCM is the main barrier for the thermal

transport. Phonon transport characteristics differ greatly at interfaces in bulk than that

of nano-scale region. As particle size decreases to nanometer scale, interface can lead

to significant phonon scattering. The heat flow within the composite materials is

impeded by the presence of the interfacial resistance, which decreases the benefit of

adding high thermal conductive filler [37, 38]. As a result, the thermal conductivity of

the composite materials is lower than that of the high thermal conductive filler. In

composite PCMs, the phonon transport can be hindered by the phonon scattering due

to the interfacial thermal resistance. There occurs a temperature discontinuity at the

interface between two different materials. This temperature discontinuity is resulted

from the thermal boundary resistance (Kapitza resistance). The thermal boundary

resistance in the interfaces between two different materials is becoming increasingly

17
important especially on the nanometer length scales [39]. Moreover, either the

different lattice constants or even different crystal structure between two different

crystals will give rise to the lattice mismatch.

3. Approaches to enhancing the thermal conductivity of PCMs and

their mechanisms

Thermal conductivity of PCM can be predicted and improved by analyzing the

microcosmic heat transfer mechanism. Morphological features of materials play an

important part in heat conduction mechanism. Fig. 10 involves the main content of

this chapter. Firstly, the methods of the chemical modification to improve the thermal

conductivity are summarized. Then the preparation methods, morphological

characterization and micro explanation of the composite PCMs are emphatically

discussed, which adds carbon-based materials, metal foam, clay minerals and other

potential matrix to improve the thermal conductivity. Finally, we provide some useful

conclusion and references to explore the high performance composite PCMs.

3.1 Chemical modification of matrices

3.1.1 Doping

The influence of high heat conducting materials, which doped matrix on the

properties depends not only on the doping amount of the matrix and its intrinsic

properties, but also on the existing form of the doped matrix in high heat conducting

materials. When no chemical reaction between the doped matrix and the medium of

the high heat conducting particle, it is mainly in the form of mischcrystal, uniformly

dispersed in the matrix or filled in the pores of the basis material. However, the doped

18
matrix reacts with the medium of the heat conducting particle, it may exist in the form

of carbide or oxide. No matter how the doping matrix exists, it is affected the

microstructure of the high heat conducting material and the results are change the

physical and chemical properties of the composite PCMs. In a word, the effect of

macroscopic doping on the micro morphology of composites is mainly reflected by

changing the pore quantity and pore size of matrix. The micro-doping results in great

changes in the surface phase composition and structure of high thermal conductivity

matrix. In addition, the thermal conductivity of composites is improved by increasing

the number of thermal conduction channels and reducing phonon scattering. In order

to improve the thermal conductivity and cyclic stability of PCM, porous materials

with doped elements can be added to improve the microstructure and surface

compatibility of PCM.

Researchers have done a lot of work about doped with special elements to an

additive substrate. Atinafu et al. [40] prepared the form-stable binary eutectic PCM by

encapsulating myristic acid (MA)/stearic acids (SA) mixture into porous carbon

matrixes. The nitrogen (N) heteroatom is introduced the porous carbons and forms

mesoporous N-doped carbons (NPC) in situ synthesis to improve the thermal

conductivity, thermal energy storage and conversion performance. The form-stable

loading content of PCM in the NPC/MA-SA composites without leakage reaches

88wt.%. Fig. 11 is thermal conductivity and heat flow of porous carbon

matrix/MA-SA composite PCMs and the experimental results show that the

NPC/MA-SA composite PCMs exhibit excellent thermal conductivity and heat

19
storage capacity. The enthalpy of the NPC/MA-SA composites are 164.33 kJ/kg with

the phase change temperature of 49.45 °C. The latent heat is up to 45.69% higher than

that of composites by post synthesis route. Moreover, the thermal conductivity of

NPC/MA-SA composite PCMs increases by 117.65% than pristine PCM and is about

43.06% larger than that of composites by post synthesis route. The introduction of N

heteroatom plays a key role in changing the textural properties of carbon materials.

The nitrogen content, N-C arrangement of amino functional groups, graphite

properties and interconnected porous carbon is conducive to form the heat transfer

network.

Mehrali et al. [41] prepared palmitic acid (PA)/nitrogen-doped graphene (NDG)

composite PCMs. NDG is obtained by chemical doping with nitrogen of graphene

oxide (GO) using the hydrothermal process. PA is dissolved in the toluene solution

with the different mass percentages (1~5 wt.%). In order to make the nano particles

uniformly disperse, the high power ultrasonication was utilized to break down the

aggregation of the NDG. Fig. 12 (a) exhibit the field emission scanning electron

microscopy (FESEM) images of the NDG. From the diagram，it can be seen that the

NDG keeps the two-dimensional (2D) graphene structures, which has high specific

surface area and volume ratio. The NDG nanosheets are randomly stacked and the

porous structure resembles crumpled silk veil waves. Fig. 12 (c) and (d) show the

transmission electron microscopy (TEM) images of the NDG and PA/NDG composite

PCMs. We can seem that the NDG is enclosed by membranes made from the PA. It

suggests that the PA adsorbed by the network structure of the NDG. The heat storage

20
density of this novel form-stable PA/NDG composite PCMs are 199.48 kJ/kg.

Furthermore, the addition of the NDG makes the thermal conductivity and specific

heat capacity of the PCM remarkably augment. The thermal conductivity of the

PA/NDG composite PCMs are 1.73 W/(m·K) and is up to about 518% higher than

that of the pure PA(0.28. W/(m·K)). The reason is that the heat-conducting carbon

network formed by the NDG layer enhances the effect of heat transfer. With the

increase of NDG content, the speed of thermal conductivity increased to a maximum

followed by a slow decrease to a constant value and thermal conductivity reach the

maximum value. In addition, the form-stable composite PCMs have an excellent

thermal reliability.

Chen et al. [42] studied the impacts of interfacial interactions between different

small molecular organic PCM and N-doped hierarchical carbon on the thermal energy

storage properties. The in-situ N-doped hierarchical three-dimensional (3D) nanoscale

porous carbon was derived from one-step high temperature pyrolysis of polyaniline

hydrogel. Fig. 13 is shown the preparation procedures of composite PCMs. The

results suggest that one-step pyrolysis process is beneficial to impregnate effectively

organic small molecule PCM to promote the phonon transport and the thermal transfer

is enhanced with the rise of the pyrolysis temperature. The improvement of the

thermal conductivity ascribes to the synergistic effect of highly interconnected

graphitized network carbon and rich graphitic nitrogen, which can also accelerate

phonon group velocity and increase the mean free path to promote faster heat flow.

Besides, the induced hydrogen bond intensity between N-doped hierarchical carbon

21
and PCM, and space restriction effect of the hierarchical pore on the PCM determine

the nanoconfinement behaviors of PCM [43]. It can increase the densification degree

of PCM and carbon skeleton, thereby reducing interfacial thermal resistance and

significantly improving thermal conductivity.

3.1.2 Graft functional groups

Grafting or post synthesis is a method of introducing organic groups into the

surface of mesoporous channels through chemical reactions between organic

precursors and functional groups on the superficies of mesoporous materials. Organic

functional groups are introduced into the channels of mesoporous by grafting and

further reactions are made to produce new active centers. As the active centers

generated are close to each other, many available organic functional groups have no

significant effect on the mesoporous structure of the matrix material. However, most

of the unevenly distributed organic functional groups are distributed on the orifice and

the external surface, which is lead to the blocking of mesoporous channels and thus

reduce the pore volume. Therefore, the characteristics of introducing organic

functional groups into composite materials: (1) as the proportion of organic groups

increases, the pore size of the matrix materials gradually decreases; (2) the

mesoporous structure of the matrix material is not changed; (3) the

hydrophilic/hydrophobic and thermal conductivity of composite materials can be

regulated by changing the type of organic groups.

Based on the above characteristics, the supporting material has been modified by

grafting to improve its comprehensive properties, such as Wang et al. [44] fabricated

22
polyethylene glycol (PEG)/CNT@Cr-MIL-101-NH2 form-stable composite PCMs via

the impregnation method. PEG/CNT@Cr-MIL-101- NH2 composite PCMs synthesis

diagram, morphological characterization and thermal conductivity curve are shown in

Fig. 14. The CNT@Cr-MIL-101-NH2 is obtained via the situ mothed to synthesis

Cr-MIL-101-NH2 and the surface of the CNTs is modified by the Cr-MIL-101-NH2

nano-particles. The PCM is absorbed by the MOFs nanoparticles due to the surface

tension force and capillary action. As a result, the MOFs closely connected with CNT

to form a porous structure of MOFs can eliminate the leakage of liquid phase PEG.

Therefore, it forms 3D network structure and the structure creates the heat transfer

network [45]. Moreover, the interfacial thermal resistance between

CNT@Cr-MIL-101-NH2 and PCM can be reduced and mean free paths of phonons

increases. Further, the thermal conductivity of the PEG/CNT@Cr-MIL-101-NH2

composite PCMs increases by 100.9% than without the introducing CNTs. Li et al.

[46] utilized paraffin and grafted CNTs to prepare the composite PCMs. Fig. 15

shows the formation process and morphological images of pristine CNTs and

CNTs/paraffin composite PCMs. The pristine CNTs (PCNTs) are more tendency to

agglomerate owing to van der Waals’ interaction and the use of chemical modification

improves the dispersibility of CNTs [47]. Further, the thermal conductivity of grafted

CNTs/paraffin composite PCMs is higher than that of PCNTs/paraffin and the thermal

conductivity of composite PCMs augment with the increase of CNTs content. When

the CNTs content is 4%, the thermal conductivity of CNTs/paraffin,

CNTs-C8/paraffin, CNTs-C14/paraffin and CNTs-C18/paraffin composite PCMs are

23
0.6454 W/(m·K), 0.7683 W/(m·K), 0.7783 W/(m·K), 0.7903 W/(m·K), respectively.

Because the well-grafted CNTs, which has larger carbon numbers and longer carbon

chains, can blend successfully into the paraffin. Hence, grafted CNTs with longer

carbon chains have the smaller the interface thermal resistance and larger thermal

conductivity with the same CNTs content. After grafting treatment, the interfacial

thermal resistance between the grafted CNTs and paraffin is reduced. According to

mechanisms of thermal conductivity, the phonon-boundary scattering is significantly

weakened and the phonon average free path is remarkably increased. As a result, the

thermal conductivity is improved.

Table 1 summarizes the effects of dopping and graft functional groups methods

on enhancing the thermal conductivity of composite PCMs. It’s indicated that

chemical treatment is helpful to improve the thermal conductivity of composite PCMs.

The main reason is that the chemical treatment can form a 3D thermal conductivity

network and reduce the surface thermal resistance, which is conducive to promoting

the rapid transfer of heat along the thermal conductivity chain.

3.2 Fabrication and characterization of composite PCMs

Mixing a material having high thermal conductivity with a PCM can be

classified as two modes. One mode is to prepare a form-stable composite PCM, in

which the PCM is absorbed into the pores within the supporting material to

completely avoid the liquid leakage after the PCM took place the phase change from

solid to liquid. This mode is called passive composite PCMs. It mainly forms a

heat-conducting chain in the middle of the composites through 3D structures (such as

24
highly graphitized network carbon, carbon foam and metal foam, etc.) or 2D structural

additives (expanded graphite and clay minerals, etc.) to reduce phonon scattering to

improve thermal conductivity; The other one is associated with adding a small amount

of a material with high thermal conductivity into the PCM to just improve its thermal

conductivity, the obtained mixture can be considered as a initiative composite PCMs

since the liquid leakage of the PCM cannot be avoided. This mode mainly forms a

heat conduction channel after the PCM is added to the one-dimensional (1D) structure

(carbon fiber, carbon nanotube and graphene, etc.) or zero-dimensional (0D) structure

additive (nanoparticle). Therefore, it can increase the phonon mean free path to

improve thermal conductivity.

3.2.1 Passive composite PCMs using three-dimensional structure additives

The 3D structure additives have many morphological structures, such as graphite

foam (GF), highly graphitized network carbon and metal foam etc. Due to the 3D

structure additives can easy form the interconnected pore network and it can provides

conductive pathways for enhancing the heat transfer in PCM matrix. Besides, the 3D

structure additives, which also can avoid the leakage of the composites in the melting

state and reduce the supercooling degree, are the ideal choice for the preparation of

the high performance PCM [48].

3.2.1.1 Addition of graphite foam in passive PCM

Graphite foam (GF) is a high-performance porous 3D structure additive with

high porosity, low density, effective thermal conductivity up to 200 W/(m•K) [49],

25
high temperature resistance, corrosion resistance and other characteristics, which can

also be mixed with most PCM compatible [50]. At the same time, compared with

metal foam, graphite foam has a higher thermal conductivity, so it has been widely

concerned [51, 52].

Karthik et al. [53, 54] used Resorcinol-Formaldehyde (RF) resin as the precursor

and polyurethane foam as the carbon source by sacrificing the macro-porous template

to prepare highly interconnected 3D graphite foam composite matrix. The graphite

foam matrix was impregnated with erythritol to prepare a composite PCMs. Fig. 16

shows the preparation of GF/erythritol composite PCMs and SEM morphological

characteristics diagram. It is found that the thermal conductivity of erythritol/GF

composite PCMs (3.77 W/(m·K)) is five times higher than that of pure erythritol (0.72

W/(m·K)). Morphologies of the samples are show in Fig. 16. It is observed that due to

the capillary force and surface tension of the porous GF, the pores of the GF are filled

with erythritol. The developed high thermal conductivity porous matrix of GF easily

forms dense thermal conduction channels in the composite PCMs. Further, accelerate

the phonon group transmission velocity and improve the thermal conductivity of

composite PCMs.

Zhang et al. [55] grew stable 3D diamond foam（DF）network structure on

diamond-like foam by hot filament assisted chemical vapor deposition (CVD)

technology and then added it to paraffin by vacuum impregnation method to prepare

high quality DF/paraffin composite PCMs. Fig. 17 shows the morphological

characteristics of DF schematic diagram of a DF consisting of a 3D interconnected

26
diamond network and a continuous DF with high thermal conductivity. It can be

observed that the 3D macro-porous skeleton of high thermal conductivity DF is

uniformly compact and interconnected. In addition, the foam matrix is completely

covered by continuous diamond film, ensuring efficient and continuous heat transfer.

When the volume fraction of DF is very low (1.3 vol%), the thermal conductivity of

DF/paraffin (6.7 W/(m·K)) is 162% higher than that of CF/paraffin (2.56 W/(m·K))

and 2580% higher than that of pure paraffin (0.25 W/(m·K)). When the thermal

conductivity of diamond particles (1800 W/(m·K)) is large, even if the volume

fraction of diamond particles (20 vol%) is increased, the thermal conductivity of

diamond particles/paraffin is only 0.45 W/(m·K), far lower than that of CF/paraffin,

which is sufficiently to demonstrate that the 3D continuous structure can promote heat

transfer. It is observed that abundant rhombohedral interconnection network can

provide a faster thermal conduction channel, which can significantly reduce

phonon-phonon and phonon-boundary scattering. The rhomboid structure can be used

to reduce the interfacial phonon scattering and improve the effective thermal

conductivity. In addition to the preparation of graphite foam composite PCMs,

Mesalhy et al. [56] also conducted experiments and simulations on the thermal storage

performance of the materials with different porosity in the system. In this way, the

best porosity of graphite foam can be provided reference for practical application.

3.2.1.2 Addition of highly graphitized network carbon in passive PCM

Highly graphitized 3D network carbon is a promising and candidate matrices

for possessing high thermal conductivity, which can provide superior interconnected

27
paths for phonon propagation. Therefore, adding highly graphitized 3D network

carbon to the PCM can effectively improve the thermal conductivity of the

composite PCMs.

Chen et al. [57] closely connected the carbon quantum dots (CQDs) of acetone

and divinylbenzene (DVB) by one-step calcination method, and under the synergism

of appropriate pyrolysis temperature and crosslinking reaction, a controllable 3D

graphitized mesoporous and macro-porous heat conducting network carbon 3D

celosia-like were constructed. PEG/ 3D porous carbon composite PCMs were

obtained by using melt impregnation method to infiltrate PEG into 3D graphitized

network carbon pores. The preparation process and micromorphology are show in

Fig. 18. The porous carbon material can significantly reduce the binding force of

PEG penetration into microporous and mesoporous scaffolds. Compared with pure

PEG (0.28 W/m·K), the thermal conductivity of composite PCMs (0.94 W/m·K)

increased by 236% and the phase change enthalpy is almost close to the theoretical

value. In addition, the composite PCMs with the addition of heat-conducting network

carbon has excellent thermal stability. Among them, the improvement of the thermal

conductivity of PEG/3D porous carbon composite PCMs is mainly due to the

increase of thermal conductivity channel in the 3D carbon skeleton and the increase

of the phonon mean free path, which is conducive to the enhancement of its thermal

conductivity.

Li et al. [58] synthesized CNT-porous carbon (PC) 3D porous core support

structure by high temperature carbonization method using CNT and ZIF-8 MOFs.

28
 This material has high porosity and large specific surface area. SA/CNTs/PC

composite PCMs were prepared by melting impregnation method under the action of

capillary force and fixed in the pores of PC wall. The preparation process and

micro-morphology are shown in Fig. 19. The close combination of SA and CNTs can

significantly reduce the interface thermal resistance. It can provide a continuous

channel for phonon transfer and realize the rapid heat transfer in the composites. In

addition, SA/CNT-PC form stable composite PCMs have good thermal conductivity

(1.023 W/m·K). Compared with SA/PC composite PCMs (0.310 W/m·K), the

thermal conductivity of SA/CNT-PC composite PCMs increased by 222.6%. It can

be concluded that 3D PC is an additive to improve the thermal conductivity of PCM.

Kholmanov et al. [59] continued to study the microstructure and thermal

conductivity of highly carbonized porous network structures. UGF-CNTs composites

were synthesized by using continuous ultrathin graphite foams (UGFs) and CNT as

raw materials through nickel-based template-assisted CVD method.

Erythritol/UGF-CNTs composite PCMs were prepared by adsorption of erythritol to

the 3D network structure of porous UGF-CNTs by melting impregnation method. The

preparation process and the morphology of the porous material are shown in Fig. 20.

They found that the thermal conductivity of UGF-CNTs/erythritol composites was 1.8

times higher than that of UGF/ erythritol composites. However, the effective thermal

conductivity of the UGF-CNTs porous structure composite synthesized by the

nickel-based template-assisted CVD method increased from 2.9 and 0.2 W/(m·K) to

4.1 and 0.3 W/(m·K), compared with the simple mixture with the same UGF and CNT

29
addition amounts of 1.8 and 0.8 wt.%, respectively. It indicates that the 3D porous

network additive formed by the bond between UGF and CNT can effectively improve

the thermal conductivity of PCM. The reason may be that the thermal conduction

speed is significantly improved by expanding the thermal conduction channel.

Yang et al. [60] synthesized porous cellulose/GNP aerogel with high thermal

conductivity by using graphene nanoplatelets (GNPs) and microcrystalline cellulose

through typical gel method, and encapsulated PEG into 3D network structure of

porous cellulose/GNP aerogel by vacuum-assisted impregnation method, which can

effectively prevent liquid PEG leakage. When GNPs content is 5.3 wt.%, the thermal

conductivity of the composites is 1.35 W/(m·K), which is 463% higher than the

composites without GNPs (0.24 W/(m·K)). The addition of high thermal conductivity

matrix is the main reason for the improvement of thermal conductivity of composite

PCMs. However, after the rapid heat treatment, the graphite oxide still has oxygen

components and structural defects, which are not conducive to phonon transmission.

But the high thermal conductivity of PEG/GNPs composites should be attributed to

the high intrinsic thermal conductivity of defect-free GNPs. Compared with the

original graphite sheet, the annealed GNPs are more effective in improving the

thermal conductivity of the composites, because they are more likely to form a

conductive network conducive to thermal conductivity, thereby reducing phonon

scattering.

3.2.1.3 Addition of metal foam in passive PCM

Due to its large specific surface area per unit volume, high thermal conductivity

30
inherent in the solid skeleton, and strong mixed disturbance characteristics of heat

flow in the curved channel, the metal foam ligament destroys the heat flow boundary

layer, thereby increasing the axial and radial heat transfer of the heat transfer skeleton

and further improving the heat transfer rate. Adding PCM to the continuous skeleton

structure and high porosity void inside the metal foam can significantly improve the

thermal conductivity of the PCM under the condition of slightly reducing the heat

storage capacity of the composite PCMs. At present, the most widely studied metal

foams include copper foam [61, 62], aluminum foam [63], nickel foam [64-67] and

titanium dioxide foam [68]. Fig. 21 shows the structure of copper foam (a), aluminum

foam (b) nickel foam (c) [62] and titanium dioxide foam. The effective thermal

conductivity of composite PCMs can be improved by adsorbing the composites into

the pores of metal foam by vacuum impregnation method.

(1) Passive PCM embedded with copper foam

It is well known that copper foam has porous structure, which possess larger

surface area to volume ratio and they have a strong mixing ability. Moreover, the

thermal conductivity of copper skeleton is high (401 W/(m·K)) [69] and has enough

more the number of thermal conductivity chains, which is conducive to the rapid

transmission of heat flow. Hence, lots of metal foam are as well commonly used as

matrices for thermal conductivity enhancement of thermal energy storage system.

Researchers often add copper foam with different porosity and pore size in PCMs to

improve the heat transfer rate of inorganic and organic PCMs, and continue to explore

excellent properties of metal foam based composite PCMs.

31
 Compared with pure cooper, copper foam with a cellular structure has better load,

adsorption capacity and thermal conductivity. Using inorganic PCM and copper foam

to synthesize composites can significantly improve its heat transfer performance. Such

as Li et al. [70] first added 2.0 wt.% disodium hydrogen phosphate hydrate (DHPD)

as nucleating agent and 0.5 wt.% carboxymethyl cellulose (CMC) as thickening agent

to the sodium acetate trihydrate (SAT). It is found that the thermal conductivity of

SAT/copper foam composite PCMs could be significantly increased with the decrease

of the porosity of copper foam. This indicates that the copper foam additive with low

porosity is more beneficial to improve the thermal conductivity of composite PCMs.

The pore size of copper foam ranged from 5 to 25 PPI, and the porosity ranged from

92.4% to 97.3%. The thermal conductivity of copper foam/SAT composite PCMs

ranged from 6.8 to 3.3 W/(m·K). When the porosity of the copper foam matrix is

92.4%, the thermal conductivity (6.8 W/(m·K)) is approximately 11 times that of the

pure SAT thermal conductivity (0.59 W/(m·K)). It is possible that the copper foam

formed many thermal conduction channels in the composite PCMs, which accelerated

the heat transfer rate. However, there are also study on the preparation of composites

with organic PCM and copper foam. For instance, Chen et al. [71] proved that copper

foam has ability to enhance the heat transfer rate of paraffin through experimental

research. They are adsorbed paraffin into the network structure of powders of

styrene-b-(ethylene-isobutylene)-b-styrene (SEBS) triblock copolymer by direct

impregnation method. On the basis, it mixed with high-density polyethylene (HDPE)

material uniformly and copper foam to prepared SEBS/paraffin/HDPE/copper foam

32
form-stable composite PCMs. The thermal conductivity of SEBS/paraffin/HDPE

(1:6:0.5) is 0.272 W/(m·K) while the thermal conductivity of SEBS/paraffin/HDPE/

copper foam form-stable composite PCMs are increased to 2.142 W/(m·K). The

thermal conductivity of the form-stable composite PCMs calculated by the empirical

formula is 2.612 W/(m·K). On the one hand, due to the low thermal conductivity of

SEBS/paraffin/HDPE (1:6:0.5), the thin layer adsorbed by the composite onto the

surface of the copper foam will increase the interface thermal resistance and reduce

the overall thermal conductivity. On the other hand, the accuracy of the empirical

formula is mainly verified by the experiment of heat transfer between water or air and

metal foam. The natural convection of the composite PCMs are relatively weak,

which is promote the heat transfer inside the composite PCMs. In a word, copper

foam can obviously promote the thermal conductivity of PCM and it is an excellent

thermal conductivity additive matrix.

(2) Passive PCM embedded with aluminum foam

Aluminum foam can be divided into two types: open-hole aluminum foam and

closed-hole aluminum foam [72-74]. Closed-hole aluminum foam is commonly used

as insulation material, but open-hole aluminum foam is often used for enhanced heat

transfer. As a kind of ultra-light porous metal material, open-hole metal foam is often

used as a material to enhance heat transfer due to its small density, large surface area,

good flow performance and high thermal conductivity of metal skeleton (167

W/(m·K)) [75]. Filling metal foam as a skeleton into PCM can improve the heat

transfer performance of the phase change heat transfer device [76,77]. In addition, the

33
thermal conductivity of composites is also closely related to the impregnation rate,

pore size and porosity etc.

Jiang et al. [63] used aluminum foam to enhance the heat transfer performance of

PCM. They took slice paraffin and SA as the PCM, which adsorbed the PCM into the

bulk porous aluminum foam under different pressures by directly impregnate method,

to prepare two kinds of parameter composite PCMs. Furthermore, they studied the

microstructure of the two composite PCMs and thermal performance. Fig. 22 shows

the optical micrograph and SEM micrograph of SA/aluminum foam (a) and

paraffin/aluminum foam (b) composite PCMs under normal pressure (c, d). The black

color is the PCM area and the white color is the aluminum foam area in the figure.

There is no crack in the interface, which is because of the high permeability of low

temperature organic PCM, van der Waals force of the metal foam, and the strong

cohesion of organic and metal foam, so that the composites have good impregnation

effect. It can be seen from the SEM micrograph that PCM has a good impregnation

effect in aluminum foam. For PCM/aluminum foam composites, the impregnation rate

of PCM in the pores of aluminum foam is more than 80%, and the number of

remaining pores is small. The lower residual porosity in the paraffin/aluminum foam

composites indicate that the impregnation effect of paraffin is better than that of SA.

The impregnation of PCM improved the thermal performance and made its ideal

energy saving materials.

In order to research the effects of different pore sizes and porosity on the

thermal conductivity of composites, Hu et al. [78] continued to study the thermal

34
conductivity enhancement of metal foam/paraffin by numerical simulation and

theoretical prediction. They filled paraffin into the pores of honeycomb cubic

aluminum foam with symmetrical structure, and used pore-scale numerical simulation

to study the thermal properties of porosity and pore size on composite PCMs. The

simulation results showed that the melting time of composite PCMs are 75.9% shorter

than that of pure paraffin. When the pore size is 10 PPI, the effective thermal

conductivity of PCM with a porosity of 95% and 70% is 3.3 W/(m·K) and 24.6

W/(m·K), respectively, which is 17 times and 123 times higher than that of pure

paraffin (0.287 W/(m·K)). The possible reason is that the smaller porosity can

coarsening the heat conducting aluminum skeleton and widen the heat flow channel,

thus it can enhance thermal conductivity. Meanwhile, the simulation results are

compared with the results of the thermal conductivity prediction model established by

Xu et al. [79] and Bhattacharya et al. [80], as shown in Fig. 23. From the figure, with

the increase of porosity, the effective thermal conductivity gradually decreases, while

the effective thermal conductivity of composite PCMs with different pore sizes of the

same porosity (such as 5 PPI, 10 PPI) is roughly the same, indicating that the effective

thermal conductivity is basically not affected by the pore size. In short, the thermal

conductivity of composite PCMs is more affected by porosity than pore sizes.

Therefore, the pivotal step to enhance the thermal conductivity is to select the

appropriate porosity of metal foam.

Further, for studying the effect of porosity and phase change behavior, which

are involve in improving thermal conductivity of metal foam/paraffin composite

35
PCMs. Atal et al. [81] utilized two different porosity aluminum foam in a shell and

tube heat storage unit to study the thermal conductivity of pure paraffin (0.25

W/(m·K)), paraffin/aluminum foam composite PCMs and pure aluminum foam (167

W/(m·K)) configurations Because of the high thermal conductivity of aluminum foam,

the addition of high thermal conductivity aluminum foam to paraffin can significantly

improve the heat transfer performance of paraffin. When aluminum foam with

equivalent porosity of 95% and 77% is added to the paraffin, the effective thermal

conductivity of the composite PCMs are 4.192 W/(m·K) and 17.29 W/(m·K),

respectively. It can be clearly observed that paraffin/aluminum foam composite PCMs

with small porosity have relatively high thermal conductivity, and the heat storage and

release time of shell and tube heat storage device is shorter. It is assumed that the heat

transfer rate can be significantly increased by applying aluminum foam to the inner

wall of the shell and tube of the heat storage device, because the thermal resistance

between the tube wall and the aluminum foam is greatly reduced. From the above, it is

also a good way to investigate the thermal conductivity of metal foam through heat

storage experiment, which can more directly explore the effect of porosity on heat

exchanger heat transfer performance.

(3) Passive PCM embedded with nickel foam

Nickel foam is a kind of metal foam with homogeneous 3D network structure, its

porosity is between 88% and 99%, and its specific surface area can reach 1000~9000

cm2/cm3, which is conducive to improve its stability and heat flux density [82]. In

order to give full play to the high thermal conductivity of open-hole nickel foam

36
network and overcome the instability of the function caused by the binder, functional

materials can be grown directly on the nickel foam. The preparation of nickel foam

based composite PCMs using nickel foam as the framework can reduce the contact

thermal resistance between the PCM and nickel foam skeleton and increase the heat

transfer capacity between the interfaces [65]. Furthermore, the optimal additives will

be selected to compare their thermal conductivity by adding different

single-component foams or bimetallic foams into PCM.

According to the specific needs of practical applications, suitable pore size of

nickel foam can be selected. Oya et al. [65] prepared composite PCMs by vacuum

impregnation method with erythritol and porous nickel with pore sizes of 100, 300

and 500mm. Fig. 24 shows the morphological characteristics of nickel foam with pore

sizes of 100, 300 and 500 mm and thermal conductivity curve. It is observed that with

the decrease of pore size, the damage degree of porous structure to the skeleton

increases, the skeleton becomes thinner and the connectivity decreases. Furthermore,

they have tested the thermal conductivity of composite PCMs. The thermal

conductivity of nickel foam/erythritol composite PCMs with the nickel foam pore size

of 100, 300 and 500 mm are 6.62, 9.36, 11.6 W/(m·K), respectively. The results show

that, the thermal conductivity of composite PCMs rises with the increase of the

aperture. The biggest thermal conductivity of composite PCMs are 11.6 W/(m·K),

which is approximately 15 times larger than that of pure erythritol (0.733 W/(m·K)).

The microstructure can be concluded that the effective thermal conductivity of the

nickel foam/erythritol composite PCMs with small pore size is reduced due to the

37
narrow heat conduction channel caused by the thin framework connecting rod

structure.

For the above research, the composite PCMs with nickel foam matrices to

enhance thermal conductivity is effective. Ling et al. [83] continues to synthesize

polydimethylsiloxane graphene-nickel foam (PDMS-G-NF) by coating graphene

nanosheets onto nickel foam followed via surface modification with PDMS, is used as

porous supporting material to prepare form-stabilized composite PCMs. SEM photos

is performed to evaluate the morphology of composite materials. It can be seen that

the treated nickel foam exhibited nano/micro-size along with rough surface composed

of stacked layers of graphene sheets. The higher magnification image reveals more

clearly the graphene nanosheets with wrinkled surface topology and folding edges on

the skeleton of nickel foam, whose intrinsic hydrophobicity is favorable to the

absorption of PCM. Fig. 25 shows the morphological characteristics of the G-NF and

the pores of PA/PDMS-G-NF are homogeneously filled by PA, which illustrates that

n-carboxylic acids have been impregnated into PDMS–G–NF due to the effect of

superoleophilicity and the surface absorption of graphene. Since the pores in the

PDMS-G-NF supporting materials are filled by the PA, the thermal conductivity of

the composites (2.262 W/(m·K)) at PA loading fraction of 59.02 wt.% increased about

14 times as compared with that of the PA (0.162 W/(m·K)). Due to the porous

property of PDMS-G-NF, heat can be transferred rapidly in the pore skeleton, which

can further increase the phonon mean free path, weaken the heat flow resistance and

significantly enhance its thermal conductivity.

38
 The comparison of the promoting effect of copper foam and nickel foam on the

thermal conductivity of paraffin has practical application value. Xiao et al. [64] also

used vacuue inpregnation method to prepare different metals foam to investigate their

thermal conductivity. They have prepared paraffin/nickel foam and paraffin/copper

foam composite PCMs. Further, the impregnation rate and thermal conductivity of

paraffin impregnated in vacuum are compared. Preparation and morphological

characteristics of paraffin/metal foams composite PCMs are shown in Fig. 26. The

surface porosity obtained by image analysis is between 90%~94%, while the volume

porosity predicted by mass fraction is about 97%. Compared with pure paraffin wax,

the thermal conductivity of the composite PCMs are significantly improved, and the

thermal conductivity of paraffin/nickel foam composite PCMs are almost three times

that of pure paraffin. On the other hand, the comparison of the promoting effect of

copper foam and nickel foam on the heat conduction of paraffin shows more

obviously improved effect of copper foam and more conducive to the thermal

conductivity additive.

Huang et al. [84] also compared and analyzed the thermal properties of the

copper foam and nickel foam-based composites. They selected myristyl alcohol (MA)

as the PCM and metal foam as the supporting framework to prepare MA/metal foam

composites by vacuum melting infiltration method. Fig. 27 shows the microstructure

of MA/metal foam composite PCMs before and after the preparation of nickel foam

and copper foam with pore sizes of 40, 70 and 90 PPI. As the large number of metal

foam skeletons support MA, it can be completely wrapped by the metal foam and the

39
surface of the composite PCMs are more smoothly. Furthermore, the thermal

conductivity of the nickel foam and copper foam composite PCMs with three pore

sizes are tested. The results show that the thermal conductivity of the MA/nickel foam

composite PCMs (40 PPI) are 0.4768 W/(m·K), which is 1.80 times higher than that

of pure MA (0.17 W/(m·K)). Meanwhile, the thermal conductivity of MA/copper

foam composite (40 PPI) is 1.452 W/(m·K), which increased by 7.51 times. Because

of the larger the hole, the lower the thermal conductivity. Further, the larger the pore

size of metal foam results the larger the interface area, the higher the thermal

resistance and the lower the thermal conductivity. The thermal conductivity of

MA/copper foam composite PCMs with the same pore size is higher than MA/nickel

foam composite PCMs. In addition, with the increase of the density of MA/metal

foam composite PCMs, the thermal conductivity significantly increased, and the heat

transfer rate of the heat storage unit per unit volume accelerated. Moreover, within a

reasonable range, increase the mass fraction of metal foam and improve the thermal

conductivity of composite PCMs.

(4) Passive PCM embedded with titanium dioxide foam

In addition to the three typical metal foams mentioned above, titanium dioxide

(TiO2) foam has attracted attention as a supporting matrix for PCMs because of their

advantages of environmentally friendly, low cost, fireproof material with high thermal

conductivity. For a PCM confined in a porous structure, the interfacial interactions

between the PCM and the porous skeleton are the decisive factors in latent heat

storage performance. Thereby, it is inevitable to explore the preparation of TiO2 foam

40
and composite PCMs, and to test thermal and mechanical properties of pore skeleton.

It is well known that metal foams have high thermal conductivity, which is

suitable to enhance heat transfer rate of composite PCMs. Hence, how to prepare

porous TiO2 foam stably and efficiently is extremely important. Yu et al. [85] used

biopolymer alginate as the sacrifice template for TiO2 nucleation template and

promoted the formation of porous TiO2 nanostructure, to synthesize layered porous

TiO2 foam by soft template method. Its microscopic morphology can be obtained that

TiO2 material has a spongy hierarchical mesoporous structure with a wide distribution

of pore diameter. Open skeleton, which be generated TiO2 nanoparticles with uniform

morphology and size, are closely connected and agglomerated to form macro-porous

foamed materials. Because this method has the advantages of uniform pores and

stable skeleton, it is used to synthesize porous matrix in composite PCMs. Li et al. [86]

synthesized layered porous TiO2 foam by soft template method and prepared

n-octadecane/TiO2 foam composite PCMs by introducing n-octadecane (OC) under

vacuum conditions. Fig. 28 shows the preparation process (a), microstructure (b),

porous structure (c) and thermal conductivities (d) of porous TiO2 foam and

composite PCMs. The carrier is TiO2 crystal and the product has layered porous

structure. Due to the effect of capillary force and interfacial tension, the nanopores are

wrapped with abundant OC, which is closely bound to the surface of layered porous

TiO2 foam. Furthermore, when OC content is 50 wt.%, the thermal conductivity of the

composite is up to 0.38 W/(m·K) with the addition of porous TiO2 foam with high

thermal conductivity. The thermal conductivity of the composite is 138% higher than

41
that of pure OC (≈0.16 W/(m·K)). The results show that the thermal conductivity of

OC can be effectively improved by adding porous TiO2 foam as substrate. Deng et al.

[87] continued to prepare a flower-like TiO2 nano-structure to support PEG.

Schematic diagram of the synthesis process and micro-structure of FLN-TiO2 (a) and

preparation process of PEG/FLN-TiO2 composite PCMs (b) are shown in Fig. 29. In

this encapsulating PCM, flower-like TiO2 is not only adding matrices to improvement

thermal conductivity but also supporting materials to prevent PCM leakage. Further,

the phase change temperatures of the composite PCMs shifted slightly as a result of

the physical force between the PEG and the TiO2 nanostructure. Li et al. [88]

synthesized porous TiO2 foam (PTF) by particle-stabilized emulsion method to

prepare paraffin/PTF composite PCMs by vacuum impregnated method. SEM images

show that the prepared PTF have 3D interpenetrating structure and uniform pore. But

solid paraffin has obvious influence on pore structure and morphology of PTF. Fig. 30

shows the schematic diagram of the preparation process, microstructure (a) and

thermal conductivity (b) of porous TiO2 foams and composite PCMs by synthesized

and prepared method. With the increase of paraffin content, the porosity of samples

shrinks, and the corresponding embedding rate decreases. In order to further improve

the thermal conductivity and adsorption capacity of PTF, sucrose is added into the

emulsion and carbonized in situ to form carbon/PTF (PTFC). The paraffin is

successfully impregnated into the porous framework to obtain a stable paraffin/PTFC

(PTFCP) composite PCMs. As a result, the thermal conductivity of PTFP composite

PCM is 0.302 W/(m·K), which improved about 0.092 W/(m·K) compared with the

42
pure paraffin (0.21 W/(m·K)) because of the high thermal conductivity of TiO2.

Further, the thermal conductivity of PTFCP composite PCM is 1.059 W/(m·K), 5.04

times of the pure paraffin. The results show that the high thermal conductivity carbon

layer on the surface of TiO2 particles can improve the thermal conductivity of

composite PCMs to some extent and provide another solution for enhancing the

thermal conductivity of PCM.

At the same time, Sol-gel method is another feasible method to prepare porous

TiO2 foam, which possess the advantages of molecular uniformity, low reaction

temperature and fast synthesis. Kimlinga et al. [89] induced synthesis of nanometer

porous TiO2 microspheres using alginate as sacrificial template by Sol-gel method.

The microtopography shows that the microsphere surface is highly porous and

consists of interconnected fibers. With the increase of Ca2+ concentration and alginate

concentration, a denser porous network structure can be observed, resulting in the

formation of TiO2 foam. This method provides a new idea for the preparation of foam

matrix of PCM. Li et al. [90] used amorphous TiO2 and SA to synthesize SA/TiO2

encapsulate PCM by Sol-gel method and continued to study the influence of the pH

values during the synthesis process. At the same time, they also adopted CNTs into

the composite PCMs to enhance the thermal conductivity. The results show that

microcapsules are more easily formed under acidic than alkaline conditions. After

adding CNTs, which are uniformly attached to the surface of microcapsules. Due to

the good thermal conductivity of CNTs and abundant thermal channel, the heat

transfer rate and thermal conductivity of composites can be improved. In a word,

43
based on TiO2 foam as matrices has high thermal conductivity, stable chemical and

stable structure, it has important application value in preparing high performance

composite PCMs.

All in all, compared with pure metal materials and carbon black, metal foam and

graphite foam are an excellent additive in improving the thermal conductivity of PCM

due to its porous structure, specific surface area and low density. Hence, it has a better

prospect used as matrices to improve heat transfer rate of composite PCMs, which has

a crucial function for the practical applications in a greater demand to the fast heat

storage and release of system. Various 3D structure additives for thermal properties of

PCM/3D structure additives composites are listed in Table 2.

3.2.2 Passive composite PCMs using two-dimensional structure additives

Since the expanded graphite (EG) has a similar 2D lamellar structure as the clay

mineral, it has good compatibility with the PCM and prevents its leakage property.

EG has abundant network pore and large surface area, where is endowed with

relatively more active sites, surface activities and lots of heat conduction chains,

which can improve the thermal conductivity of the composite PCMs [91]. In addition,

most clay minerals also have pore network structure, large surface area and relatively

high thermal conductivity. Therefore, the passive PCM can be quickly adsorbed into

the pore structure of clay minerals to form-stabilized composite PCMs. However, due

to the small pore openings and narrow interval between layers of clay minerals, the

PCM added are limited under certain circumstances. The interaction between PCM

and clay minerals mainly depends on hydrogen bond, capillary force, van der Waals

44
force and surface tension. These interactions can limit the PCM in the molten state to

the clay mineral structure and prevent their leakage. SiO2 is used as the supporting

material to add clay minerals to the PCM, which could effectively prevent PCM

leakage due to its three-layer reticulated crystal structure [92-97]. Expanded perlite,

sepiolite, attapulgite and expanded vermiculite have large specific surface areas

[98-105]. The interlayer spacing of kaolin is small, making it difficult for the PCM to

compound with kaolin [106]. Diatomite and bentonite have great porosity and pore

space, and it can also effectively prevent the leakage of PCM [98, 99, 107,108]. As

clay minerals have good dispersion, they are not only widely used in form-stable

PCM, but also used as common additives in microencapsulated composites to enhance

their thermal conductivity. Plentiful matrices of 2D structure additives for thermal

conductivity enhancement of metal foam/PCM composites are listed in Table 3.

3.2.2.1 Addition of expanded graphite in passive PCM

Expanded graphite is one of the most popular additives due to its inherent

advantages of high thermal conductivity, chemical stability, low density, large surface

area, high surface activity, good adsorption performance and biocompatibility, EG has

been widely studied and applied in the application of composite PCMs [109, 110].

Many scholars have studied the methods of adding EG into the PCM to

improve the thermal conductivity of the composite PCMs. Wu et al. [111] synthesized

different parameters SA/EG form-stable composite PCMs, in which liquid SA was

adsorpted into EG additives with different contents and the mixture was compressed

into blocks of shapes stabilized with different densities by melting adsorption and

45
pressing molding. Fig. 31 shows the microstructure of pure EG and SA/EG composite

PCM. The figure shows that EG matrix has a worm-like microporous network

structure, which has high surface activity and large specific surface area, thus is easy

to absorb molten SA. In addition, the compressed composite PCM samples show

regular graphite sheets. Since the thermal conductivity of EG is much higher than that

of SA, it presents obvious anisotropy after compression. The maximum difference

between axial thermal conductivity (6.41 W/(m·K)) and radial thermal conductivity

(23.27 W/(m·K)) is nearly 4 times. When EG content is less than 25 wt.%, the thermal

conductivity of EG/SA composite PCM increases with the increase of EG content.

While EG content exceeds the optimal value of 25wt.%, the thermal conductivity of

EG/SA composite PCM slowly decreases. Furthermore, the thermal conductivity of

EG/SA composite PCM changes similarly with the filling density. With low EG

content, the formation of thermal conductivity chain can be promoted with the

increase of EG content, while the regularity of graphite sheet layer can be reduced

with high EG content. For low-density samples, the air thermal resistance can be

reduced as the density increases, while the high-density samples can increase the

interfacial thermal resistance and reduce the thermal conductivity of form stable

composite PCMs.

Amin et al. [112] investigated the thermal properties of beeswax/graphene

composite PCMs. Morphology and preparation of beeswax/graphene nano-PCM is

shown in Fig. 32. The graphene nanosheets disperse well in beeswax and have no

agglomeration phenomenon. The melting point decreases but the solidification point

46
increases with the increase of the mass fraction of the graphene nanosheets. Compared

with the pure beeswax, the melting enthalpy increases by 22.32% due to the Brownian

motion and particle clustering mechanisms. The thermal conductivity of the

composite PCMs increases when the mass fraction of the graphene nanosheets varies

from 0.05% to 0.3%. Exactly, the enhancement of thermal conductivity has a linear

relationship with the increase of graphene content within a certain range. With the

concentration of graphene continues to increase, the thermal conductivity

enhancement is nonlinear because of the agglomeration of the nanoparticles. This

indicates that in the low concentration stage, heat conduction channels are formed in

the interior of composites, while the concentration of graphene increased, the

agglomeration of graphene nanocrystalline sheets make the heat conduction channels

disordered and their heat transfer is consumed. However, the thermal conductivity

decreases gradually with the increase of temperature for the same graphene mass

fraction. The thermal conductivity of the composite PCMs reach to 2.89 W/(m·K)

when the temperatures is 40 ᴼC and the graphene concentration is 0.3%. The main

reason is that the heat conduction process is weakened, while the convective heat

transfer process, which is dominated by beeswax liquid, is enhanced and thus its heat

conduction performance is reduced to some extent.

Tian et al. [113] used paraffin as the PCM, ethylene-vinyl acetate (EVA) as

supporting material, EG and carbon fiber (CF) of different dimensions as high thermal

conductivity matrix to synthesize form-stable composite PCMs. Both the dimension

and the structured of EG and CF are different, which leads to the different contact

47
ways between EG and CF. The experimental results indicate there exists synergistic

enhancement effect of CF and EG on the thermal conductivity because of the

complementary structure and morphology between CF and EG. Fig. 33 shows the

morphological characterization, and α, β, γ represent point contact, line contact and

face contact, respectively. The thermal conduction mechanism is different in the

heating and cooling processes and gives rise to the difference of synergistic thermal

conduction between the cooling process and the heating process. The phonons play a

crucial part in the heat transfer for the solid phase composite PCMs. The 1D rod-like

structure of CF makes the paraffin and EVA form the orienting arrangement, which is

in favour of the phonon transport. The convection becomes the principal heat transfer

way with the generation of the phase change in the heating process. It is opposite to

the cooling process. The optimal content of CF is between 10 wt.% and 20 wt.%,

otherwise some CF will agglomerate corresponding to the case of ε in the Fig. 33.

Meanwhile, the crystalline structure of EVA would be destroyed and caused the

leakage of PCM. Moreover, more interfaces will be generated and makes thermal

resistance augment, which will obstruct the heat transfer. Hence, the thermal

conductivity rises with the increase of CF content when the content of CF is under the

optimal range. Conversely, the thermal conductivity will decline rapidly as soon as the

CF content exceeds the optimal range. In addition, the horizontal thermal conductivity

of composite PCMs are higher than the longitudinal thermal conductivity. The high

temperature not only excites molecular chains of EVA and paraffin but also facilitates

the phonon propagation. As a result, the thermal conductivity of the form-stable

48
composite PCMs augments with the rise of the temperature.

Zhang et al. [114] investigated the thermophysical properties of

high-temperature composite PCMs utilizing ternary carbonates

Li2CO3-Na2CO3-K2CO3 with three different carbon materials: EG, graphene

nanosheets (GNSs) and multi-walled carbon nanotubes (MWCNTs). Fig. 34 shows

the structure of carbonates with carbon materials. EG has the micron-level size and

loose porous worm-like structure, which is special 3D layered structures and tends to

form the continuous heat conduction path. The carbonate salts are not only prone to

crystallize on the surface of the EG and but also implant into the pores of the EG. For

the GNSs, the 2D plane structure makes the thermal conductivity along this plane

enhance. When carbonate salts permeate the crystal structure of GNSs, it can be

attached to MWCNTs via the different styles and forms composite PCMs. However,

the thermal conductivity perpendicular to the GNSs plane is a little smaller than EG.

Among three carbon materials, MWCNTs provide the minimum levels of

improvement on the thermal conductivity of ternary carbonates. MWCNTs ascribes to

the 1D structure and the heat conduction path is based on the axial direction. The

experimental results indicate that three carbon materials express the significant

improvement in the thermal conductivity. EG is the best fruitful and the thermal

conductivity increases by 59.1%. The average thermal conductivity of carbonate salts

with EG, GNSs and MWCNTs is 2.663, 2.225 and 2.089 W/(m·K), respectively. This

phenomenon indicates that the phonon group velocity of heat flow is the fastest in the

3D EG carbon skeleton, which results in the highest thermal conductivity.

49
3.2.2.2 Addition of clay minerals in passive PCM

Because of its porous properties, clay minerals can be used as the supporting

matrix of PCM to prevent leakage, which has been studied by many researchers. Peng

et al. [93] selected montmorillonite (Mt) as wall material and SA as core material, and

obtained Mt/SA microcapsule composite PCMs coated with SiO2 by tetraethyl

orthosilicate (TEOS) hydrolysis and condensation polymerization using self-assembly

method. Fig. 35 (a1, a2) shows the morphological characteristics of Mt/SA

microcapsule composite PCMs. The polymerized particles of Mt/SA microcapsule

adhere to each other without free Mt. It can be particularly visible that Mt forms

effective self-assembled nested microspheres on the surface of SA. But it seems to

only destroy some Mt/SA microcapsules with SA attached to the surface and the

nucleocapsid structure is slightly deformed. Moreover, the Mt is hydrophobic due to

the insertion of cetyltrimethylammonium bromide (CATB). The specific synthesis

process of Mt/SA microcapsules is shown in Fig. 35 (a). Firstly, Mt and SA droplets

are self-assembled through hydrophobic and electrostatic interaction. Secondly, TEOS

are added to the surface of the SA droplet coated with Mt for hydrolysis and

condensation. In the end, it can construct the silica gel matrix network, which can

improve the structural stability of Mt/SA microcapsule. Fig. 35 (b) is a schematic

diagram of the heat conduction pathway of Mt/SA microcapsules. Mt and SA droplets

are self-assembled by surfactant to form microcapsules, and the SiO2 silica gel matrix

network is constructed to form the heat conduction network. The reason is that

hydrogen bands may be generated between SA, Mt and SiO2 matrix. The hydrogen

50
band in Mt/SA microcapsules can improve the thermal conductivity of microcapsules.

The surface convection heat transfer can be promoted through the silica gel shell, and

then the heat is transferred from Mt to SA.

Fu et al. [95] continued to study the effect of microcapsule slurry flow on

thermal conductivity. They employed n-tetradecane (Tet) as core and polystyrene (PS)

and SiO2 as composite shell, a novel Tet@PS-SiO2 nano-encapsulated PCM slurry for

cold energy storage to obtain by dispersing nano-encapsulated PCM into base fluid by

Sol-gel method. Fig. 36 shows the synthesis schematic of Tet@PS-SiO2, TEM images

of Tet@PS and Tet@PS-SiO2. It indicated that the thermal conductivity of the slurry

can be enhanced by the grafting SiO2 of on the PS shell. It's also worth mentioning

that the thermal conductivity of slurry can be strengthened owing to micro-convection

effects in the case of moving. The reason for the enhanced thermal conductivity may

be that the SiO2 shell has a high thermal conductivity and its convective heat transfer

increases during the flow process.

Zhang et al. [96] also taken OC as the core material and SiO2 as the wall material

to prepare OC/SiO2 microcapsule PCM by using Sol-gel method. The encapsulation

of OC is shown in Fig. 37. Specifically, silica sol homogeneous solution encapsulating

OC is obtained through hydrolysis and condensation reaction, silica sol-gel process

finished with ethanol washing get OC/SiO2 microcapsules. It is observed that the

silicon microcapsules are spherical in shape and have clear core-shell structure by

showing SEM images in Fig. 37. In addition, when microcapsules are synthesized at

pH=2.45, the polycondensation rate matched the self-assembly of the oligomer on the

51
surface of the OC micelles and the polycondensation between the silanol groups,

which enabled the spherical microcapsules to maintain a complete and compact

smooth shell. Moreover, the thermal conductivity of solid pure OC is 0.1505 W/(m·K),

and that of pure silica gel shell is 1.296 W/(m·K). Obviously, the thermal conductivity

of silicon microcapsules increased with the addition of SiO2. When the mass ratio of

OC/TEOS is 1:1, the thermal conductivity of the microcapsule increased to 0.6213

W/(m·K). However, when the mass ratio of OC/TEOS is increased to 7:3, the thermal

conductivity of the microcapsules only increased to 0.3751 W/(m·K), indicating that

the porous and thin packaging shell is conducive to heat transfer. We can show that

SiO2 wall materials could form a continuous thermal conductivity network. Therefore,

the heat transfer performance of OC/SiO2 microcapsule PCM is improved when high

heat conduction SiO2 is used as the wall material of the microcapsule.

In order to further improve the thermal conductivity of composite PCMs, Lv et al.

[115] appended EG with different contents in EP and OC to prepared OC/EP/EG

composite PCMs by using vacuum impregnation method. Fig. 38 shows schematic

diagram of the preparation and SEM images of OC/EP composites and OC/EP/EG

composite PCMs. SEM images shown that EP has a rich pore network as well as OC

is well absorbed into the pore network structure on the surface of EP and EG, which

can restrict the flow of PCM in the molten state. The thermal conductivity of pure OC

is 0.4229 W/(m·K) and decreased with the increase of temperature. However, the

addition of EP in the PCM causes the thermal conductivity of the composite PCMs to

slightly increase with the increase of temperature. In addition, when the addition

52
amount of EP is 60%, the thermal conductivity of OC/EP composite PCM is 0.4336

W/(m·K). It indicated that the addition of EP improvement the thermal conductivity

of OC has better effect and the thermal conductivity of OC/EP composite PCMs

increased with the increase of EP mass fraction. Moreover, when the addition amount

of EG is 15%, the thermal conductivity of OC/EP/EG composite PCM is 0.4336

W/(m·K). It indicated that with the increase of EG mass fraction, the thermal

conductivity of OC/EP/EG composite PCMs raise and the change trend of the thermal

conductivity of OC/EP composite PCMs increased. Further, it forms large number of

thermal conductivity channels and promote the rapid heat transfer.

Lv et al. [116] selected kaolin with different particle sizes and mass fractions

and prepared paraffin/kaolin composite PCMs by using vacuum impregnation method.

Fig. 39(a) shows the microstructure of kaolin and paraffin/kaolin composite PCMs.

The surface of kaolin is coated with paraffin wax or embedded in the crystal structure.

Due to the irregular morphology of kaolin, the morphology of paraffin/kaolin

composites is also irregular. Because of the large surface area of the paraffin/kaolin

composite PCMs, the surface of the composite PCMs become compact and smooth

with the addition of large particle size kaolin. Fig. 39(b) shows the thermal

conductivity of paraffin/kaolin composite PCMs with different particle sizes (b1) and

mass fractions (b2). It is observed that the thermal conductivity of paraffin/kaolin

composite PCMs are positively correlated with particle size, but negatively correlated

with temperature. When the temperature is 20℃, the thermal conductivity of pure

paraffin is 0.287 W/(m·K) and maximum thermal conductivity of paraffin/kaolin

53
composite PCMs is 0.547 W/(m·K). The reason is that phonon-phonon scattering is

extremely easy to occur on the contact surface between paraffin and kaolin, which

will generate a large amount of thermal resistance and shorten the phonon mean free

path. In addition, the large number of phonons will collide with each other in the

interface area, which will intensify phonon scattering and significantly reduce the

thermal conductivity. Furthermore, the specific surface area of kaolin decreases with

the increase of particle size, and the smaller the specific surface area is the better.

Therefore, the thermal conductivity of composites with large kaolin particles is higher

than that of composite PCMs with small kaolin particles. In addition, the thermal

conductivity of paraffin/kaolin composite PCMs decreased with the increase of

temperature, which is caused by the shortening of phonon mean free path. With the

increase of temperature, the number of phonons increases obviously, which leads to

the increase of collision frequency. Therefore, phonon-phonon scattering becomes

more frequent, phonon mean free path decreases, and thermal conductivity decreases.

Wei et al. [117] further studied the thermophysical properties of ternary eutectic

salts with expanded vermiculite (EV) and Al2O3 composites. They are primarily

synthetized the lauric-myristic-stearic acid (LA-MA-SA) eutectic mixture by using

ultrasonic heating method, then selected EV treated with nitric acid (aEV) and further

added Al2O3 to obtain aEV/Al2O3 (aEV/AO) supporting matrix with excellent

performance, and finally prepared the LA-MA-SA/AEv/AO composite PCMs by

using vacuum impregnated method. As shown in Fig. 40, which shows the

microscopic morphological images of EV, aEV, aEV/AO, LA-MA-SA/aEV/AO. The

54
EV is observed to have a thick layered structure, a small amount of delamination

occurred on the surface of aEV and pore structure began to further form by treating

nitric acid. However, aEV/AO maintained thin laminar morphology and the number

of pore matrix structure raised. Hence, In LA-MA-SA/aEV/AO composite PCMs,

LA-MA-SA are fully absorbed into the pores of aEV/AO. In addition, the thermal

conductivity of the composite PCMs tested results that the thermal conductivity of the

aEV (0.389 W/(m·K)) is smaller than that of the EV (0.414 W/(m·K)). The reason for

the decrease of thermal conductivity is that the increase of defects caused by using

acid treatment would aggravate phonon scattering. Owing to increase by Al2O3 on the

supporting matrix, the thermal conductivity of aEV/AO has reach 0.563 W/(m·K).

Moreover, the thermal conductivity of LA-MA-SA/EV, LA-MA-SA/aEV and

LA-MA-SA/aEV/AO composite PCMs are 0.513, 0.448 and 0.671 W/(m·K),

respectively, which are 37.5%, 30.8% and 156.1% higher than that of the composite

PCMs of LA-MA-SA (0.262 W/(m·K)). The reason may be that Al2O3 has good

thermal conductivity and it is evenly dispersed in the composites, which can form a

thermal conductivity chain and enhance its heat transfer performance.

Qian et al. [118] resolved silver nitrate by hydrothermal synthesis to prepare Ag

nanoparticle (AgNP) additive as first step. Afterwards diatomite (Dt) was modified for

filling AgNPs by alkali and sulfuric acid leaching ordinal treatment. Finally, using

PEG and modified AgNPs were prepared high thermal conductivity PEG/Dt/Ag

form-stable composite PCMs via melting blending method. The corresponding

preparation process and morphological characteristics as well as thermal conductivity

55
variation of composite PCMs are shown in Fig. 41. Since fewer impurities of Dt is

treated via sulfuric acid leaching, which is improved obviously thermal conductivity

of composite PCMs by using hydrothermal synthesis and vacuum impregnation.

Additionally, the high thermal conductivity of metallic silver (429 W/(m·K)), the

thermal conductivity of Dt itself is also high and PEG is also impregnated into the

pores of Dt, its thermal conductivity is significantly improved. Interestingly, after the

addition of AgNPs, the thermal conductivity of PEG/Dt/Ag composite PCMs are 127%

higher than PEG/Dt composite PCMs. It indicated that the addition of AgNPs can

better improve the thermal conductivity of PEG/Dt/Ag composite PCMs.

Li et al. [119] prepared three kinds of SA/FG/B, SA/FG-CNF/B and

SA/FG-CNF-Bm composite PCMs by means of silane coupling agent modified

bentonite (Bm) and flake graphite-carbon nanofiber (FG-CNF) through chemical

bonding coupling supporting materials and melting blending with SA. The preparation

process, morphological characteristics of FG-CNF-Bm and SA/FG-CNF-Bm

composite PCMs are synthesized as shown in Fig. 42. It can be observed that Bm is

closely attached to the surface of FG-CNF and wrapped the whole CNF, resulting in

an increase in the contact area, thereby improving the thermal conductivity of

FG-CNF-Bm. In addition, the porous network structure generated by CNF provides a

larger filling space for SA. Significantly, the SA is uniformly fixed in the

FG-CNF-Bm mesh pore structure, which improves the adsorption capacity of the

composite PCMs and effectively prevents the leakage of molten SA. Consequently,

the thermal conductivity of FG, FG-CNF, FG/B, FG-CNF/B, FG-CNF/Bm,

56
FG-CNF-Bm, SA, and FG-CNF-Bm/SA composite PCMs are determined as 5.471,

5.944, 4.176, 4.499, 4.291, 4.595, 0.267 and 2.803 W/(m·K), respectively. According

to the phonon thermal conductivity mechanism, excessive interfacial pores between

the PCM and the added matrix will increase the surface scattering of phonons,

resulting in a significant reduction in thermal conductivity [53]. Compared with

FG-CNF, the thermal conductivity of CNF grown on the surface of FG (5.471

W/(m·K)) is lower than that of FG-CNF (5.944 W/(m·K)), while the thermal

conductivity of FG-CNF/B (4.499 W/(m·K)) is higher than that of FG/B (4.176

W/(m·K)). It is mainly attributed that CNF is filled in the gap between FG, while the

surface CNF matrix combined with microscale Bm particles can increase the contact

area. Thanks to the low thermal conductivity of bentonite (0.82 W/(m·K)) [120], the

thermal conductivity of pure bentonite is lower than FG and FG-CNF samples. But

the thermal conductivity of FG-CNF-Bm (4.595 W/(m·K)) is relatively higher than

FG-CNF/Bm (4.291 W/(m·K)). It may be that the successful coupling of chemical

bonds reduced the interface thermal resistance between FG-CNF and Bm. Hence, it

can significantly improve the thermal conductivity. For this reason, CNF not only

obtains a larger contact area to promote heat conduction, but also provides more heat

conduction channels for heat transfer through chemical bond coupling. Compared

with the thermal conductivity of pure SA (0.267 W/(m·K)), the thermal conductivity

of SA/FG-CNF-Bm composite PCM (2.803 W/(m·K)) is increased by 10.50 times.

Mainly, FG-CNF-Bm has larger contact area and successfully coupled chemical bonds,

further forming more effective thermal conduction paths, which greatly improves the

57
thermal conductivity of the composite PCMs as well as prominently reduces the

charging and discharging time of the system.

On the whole, the EG and clay minerals of 2D layer as porous support materials

to prepare high performance passive composite PCM is significant value for thermal

storage. Especially, it has excellent effect in preventing the leakage of PCM in molten

state. Table 3 summarizes the preparation methods of passive composite PCMs and

summary of improving thermal conductivity of 2D structure additive as supporting

materials.

3.2.3 Initiative composite PCMs using one-dimensional structure additives

The 1D structure additives have many morphological structures, such as carbon

fiber (CF), carbon nanotubes (CNTs) and rod-shaped graphene etc. Due to its

excellent 1D thermal conductivity, even just the addition of a small amount of 1D

structure supporting materials can significantly improve the thermal conductivity of

the composite PCMs. In addition, 1D structure additives are lighter than metal or

ceramic additive materials, which has a wider range of practical applications. Besides,

the 1D structure additives, which also has good dispersion in the melting state and

reduce the supercooling degree, are the ideal choice for the preparation of the high

performance PCM.

3.2.3.1 Addition of carbon fiber in initiative PCM

CF and CNTs are 1D additional matrix and CF materials can be obtained by high

temperature carbonization in inert gas. CF also has the advantages of low density,

high temperature corrosion resistance and high thermal conductivity. Mesophase

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pitch-based CF has highly crystalline graphite structure which is parallel to the

orientation of fiber axis and its longitudinal thermal conductivity exceeds 1000

W/(m·K) [121]. In addition, it can absorb almost all organic PCM, so it is one of the

best materials to improve the thermal conductivity of organic PCM [122]. Adding CF

into PCM can significantly improve the thermal conductivity of composite PCMs, in

which the length, diameter, the added mass fraction and distribution mode of CF [123]

will affect the thermal conductivity of composite PCMs [121].

This has aroused the researchers' interest in studying more clearly the effect of

the addition on the thermal conductivity of composite PCMs. Zhang et al. [124]

prepared composite PCMs samples by filling a series of short carbon fiber (SCF) with

different aspect ratios in erythritol. As shown in Fig. 43, the morphological

characteristics of C5 and C25 with different mass fractions in SEM enlarged images

show that C5 and C25 are easily bound to erythritol. In addition, SCFs has no

aggregation and coupling, and its distribution is relatively uniform, while the addition

of SCFs directly affects the size of grain. The larger the content of SCFs, the smaller

the grain size. Adding more SCFs can promote the heat transfer rate of composite

PCMs. As the mass fraction of SCF increases, the thermal conductivity presents a

nonlinear increase. When the additive volume of C25 and C5 composite PCMs are

10%, the maximum thermal conductivity reaches 3.92 W/(m·K) and 2.46 W/(m·K),

respectively, which are 407.8 % and 242.9 % higher than that of pure erythritol (0.77

W/(m·K)), respectively. The larger aspect ratio of CF and the larger thermal

conductivity of the composite PCMs. Because the crossbar is larger than CF, it is

59
easier to form a thermal conduction network in composite PCMs. On the one hand,

when the two kinds of aspect ratio of different additives to form composite PCMs

have the same structure, the interface thermal resistance are equal, so the total thermal

resistance depends on the SCFs of PCCs and erythritol total contact area of the

interface, C5 composite PCMs 8.2% larger than C25 interface, interface of the large

number of small diameter and C5, lead to more of the top and bottom of the

connection between the CF. On the other hand, the connection state of the additive is

closely related to the composite PCMs. When low content of C25 is added, CF in the

matrix is connected to each other through contact nodes, forming more local networks

and thus improving thermal conductivity.

Jiang et al. [125] employing CF in paraffin wax to bond with polymer binder,

which formed a stable network after carbonization, prepared a kind of porous mesh

carbon bonded CF composite PCMs (CBCF-CPCM) with fixed carbon bond. Fig. 44

shows the microstructure of CBCF, CBCF-CPCM and thermal conductivity curve. It

can be seen that CF is oriented in the xy plane, as the heat transfer is more likely to be

carried out along the fiber direction, resulting in the significant improvement of the

thermal conductivity of CBCF-CPCM compared with pure paraffin. In the z direction,

the arrangement of carbon fibers tends to overlap, so the number of nodes forming the

heat conduction network is limited. In addition, the cross section of CF can directly

form the heat transfer path, in which the carbon crystal plane is short and discrete

according to the arrangement of the crystal layers. Therefore, the thermal conductivity

outside the plane will be greatly reduced. Fig. 44 is a schematic diagram of heat

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conduction network formed by bonding between CFs. The powder phenolic resin is

evenly distributed on the surface of CFs. When the phenolic resin melts at high

temperatures, gravity causes the liquid phenolic resin to slide along the surface of the

CF. Further, the liquid phenolic resin is bonded together with CF, when they reach the

point of contact between the CFs. After carbonization and heat treatment, the CFs are

held in place to form a stable thermal conductivity network.

Two preparation methods have been carried out by Nomura et al [126],

erythritol was employed as the PCM and CF considered as the heat conduction

enhancer. Erythritol/CF composite PCMs by melt dispersion (MD) and hot press (HP)

were prepared to improve the content of CF in erythritol. Fig. 45 is a schematic

diagram of composite PCMs prepared by (a) MD method and (b) HP method as well

as curve diagram of effective thermal conductivity of composite samples changing

with the content of CFs. The results show that HP method is easy to form the

percolating filler network in composite PCMs. Compared with the composite PCMs

prepared by MD method, the addition of CF is less and the thermal conductivity is

higher. In addition, high CF content can promote the formation of the percolating

filler network. In order to control the filling ratio of CF in PCM, the diameter

distribution of PCM particles can be controlled. Because in the process of HP, CF in

the state of uniform mixing is distributed around the PCM particles. Because the PCM

particles are stationary and solid during the HP process. When CFs are mixed with

erythritol, the morphological characteristics of erythritol have great influence on the

configuration of CFs. Under this condition, it is easy to form a network structure

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permeating CFs, because the PCM particles are initially in contact with each other.

Meanwhile, the gap around the PCM particles filled with CFs are in a seepage state.

In this way, HP method can easily form the seepage structure of high thermal

conductivity filler. The large filling gap between PCM particles and CF makes the

composite PCMs with high filling ratio have abundant thermal conductivity network

structure. Furthermore, the phonon group velocity of transfer and mean free path

increased to improve the thermal conductivity of the composite PCMs.

3.2.3.2 Addition of carbon nanotubes in initiative PCM

CNTs are characterized by large specific surface area, uniform micropores,

unique physical and chemical properties, low density and high thermal conductivity

(2000~6000 W/(m·K)) [127], which are considered as a potential high thermal

conductivity additive. MWCNTs can be used as an additive for some other chemical

adsorbents to improve their heat transfer characteristics [128]. Since CNT is 1D

nano-addition material, it has excellent nano-scale effect, low density and high

thermal conductivity [129]. According to relevant experiments, the thermal

conductivity of single CNT is higher than 3000 W/(m·K) [130]. The excellent thermal

conductivity of CNTs makes it an ideal additive matrix for the preparation of

composite PCMs. CNTs are divided into single wall CNT (SWCNT) and multi-wall

(MWCNT), in which SWCNT is curly made of monolayer graphene. In the process of

winding the graphene layer into a cylinder, the dangling bonds are rapidly combined

on the boundary, which made the axis of CNTs randomly distributed. Carbon atoms

are wound into a helical hexagonal grid to form CNTs. When the graphene surface is

62
aligned longitudinally along the axis of SWCNT, a 2D geometry similarly to graphene

surface is generated [131]. MWCNT has excellent thermal, electrical and mechanical

properties, which have broad application prospects [132]. After calculation, at the

temperature of 100 K, the thermal conductivity of single MWCNT is 37000 W/(m·K),

and its macroscopic thermal conductivity can reach 6000 W/(m·K) [133]. At room

temperature, the thermal conductivity of single MWCNT can be compared with the

diamond, and even reach a higher value [134]. Based on the above excellent

properties, mixing CNTs in PCM to improve the thermal conductivity of composite

PCMs have attracted great attention of researchers [135].

Zhang et al. [136] used CNTs as heat conduction enhancement agent and

expanded perlite (EP) as leakage inhibitor to prepare paraffin-CNTs/EP composite

PCMs by vacuum impregnation method. The preparation process of composite PCMs

are shown in Fig. 46. Firstly, anhydrous ethanol is mixed with CNTs by ultrasonic

treatment, and paraffin is added into the mixed solution and mixed evenly. Then, a

constant temperature water bath is used for a period of times from melting state to

solidification state and mixed evenly. Behind, it is transferred to a vacuum drying

oven at a certain temperature and impregnated to obtain a paraffin-CNTs/EP

composite PCMs. Schematic diagram of the morphological characteristics of CNTs

are shown in Fig. 46. CNTs show a slender silky appearance, and the large number of

CNTs agglomerate due to van der Waals forces. CNT is completely wrapped by

paraffin and evenly dispersed in the pores and surface of EP, which can promote the

formation of heat conduction channels in paraffin-CNTs/EP composite PCMs. In

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addition, the thermal conductivity of paraffin-CNTs/EP composite PCMs are tested.

At room temperature, the thermal conductivity of pure PA and EP are 0.204 W/(m·K)

and 0.058 W/(m·K), respectively. When the filling amount of CNTs is zero, the

thermal conductivity of paraffin-CNTs/EP composite PCMs are only 0.107 W/(m·K),

which is caused by the low thermal conductivity of EP. With the increase of CNTs

content, the thermal conductivity of paraffin-CNTs/EP composite PCMs increased.

While the filling amount of CNT is 5.27%, the thermal conductivity of

paraffin-CNTs/EP composite PCMs are 0.516 W/(m·K). Because the added CNTs

have a high thermal conductivity and are evenly dispersed in PA, they can form a high

thermal conductivity network with a high aspect ratio. With the increase of the mass

fraction of CNTs, the thermal conductivity network becomes closer, which further

enhances the thermal conductivity of paraffin-CNTs/EP composite PCMs.

In order to improve the thermal conductivity of polyethylene glycol, Qian et al.

[137] synthesized PEG/SWCNTs nano-composite PCMs by impregnation method. Fig.

47 shows the process of preparation and the morphological characteristics of

SWCNTs and PEG/SWCNTs nano-composite PCMs. It is obvious that SWCNT

presented a uniform and densely distributed network composed of carbon rods and

rough surfaces. In contrast, PEG/SWCNTs nano-composite PCMs, SWCNTs formed a

more interconnected thermal conductivity network. On the one hand, the addition of

SWCNTs to PEG/SWCNTs can improve the adsorption efficiency of PEG to a certain

extent up to 98%. One the other hand, the thermal conductivity of the composites is

significantly improved by increasing the content of SWCNTs. The thermal

64
conductivity of the composites in solid state (3.43 W/(m·K)) is 1329% and in liquid

state is 533% higher than pure PEG (0.24 W/(m·K)). The reason for this result may be

that SWCNTs form many heat conduction channels in the composites. In fact, solid

PEG is mainly heat conduction and fixed SWCNTs heat conduction channels could

improve its heat transfer performance. However, the heat transfer of liquid PEG is

dominated by convection and the heat conduction channels of SWCNTs is easy to

agglomerate, which reduces its effect of improving heat conduction ability.

After the structural modification of MWCNT, Putra et al. [138] prepared three

amorphous PCMs: untreated MWCNTs/beeswax, ball-milled MWCNTs/beeswax and

acid-treated MWCNTs (A-MWCNTs)/beeswax. Fig. 48 shows the morphological

characteristics of pristine MWCNT and A-MWCNT. The surface of pristine MWCNT

is smooth and shaped like a rod and strong acid oxidizes MWCNT to form

A-MWCNT. The surface of A-MWCNTs is shown in Fig. 48 (c): compared with

pristine MWCNT, A-MWCNT rods are short and thick, which converge and become

denser, and the surface is relatively rough. This is mainly due to the strong acid

oxidation resulting in the reduction of MWCNT impurities. A-MWCNT can

physically absorb beeswax into its pores. The higher the percentage of A-MWCNT,

the more beeswax is absorbed into the pores of MWCNT, and the less beeswax in

surface, thus can prevent the leakage of beeswax. On the other hand, after the addition

of MWCNTs, the thermal conductivity will increase significantly. The thermal

conductivity of formalized beeswax/A-MWCNT samples is higher than pure beeswax

(0.25 W/(m·K)) [139] and paraffin (0.287 W/(m·K)) [140]. When the mass fraction of

65
A-MWCNT is 20wt.% and 5wt.%, the thermal conductivity of beeswax/A-MWCNT

form stable PCM samples is 0.58 and 0.46 W/(m·K), respectively, which indicated

that MWCNTs could also significantly improve the thermal conductivity of beeswax.

The beeswax of the acid-treated MWCNTs is tightly absorbed, which can reduce the

interfacial phonon group transmission, thus improving its thermal conductivity.

Wang et al. [141] prepared CNT composites consisting of PA as the matrix and

MWCNTs as the additives. The added MWCNTs are treated by four different

chemical/physical methods, which synthesized P-MWCNTs (untreated) (a),

B-MWCNTs (b), M-MWCNTs (c), A-MWCNTs (d), and G-MWCNTs (e). The

Schematic diagram and microscopic morphology of MWCNTs processed is shown in

Fig. 49. At a specified temperature under solid state, the thermal conductivity

enhancement is in the order of M-MWCNT/PA > A-MWCNT/PA > B-MWCNT/PA >

P-MWCNT/PA > G-MWCNT/PA. Whereas the order changes into M-MWCNT/PA >

A-MWCNT/PA > G-MWCNT/PA > B-MWCNT/PA > P-MWCNT/PA at a specified

temperature under liquid state. Furthermore, the thermal conductivity enhancement

ratios of G-MWCNT/PA surpass the corresponding values of B-MWCNT/PA and

P-MWCNT/PA. The key reason for the difference in thermal performance is the lower

intrinsic CNTs conductivity after treatment, due to scattering of heat carrying phonons

by interactions with the surroundings or defects and the other one is the contact

thermal resistance on the surface of CNTs. In addition, in addition to the

chemical/physical treatment of carbon nanotubes, the main factors affecting the

thermal conductivity of the composite phase-change materials are length, thickness,

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mass fraction and type. Fan et al. [142] also compared different lengths of CNTs with

CFs and graphene and Liu et al. [143] further studied that CNTs can significantly

enhance the thermal conductivity of the microcapsule composite PCM, which has

important research value for improving the heat storage performance of the

microcapsule.

3.2.3.3 Addition of rod-shaped graphene in initiative PCM

Rod-shaped graphene is a new kind of monolayer 1D structure material, which is

similarly to graphite nanocrystalline sheets in microstructure. It has unique physical

properties such as strong mechanical stability, good thermal conductivity and large

specific surface area [144]. According to recent studies, graphene has better thermal

conductivity than CNTs [145]. The thermal conductivity of single-layer graphene is as

high as 5300 W/(m·K), and even some studies have shown that its thermal

conductivity can reach 6600 W/(m·K) [146]. Adding graphene to the PCM can

improve the thermal conductivity of the composite PCMs, so graphene has great

advantages in improving the thermal conductivity of the PCM. A lot of research work

is being done on the preparation of high thermal conductivity graphene-based

composite PCMs.

Zhong et al. [147] utilized 3D graphene aerogel (GA) and octadecanoic acid (OA)

to produce GA/OA composites by the modified Hummers’ method. Fig. 50 is

preparation process and morphological characteristics of GA/OA composite PCMs.

The inherent flexibility of graphene sheets is a crucial property for constructing the

3D macrostructures. The 3D porous network with interconnection of unfilled GA is

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shown that pore sizes of the network is about several micrometers and the pore walls

consist of thin layers of stacked graphene sheets. Approximately 95% of the pores in

GA are interconnected, which allows it to be easily saturated with the molten OA.

Calculated results indicated that the OA filled about 98% of the available pore volume

in the GA. The fracture surface of GA/OA composite PCMs are indicated that

basketwork of the GA remains very well and no evidence is seen of interfacial

separation or cracking in the foam structures. After being filled with OA, the GA is

clothed in the OA as well as interfaces of the OA and the graphene combine

compactly due to the good wetting property between the two phases. Compared with

the CNT, the GA is a homogeneous holder material for the PCM, which can avoid the

agglomeration, structural deformation and thermal contact resistance.

Yang et al. [148] used graphene oxide (GO) and GNP as additives, polyethylene

glycol (PEG) as PCM to prepare PEG/HGA composite PCMs via vacuum

impregnation method. GO nanosheets formed a 3D supporting network to keep the

form-stable PEG during phase change and GNP dispersed uniformity along the

network structure of GO and thus a thermal conductive path way is constructed. The

aromatic regions offered active sites to make it possible to interact with other aromatic

molecules through π-π supramolecular interactions. Preparation and morphological

images of the PEG/HGA composite PCMs are shown in Fig. 51. The thermal

conductivity of PCM can be improved remarkably main reason that GNP, as a thermal

conductive filler, established a well-developed 3D heat conduction pathway with the

support of GO and the structure of HGA can be kept after freeze drying and vacuum

68
impregnation. The 3D thermal conduction pathway formed is more perfect and the

thermal resistance is reduced. Furthermore, Choi et al. [149] compared the effects of

three carbon-based additives: MWCNTs, EG and graphene, on the thermal

conductivity improvement of PCM. They found that graphene has the best thermal

conductivity for PCM, which is attributed to its smaller interfacial thermal resistance

and faster thermal conduction. In addition to the above researches on 1D graphene,

there are also researches on porous graphene foams, such as Chen et al [150] and Li et

al [151]. We can predict that graphene foam is also a novel type of high thermal

conductivity additive with great potential, which will play an important role in the

preparation of high performance composite PCMs.

To sum up, 1D structure additives have the advantages of high thermal

conductivity, low density and stable chemical property, etc. Obviously, the high

thermal conductivity of matrices is profitable for the improvement of thermal

conductivity in PCM. Further, many factors affect the high thermal conductivity of the

added substrate, such as porosity, specific surface area and length-width ratio, etc.

CFs, CNTs and rod-shaped graphene possess large length-width ratio, where CFs and

CNTs have chemical attack resistance and corrosion resistance, and rod-shaped

graphene with a special structure of a single layer 1D structure, shows distinctive

chemical and physical properties. Thermal conductivity enhancement of abundant 1D

structure additives is listed in Table 4, which manifested that 1D structure additives

are wonderful matrices in the aspect of improving the thermal conductivity of

initiative PCM.

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3.2.4 Initiative composite PCMs using zero-dimensional structure additives

In addition to the above additives, the 0D structure additive, such as

ceramic-based and nanoscale-based nano particles, have received considerable

attention in the preparation of composite PCMs due to large specific surface area,

strong interface interaction and homogeneity as well as dispersion. It also includes a

mixture of bio-based additives concentrated carbon nano-materials [152]. Owing to

possess high thermal conductivity, the addition of a small amount of 0D structure

additives supporting materials can significantly improve the thermal conductivity of

the initiative composite PCMs [153]. As a result, it can be used as an additive for form

stable PCM and as a heat conduction of microcapsule composites. Further, the heat

transfer performance of composite PCMs can be significantly improved by adding

nanoparticles to PCM in a certain way and proportion. For the lack of free electrons in

the process of heat conduction, heat flow is predominantly transmitted by phonons. In

addition to BeO, most metal oxide additives such as aluminum oxide (Al2O3),

titanium dioxide (TiO2) and copper oxide (CuO) have relatively high thermal

conductivity [154-157]. Non-oxide additives such as boron nitride (BN) [158-161],

silicon nitride (Si3N4) [162] silicon carbide (SiC) [163, 164] and MOFs [44, 45] have

strong interatomic bond energy and crystal structure, which can significantly reduce

phonon scattering and show high thermal conductivity. In particularly, AlN and BN

additives are widely used to prepare high performance composite PCMs.

Tang et al. [165] prepared composite PCMs by in-situ doping Al2O3 and PEG

with ultrasonic assisted Sol-gel method, which significantly enhanced the thermal

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conductivity of PEG/SiO2-Al2O3 hybrid stereotyped composite PCMs. The reason

may be that one end of spherical micron particles is anchored on the surface of Al2O3

and the other end diverges outward. Evidently, this composite structure greatly

improves the dispersion of PEG/SiO2. Furthermore, compared with PEG/SiO2, the

thermal conductivity of Al2O3 with 3.3 wt.% in the original PCM increases by 12.8%.

Since Al2O3 skeleton greatly reduced the contact thermal resistance and interface

thermal resistance, it can form more stable thermal conduction channels in the matrix,

which is beneficial to phonon transmission. Additionally, PEG/SiO2-Al2O3 hybrid

structure not only improves PEG/SiO2 dispersion and eliminates agglomeration, but

also it constructs a continuous PEG/SiO2 heat conduction chain with Al2O3 micron

particles as anchor points. The AlN shell layer is formed on the surface of Al2O3 and

SiO2 by carbon thermal reduction and nitriding, which can produce the nucleated shell

particles of Al2O3@AlN and SiO2 @Si3N4, which can enhance the heat transfer

between AlN and Al2O3 as well as enhance its thermal conductivity.

Nourani et al. [166] also prepared a novel nano-composite PCMs (NCPCMs)

using paraffin as PCM, Al2O3 nano-particles as fillers and sodium stearyl lactate (SSL)

as surfactant. When the content of Al2O3 is 2.5, 5, 7.5, 10 wt.% and the mass fraction

of SSL/Al2O3 is 1:3.5, the dispersion of nano-particles in paraffin wax is significantly

improved. The experimental results show that the effective thermal conductivity

enhancement ratio of samples containing 10.0 wt.% nano-Al2O3 in solid and liquid

state is 31% and 13%. What is more, the melting rate of samples increased by 27%. In

addition, the thermal conductivity tested in the 45-55 ℃ , its effective thermal

71
conductivity increased under the temperature of 55℃. Since the influence of

temperature, it can be changed the orderly structure of solid composite PCMs and the

number of molecules of vibrations probably increased. When NCPCMs changes to

liquid state, the ordered solid phase structure changes into disordered liquid phase

structure and it may be diminished the effective thermal conductivity of the

composites. Compared with the disordered structure in liquid state, the ordered solid

structure can enhance the heat transfer between nano-Al2O3 particles and paraffin wax.

Therefore, the effective thermal conductivity increases more in solid state than in

liquid state.

Mohamed et al. [167] synthesized composite PCMs by fully adsorption of

paraffin wax and microcrystalline wax loaded with α-Al2O3 (0.5, 1 and 2 wt.%) with

different mass fraction further studied their thermal conductivity and thermal storage

performance. The experimental results show that the higher the loading mass fraction

of α-Al2O3 in paraffin wax composite PCMs, the better its thermal conductivity and

latent heat storage performance. At the temperature of 293 K~323 K, the nano-Al2O3

particles with different mass fraction are loaded into the PCMs, which resulted in

significant enhancement of thermal conductivity. Therefore, nano-alumina particles

could obviously improve the thermal conductivity of the composite PCMs.

Furthermore, the thermal conductivity of the composites increases with the increase of

phase change temperature. In addition, the thermal conductivity of six kinds of

composite PCMs are higher than that of pure paraffin wax and microcrystalline wax.

It indicates that the addition of nano-Al2O3 and paraffin can regulate the range of

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phase change temperature in the composite PCMs and enhance thermal load response

rate of heat storage.

Jiang et al. [168] employed paraffin wax core and poly (methyl methacrylate

comethyl acrylate) shell modifying with nano alumina (nano-Al2O3) inlay to produce

microcapsule PCMs via emulsion polymerization. The SEM images of paraffin

morphological characteristics modified with different percentages of nano-Al2O3 are

shown in Fig. 52. It can be seen that the average particle size apparently became small

for the sample synthesized at the nano-Al2O3 mass of more than 16%. Since

nano-Al2O3 is equivalent to nucleating agent, when the number of nucleating agents

increase and the particle size will decrease. Furthermore, thermal conductivity rapidly

improves by the mass fraction of nano-Al2O3 increasing, which is nearly linear

correlation between the thermal conductivity and the addition level of nano-Al2O3.

The high thermal conductivity channel formed by nano-Al2O3 evenly distributed in

PCM is the fundamental reason for promoting the improvement of thermal

conductivity.

Sharma et al. [169] prepared nano-enhanced organic PCMs of PA/TiO2 by

melting blending method using PA and TiO2 nano particles with different mass

fractions. The preparation process and morphological characteristics of the sample of

the composite PCMs are shown in Fig. 53. Since the repulsion of the surfactant, TiO2

nanoparticles are evenly dispersed in PA. In some regions, the melting of the PCM

near the PA block, which is mainly caused by the concentration of electron beams at a

specific location. Moreover, thermal conductivity of PCM significantly improve by

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the mass fraction of nanoparticles increasing. When 0.5, 1, 3, and 5 wt.% of TiO2

nano particles are supplemented in all else being equal, the thermal conductivity

increased by 12.7%, 20.6%, 46.6% and 80%, respectively. Significantly, the thermal

conductivity of composite PCMs are approximately proportional to the mass fraction

of TiO2 nano particles. Since the agglomeration of abundant TiO2 nano particles

occurs in mixture, which results in the nonlinear increase of thermal conductivity.

Further, the thermal conductivity of the composite PCMs are larger than that of pure

PA and it can promote to melt and solidification of the composite PCMs. At the same

time, it may be that TiO2 nano particles are evenly dispersed in PA, which is

equivalent to the addition of nucleating agent, thus reducing the degree of

supercooling and further shortening the melting and solidification time.

Su et al. [170] prepared composite PCMs containing hexagon boron nitride

(HBN) eutectic crystals using OC and SA, and introduced HBN to significantly

improve the thermal conductivity of the composite PCMs. The chemical adhesion,

crystalline phase and morphology of eutectic mixture/HBN composite PCMs are

further tested. Fig. 54 shows the morphological characteristics of the HBN, SA-ODE

eutectics, PCM1, PCM2 and PCM3 composites. From the diagram shows that there is

no chemical reaction between SA-ODE eutectic and HBN, and the composite PCMs

had good thermal stability. Moreover, the thermal conductivity of melting/solidifying

composite PCMs increased significantly by addition of HBN medium, while the latent

heat of phase change decreased slightly. Furthermore, under liquid phase conditions,

the mass fraction 5, 10, 15wt.% of HBNs added into SA-ODE to form composite

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PCMs and the thermal conductivity of eutectic mixture is 0.1586, 0.1764, and 0.1863

W/(m·K). After the introduction of HBN, the thermal conductivity increased by

0.0074, 0.0252 and 0.0351 W/(m·K), which means that the thermal conductivity

increased by 4.9%, 16.7% and 23.2%, respectively. Undoubtedly, the new composite

PCMs have higher thermal conductivity than other composite PCMs. Obviously, the

introduction of HBN will improve the thermal conductivity of SA-ODE eutectic

mixtures in both solid and liquid phase environments. The reason is that HBN packing

with high aspect ratio is easy to form network structure and improve thermal

conductivity. Interestingly, the quasi-percolation behavior can be observed when the

HBN particle network is constructed, but the thermal conductivity does not follow the

percolation rule. Moreover, hybrid micron HBN and SA-ODE are filled with eutectic

mixtures meanwhile the hybrid particles uniformly distributed in the matrix are easy

to establish a heat conduction network when the appropriate specific sequence is

suitable. Eventually, the HBN particles form an effective connection point between

SA-ODE, which promotes the formation of heat conduction network and the effect of

interfacial phonon transmission.

Fang et al. [171] filled HBN nano-sheets with paraffin wax to produce a series of

novel paraffin-based composite PCM samples by supplement HBN nano-sheets (mass

fraction: 0, 1, 2, 5 and 10 wt.%). The presence of HBN nano-tubes (up to 10wt.%)

resulted that the thermal conductivity increases reach 60% and the latent heat of

melting decreases less than 12%. Since the thermal conductivity of the HBN

nano-sheets has been improved and the melting/frozen rate also has been increased by

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25%, which can prove the superior applicability of composite PCMs. Fig. 55 shows

the microscopic morphology characteristics of HBN nano-sheet. Because the thermal

conductivity increase largely depends on the shape, size and thickness of HBN

nano-sheets, which may become a research hotspot in the future for the influence of

these geometric parameters.

Yang et al. [172] used OC as the core material and polymethyl methacrylate

shell as wall material to synthesize a novel microcapsule PCMs by supplemented with

modified Si3N4 powder. When modified microcapsules fill a certain amount of Si3N4,

the heating rate is positively correlated with the addition level of Si3N4, which

indicated that Si3N4 can significantly improve the thermal conductivity of the

microcapsules. Fig. 56 shows an improved Si3N4 microcapsule synthesis method and

morphological characteristics of microcapsule composite PCMs. Frankly, adding

Si3N4 particles will increase the thermal conductivity. When the amount of Si3N4

increased to 10g, the thermal conductivity increased by 56.8% to 0.3630 W/(m·K).

The most reason is that the microcapsule isolation structure reduces the interfacial

thermal resistance between the thermal conducting particles and the matrix, which is

wrapped around the matrix particles rather than uniformly entering and distributing

inside the matrix particles, and it can significantly improve its thermal conductivity at

a lower addition level.

Yuan et al. [173] prepared a novel composite PCMs by introducing SiC/EG heat

conducting skeleton and adding it to the mixture of PA and epoxy resin (ER). Since

the thermal conductivity of SiC is similarly to EG, but the volume resistivity is much

76
higher than that of EG, the high thermal conductivity and volume resistivity of SiC to

prepare the composite PCMs have high thermal conductivity and low electrical

conductivity. Fig. 57 shows the morphological characteristics and preparation of SiC

and composite PCMs. It can be clearly seen that the size of SiC particles is evenly

distributed. After adding granular SiC, the morphology of the samples becomes

sufficiently dense and SiC particles can be effectively filled in the network pores. The

thermal conductivity of the composite PCMs increases with the increase of SiC added

content reach 15 wt.%, the thermal conductivity of 2.0 W/(m·K) continues to grow

and the volume resistivity reach the maximum of 12.5×1011 Ω·cm, and the composite

PCMs have the best comprehensive performance. Moreover, when the content of SiC

from 15 wt.% increase to 20 wt.%, the thermal conductivity increased from 2.0

W/(m·K) to 2.8 W/(m·K)) and volume resistivity decreased to 7.7×1011 Ω·cm from

12.5×1011 Ω·cm. When adding appropriate amount of SiC in the composite PCMs,

SiC particles in EG pores may block the electron transmission path, thus increasing

the volume resistivity. In the case of high silicon carbide content, EG and SiC form

the large number of continuous skeletons in the composite PCMs, which may lead to a

sharp increase in thermal conductivity and a significant decrease in volume resistivity.

Chen et al. [174] used Cr-MIL-101-NH2 (MOFs) as porous support material,

carbon quantum dot (CQD) as fluorescence active material and SA as heat storage

material to design and prepare MOFs/CQD/SA photoluminescence-functionalized

composite PCMs by melting impregnation method. Fig. 58 shows the preparation (a)

and excitation fluorescence (b) schematic diagram, and phase change enthalpy (c) of

77
photoluminescence functionalized composite PCMs. From the figure, the unique

structure of the material can effectively prevent the conventional polymerization

induced fluorescence quenching process to obtain excellent heat storage and

fluorescence capture properties. After adding CQDs to MOFs, as CQDs is inserted

into some micro/meso pores of MOF scaffolds, CQDs occupied the pores of MOF and

its specific surface area as well as pore volume are relatively reduced. Because the

molecular length of stearic acid is small, the average pore diameter of the MOFs/CQD

composite scaffold is large enough that the SA molecule can rotate freely. Therefore,

the high heat storage density of SA can be ensured by adjusting the width of the

channel. Because of the large capillary force of porous MOFs/CQD skeleton, a large

amount of SA can be fixed in the pores of MOFs/CQD, which can not only prevent

the leakage of liquid SA, but also improve the transmission capacity of photons and

heat. Moreover, the hydrogen bond between SA and MOFs helps to adsorb more SA

and increase the load of SA. However, the hydrogen bond is the stronger and SA

chain is restricted thought the free stretching and crystallization to some extent.

Therefore, the latent heat is lower than the theoretical value. Further, the insertion of

CQDs will weaken the hydrogen bond between SA and MOFs, making SA more

capable of free stretching and crystallization, thus it can be increased the latent heat of

SA/MOFs/CQD composite PCMs. With the increase of CQD content, the hydrogen

bond interaction between SA and MOFs gradually weakens. Therefore, increasing

more CQDs are helpful to increase the latent heat value of composite PCMs, which is

gradually close to the theoretical latent heat.

78
 Tang et al. [175] synthesized high porosity carbons (HPCs) by controlling

carbonized MOFs method and added into PEG to prepare PEG/HPCs composite

PCMs. The migration and aggregation of ZnO fine particles by evaporating in the

carbon matrix produced many micropores, mesoporous and nano-channels, thus

obtaining HPCs with high specific surface area and large pore volume. The material

has high adsorption capacity and storage capacity of PEG, and the microporous and

mesoporous pore channels can induce large surface tension and capillary force, thus

ensuring the high thermal stability of the composites. In addition, the graphite of

disordered porous carbon has a small structure, large specific surface area and

relatively high thermal conductivity. The thermal conductivity of the PEG/HPCs

composite PCMs (0.42 W/(m·K)) are about 56% higher than that of pure PEG (0.27

W/(m·K). It is suggested that HPCs can effectively improve the thermal conductivity

of PEG.

Li et al. [176] firstly empolyed in situ deposition method and calcining method

to load ZIF-67 on EG surface to generate Co3O4/EG with 3D interconnected network

structure. Further, it can be used melting impregnation method and dispersed it in SA

to prepare SA/Co3O4/EG amorphous composite PCMs. Due to the abundant pores and

large specific surface area of Co3O4/EG, the thermal performance of SA is effectively

improved to achieve good form stable effect and prevented the leakage of molten SA.

The preparation process, SEM images and thermal conductivities are shown in Fig. 59.

From the figure, the thermal conductivity of SA/Co3O4/EG composite PCM

containing 10% Co3O4/EG of 2.53 W/(m·K) is higher than 7.67 times with pure SA.

79
The high surface area and abundant fractional pore volume of Co3O4/EG additives

provide an effective fractional heat transfer pathway for SA, thus can improve its

thermal performance.

The 0D structure particles with high thermal conductivity also play an

important role in improving the thermal conductivity of the PCM. They mainly

increase the heat flow by forming a thermal conductivity chain evenly dispersed in the

PCM and increase the phonon group velocity and mean free path to a certain extent.

In addition, during the heterogeneous nucleation process of PCM, nucleation work

reduces with the increased the nucleation area and the solidification process is

accelerated, thus significantly reducing the supercooling degree of the nano particles.

The results of 0D structure additives/PCM composites are listed in Table 5.

Comparing with pure PCM, there is a remarkable improvement in thermal

conductivity.

4. Conclusions and perspectives

Phase change energy storage technology, with potentially high energy density

and stable output temperature and energy, is regarded as one of cost-effective and

large-scale heat storage methods. The key to develop low cost and compact heat

storage system is to develop high performance PCM for more efficient storage of

industrial waste heat and solar energy heat. In the way to obtain high performance

PCM, some challenges still remain:

1. Thermal conductivity is one of the critical parameters of PCM and thermal

energy storage system.

80
 Unlike sensible and thermochemical materials, thermal storage efficiency of

composite PCMs greatly depends on thermal conductivity; however, in previous

reviews of PCM, little attention has been devoted to summarizing high thermal

conductivity additives. Another issue concerning interface between PCM and heat

conducting matrix is random, making it hard to accurate predict for the thermal

conductivity of composite PCMs. Therefore, it is necessary to further study the

combination forms of two or multi-phase composite PCMs.

2. Due to the particularity of the PCM in the structure as well as physical and

chemical properties, it is complicated to explain the thermal conductivity of the PCM

by using the phonon thermal conductivity mechanism.

Though the electrons of most inorganic non-metallic materials are bound, which

cannot be used as heat conduction carriers and phonon heat conduction mechanism is

used to explain the phenomenon of heat conduction. However, the heat conducting

matrix and the PCM may not belong to the same heat conducting mechanism, so their

experimental results are far from satisfactory. Based on these experiences, unified

research is recommended for phonon, electron and photon thermal conductivity

mechanism. Further, this review explores a predicting of thermal conductivity for the

multi-phase system of composite PCMs, and conducts theoretical prediction and

experimental research on it.

3. Since the heat flow follows the principle of least resistance, the addition of

high thermal conductivity matrix in the composite PCM is bound to cause the heat to

flow along the thermal conductivity skeleton. The heat flow intensity and heat

81
conduction rate of common additives are extremely small for the high-performance

heat conduction matrix with a large number of heat conduction chains. Therefore,

some high thermal conductivity additives, such as highly graphitized network carbon,

graphene foam and HBN nanoparticles, are proposed to improve the thermal

conductivity of the composite PCMs. Nevertheless, because the difficulty in preparing

these high thermal conductivity additives, the porous skeleton is prone to collapse and

the reaction conditions need to be controlled with great discretion.

4. Broadening the heat flow channel is one of the methods to reduce phonon

scattering, which is extremely key to improve the effective thermal conductivity of

composite PCMs.

Heat flow channel provides an important carrier for phonon transfer. Widening

heat flow channel can be considered an effective way to improve the thermal

conductivity of composite PCMs. New additives, such as 3D network carbon, TiO2

foam and MOFs with different pore sizes and porosity have been proposed, whose

effectiveness was verified through experimental testing. It is expected that heat

storage system will yield improved performance by reducing the time which requires

to be heated during both charging and discharging. Composite PCMs have been

adopted in some heat storage systems to realize simple and compact design and low-

cost serial production.

The challenges mentioned here indicate not only that industrial waste heat and

solar energy storage by PCM is nothing near reaching the optimal thermal storage

performance, but they also point the directions toward future investigation of

82
high-value composite PCM and cost-effective thermal storage system. Right now

research activities devoted to thermal conductivity of composite PCMs are

extensively increasing. As a positive outcome, the preparation method, microstructure

and phonon thermal conduction mechanism of the composite PCMs and various heat

storage systems with high performance have been studied and tested. These projects

demonstrate that a heat storage system designed using PCM is a high-value and

large-scale heat storage option. To bring the phase change heat storage solution into a

broader market, more intensive studies in fields of phonon thermal conductivity

mechanism, development of high performance composite PCMs and efficient and

compact phase change heat storage system are still required.

Acknowledgments

This project is supported by the National Natural Science Foundation of China

(Grant No. 21546014). The authors also wish to thank the reviewers and editor for

kindly giving revising suggestions.

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94
List of Tables

Table1. Summary of chemical modification for thermal conductivity enhancement in composite PCMs

Table 2. Comparison of thermal conductivity of passive composite PCMs formed by three-dimensional structure additives and preparation methods

Table 3. Thermal properties of two-dimensional structure additives/PCM passive composite PCMs

Table 4. Preparation methods of initiative composite PCMs and summary of improving thermal conductivity of one-dimensional structure additives

Table 5. Main results of zero-dimensional structure additives/PCM initiative composite PCMs

156
 Table1. Summary of chemical modification for thermal conductivity enhancement in composite PCMs
Thermal
Method of Thermal conductivity
conductivity of Improvement
chemical PCMs chemical processing Composite PCMs of Composite PCM kc References
PCMs kp (%)
modification W/(m·K)
W/(m·K)
Nitrogen doped
MA-SA 0.17 NPC/MA-SA 0.37 217.65% [40]
porous carbon
Doping Nitrogen doped
PA 0.28 PA/NDG 1.73 617% [41]
graphene
Paraffin 0.28 Mesoporous carbons Paraffin/ C-900-85 0.35 125% [43]

(PEG) /CNT@
PEG 0.298 CNTs grafted MOFs 0.464 200.9% [44]
MOFs

SA 0.18 MIL-101-NH2 SA/MOFs 0.51 283.3% [45]

Graft functional
groups Paraffin 0.2312 Grafted CNTs-C18 Paraffin/CNTs 0.7903 341.68% [46]
n-octadecane-
Octadecyl amine-
melamine
n-octadecane 0.19 grafted graphene 0.26 136.84% [47]
formaldehyde (MF)
oxide (GO-ODA)
resin/GO-ODA

157
 Table 2. Comparison of thermal conductivity of passive composite PCMs formed by three-dimensional structure additives and preparation methods
Thermal
Thermal conductivit
Three-dimensio
conductivity Preparation methods y of Improvement
PCM type nal structure Fraction of matrices Ref.
of PCM kp composite (%)
additives
W/(m·K) PCM kc
W/(m·K)
Ultrathin-graph Chemical vapor deposition (CVD)
Paraffin wax and
0.2, 0.81 ite foams 2.30, 2.81 UGFs =1.23 vol.% 1150%, 346.9% [49]
erythritol
(UGFs)
Solid: 0.21 Graphite foam Molten embed
Paraffin --- --- --- [51]
Liquid: 0.12 matrix saturated
Vacuum assistance impregnation method Carbon foam
Paraffin 0.354 Carbon foam 1.198 338.4% [52]
=13.93wt.%
Incipient wetness impregnation method Graphite
Erythritol 0.72 Graphite foam 3.77 523.6% [53]
foam=25wt.%
Solid: 0.24, Impregnation method Solid: 2.6, Graphite Solid:1083%,
Paraffin wax Graphite foam [54]
Liquid:0.11 without any vacuum Liquid:1.8 foam=22wt.% Liquid:1636%
Three-dimensio Vacuum impregnation
nal (3D) method
Paraffin 0.25 6.70 3D DF=1.3 vol.% 2680% [55]
diamond foam
(DF)
Poly-ethylene Physical
3D network Divinyl
glycol 0.28 mixing and impregnation method 0.94 336% [57]
carbon benzene=3 wt.%
(PEG)
Wet impregnation method CNTs/PC=25
SA 0.341 CNTs/PC 300% [58]
1.023 wt.%
Solid: 0.78 Ni template-assisted CVD method UGF =1.8 wt.% Solid:
Erythritol UGFs 4.09 ± 0.3 [59]
Liquid: CNT= 0.8 wt.% 486%-563%
158
 0.326

Cellulose/GNP Vacuum-assisted impregnation

PEG 0.24 1.35 GNPs =5.3 wt.% 563% [60]
aerogel method
Thermal
Thermal
Three-dimensio conductivity of
conductivity Improvement
PCM type nal structure Preparation methods Porosity Pore size composite PCM kc Ref.
of PCM kp (%)
additives (W/(m ⋅ K)) or
W/(m·K)
shortened time (s)
Molten embedding
Paraffin 0.3 Copper foam 0.95 5 PPI 68s 120.5% [62]
method
SA and sliced Bulk porous Al Vacuum impregnation
0.24 65~70% <1mm --- --- [63]
paraffin foam method
Nickel
Nickel foam: foam: Paraffin /nickel
Nickel foam
Vacuum impregnation 97.17% 5 PPI foam: 1.2; 393.4%;
Paraffin 0.305 and copper [64]
method copper foam: copper Paraffin /copper 1606.6%
foam
96.58% foam: foam: 4.9
10 PPI
Copperfoa
Copper foam: Paraffin /copper
m:25 PPI
Copper foam Vacuum impregnation 88.89% foam: 16.01 4522.6%;
Paraffin 0.354 nickel [65]
and nickel foam method nickel foam: Paraffin /nickel 658.2%
foam:
90.61% foam: 2.33
25 PPI
Spherical
graphite (SG) conventional Erythritol/SG: 4.72
Erythritol 0.733 --- --- 643.9% [66]
and nickel dispersion technique
particles

159
 Vacuum impregnation Erythritol/porous
Erythritol 0.733. Porous nickel 0.85 500 mm 1582.5% [67]
method nickel:11.6
Porous TiO2 No surfactant Paraffin/PTF-carbo
Paraffin 0.302 0.88 30 nm 350.7% [68]
foam (PTF) impregnation method n: 1.059
Solid:0.3, Copper Vacuum impregnation
Paraffin 0.97 25 PPI --- --- [69]
Liquid:0.1 foam method
Modified
Sodium acetate Vacuum impregnation
0.59 Copper foam 0.924 15 PPI SAT/copper foam: 1154.5% [70]
trihydrate (SAT) method
6.8
SEBS-paraffin-HD
SEBS/paraffin/HD Direct impregnation
0.272 Copper foam 0.98 20 PPI PE/copper foam: 787.5% [71]
PE method
2.142
Solid:0.423, Aluminium Aluminium foam=6
n-eicosane Numerical simulation 0.94 8 PPI 400%~500% [74]
Liquid:0.146 foam wt.%
Copper/
Paraffin/copper-alu
Paraffin 0.2 aluminium Numerical simulation 0.95 --- 3700% [75]
minium foams: 7.4
foam
Aluminum Pore-scale numerical Paraffin/aluminum
Paraffin wax 0.2 0.95 10 PPI 12300% [77]
foam method foam: 24.6
Paraffin/aluminum
Aluminum Vacuum impregnation 0.95 6916%;
Paraffin wax 0.25 --- foam: 17.29 and [81]
foam method 0.77 1676.8%
4.192
Graphene
Chemical vapor Paraffin/graphene-n
Paraffin 0.19 coated nickel 0.9 12.7 PPI 2300% [82]
deposition (CVD) ickel foam: 4.6
(GcN) foam
Graphene– Paraffin/PDMS-G-
Paraffin 0.162 Melting blend method --- --- 1396.3% [83]
nickel foam NF: 2.262

160
 MA/nickel foam:
Myristyl alcohol Nickel foam Vacuum melting 0.4768 280%;
0.1701 --- 40 PPI [84]
(MA) copper foam infiltration MA/copper foam: 851%
1.4520
Vacuum infiltration n-octadecane/Ti
n-octadecane 0.16 TiO2 foam --- --- 238% [86]
method O2 foam: 0.38
Porous TiO2 Vacuum impregnation Paraffin/carbon/PT
Paraffin 0.21 0.87 --- 504% [88]
foam method. F: 1.059

161
 Table 3. Thermal properties of two-dimensional structure additive/PCM passive composite PCMs
Thermal
Two-dimensional Fraction Thermal conductivity of
conductivity of Improvement
PCM type structure additives Preparation methods of composite PCM kc References
PCM kp (%)
matrices W/(m·K)
W/(m·K)
Montmorillonite and 61.5
Stearic acid --- self-assembly method --- --- [92]
SiO2 wt.%
In-situ
Polystyrene-silica
n-tetradecane (Tet) 0.3721 polymerization 1.0 wt.% Tet@PS-SiO2: 0.4341 116.7% [95]
(PS-SiO2)
method
n-octadecane/silica:
n-octadecane 0.1505 Inorganic silica sol–gel method 50 wt.% 412.8% [96]
0.6213
Direct-synthesis 4wt.%; Paraffin/Al2O3: 0.919; 459.5%;
Paraffin 0.2 Al2O3 and SiO2 [97]
method 2 wt.% Paraffin/SiO2: 0.724 362%
Galactitol hexa
55, 67, 52 GHM/vermiculite-EG:
myristate (GHM) Diatomite, perlite, Vacuum 218.2%;
0.11, 0.10 wt.% and 0.24; [98]
and galactitol hexa vermiculite and EG impregnation method 240%
5 wt.% GHL/diatomite-EG: 0.24
laurate (GHL)
Xylitol penta 22, 17,
Gypsum, cement,
palmitate (XPP) Vacuum adsorption 67, 48 42 XPP/gypsum: 0.28; 280%;
0.10, 0.11 perlite, diatomite, [99]
and xylitol penta method wt.% and XPS/cement-EG: 0.20 181.8%
vermiculite and EG
stearate (XPS) 10 wt.%
Direct mixing Paraffin/expanded
Paraffin 0.2 Expanded perlite 20 wt.% 260% [100]
method perlite: 0.52
Lauric acid/stearic Melting 62.5
--- Modified sepiolite --- --- [101]
acid (LA-SA) adsorption method wt.%
Stearic–capric acid Activated-attapulgite Vacuum fusion
--- 50 wt.% --- --- [102]
eutectic (S–C) (a-ATP) absorption method
Capric–palmitic --- Attapulgite Melting blending and 65 wt.% --- --- [103]
155
 acid vacuum absorption
method
Modified expanded Direct vacuum 47.1
SA 0.21 SA/MEV: 0.52 247.6% [104]
vermiculite (MVE) impregnation method wt.%
21.9
Expanded Physical blending
Polyethylene wt.%,
0.06 Vermiculite (EV) and impregnation PEG/EV-Ag: 0.68 1230% [105]
glycol (PEG) 19.3
silver nanowire (Ag) method
wt.%
Vacuum
Paraffin 0.2 Kaolin 18 wt.% Paraffin/kaolin: 0.77 385% [106]
impregnation method
Vacuum
Paraffin --- Diatomite 20 wt.% --- --- [107]
impregnation method
Vacuum
Graphite and
SA 0.26 impregnation 31 wt.% SA/G-B: 0.77 296.2% [108]
bentonite
method
SA-BA eutectic Melting blend -
0.3396 EG 5.381 EG=16 wt.% 1584.51% [109]
mixture solidification form stable
Self-assembly
Paraffin 0.369 EG 10.37 EG =30 wt.% 2810% [110]
method
Melting blend -
SA 0.18 EG 23.27 EG=25 wt.% 13000% [111]
solidification form stable
Beeswax 0.25 Graphene Ultrasonic method 2.89 Graphene=0.3 wt.% 1156% [112]
EVA and paraffin --- EG and CF Vacuum impregnation 2.10 EG=70%, CF=30% --- [113]
2.663, EG =1.0 wt.% 159.1%,
Li2CO3-Na2CO3-K2C EG, GNSs Solution- evaporation
1.674 2.225, GNSs=1.0 wt.% 132.9%, [114]
O3 and MWCNTs technique
2.089 MWCNTs=1.0 wt.% 124.8%
Expanded perlite Vacuum
Octadecanol (OC) 0.4336 15 wt.% OC/EP-EG: 5.8550 1350.3% [115]
(EP) and EG impregnation method
Paraffin 0.33 Kaolin Vacuum 40 wt.% Paraffin/kaolin: 0.413 125.2% [116]

156
 impregnation method
Lauric-myristic- Al2O3-loaded
Vacuum 29.3 LA-MA-SA/aEV-AO:
stearic acid 0.262 expanded vermiculite 256.1% [117]
impregnation method wt.% 0.671
(LA-MA-SA) (aEV/AO)
Vacuum 31%, 7.2 PEG/diatomite-AgNP:
PEG 0.3612 Diatomite/AgNP 227% [118]
impregnation method wt.% 0.82
Flake
graphite-carbon
Vacuum 41.18wt.
SA 0.267 nanofiber-modified SA/FG-CNF-Bm: 2.803 1049.8% [119]
impregnation method %
bentonite
(FG-CNF-Bm)
Capric Vacuum
0.18 Bentonite clay, EG 5 wt.% Bentonite/CA/EG: 0.77 427.8% [120]
acid (CA) impregnation method

157
 Table 4. Preparation methods of initiative composite PCMs and summary of improving thermal conductivity of one-dimensional structure additives
Thermal
Thermal
conductivity of
conductivity One-dimensional Improvement
PCM type Preparation methods composite Fraction of matrices Ref.
of PCM kp structure additives (%)
PCM kc
W/(m·K)
W/(m·K)
Melting blend -
Erythritol 0.77 SCF (C5, C25) 3.92 C25=10 wt.% 509.1% [124]
solidification form stable
k//=13.82, Graphite fiber 5758.3%,
Paraffin wax 0.24 Graphite fiber Slurry molding method [125]
k⊥=1.31 =38.6 wt.% 545.8%
Melt-dispersion
kMD≈3.5, CFHP=20.6 vol.%, 3820%,
Erythritol 0.733 CF method, Hot-press [126]
kHP≈28 CFMD=20.4 vol.% 478%
method
Ultrasonic vacuum
Eicosane 0.22 CNTs 0.32 CNTs = 1wt.% 145.5% [127]
impregnation method
Li2CO3- K2CO3 Solution evaporation
0.618 SWCNT 0.97 SWCNT=1.5wt.% 156.98% [128]
eutectic salts method
Paraffin wax 0.25 MWCNT Two-step technique 0.92 MWCNT = 5 vol.% 367% [133]
Vacuum impregnation
Paraffin 0.204 CNTs 0.516 CNTs =5.27wt.% 253% [136]
method
PEG 0.24 SWCNTs melt-mixing method 3.43 SWCNTs=10 wt.% 1429.17% [137]
Beeswax 0.25 MWCNT Impregnation method 0.58 MWCNT =20wt.% 232% [138]
Graphene =
Beeswax 0.25 Graphene Ultrasonic method 2.89 1156% [139]
0.3wt.%
Liquid:
Vacuum impregnation GO sheets = 51.7 Liquid: 323%,
Paraffin wax 0.305 GO sheets 0.985 [140]
method wt.% Solid: 343%
Solid: 0.287
Acid oxidation method, MWCNTs=1.0
Palmitic acid (PA) 0.223 (25 ) MWCNTs 0.339 151.6% [141]
Mechanochemical wt.%
158
 reaction method, Ball
milling method, grafting
method
Graphene oxide GO and CNT
In-situ polymerization
Dodecanol 0.1296 (GO) and carbon 0.3821 hybrid filler = 0.6 295% [143]
method
nanotube (CNT) wt.%
3D graphene Modified Hummers’ 3D GA =20
Octadecanoic acid (OA) 0.184 2.635 1432.1% [147]
aerogel (GA) method vol.%
Polyethylene glycol Hybrid graphene Vacuum impregnation GO=0.45wt% and
0.31 1.43 461% [148]
(PEG) aerogels (HGA) method GNP=1.8 wt.%
Porous
Vacuum impregnation
Paraffin 0.21 Al2O3@graphite 0.76 Porosity: 84% 362% [151]
method.
foams (PAGFs)

159
 Table 5. Main results of zero-dimensional structure additives/PCM initiative composite PCMs
Thermal conductivity High thermal Thermal conductivity of
Fraction of Improvemen
PCM type of PCM kp conductivity Preparation methods composite PCM kc Ref.
matrices t (%)
W/(m·K) additive W/(m·K)
Molten embed Solid: 2.75
Solid: 0.25 Graphite-based
Paraffin Liquid: Graphite=10 wt.% 1100% [152]
Liquid: 0.16 nanocomposites
0.16
Impregnation,
Erythritol 0.70 EG compression and 12.51 EG=10 wt.% 1738% [153]
sintering
TiO2, sodium
Ultrasonic dispersion
Paraffin 0.147 stearoyl lactylate 3 wt.% Paraffin/TiO2-SSL:0195 132.7% [154]
method
(SSL)
Flower-like TiO2
Polyethylene Physical blending and
--- nanostructure 49.8 wt.% --- --- [156]
glycol (PEG) impregnation method
(FLN-TiO2)
Eutectic hydrate Boron nitride Physical blending and
0.131 4 wt.% EHS/BNF: 1.359 1037% [158]
salt (EHS) foams (BNFs) impregnation method
h-BN porous Vacuum impregnation
Paraffin 0.12 18 wt.% Paraffin/ h-BN: 0.85 708.3% [159]
scaffolds method
Boron nitride
4 wt.% GO
Polyethylene (BN) and Facile solution
0.273 and 30 PEG/BN-GO: 3.00 1100% [160]
glycol (PEG) graphene oxide blending method
wt.% BN
(GO)
Boron nitride Molecular dynamics
n-eicosane 0.33 10 wt.% n-eicosane/BN: 5.18 1569.7% [161]
(BN) simulation
Ultrasonic dispersion Paraffin/nano-Si3N4:
Paraffin 0.2293 Nano-Si3N4 10 wt.% 135% [162]
method 0.309
Sodium acetate 0.79 Silicon carbide Vacuum impregnation 15 wt.% SAT/bentonite-SiC: 121.7% [163]
160
trihydrate (SAT) (SiC), bentonite method 0.9614
Silicon carbide
nanowires
Polyethylene Vacuum impregnation 3.29 wt.%,
0.06 network (SiC PEG/EVM-SiC: 0.53 880% [164]
glycol (PEG) method 23.59 wt.%
NWs) and
(EVM)
Ultrasound-assisted
PEG 0.297 SiO2-Al2O3 12.6 wt. % PEG/SiO2-Al2O3: 0.435 146.5% [165]
sol-gel method
Solid:0.197, Blending and vacuum Solid:0.259, 131.5%
Paraffin Nano-Al2O3 10.0 wt.% [166]
Liquid:0.148 impregnation method Liquid:0.167 112.8%
Paraffin/α
Paraffin wax,
0.33; Blending and vacuum nano-alumina:0.53 160.6%
Microcrystalline α nano-alumina 2.0 wt. % [167]
0.18 impregnation method Microcrystalline/α 761.1%
wax
nano-alumina:1.37
Emulsion
Paraffin/nano-Al2O3:
Paraffin wax 0.2442 Nano-Al2O3 polymerization 38 wt.% 156.3% [168]
0.3816
method
Palmitic acid TiO2 PA/TiO2
0.194 Two-step method 5 wt.% 180% [169]
(PA) nanoparticles nanoparticles=0.35
n–octadecane/stea
Hexagonal boron Melt mixing-stirring
ric acid eutectics 0.2982 15 wt.% ODE-SA/HBN: 0.3272 109.7% [170]
nitride (HBN) adsorption method
(ODE-SA)
Paraffin/HBN
Paraffin 0.265 HBN nanosheets Two-step method 10 wt.% 200% [171]
nanosheets: 0.53
n-octadecane Silicon nitride Ultrasound-modified
0.232 30 wt.% ODE/Si3N4: 0.3630 156.8% [172]
(ODE) (Si3N4) method
Melt mixing-stirring
Paraffin 0.239 SiC-EG 28 wt.% Paraffin/SiC-EG: 3.2 1338.9% [173]
adsorption method
SA 0.26 MOFs/CQD Physical mixing and 30% SA/MOFs/CQD: 0.41 158% [174]

161
 impregnation method
High porosity Physical blending and
PEG 0.27 7.5% PEG/HPCs: 0.42 156% [175]
carbons (HPCs) impregnation method
Physical blending
And vacuum
SA 0.33 Co3O4/EG 10% SA/Co3O4/EG: 2.53 767% [176]
impregnation
methods.

162
Figure Captions

Fig.1. Classification of phase change materials

Fig.2. Structure of this review article

Fig.3. Heat transfer diagram in crystal heat conduction

Fig.4. Spring vibration heat transfer system composed of crystal atoms and abstract phonons

Fig.5. Temperature curve with length and phonon energy diagram

Fig.6. Schematic diagram of three phonon scattering modes

Fig.7. Three-phonon N process (a) and U process (b)

Fig.8. Strategies of phonon engineering categorized into methods affecting each component of phonon

thermal conductivity

Fig.9. Phonon mean free pathways for three different phonon scattering modes

Fig.10. Approaches of thermal conductivity enhancement

Fig.11. Thermal conductivity and heat flow of porous carbon matrix/MA-SA composite PCMs

Fig.12. (a) Field emission SEM images of NDG, TEM images of (b) NDG and (c) PA/NDG composite PCM

Fig.13. Preparation schematic illustration of the N-doped hierarchical porous carbon based composite PCMs

Fig.14. PEG/CNT@Cr-MIL-101-NH2 composite PCM synthesis diagram, microstructure and thermal

conductivity curve

Fig.15. TEM images of the formation process and products of grafted CNTs: (a) CNT-C8, (b) CNT-C14 and

(c) CNT-C18

Fig.16. Preparation of graphite foam/erythritol composite PCMs and SEM microstructure diagram

Fig.17. SEM diagram shows the diamond foam schematic diagram of a diamond foam consisting of a 3D

interconnected diamond network and a continuous diamond foam with high thermal conductivity

Fig.18. Schematic illustration and thermal conductivity of PEG8000/CQDs-derived 3D porous carbon

composite PCMs

Fig.19. Schematic illustration for the synthesis of SA/CNT@PC composite PCMs and the TEM and SEM

images of (a) CNTs; (b) CNT@ZIF-8; (c) CNT/PC; (d) SA/CNT@PC.

Fig.20. SEM image of neat UGF, UGF-CNT hybrid structure, CNT tip covered by an Al2O3 layer, UGF-CNT

hybrid foam, CNT networks formed inside the UGF pore and schematic of CNT growth on the UGF,

and the thermal conductivity data of composite materials.

93
Fig.21. Copper foam (a), aluminum foam (b), nickel foam (c) and titanium dioxide foam (d)

Fig.22. Optical micrographs of SA/Al foam (a, c) and paraffin/Al foam (b, d) composite PCMs prepared by

embedding method and constant pressure impregnation method.

Fig.23. Composite PCMs numerical model and the diagram of effective thermal conductivity changing with

porosity

Fig.24. SEM images of porous nickel with 100, 300, 500 mm in pore size, together with schematic bone

structure and the effective thermal conductivity and volume heat storage density of each composite

PCMs

Fig.25. SEM images of (a) G-NF, (b) graphene films on the surface of G-NF, (c) PA-PDMS-G-NF and (d)

structure of pores of PA-PDMS-G-NF

Fig.26. Preparation of paraffin/Al foam and paraffin/Cu foam composite PCMs (a) as well as images of metal

foam (b) and paraffin/metal foam composite PCMs (c)

Fig.27. SEM photographs and real products of nickel foam (a, b) and copper foam (c, d) before and after

preparation with pore size 40 PPI

Fig.28. Preparation process (a), microstructure (b), porous structure (c) and thermal conductivities (d) of

porous TiO2 foam and composite PCMs

Fig.29. Schematic diagram of the synthesis process and microstructure of FLN-TiO2 (a) and preparation

process of PEG/FLN-TiO2 composite PCM (b)

Fig.30. Schematic diagram of the preparation process, microstructure (a) and thermal conductivity (b) of

porous TiO2 foams and composite PCMs by particle-stabilized emulsion method and the vacuum

impregnation method

Fig.31. SEM pictures of the form-stable EG/SA CPCMs: (a) EG matrix; (b) EG/SA sample.

Fig.32. Preparation of beeswax/graphene nano-PCM and SEM image

Fig.33. SEM images of the FSPCMs: (a) FSPCM-CF0, (b, c) FSPCM-CF20 and (d) FSPCM-CF40

Fig.34. SEM diagram and structure diagram of carbonate composite with three additives :(a) EG, (b) GNSs, (c)

MWCNT

Fig.35. (a) Schematic illustration of Mt/SA microcapsule fabrication, SEM images of (a1) Mt/SA

microcapsules and (a2) Mt/SA composite PCMs, and (b) the interfaces and thermal conduction

pathway in Mt/SA microcapsules

94
Fig.36. Synthesis schematic of Tet@PS-SiO2 and TEM images of Tet@PS and Tet@PS-SiO2

Fig.37. Schematic formation of the silica-microencapsulated n-octadecane via a sol–gel process

Fig.38. Schematic diagram of the preparation and SEM images of OC/EP and OC/EP/EG composites

Fig.39. Curves of the thermal conductivity of paraffin/kaolin composite PCM with diverse mass fraction and

particle sizes of kaolin at different temperature and SEM images of (a) kaolin (b) paraffin/kaolin

Fig.40. Schematic diagram of the preparation process of composite PCMs and SEM images of the (a) EV, (b)

aEV, (c) aEV/AO and (d)LA-MA-SA/aEV/AO

Fig.41. (a) Principle of preparation of Dt modified by AgNP and (b) vacuum impregnation processing image

of composite PCM and microstructure and thermal conductivity curve of PEG/Dt/AgNP composite

PCMs

Fig.42. Scheme of preparation route of composite as well as SEM images of FG-CNF-Bm and

SA/FG-CNF-Bm composite PCM

Fig.43. SEM images of SCFs and SCFs/erythritol composite PCMs: (a, c) C5 and C5/erythritol as well as (b, d)

C25 and C25/erythritol

Fig.44. Schematic diagram of CBCF binding process and microstructure and thermal conductivity curve of

CBCF-PCM

Fig.45. Schematic diagram of composite PCM prepared by (a) melting dispersion method and (b) hot press

method, and curve diagram of effective thermal conductivity of composite samples changing with CF

Fig.46. Schematic diagram of composite PCMs and the morphology of (a) PA-CNTs and (b) PA-CNTs /EP

composite PCMs

Fig.47. Melt mixing method for preparation of PEG/SWCNs nanocomposites and microstructure of SWCNs

and composite PCMs

Fig.48. Microstructure of (a) beeswax, (b) untreated CNTs and (c) acid-treated CNTs

Fig.49. Schematic diagram and microscopic morphology diagram of MWCNTs processed by physical and

chemical methods

Fig.50. Preparation process of GA/OA composite PCMs and microstructure of: (a) porous structure of 3D GA,

(b) composite PCMs

Fig.51. Preparation of PEG/HGA composite PCMs and corresponding SEM images of (a) GO, (b) GNP, (c, d)

HGA, (e) pure PEG and (f) PEG/HGA composite PCMs

95
Fig.52. SEM images of paraffin microcapsules modified with different percentages of nano-Al2O3: (a)0%,

(b)5%, (c) 16%, (d)27%, (e) 33% and (f) 38%

Fig.53. Preparation steps of PA/TiO2 composite PCMs and FESEM images of (a) TiO2, (b) PA/TiO2

nano-enhanced organic PCMs

Fig.54. SEM images of the (a) HBN, (b) SA – n–octadecane eutectics, (c) CPCM1, (d) CPCM2 and (e)

CPCM3

Fig.55. Microscopic characterization of the h-BN nano-sheets. (a) SEM image on the h-BN nano-sheets and (b)

isolated h-BN nano-sheet as well as (c) TEM image of h-BN nano-sheets and (d) dispersion of the

h-BN nano-sheets in paraffin

Fig.56. Schematic of synthetic strategy for microcapsules with modified silicon nitride as well as SEM

micrographs of (a) silicon nitride and (b) microcapsule samples

Fig.57. Schematic diagram for the preparation of the composite PCMs and SEM images of (a) SiC, (b) 50

wt.% PA, 20 wt.% SiC, 3 wt.% EG, 27 wt.% ER composite PCMs

Fig.58. Preparation (a) and excitation fluorescence (b) schematic diagram, and phase change enthalpy (c) of

photoluminescence functionalized composite PCMs

Fig.59. Preparation process, SEM images and thermal conductivities of (a) EG, (b) ZIF-67, (c) ZIF-67/EG, (d)

Co3O4, (e) Co3O4/EG, (f) SA/Co3O4/EG

96
List of Figures

Fig.1. Classification of phase change materials

97
Fig.2. Structure of this review article

98
Fig.3. Heat transfer diagram in crystal heat conduction

99
Fig.4. Spring vibration heat transfer system composed of crystal atoms and abstract phonons

100
Fig.5. Temperature curve with length and phonon energy diagram

101
 Phonon-phonon
interaction

P P
P P P

P
P

P P P
P
P rt
Ph
on P s po s
n
on ra ace
col -im p P o n t te r f
li si u r on in
on ity P h ross
ac

Fig.6. Schematic diagram of three phonon scattering modes.

102
Fig.7. Mathematical representation of phonon-phonon collision modes: N process and U process

103
Fig.8. Strategies of phonon engineering categorized into methods affecting each component of

phonon thermal conductivity

104
Fig.9. Phonon mean free pathways for three different phonon scattering modes

105
Fig.10. Approaches to improve thermal conductivity of PCMs

106
Fig.11. Thermal conductivity and heat flow of porous carbon matrix/MA-SA composite PCMs

107
Fig.12. (a) Field emission SEM images of NDG, TEM images of (b) NDG and (c) PA/NDG

composite PCMs

108
Fig.13. Preparation schematic illustration of the N-doped hierarchical porous carbon based

composite PCMs

109
Fig.14. PEG/CNT@Cr-MIL-101-NH2 composite PCM synthesis diagram, microstructure and

thermal conductivity curve

110
Fig.15. TEM images of the formation process and products of grafted CNTs: (a) CNT-C8, (b)

CNT-C14 and (c) CNT-C18

111
 (a)

Fig. 16. Preparation of graphite foam/erythritol composite PCMs and SEM microstructure

diagram

112
Fig. 17. SEM diagram shows the diamond foam schematic diagram of a diamond foam consisting

of a 3D interconnected diamond network and a continuous diamond foam with high thermal

conductivity

113
Fig. 18. Schematic illustration and thermal conductivity of PEG8000/CQDs-derived 3D porous

carbon composite PCMs

114
Fig. 19. Schematic illustration for the synthesis of SA/CNT@PC composite PCMs and the TEM

and SEM images of (a) CNTs; (b) CNT@ZIF-8; (c) CNT/PC; (d) SA/CNT@PC

115
Fig. 20. a) SEM image of neat UGF; b) Schematic of CNT growth on the UGF; c) SEM image of

the UGF-CNT hybrid structure; d) Higher magnification SEM image of a CNT tip covered by an

Al2O3 layer; e) SEM images of a UGF-CNT hybrid foam. f) CNT networks formed inside the

UGF pore; g) The thermal conductivity data of composite materials

116
Fig. 21. Copper foam (a), aluminum foam (b), nickel foam (c) [103] and titanium dioxide foam (d)

[126]

117
 (a) (b)

(c) (d)

Fig. 22. Optical micrographs of SA/Al foam (a, c) and paraffin/Al foam (b, d) composite

PCMs prepared by embedding method and constant pressure impregnation method

118
Fig. 23. Composite PCMs numerical model and the diagram of effective thermal conductivity

changing with porosity

119
 Fig. 24. SEM images of porous nickel with 100, 300, 500 mm in pore size, together with

schematic bone structure and the effective thermal conductivity and volume heat storage density

of each composite PCMs

120
Fig. 25. SEM images of (a) G-NF, (b) graphene films on the surface of G-NF, (c) PA-PDMS-G-NF

and (d) structure of pores of PA-PDMS-G-NF

121
Fig.26. Preparation of paraffin/Al foam and paraffin/Cu foam composite PCMs (a) and images of

metal foam (b) and paraffin/metal foam composite PCMs (c)

122
Fig. 27. SEM photographs and real products of nickel foam (a, b) and copper foam (c, d) before

and after preparation with pore size 40 PPI

123
Fig. 28. Preparation process (a), microstructure (b), porous structure (c) and thermal conductivities

(d) of porous TiO2 foam and composite PCMs

124
Fig. 29. Schematic diagram of the synthesis process and microstructure of FLN-TiO2 (a) and

preparation process of PEG/FLN-TiO2 composite PCM (b)

125
 Fig. 30. Schematic diagram of the preparation process, microstructure (a) and thermal

conductivity (b) of porous TiO2 foams and composite PCMs by particle-stabilized emulsion

method and the vacuum impregnation method

126
 (a) (b)

Fig. 31. SEM pictures of the form-stable EG/SA CPCMs: (a) EG matrix; (b) EG/SA sample.

127
Fig.32. Preparation of beeswax/graphene nanometer PCM and SEM image

128
Fig.33. SEM images of the FSPCMs: (a) FSPCM-CF0, (b, c) FSPCM-CF20 and (d)
FSPCM-CF40

129
Fig.34. SEM diagram and structure diagram of carbonate composite with three additives :(a) EG,

(b) GNSs, (c) MWCNT

130
Fig.35. (a) Schematic illustration of Mt/SA microcapsule fabrication, SEM images of (a1) Mt/SA

microcapsules and (a2) Mt/SA composite PCMs, and (b) the interfaces and thermal conduction

pathway in Mt/SA microcapsules

131
Fig.36. Synthesis schematic of Tet@PS-SiO2 and TEM images of Tet@PS and Tet@PS-SiO2

132
Fig.37. Schematic formation of the silica-microencapsulated n-octadecane via a sol–gel process

133
Fig. 38. Schematic diagram of the preparation and SEM images of OC/EP and OC/EP/EG

composite PCMs

134
Fig. 39. Curves of the thermal conductivity of paraffin/kaolin composite PCM with diverse mass

fraction and particle sizes of kaolin at different temperature and SEM images of (a) kaolin (b)

paraffin/kaolin

135
Fig. 40. Schematic diagram of the preparation process of composite PCMs and SEM images of the

(a) EV, (b) aEV, (c) aEV/AO and (d)LA-MA-SA/aEV/AO

136
 Fig.41. (a) Principle of preparation of Dt modified by AgNP and (b) vacuum impregnation

processing image of composite PCM and microstructure and thermal conductivity curve of

PEG/Dt/AgNP composite PCMs

137
Fig. 42. Scheme of preparation route of composite as well as SEM images of FG-CNF-Bm and

SA/FG-CNF-Bm composite PCM

138
Fig .43. SEM images of SCFs and SCFs/erythritol composite PCMs: (a, c) C5 and C5/erythritol as
well as (b, d) C25 and C25/erythritol

139
Fig. 44. Schematic diagram of CBCF binding process and microstructure and thermal conductivity
curve of CBCF-PCM

140
Fig. 45. Schematic diagram of composite PCM prepared by (a) melting dispersion method and (b)

hot press method, and curve diagram of effective thermal conductivity of composite samples

changing with CF

141
Fig. 46. Schematic diagram of composite PCMs preparation and morphology of (a) PA-CNTs and

(b) PA-CNTs/EP composite PCMs

142
Fig. 47. Melting blend method for preparation of PEG/SWCNs nanocomposites and

microstructure of SWCNs and composite PCM

143
Fig. 48. Microstructure of (a) beeswax, (b) untreated CNTs and (c) acid-treated CNTs

144
Fig.49. Schematic diagram and microscopic morphology diagram of MWCNTs processed by

physical and chemical methods

145
Fig. 50. Preparation process of GA/OA composite PCMs and microstructure of: (a) porous

structure of 3D GA, (b) composite PCMs

146
Fig. 51. Preparation of PEG/HGA composite PCMs and corresponding SEM images of (a) GO, (b)

GNP, (c, d) HGA, (e) pure PEG and (f) PEG/HGA composite PCMs

147
Fig. 52. SEM images of paraffin microcapsules modified with different percentages of nano-Al2O3:

(a)0%, (b)5%, (c) 16%, (d)27%, (e) 33%, and (f) 38%

148
Fig. 53. Preparation steps of PA/TiO2 composite PCMs and FESEM images of (a) TiO2, (b)

PA/TiO2 nano-enhanced organic PCMs

149
Fig. 54. SEM images of the (a) HBN, (b) SA – n–octadecane eutectics, (c) CPCM1, (d) CPCM2

and (e) CPCM3

150
 Fig. 55. Microscopic characterization of the h-BN nano-sheets. (a) SEM image on the h-BN

nano-sheets, and (b) an isolated h-BN nano-sheet as well as (c) TEM image of h-BN nano-sheets,

and (d) dispersion of the h-BN nano-sheets in paraffin

151
Fig. 56. Schematic of synthetic method for microcapsules with modified silicon nitride as well as

SEM micrographs of (a) silicon nitride and (b) microcapsule samples

152
Fig. 57. Schematic diagram for the preparation of the composite PCMs and SEM images of (a)

SiC, (b) 50 wt.% PA, 20 wt.% SiC, 3 wt.% EG, 27 wt.% ER composite PCM

153
Fig.58. Preparation (a) and excitation fluorescence (b) schematic diagram, and phase change

enthalpy (c) of photoluminescence functionalized composite PCMs

154
Fig. 59. Preparation process, SEM images and thermal conductivities of (a) EG, (b) ZIF-67, (c)
ZIF-67/EG, (d) Co3O4, (e) Co3O4/EG, (f) SA/Co3O4/EG

155
Highlights

• Thermal conduction mechanism of phonons in PCM is analyzed.

• The morphology, preparation method and thermal conductivity of composite PCMs

are reviewed.

• Phonon heat transfer mechanism and enhanced thermal conductivity of composite

PCMs are verified.

• It provides insights into the phonon heat transfer mechanism of high performance

composite PCMs inside the adding novel thermal conductivity matrices.

 Shanghai University of Electric Power
College of Energy and Mechanical Engineering
Dr. Ting Yan nd prof. W.G. Pan, No. 2588 Changyang Road, Yangpu
District, Shanghai 200090, China E-mail: [email protected] (Ting Yan),
[email protected] (W.G. Pan) and wshaofei1217 @163.com (S.F. Wu)

2019-09-29

Conflict of interest section

All authors of the manuscript have no real or potential conflicts of interest related to
their work, including any financial, personal or relationship with others or other
organizations, that have no adverse effect on their work during the three years prior to the
submission of the manuscript.

Manuscript author: S.F. Wu, Ting Yan, Z.H. Kuai and W.G. Pan

College of Energy and Mechanical Engineering

Shanghai University of Electric Power
Shanghai 200090, China