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2nd 2nd International

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A comprehensive review ofSymposium
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on District Heating aspects of
and Cooling
A comprehensive review of recent advances in materials aspects of
phase change materials in thermal energy storage
phase change
Assessing materials
the feasibility in thermal
of using energy
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demand-outdoor
Charalambos N. Elias, Vassilis N. Stathopoulos*
temperature function
CharalambosforN.a Elias,
long-term
Vassilisdistrict heat demand forecast
N. Stathopoulos*
Laboratory of Chemistry and Materials Technology, Department of Electrical Engineering, School of Technological Applications, Technological
a,b,c Educational a
Institute a Electrical
of Sterea Ellada, b Campus,
34400Engineering,
Psachna SchoolEvia, Greece c Applications, Technological
c
I. Andrić
Laboratory of Chemistry and
*, A. Pina , P. Ferrão , J. Fournier ., B. Lacarrière , O. Le Corre
Materials Technology, Department of of Technological
Educational Institute of Sterea Ellada, 34400 Psachna Campus, Evia, Greece
a
IN+ Center for Innovation, Technology and Policy Research - Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal
b
Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France
Abstract c
Département Systèmes Énergétiques et Environnement - IMT Atlantique, 4 rue Alfred Kastler, 44300 Nantes, France
Abstract
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of Alvalade, Elsevier in Lisbon license
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(Portugal), was used as a case study. The district is consisted of 665
This is an open access article under the CC BY-NC-ND license (https://creativecommons.org/licenses/by-nc-nd/4.0/)
Selection
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Keywords: thermal
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Keywords: energy
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considered). However, after introducing renovation
scenarios, the error value increased up to 59.5% (depending on the weather and renovation scenarios combination considered).
The value of slope coefficient increased on average within the range of 3.8% up to 8% per decade, that corresponds to the
decrease in the number of heating hours of 22-139h during the heating season (depending on the combination of weather and
renovation scenarios considered). On the other hand, function intercept increased for 7.8-12.7% per decade (depending on the
coupled scenarios). The values suggested could be used to modify the function parameters for the scenarios considered, and
improve the accuracy of heat demand estimations.

© 2017 The Authors. Published by Elsevier Ltd.

Peer-review under
* Corresponding responsibility
author. of the Scientific Committee of The 15th International Symposium on District Heating and
+30-22290-99688
Cooling. vasta@teiste.gr
E-mail address:author.
* Corresponding +30-22290-99688
E-mail address: vasta@teiste.gr
Keywords:©Heat
1876-6102 2018demand; Forecast;
The Authors. Climate
Published bychange
Elsevier Ltd.
This is an open
1876-6102 access
© 2018 Thearticle under
Authors. the CC BY-NC-ND
Published license (https://creativecommons.org/licenses/by-nc-nd/4.0/)
by Elsevier Ltd.
Selection
This is an and
openpeer-review under
access article responsibility
under of the 2ndlicense
the CC BY-NC-ND International Conference on Sustainable Energy and Resource Use in Food Chains,
(https://creativecommons.org/licenses/by-nc-nd/4.0/)
ICSEF2018.
Selection and peer-review under responsibility of the 2nd International Conference on Sustainable Energy and Resource Use in Food Chains,
ICSEF2018.
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
1876-6102 © 2019 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling.
This is an open access article under the CC BY-NC-ND license (https://creativecommons.org/licenses/by-nc-nd/4.0/)
Selection and peer-review under responsibility of the 2nd International Conference on Sustainable Energy and Resource Use in Food
Chains, ICSEF2018.
10.1016/j.egypro.2019.02.101
 386 Charalambos N. Elias et al. / Energy Procedia 161 (2019) 385–394
2 Elias C N.and Stathopoulos V N/ Energy Procedia 00 (2018) 000–000

1. Introduction

Nowadays global energy needs rise more slowly but will be still increased by 30% till 2040 [1]. Fossil fuels are
still supporting the energy demand of modern society while coal will be intensively used in the future as it plays an
important role in the security of supply in developed countries. At the same time it is a key enabler for their economic
growth and development. Coal, oil and natural gas reserves though are not infinite and have a very negative impact
on environmental quality despite climate change mitigation strategies have high efficiency technology to be utilised.
Development of energy technologies and industrial waste heat recovery are becoming more and more important to
face the problems of energy crisis and environmental pollution.
A global energy transition towards cleaner energy production and more efficient use of it is gaining up momentum
although it is not moving still at the desirable speed, being slower than required for meeting emissions targets. In 2015
an increased growth in renewable energy consumption in the context of the other primary energy sources is reported.
The percentage of renewable energy in electricity production is also improved. Considering the high contribution of
electricity sector in global greenhouse (GHG) emissions (approx. 25%) this is a positive development. On the other
aspect as rare earth elements, are extensively used in renewable energies, creating new dependencies in the value chain
may rapidly introduce possible future barriers to growth [2].
However, due to the high and immediate demand for power in society, renewable energies are not currently
technically and economically viable to fully replace fossil fuels based power generation. At the same time the demand
and supply gap for energy sources is widening day by day. The fact that the energy can neither be created, nor destroyed
has emerged scientific research in the direction of storing the different forms of energy by diverse devices. The storage
of energy in suitable and clean forms, which can conventionally be converted into the required form, is today a
challenge to the technologists. Energy storage including batteries has been characterised by rapid change, driven by
industrial demand to manage system volatility and lower costs. A global storage market of 1.4 GW/y by 2020 is
projected [2]. Thus due to the intermittency of renewables e.g. solar power thermal energy storage is of particular
importance. Additionally, systems for industrial waste heat recovery can offer significant energy savings and
substantial reductions in greenhouse gas emissions (GHGs). Industry is consuming about 28% of energy demand and
is responsible for 21% of GHG emissions. About €45 billion for 2018 waste heat recovery market is projected in
Europe. A significant potential for heat recovery exists in heating processes as in some cases up to 50% of generated
heat is wasted. In order to materialise this projection, improvement in heat recovery equipment and or heat storage
systems is required [3, 4]. Energy efficiency is also crucial if organisations are to remain competitive or viable
considering the applied or future environmental regulations.
Under this concept thermal energy storage is of particular interest to researchers worldwide as related directly to
efficient utilisation of both conventional fuels and renewables resources i.e. solar, waste to energy systems,
cogeneration systems as well as industrial waste heat recovery technologies. Thermal energy storage using phase
change materials is a rapidly growing research area. In this comprehensive paper special attention is given to the latest
reports in the field PCMs nano, micro and macro encapsulation as well as on materials aspects critical for PCMs
application in TES. This paper attempts to provide a useful short overview of the current status of PCM science and
technology.

2. Thermal energy storage

Thermal energy storage is feasible in three modes:

i) Sensible thermal (heat) storage (SHS) that is made by increase or decrease of temperature of a storage
medium, such as water, oil, or ceramic materials. The heat stored is dependent on the specific heat capacity of the
material. In this case a temperature change is in a linear relationship with temperature. SHS is currently
commercialised either in industrial applications, residential water heaters or hot water storage on district-heating
networks. Also, building materials with very high thermal capacity can provide substantial energy storage on
timescales of months. The drawback of sensible thermal storage is low energy density and loss of thermal energy at
any temperature.
ii) Latent thermal (heat) storage (LHS) involves heat transfer due to a phase transformation taking place in a
suitable material in a specific and rather narrow temperature window e.g. molten salt, paraffin, or water/ice. Phase
 Charalambos N. Elias et al. / Energy Procedia 161 (2019) 385–394 387
Elias C N and Stathopoulos V N / Energy Procedia 00 (2018) 000–000 3

transitions can be solid–liquid (melting and freezing), liquid–gas such as evaporation and condensation or solid-solid
changes in crystalline structure while the temperature for heat capturing or release can be tailored by the material
selection. The energy stored is associated to the chemical bonds rearranging in the bulk structure of the material. Thus
LHS provides a high energy storage density and as a consequence it is far more efficient than SHS.
iii) Thermochemical storage (TCS) is succeeded via a reversible chemical reaction involved. Amount of energy
stored is demanded in one reaction direction and energy yielding is by the reverse direction. It provides the highest
energy density of all TES approaches but stability issues exist. Also reaction involved do not sustain constant
efficiency without degradation over time. Furthermore TSC is lacking in depth understanding as limited research
effort has been applied still [5, 6].
As electricity is the major form of energy in use; thermal storage can produce electricity via steam generation for
a conventional thermal power plant. However, the heat recovered or stored can be more efficiently used directly in
industrial process or for facilities heating. Such a means of utilisation requires less infrastructure and avoids energy
conversion losses. As 34% of energy demand is consumed in buildings and urbanisation still increasing in most areas
of the world, innovative technologies and construction design can be instrumental in achieving long-term
sustainability of the global energy system. In this context one of the major advantages of thermal energy storage is
that apart from storing thermic loads it can also regulate temperature for example in buildings towards decreasing the
energy demand. It can be used for air-conditioning loads and/or refrigeration purposes i.e. food products and sensitive
materials. This is currently an emerging sector and a growing market.

3. Phase change materials

Materials that utilize LHS are known as phase change materials (PCMs). PCMs are a group of materials which
exchange amount of thermal energy as latent heat within a narrow temperature range involving a phase transformation.
Outside this temperature window PCMs may exchange typical sensible heat. Most common phase changes occurring
are solid-liquid and solid-solid. Solid–gas or liquid–gas phase transition applications are limited due to the large
volume change in PCM despite the high energy transfer involved in such phase changes [3, 7, 8].
In the last decade PCMs are widely studied for TES due to the need of processes and applications of increased
energy efficiency [5, 9-22]. A Scopus search on September 2018 under the term “phase change materials” and further
limited under “thermal energy storage” returns 1391 hits just for 2018. In Figure 1a is shown the yearly distribution
since the energy crisis of early 70s described by the above keywords indicating the recent blooming scientific interest.

Figure 1. a) The number of articles dedicated to PCMs and TES for the period 1971-2018. Source Scopus; b) classification of PCMs

PCMs can be efficiently applied either on thermal regulation TES systems or for plain thermal storage TES systems.
PCM-TES systems for thermal regulation have a great potential in buildings and space air conditioning mitigating
large temperature fluctuations. PCMs with a working window in the human comfort temperature zone (10-25° C) help
saving large amounts of energy spent to regulate living conditions temperature. Additionally several other
388 Charalambos N. Elias et al. / Energy Procedia 161 (2019) 385–394
4 Elias C N.and Stathopoulos V N/ Energy Procedia 00 (2018) 000–000

technological fields may benefit of temperature regulating PCM-TES systems such as batteries [23-26], aerospace
[27, 28], textiles [29, 30] and photovoltaics [26, 31]. In PCM-TES systems for thermal storage PCMs are mainly used
as waste heat storage tanks for industrial processes, buildings applications, agriculture applications or even fuel cells
[10, 18, 21, 29, 32-34].
PCMs can be classified according to their chemical nature as organic, inorganic and eutectics or by the phase
transition they undergo as solid-liquid PCMs, solid-solid PCMs, solid-gas PCMs and liquid-gas PCMs (Figure 1b).
According to their chemical nature PCMs can be i) organic: mainly paraffins or non-paraffins such as esters, fatty
acids, alcohols and glycols or polymers i.e. PEG, ii) inorganic involving salt hydrates and/or alloys and metals and
finally iii) eutectics involving mixed PCMs as organic–organic, inorganic–inorganic and inorganic–organic. Since the
first application of PCM by NASA in aerospace field [27], a vast list of materials and mixtures of two or more materials
have been investigated for their use as PCM. Very interesting is a recently described procedure using conventional
chemistry and biocatalysis to transform non-edible animal fat into eutectic organic PCMs [35, 36]. A representative
list of available and studied PCMs can be found here [9, 20].
PCMs are used according to their working temperature ranges (-20° C to +200° C or above) (Figure 1b). There are
four different temperature ranges accordingly the application: low temperature range (-20° C to +5° C) where the
PCMs are typically used for domestic and commercial refrigeration; medium low temperature range (+5° C to +40°
C) where the PCMs are typically applied for heating and cooling applications in buildings; medium temperature range
for solar based heating, hot water and electronic applications (+40° C to +80° C); and high temperature range (+80°
C to +200° C or above) for absorption cooling, waste heat recovery and electricity generation [22].
Materials selection though is a complicated task considering the list of desired properties of the PCM related to
TES application [20, 37-39]:
 Phase transition temperature in the desired operating  High nucleation rate
range  Adequate rate of crystallization
 High latent heat of phase transition per unit volume  Chemical stability
 High specific heat to contribute in sensible thermal  Fully reversible freeze/melt cycle
storage  Compatibility with the construction materials
 High thermal conductivity of both phases  Non corrosive to the construction materials
 Limited volume change on phase change  Non-toxic, non-flammable and non-explosive for
 Low vapour pressure at the operating temperatures safety
 Favourable phase equilibrium  Readily available in large quantities and at low cost
 High density
 No supercooling
In practice, there are no PCMs to fully meet all chemical, physical and economical requirements to date. Organic
PCMs in general are chemically and thermally stable, they are non-corrosive to metals, recyclable and they can have
high latent heat of fusion. On the negative aspect is their flammability, a phase change enthalpy lower than other type
of PCMs, their low thermal conductivity, subcooling, and material issues raising by their questionable compatibility
with polymer containers or encapsulation media. Inorganic PCMs are of low cost, comparable better thermal
conductivity and high phase change enthalpy. On the other side stands their corrosive nature, the sub-cooling, the
phase segregation and separation and the lack of thermal stability.
The aforementioned weaknesses keep PCMs from wide practical use. Since LHS is mainly working reversibly at
the solid–liquid transition a suitable encapsulation, tank container or matrix to host the PCM used is required to prevent
leakage placing the material aspects in priority. Another major subject of scientific interest is the thermal performance
aspects of PCMs. In particular, the improvement of PCM thermal conductivity and/or the heat flow among PCM and
its local environment thus improving the thermal energy charging and discharging rates of a LHS system.
The performance enhancement methods for LHS-TES systems with PCMs have been classified into three
categories [19]: 1) enhancing thermal conductivity by nanoadditives and porous media, 2) extending heat transfer
surface using finned tubes, heat exchanger designs and encapsulated PCMs and 3) improving heat transfer uniformity
by multiple PCMs and thermodynamic analysis and optimisation. However encapsulation technologies such as shape
stable PCM structures, macro-, micro-, and nanoencapsulation, nanoadditives and composites are overlapping
affecting both thermal conductivity and heat transfer surface.
 Charalambos N. Elias et al. / Energy Procedia 161 (2019) 385–394 389
Elias C N and Stathopoulos V N / Energy Procedia 00 (2018) 000–000 5

Various heat exchangers, heat pipes, finned tubes units have been studied in LHS principle since the first approach
of Shamsundar and Srinivasan four decades ago [40]. These efforts mainly focused to extend heat transfer surface and
on the heat transfer during the storage/release of thermal energy in PCM. Antoni Gil et al. [41] studied experimentally
the effect of adding fins in LHS systems. The addition of fins increased the effective thermal conductivity accordingly
thermal power supplied to the PCM. A comprehensive list of related recent work can be found in the relevant work of
Amini et al [32] and in our recent paper [10] and the references there in.
In the encapsulated systems PCM is mainly encased in containers where the heat transfer fluid flows around them.
Such containers can be in micro [37], nanoscale [38] as well as in the macroscale for building envelope materials and
shape stable PCMs [21]. For the case of compact LHS systems a metal tank is used as a container for the working
PCM. However polymer tanks start to dominate the market as pre-fabricated modular units of low thermal losses, low
weight and easy low cost manufacturing. They are recyclable and show excellent corrosion resistance against salt
hydrate PCMs.
The present paper will focus only on typical recent encapsulation studies and issues related to materials in contact
with PCMs that have been identified. Some indicative interesting findings will be discussed and most of the recent
related reviews are reported.

4. Recent studies on encapsulation and material aspects of PCMs

As buildings are exceptionally high electrical consumers the application of PCMs has been discussed as a solution
to reduce the high-energy building’s consumption. The use of PCM macro-encapsulation in building is a promising
approach but there are still some barriers for large scale application in the building industry. The basic issue is that a
PCM has fixed optimum melting temperature while the building energy needs differ in summer and in winter. PCM
macro-encapsulation would be very energy efficient if PCM thermal storage temperature range could be utilised all
the time during the year. For this reason, the combined use of two types of PCM with different melting temperatures
was proposed in a two-layer PCM panel structure [42, 43]. On the other aspect, the heat transfer of the two PCM was
affected by each other, decreasing the thermal efficiency.
Under the concept towards energy efficient buildings [44] eight PCMs with different melting points were analysed.
This analysis was carried out through a dynamic simulation of the energy performance of a building located in the
North of Portugal. It was found that the materials studied led to a small reduction in energy requirements for heating
and higher for cooling. However, when the cost-effectiveness of the investment was analysed, it was verified that the
high initial investment is not offset by the reduction in operational costs. Under the same concept for overall technical
and economic feasibility, three demonstration sites of integrated solutions for residential building energy storage using
PCM-TES combined with solar and geothermal technologies, are currently prepared in Austria, Spain and Cyprus
respectively [45].
Buildings energy consumption can be reduced by passive elements of architectural and structural nature. Serrano
et al. [46] developed a novel form-stable PCM with the addition of a new shape-stabilised phase change material in
ceramic elements of large porosity. The samples exhibited a high long-term thermal stability. Olivieri et al. [47]
studied a PCM-enhanced mortar containing microencapsulated PCM towards thermally active precast walls.
Incorporated PCMs intended to be used as the innermost layer actively controlled by an integrated hydronic system.
They showed that the combination of silica fine aggregate and an antifoaming admixture producing mortars with
statistically significant higher values of conductivity, diffusivity and effusivity. They concluded that when increasing
the amount of PCM the energy storage potential is enhanced, but both thermal conductivity and density decrease
reaching a thermal inertia upper limit. Moreover, due to the effusivity and invariant heat flux values found among the
investigated mortars they suggest that focus should be on diffusivity in order to define the most appropriate heat
penetration rates and activation times for an efficient operation of such a precast radiant system. Rao et al. [41]
developed a novel composite PCM/expanded perlite used as exterior and interior envelope materials for passive solar
energy utilisation. Eutectic hydrated salt (EHS) consisted of sodium carbonate decahydrate and disodium hydrogen
phosphate dodecahydrate with a mass ratio of 5:5 was prepared as the PCM with a phase change temperatures of 26
and 94° C and combined with three different kinds of expanded perlites (EP1-3) as supporting materials. Compared
the 70%EHS/EP2 insulation panel with the pure EP2 insulation panel, could decrease the maximum temperature
during the melting process and prolong the time of heat preservation in the cooling process.
390 Charalambos N. Elias et al. / Energy Procedia 161 (2019) 385–394
6 Elias C N.and Stathopoulos V N/ Energy Procedia 00 (2018) 000–000

Another aspect is the environmental impact of used PCM in building envelope applications. The ease of separating
PCM from shells gives PCM macro-encapsulation advantage in terms of recycling. Recycling and reusing the PCM
formerly applied in building envelopes brings in both environmental and economic benefits. Also, it is important to
understand and evaluate the overall performance of PCM systems in practice for a lifetime of more than 25 years.
Finally, the researchers have to take account of their performance degradation with melting cycles. In year 2018 two
reviews for building envelope applications of PCMs are published providing a thorough overview of the particular
technology status [21, 48].
Metal fabricated tanks are the most common for the compact latent heat storage group due to their availability,
price, and manufacturability. Since TES-PCM system must be resistant to corrosion to ensure a suitable working
lifetime, extensive research has been conducted. Results of the corrosion behavior of stainless steel, carbon steel, Al
and/or Cu alloys in contact with inorganic [49-55] mainly but also organic [52, 56-61] PCMs are reported. Stainless
steel is proved inert against all PCMs. Organic PCMs are also not aggressive to metal containers.
Polymer materials are also becoming common in the design of latent storage systems of macro-encapsulated PCMs
or as tank containers mainly due to their introduction to the market for sensible (water) energy storage systems [62-
64]. In general polymer tanks products can be delivered as pre-fabricated modular units of low weight and low cost if
produced in large scale. In addition, their recyclable nature and chemical inertness against salt hydrate PCMs make
them interesting as engineering materials for latent heat storage encapsulation and containers items. However, the
compatibility issue of the plastic to containing organic PCMs is still not fully addressed. Anghel et al. [65] developed
and tested a polyethylene glycol-epoxy resin-aluminum nanopowder composite PCM encased, in a spherical
polypropylene (PP) macro capsules but no reference to compatibility or aging issues was made. Lazaro et al. have
conducted a compatibility experimental study on a various organic and inorganic PCMs in low temperature contact
with materials such as PP, PET, HDPE, LSPE and LDPE polymers suggested for cold thermal energy storage (CTES)
units [52]. LSPE showed high mass variations and large deformations. PET and PP proved to be the best encapsulation
materials for the organic PCM while HDPE for the inorganic PCM tested. No further discussion was made on the
reasons for the incompatibility observed.
Perspex was studied by Browne et al. [63] in contact with fatty acids for a period of 722 days at 45oC showing
marginal corrosion. Recently commercial HDPE spheres encapsulating organic PCM showed failure after heating -
cooling cycles when used in domestic hot water tank applications [66]. Severe degradation accompanied by leakage
of PCM was found. Authors suggested 25 heating cooling cycles to reach a stable state of the HDPE spheres to prevent
leakage. They also noted the alternative option of using a suitable coating for the external surface of the spheres to
prevent leakage. No specific coating material was named.
Our group recently studied four commercially available organic PCMs with melting point in the temperature range
44-58oC when in contact with engineering polymers: HDPE and PP which are used for the design and manufacturing
of thermal energy storage tanks and encapsulation media. Polymer specimens were immersed in the PCMs for a period
up to 40 days under high temperature. The mass change, the mechanical strength and properties of the polymers were
tested. The wt% uptake reached 6.4wt% for PP and 5.8wt% for HDPE and the strength of HDPE was immediately
decreased by Day 7 but at a significant level restored after Day 28. No such effect was found for PP. Surface wetting
and thermal analysis (DSC) proved an in depth distribution over time of the absorbed PCMs. This had a significant
effect on the mechanical strength of the polymers. An epoxy-based resin was also evaluated under the same conditions,
proved stable and was suggested as candidate protective coating [13]. Very recently the same group reports a study
on 3D printed polylactid acid (PLA) properties in contact with commercially available organic PCMs (A44, A58) in
order to be evaluated as TES encapsulation or tank material. The contact period was 40 days in the medium
temperature region. Insignificant mass uptake up to 0.012%/cm2 for the case of A44 and 0.045%/cm2 for A58 was
recorded. At the same time PLA crystallinity was found to improve over contact time as calculated by differential
scanning calorimetry. The authors concluded that PLA may be a promising candidate structural material for thermal
energy storage systems and these initial results are supporting the concept of structure on-demand encapsulation media
design by PLA 3D printing additive manufacturing [67].
The encapsulation of PCMs into micro and nanocapsules although it engages advanced materials chemistry
preparation methods leads to shells with multifunctional and smart properties. Thus PCM capsules can provide one or
more of the following crucial features of controlled thermal energy release, prevention of material exchange with
environment, protection against degradation during heat uptake/release cycles, increased PCM surface area and heat
 Charalambos N. Elias et al. / Energy Procedia 161 (2019) 385–394 391
Elias C N and Stathopoulos V N / Energy Procedia 00 (2018) 000–000 7

conductivity and the possibility to use the capsules in powder or paste form as additives to convenient materials
(concrete, foam, paint, etc.). Recommended recent review papers are published by Shchukin and coworkers
highlighting nanoencapsulation advances [38] and by Giro-Paloma et al. for microencapsulation [37]. Recently, Lu et
al. reported a nanoencapsulation study of green PCMs [68]. Green phase change nanofibers mats with core-shell
structure based on paraffin wax emulsion (PWE) and polyvinyl alcohol (PVA) was obtained by a coaxial
electrospinning approach. After 500 heating-cooling cycles only a slightly decreasing tendency on the enthalpy but
also good TES stability could be observed. Şahan et al. [69] used SiO2 as shell material to microencapsulate two
different organic PCMs, a paraffin and stearic acid, in 20–700nm capsules by an in situ emulsion interfacial hydrolysis
and polycondensation technique. Quan et al. [68] reported a sol-gel approach to microcapsules containing n-eicosane
as the core and Fe3O4/SiO2 composite material as the shell adhered on wood surface. Recent works also report the use
of microencapsulated octadecylamine-grafted graphene oxide as PCMs in a melamine-formaldehyde (MF) resin as
the shell material via in-situ polymerization [70] and microcapsules with a thermally conductive shell based on
triethoxyvinylsilane - methyl methacrylate copolymer with an aluminium nitride/oxide coating as nanosized thermal
interface [71]. The properties of PCM were also enhanced by encapsulation in carbon based cellular structures [72]
and nanomaterials composites as recently reviewed for sunlight-driven energy conversion and storage [73, 74].

5. Conclusions

The emerging issue of energy efficiency is boosting the research effort in the field of PCMs over the past years.
Large number of papers has been published dealing with various aspects of PCMs in thermal energy storage
technologies. Of particular interest is the enhancement of PCMs properties and applicability by shape stablilisation
and encapsulation approaches. Although valuable results have been obtained so far along with the progress made
many open issues still remain. In nano and microencapsulation as well as in the macro encasement of PCMs by
engineering materials; material issues are still to be solved before advancing latent heat thermal energy storage
technologies and facilitating large scale applications.
In particular although engineering polymers that dominate the market, are widely used in contact with various
organic PCMs even as market products, they are still to be optimised for such applications. The studies so far clearly
show that cautious use is strongly recommended. Further studies are needed for suitable material selection or
customised solutions especially when medium or high PCM working temperatures (Figure 1b) are to be applied.
Nanoencapsulation is a dynamic and maybe the most promising sector for the enhancement of PCMs properties.
This high potential is driven by the superiority of structural features of nanosized capsules but it is still hindered by
the advanced chemical methodologies required for the development of such nanostructures. Also the behavior of
PCMs phase transitions in confined nanodomains is still to be explored. The development of high throughput
preparation methods of nanoencapsulated and or nanoenhanced PCMs will reduce costs and increase application
potential.
Finally, another aspect for future concern is the improvement of the environmental features of PCMs by developing
non fossil fuel derived organic, renewable, recyclable and safe PCMs. As PCMs are emerging on various applications
as energy storage materials including applications in our living space and buildings elements, the environmental as
well as health and safety aspects are becoming of paramount importance and should be closely followed.
The need for better and more efficient PCMs challenges material science to introduce features and functionalities
that will improve both PCMs performance and viability. The rapid developments in material science will move
forward PCM based thermal energy storage and engineering solutions in the roadmap for cleaner energy.

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