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Recent advances in phase change materials

for thermal energy storage
Cite this: Chem. Commun., 2024,
60, 1690
Mary Anne White, * Samer Kahwaji and John A. Noël

Efficient storage of thermal energy can be greatly enhanced by the use of phase change materials
(PCMs). The selection or development of a useful PCM requires careful consideration of many physical
and chemical properties. In this review of our recent studies of PCMs, we show that linking the
molecular structures of organic molecules to their physical properties can be used to focus attention on
the most useful PCMs, including eutectic mixtures. Two of the major limitations concerning broader use
Received 12th December 2023, of phase change materials are low thermal conductivity, especially for organic phase change materials,
Accepted 17th January 2024 and suitable containment. We have addressed both issues in our recent investigations of novel form-
DOI: 10.1039/d3cc06063b stable composite PCMs with a freeze-cast matrix. The use of thorough experimental investigations,
including cycling of materials hundreds or thousands of times through the melt-freeze processes,
rsc.li/chemcomm promotes our goals of advancing the use of PCMs for increased energy efficiency and sustainability.

1 Introduction renewables are not operable: photovoltaics do not work in the

dark, and wind turbines require wind.
1.1 Global outlook and need Less well known is the fact that about 40% of the energy
The environmental and climate change problems related to production for buildings is used as heat,1 while about 70%
combustion of petroleum-based products for energy produc- of the energy produced globally is wasted as unwanted heat.2
tion are a central focus worldwide at present. Renewable energy The mismatch between heat production and heat waste could
sources are a large part of the answer, although a critical (and be ameliorated by the use of thermal energy storage materials.
often weak) link can be the storage required for times when the Furthermore, the efficiency of storage of heat as heat can be
exceptionally high, 490%,3 especially opening opportunities
Department of Chemistry and Clean Technologies Research Institute, Dalhousie when energy is required for heating. (The inefficiency of
University, Halifax, Nova Scotia, Canada. E-mail: [email protected] capturing solar energy through a photovoltaic element, and

Mary Anne White has been a facu- Samer Kahwaji obtained his PhD
lty member at Dalhousie Univer- in Physics from Dalhousie Uni-
sity since 1983, now as Harry versity, and then joined Prof-
Shirreff Professor of Chemical essor Mary Anne White’s group
Research (Emerita). She has where he researched phase change
devoted her career to investiga- materials (PCMs) for thermal
tions of thermal properties of energy storage and thermal buf-
materials, with applications fering applications. His studies
including thermal energy storage. focused on the identification and
An award-winning teacher and preparation of useful PCMs, the
researcher, she has more than 200 characterization of their thermo-
publications, including a textbook physical properties, long-term
Mary Anne White (Physical Properties of Materials, Samer Kahwaji stability, and chemical compati-
now in its 3rd edition), and is co- bility with containment materials.
inventor on 15 patents. She was founding director of Dalhousie’s During his work on PCMs, Samer collaborated on research projects for
Institute for Research in Materials (now Clean Technologies Research industry involving the incorporation of PCMs in buildings and in
Institute). She holds three honorary doctorate degrees and is an Officer portable electronics.
of the Order of Canada.

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then storing that as electrical energy for later use for heating
means a staggering ]70% loss, highlighting the importance of
storing heat as heat when its end use is heat. In the context of
this work, we generally mean heating or cooling when we refer
to thermal energy storage.) The significant opportunity to
efficiently scavenge waste heat for later use, amounting to
1015 W h per year in Europe alone,4 is under-appreciated by
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the public and even by many renewable energy researchers.

Thermal energy storage is the motivation of the present work,
which presents our recent advances in phase change materials
for thermal energy storage, within a global context.
In the simplest of terms, a thermal energy storage material
could be any large thermal mass, such as brick or rock, that can
be heated and thereby store energy for subsequent radiation. Fig. 1 Thermal energy stored relative to 38 1C, per unit mass, for water via
Such materials, called ‘sensible heat storage materials’, store its heat capacity (eqn (1)) and for dodecanoic acid via its heat capacity and
heat by virtue of their heat capacity.5 Examples of sensible heat enthalpy of transition at 43.6 1C (eqn (2)). Data from literature sources for
storage abound, from the moderating influence of a large body water9 and dodecanoic acid.8

of water on the regional climate (with water acting as the

thermal energy storage material), to the bricks in an electrical
where DtrsH is the gravimetric transition enthalpy change, cp,1 is
thermal storage heater that facilitates shifting of day-time use
the temperature-dependent specific heat capacity of the low-
of the electrical grid to off-peak times. Although sensible heat
temperature phase, and cp,2 is the temperature-dependent
storage materials can be relatively inexpensive, the volume and
specific heat capacity of the high-temperature phase. If the
mass required for significant energy storage can be so high that
transition has an especially large enthalpy change in the
they are not feasible for all applications.
temperature range required for thermal energy storage, the
However, materials that undergo a phase change (‘phase
mass and volume of the phase change material can be much
change materials’, PCMs) can provide compact thermal energy
less than for a sensible heat storage material. Such phase
storage solutions in certain conditions.5
change materials were pioneered more than 70 years ago by
1.2 Phase change materials Mariá Telkes.7 See Fig. 1 for an illustration of the merits of
PCMs where, over the range of the transition temperature, a
A sensible heat storage material of mass m stores heat Q, over
phase change material (dodecanoic acid8 in this example)
the temperature range of heating (T1 to T2), such that:6
stores considerably more thermal energy per unit mass than
ð T2
a sensible heat storage material (water9 in this example).
Q¼ mcp ðTÞdT; (1)
T1 Although, in principle, any type of phase change has a
transition enthalpy change that could be used to store thermal
where cp is the temperature-dependent specific heat capacity at energy, in practice, most PCMs make use of melting (aka
constant pressure. However, a material undergoing a phase fusion).5 One reason is the rather large enthalpy of fusion,
change at a transition temperature, Ttrs, intermediate between relative to solid–solid transitions. Although vaporization has a
T1 and T2 has an additional contribution to the heat stored:6 large enthalpy change, the volume change associated with
ð Ttrs ð T2 melting is much less, making containment easier. (However,
Q¼ mcp;1 ðTÞdT þ mDtrs H þ mcp;2 ðTÞdT; (2) note that the fluid in a refrigeration unit undergoes a
T1 Ttrs
vaporization-liquefaction cycle to extract heat, so it is, in its
essence, a phase change system.) We focus here on the materi-
als aspects of phase change materials as the starting point for
John Noël completed a bachelor’s
thermal energy storage systems, but design of the systems for
degree at the University of Guelph
use with PCMs is also important.10
before obtaining his PhD in
chemistry from Dalhousie Univer-
sity in 2018 under the supervision 1.3 Selection of phase change materials
of Professor Mary Anne White. Many criteria must be met simultaneously to achieve a useful
John’s graduate research focus phase change material. The most important criterion for selec-
was phase change materials for tion of a useful phase change material for a given application is
thermal energy storage, with parti- the transition temperature. From Fig. 1, it can be seen that in a
cular interest in their nucleation working temperature range of 38 to 42 1C, water is a better
behaviour and the use of freeze- thermal energy storage material than dodecanoic acid by about
cast ceramics to enhance their a factor of 2, whereas from 42 to 44 1C, which includes the
John A. Noël thermal conductivity. dodecanoic acid transition temperature of 43.6 1C, dodecanoic

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acid stores nearly 10 times as much thermal energy per unit slow rate of energy transfer such as in the case of supercooling,
mass as water. Fortunately, there are hundreds of potential can, in some instances, be resolved with control of the phase
phase change materials to choose from, including organics, change by application of light, pressure, electrical bias, and/or
inorganics and metals,4,11–14 with a wide range of phase transi- mechanical means.16–18) The transition also should not be
tion temperatures. modified by phase separation over time, or by chemical degra-
The next most important criterion for a phase change dation of the sample (e.g., from reaction with the container or
material is its enthalpy of transition, with higher values prefer- the atmosphere).
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able. See Section 2.2 below for some considerations related to Two points require special mention in this regard.
the molecular structure of an organic material and its enthalpy One is that reliable measurement of the physical properties,
of fusion. including uncertainty analysis, over thousands of cycles, is
Another physical property that should be satisfied is small required to ascertain any change in melting point, freezing
volume change on transition. A relatively small volume change point or enthalpy of transition as a function of use.19 We note
(o5%) is usual for melting points of many PCMs; in cases that one useful family of PCMs was (incorrectly) stated to be
where data are not available, the change in density with the subject to degradation in a study presented with inadequate
transition should be determined because, if it is large, contain- uncertainty analysis, until a more accurate and precise study20
ment issues could ensue after the thousands of thermal cycles showed otherwise. Unfortunately, the literature concerning
required for most applications. For example, the large (B10%) phase change materials is generally sparse with regard to
volume change for water on freezing provides sufficient thermal uncertainty analysis, as we have detailed elsewhere.19
stress to fracture rocks. The second point is that determinations of degradation with
High thermal conductivity is also a preferred physical prop- materials that could potentially contact the PCM in its applica-
erty for many applications. The thermal conductivity of a pure tions are essential but rarely studied. Such a line of investiga-
PCM is an intrinsic property, and, if low, can be troublesome tion has proven to be useful in recent studies of paraffin21 and
for applications in which rapid transfer of heat flow is required. fatty acid8 PCMs.
An example from a study of dodecanoic acid15 which has a low Of course, cost of a PCM is a substantial issue, especially
thermal conductivity of 0.24 W m1 K1 in the solid state when large quantities (100s of kg) are required for a significant
just below its melting point,8 is shown in Fig. 2. In the solid installation. Even based on commodity pricing, the cost of a
form, the only avenue for heat transfer is conduction through potential PCM with a transition temperature of 50 1C ranges
the material, whereas in the liquid, convection also plays a considerably, from USD 500 per metric ton for a fatty acid, to
role. Recent advances to enhance thermal conductivity are USD 2000 for an alcohol, to about USD 15 000 for an alkane or
discussed below. diamine.22 Containment costs are also an important considera-
Thermal energy storage applications of PCMs generally tion. Similarly, safety of the PCM and the PCM-container unit
require thousands of times over the phase transition and back must be considered.
to the original phase (typically melt-freeze cycles). Therefore, it The PCM is generally derived from organic materials or
is important to have excellent reproducibility of the transition, minerals, and the sustainability of its production, use and
not modified by inherent hysteresis, which can lead to super- disposal should be considered. One important benchmark is
cooling. (The matter of supercooling is discussed further below the energy (and resultant greenhouse gas emissions) associated
in the context of our contributions; we also mention here that a with production of the PCM, compared with the energy payback

Fig. 2 (a) Placement of heat exchange coil into molten dodecanoic acid phase change material. The storage tank was a residential hot water heat tank,
modified to half its initial height, to have a volume of 60 L, scaled to be appropriate for real-time thermal energy capture from a thermal solar collector. A
40% ethylene glycol – 60% water mixture was used as heat transfer fluid in the solar loop. While charging of the system (i.e., melting of the PCM) was
efficient, discharging was very slow.15 (b) The thermally insulating layer of PCM that formed on the cold heat exchange tubing (shown here from a
separate experiment in which copper tubing was only partially immersed in the PCM), preventing efficient removal of the stored heat from the system,
owing to the low thermal conductivity of dodecanoic acid.8

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period when used in conjunction with a renewable energy pumps), in commercially available products,28 as well as pro-
source. In a life cycle analysis, we have shown that the energy ducts in development as shown in Fig. 3.33
payback time for production of dodecanoic acid PCM used for Other large-scale applications of PCMs include transporta-
storage for a solar thermal hot water system can be two years or tion and storage of temperature-sensitive goods. Of particular
less,23 which bodes well for the expected useful lifetime of the note are PCM-cooled trucks with reduced operating costs and
PCM of several decades. More recent life cycle assessments of emissions relative to fossil fuel based refrigeration.28 Other
PCMs include materials based on palm oil,24 and building- PCM-based storage solutions include coolers and freezers for
integrated solar thermal systems,25 but the need for additional
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areas with unstable electrical grids, or for solar-powered appli-

life cycle analyses of specific PCMs (generic PCMs are not cations, and for storage and transport of temperature-sensitive
suitable substitutes) has been made clear.26 medical products including vaccines.28
The desired features of PCMs are summarized in Table 1. At medium scale, applications including those for the
human body, such as regulation of body temperature via
1.4 Applications of phase change materials PCM blankets, pillows and clothing, heat and cold therapy,
neonatal and prosthetic temperature regulation.28
Phase change materials have been used for thermal energy Electronic devices can be enhanced through the use of PCMs
storage and temperature buffering for thousands of years, with at very small scale; examples include thermal management of
ice/water as the PCM. Ice is still a prevalent and cost-effective batteries and other electronic devices including laptops and
PCM; for example, the Goldman Sachs headquarters in New smart phones, as the PCMs are compact and passive in their
York saves USD 50 000 per month on their utility bill during the operation.28,34
summer by using off-peak power to freeze ice used for their air
conditioning chillers.27 Of course, the main detractor for the
use of ice as a PCM is its transition temperature, which limits 1.5 A look ahead
its use to temperatures near 0 1C. In this review, we summarize recent phase change materials
In applications, PCMs can be used in bulk (as in the ice studies from our laboratory, including the basics of the rela-
chiller), macroencapsulated (e.g. for use with building materi- tionships between structure and properties for organic PCMs,
als), microencapsulated (limited to organic PCMs) or formu- the use of organic eutectic mixtures, supercooling of organic
lated into composite materials. Heat exchange and design PCMs, and novel form-stable PCMs to address the issues of
also play important roles in the form used for particular containment and low PCM thermal conductivity. We also
applications. discuss economic factors in terms of organic PCMs and espe-
Excellent overviews of PCM products presented by field of cially commodity PCMs, and sustainability matters as assessed
application,4,28 and another review based solely on PCMs for by life cycle analysis. Throughout our work we emphasize
food applications,29 were both published recently. Details con- reliable determination of thermal properties of PCMs, includ-
cerning a selection of notable PCM systems at work in office ing cycling thousands of times through the transition.
buildings, factories, schools, greenhouses, homes, etc. around
the world are described elsewhere.30 In the interests of brevity,
applications are summarized here, and in Table 2.
At large scale, PCMs are used in solar thermal projects such 2 Organic phase change materials
as Andasol, a concentrating solar project in southern Spain, in
which molten salt PCMs allow operation for more than 7 hours 2.1 Motivation
when solar power is not available.5,31,32 PCMs also are used in a Inorganic PCMs have some advantages over organics, especially
wide range of passive and active building applications, increas- their applications at high temperatures. However, some ele-
ing the thermal storage and/or release. Applications include ments used in inorganic PCMs are detrimental to the environ-
building materials (e.g., PCM added to plaster board) and ment, whereas organics can be both safer and less costly. For
components (e.g., floor heating, ceiling cooling, space heating these reasons, we have focused our more recent PCM studies on
and cooling, domestic hot water, thermal buffer on heat organic molecular systems.

Table 1 Desirable properties of a phase change material for thermal energy storage

Property Desirable consideration

Transition temperature Well matched with temperature range of application
Enthalpy of transition High (4100 J g1)
Volume change on transition As small as possible
Thermal conductivity As high as possible to have rapid flow of thermal energy into and out of the material
Stability Good thermal and chemical stability, without hysteresis or phase separation or degradation, after thousands
of cycles over the transition
Cost Material and containment cost appropriate to application and expected fiscal pay-back
Safety Safe, in consideration of potential for leakage or other exposure
Sustainability Production, use and disposal should have low impact on the environment, as determined by a life cycle analysis

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Table 2 Current applications of phase change materials. Information mainly from ref. 28

General application area Specific use Detailed examples

Building applications Building materials PCMs integrated into gypsum boards, plaster, concrete, clay
Building components Glass elements filled with PCM
Floor heating PCM integrated into floor system
Cooling ceilings PCM integrated into ceiling materials
HVAC storage PCM (especially ice) used for remote or even district cooling or heating
Domestic hot water Thermal insulation for hot water tanks
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Thermal buffer on heat pumps PCM as thermal storage for heat pump to increase efficiency

Cold chain applications Independent transport containers PCM provides temperature buffer for temperature-sensitive goods
Transport containers for PCM providing thermal insulation for container that is charged during
trucks and trains non-operational times and thus does not rely on truck/train fuel or power
Storage solutions PCM backup to maintain temperature of storage in case of power loss

Human body applications Clothing PCM integrated into clothing or footwear to buffer temperature
Sleeping equipment Microencapsulated PCMs in blankets, pillows and mattresses for
temperature control
Protective garments PCM incorporated into outerwear for firefighters’ thermal protection

Medical applications Heat and cold therapy PCM incorporation into heat cushions and cold packs
Neonatal treatment PCM incorporation into sleep sack for temperature control
Prostheses PCM incorporation into prosthesis for thermal comfort
Storage and transport PCMs used in cold chain applications, e.g. temperature-sensitive vaccines

Mobility applications Preheating combustion engines Latent heat of PCM used to preheat cold cars using thermal energy from
engine block
Cabin heating and cooling PCMs used in thermal energy storage and release in electric vehicles for
in electric vehicles which battery use for heating and cooling would not be feasible

Electronics applications Cooling data centres PCMs used to buffer thermal output from computers
Cooling telecom equipment PCMs used to buffer thermal output from telecom equipment
Thermal management of batteries PCMs used to prevent overheating of batteries and other electronic devices
and other electronic devices

Industrial applications Process cooling PCM frozen using off-peak power to reduce cooling costs
Solar food drying Temperature stabilization using PCM during drying leads to higher-quality
product
Waste heat scavenging PCM can be used as mobile heat storage medium
Solar thermal PCMs allow operation of solar thermal power when sun is not shining

Other Air dryer for compressors PCM use in energy-saving refrigerant air dryer
Closed-circuit breathing apparatus PCM used to reduce temperature of re-breather air to minimize stress to user
Mechanical actuators, switches, valves Change in density of PCM over transition can act as actuator

2.2 Relationship between properties and molecular structure detailed compendia of thermodynamic data for nearly 7000
The key criteria that must be met for a PCM to be useful are the organic molecules,37,38 to prepare an entropy of fusion distri-
appropriate temperature range for the transition and high bution diagram, as shown in Fig. 4.39 At low entropy of fusion,
enthalpy change. Although some potential PCMs make use of DfusS o 30 J K1 mol1, are molecules for which the solids
solid–solid transitions,35 in general their enthalpy changes are exhibit dynamical disorder in the solid state, such as cubane
low, and further discussion will be confined to the melting which rotates on its lattice sites just below the melting point.40
transition. We refer hereafter to temperature of fusion, Tfus, The high entropy of the solid reduces DfusS relative to most
and enthalpy change of fusion, DfusH. These two properties are compounds. There is a peak in the entropy of fusion distribu-
related via the entropy of fusion, DfusS:36 tion at about 60 J K1 mol1, which corresponds to organic
materials that form ordered crystals of rigid molecules. The
DfusH = TfusDfusS. (3) region with high values of DfusS, which are typically flexible
molecules (which gain considerable disorder on melting), is of
In general terms, a large value of DfusS could be expected to considerable interest (see eqn (3)) as high values of DfusH could
correlate with a high enthalpy of fusion, DfusH, which is one of be expected, which is promising for PCMs. Examples include
our goals for a useful PCM. alkanes (aka paraffins) and fatty acids. (Note that in referencing
A thermodynamic generalization is that entropy of vaporiza- ‘fatty acids’ as PCMs, we refer to saturated fatty acids which are
tion, DvapS, for many molecular fluids is ca. 90 J K1 mol1; this quite stable; unsaturated fatty acids can easily oxidize and
finding is known as Trouton’s rule after its discoverer.36 In the become rancid.) Of special note are hydrogen-bonded mole-
absence of such a generalization for fusion, we made use of two cules, which can have exceptionally high melting points due to

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alcohols, and sugar alcohols can be considered as potential

PCMs, due to their high values of DfusH. Generally, within a
given molecular organic family, the higher the molar mass, the
higher the melting point. When isomers are taken into account,
materials with longer alkyl chains have higher melting points
and generally higher DfusH and higher thermal energy storage
density.39
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The discussion above has been with reference to molar

thermodynamic properties. Even though molar values are of
theoretical importance as a construct, gravimetric values are
of greater practical importance. Using the same literature
sources37,38 for thermodynamic data of nearly 7000 organic
molecular materials, we have prepared a distribution curve22
for gravimetric enthalpies of fusion (J g1) as shown in Fig. 5.
Most of the B7000 organic compounds shown in Fig. 5 have
Fig. 3 An electric thermal storage home supplemental heating system values of DfusH 4 100 J g1, making them suitable for use as
using phase change materials.33 The PCM containers, which are the two phase change materials, again higher values of DfusH are better.
pairs of metal boxes at the right (background) of the photo, hold about Detailed consideration of the compounds with high gravimetric
200 kg of sodium acetate trihydrate PCM. The oil-fired furnace is the beige
enthalpies of fusion confirms the importance of flexibility of
box shown on the left (foreground). In operation, the PCM is heated using
off-peak electrical power and melts at 58 1C, then is supercooled to room the molecules and the importance of hydrogen bonding.22
temperature. When home heat is required, PCM crystallization is triggered, Although melting points tend to increase with increasing
and the resultant latent heat of crystallization is delivered to a heat- molar mass within a given family, molecules with alkyl chains
exchange fluid flowing through the PCM. This heat is transported to a tend to show even–odd effects (see Fig. 6)22 due to distinct
heat exchanger insert in the furnace’s hot air blower (tubes can be seen
packing arrangements for even and odd numbers of alkyl
entering and exiting the heat exchanger on the left side of the photo) and
then the warm air is distributed to the rest of the house by the furnace’s chains (ending in a ‘zig’ or a ‘zag’).41,42 Linear relationships
fan. The electric thermal storage system, which provides thermal energy between molar (denoted with subscript m) enthalpy changes
through off-peak electricity, is a more cost efficient and environmentally (here referred to as DtrsHm to indicate the inclusion of solid–
effective heating system than the oil-burning furnace, and the latter is only solid transitions near the melting point, in addition to DfusHm)
used as an auxiliary heat source.
and number of carbons in the alkyl chain, n, represented as:

DtrsHm = b0 + b1n (4)

and between the corresponding molar entropy changes, DtrsSm,

and n as:

DtrsSm = c0 + c1n (5)

were found for odd and even n for long-chain alkanes, alcohols
and fatty acids, with nearly parallel lines for odd and even n

Fig. 4 Distribution of molar entropies of fusion of 6828 organic com-

pounds. Individual data values were taken from Acree and Chikos.37,38
Binned data from ref. 39.

their strong intermolecular interactions relative to their analo-

gues without H-bonding, leading to higher values of Tfus, and
higher DfusH even if DfusS is relatively normal.39 Fig. 5 Number of molecular organic compounds with a given range of
This structure–property approach informs why molecular gravimetric enthalpies of fusion, DfusH expressed in J g1, based on
organic families, including alkanes, fatty acids, long-chain published summaries of literature data.37,38 Reproduced from ref. 22.

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experimental uncertainty, the thermal properties of fatty acids

do not degrade with lowered purity20 or with 3000 cycles
through the melting-freezing process,8 making fatty acids espe-
cially attractive for use as PCMs.
Based on similar approaches to understanding of the rela-
tionship between structure and thermodynamics of phase
changes, a new family of metal–organic phase change mate-
rials has been proposed and achieved recently.44 Extended
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hydrogen-bonded networks and high densities of coordination

bonds contribute significantly to their high enthalpy changes
on melting.

2.3 Eutectic mixtures

Common long-chain saturated fatty acids have melting points
Fig. 6 Temperatures of fusion (melting) for nine families of long-chain, ranging from ca. 10 1C to 70 1C.22 However, a binary mixture
unbranched organic molecular solids, as a function of chemical family and
total number of carbons in the compound. Lines are drawn between data
of such fatty acids can form a eutectic, which melts at a fixed
points for some families, to emphasize odd–even effects, as described in temperature, lower than either of its two components.45 The
the text. Reprinted from ref. 22. eutectic composition can be predicted reasonably well using
ideal mixture thermodynamics,46 with composition predictions
within ca. 0.03 mol % in cases that have been studied experi-
within a given chemical family.43 The slopes, b1 and c1, were mentally.47 However, the prediction should be used as a guide,
found to be nearly identical regardless of chemical family and as not all binary fatty acids phase diagrams are so simple. For
even/odd n, indicating a nearly constant increase in DtrsHm example, dodecanoic acid-tetradecanoic acid has a peritectic in
(and DtrsSm) per additional –CH2– group.43 However, the addition to the eutectic, leading to a significant difference in
enthalpy intercept, b0, reflects the structure, with least negative eutectic composition (predicted at 0.65 mole fraction dodeca-
b0 for fatty acids, then alcohols and alkanes, corresponding to noic acid; experimentally found to be at 0.71 mole fraction
the existence of strong intermolecular interactions in fatty acids dodecanoic acid).47 Multiple melt-freeze cycles near but slightly
in both the solid and liquid state, in comparison with alcohols off the eutectic composition would eventually lead to phase
and alkanes in which intermolecular interactions would be separation and degradation of thermal properties, so precise
weaker in the liquid than the solid.43 If such linear thermo- determination of the eutectic by experimental measurements,
dynamic relationships are more general for organic phase including use of a Tamman plot,45,48 is recommended. New
change materials, they would allow estimates of enthalpy high-throughput techniques offer considerable promise in this
changes for potential PCMs for which experimental data are regard.49
not available. Fig. 7 shows the predicted melting points of binary eutectics
Even-carbon compounds tend to have higher melting of fatty acids, offering a wide range of melting points, and
points, which means the even-carbon compounds have melting indicating the potential to tailor the melting point to the
points corresponding to longer chains for odd numbers of application requirements.47 (Again, such predictions require
carbons.22 This is useful information, especially since material experimental confirmation.) Furthermore, fatty acid eutectic
costs tend to increase with longer carbon chains, and generally mixtures at their precise eutectic composition can maintain
odd-chain compounds are much more expensive than even Tfus and DfusH within experimental uncertainty over 3000 melt-
chains.22 Furthermore, even-chain alkanes, linear 1-alcohols freeze cycles,45 even when part of a composite,50,51 showing the
and saturated fatty acids have higher gravimetric enthalpies of promise of fatty acid eutectic mixtures.
fusion than corresponding odd-chain compounds.22 These Other pertinent PCM properties for eutectic mixtures,
factors make even-chain compounds greatly preferable to those including DfusH and heat capacity, also can be predicted with
with odd chains for use as PCMs. the simple ideal mixture considerations,46,47 with accuracy in
Consideration of families of potentially practical organic DfusH within a few percent of experimental values.47
PCMs, namely alkanes (paraffins), saturated fatty acids, linear Eutectic mixtures have broad applications in terms of
alcohols, esters, diamines, dinitriles, diols, dioic acids, and extending the available melting temperatures in many types
diamides, show potential PCMs over a wide range of melting of PCMs. Eutectics can be binary (two-component) as described
points, from 70 1C to 200 1C.22 For a given required melting above, or ternary, or even more complex, and the components
point, the gravimetric enthalpy change would be highest (and can be all organic, all inorganic or organic with inorganic.
consequently the required mass would be lowest) for an even- Some of the organic components of eutectics considered as
chain alkane, fatty acid or alcohol.22 Cost of thermal storage for phase change materials include paraffins, fatty acids, alcohols,
a given quantity of energy via melting of a fatty acid would be esters, diols and sugar alcohols.52 Salt hydrate eutectics cycle
4 to 30 times less than an alkane or alcohol with a similar better and are less prone to phase separation than pure salt
melting point.22 Furthermore, we have shown that, within hydrates.52 Metal alloy eutectics are useful for high-temperature

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they are composed,52 and have significant applications in con-

centrated solar power.53 In all cases, care should be taken to use
the precise composition of the eutectic (which may be a little
removed from the composition derived from ideal mixture theory)
to promote stable properties after many melt-freeze cycles.

2.4 Supercooling in organic PCMs

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From consideration of enthalpies of fusion of potential organic

PCMs (Fig. 5), one family stands out as having excellent poten-
tial for thermal energy storage: sugar alcohols. See data54–61 in
Table 3 for a summary. The sugar alcohols have exceptionally
high gravimetric enthalpies of fusion (several are 4300 J g1),
associated with the hydrogen-bonded networks in the solid
Fig. 7 The melting points, Tmpt, of 15 pure long-chain saturated fatty acid state that are disrupted on melting. However, they are prone to
PCMs and the extended range of Tmpt predicted for ideal binary eutectic supercooling, with crystallization temperatures significantly
mixtures of these fatty acids. The eutectic mixtures extend the lower range lower than their melting points. Again, this is related to
of Tmpt to 22 1C and provide values of Tmpt that are not otherwise
hydrogen-bonding, as nucleation (and crystallization) of sugar
available from individual fatty acids. Reprinted with permission from ref. 47.
alcohols requires the correct orientation of hydrogen bonds,
out of many possible arrangements. Many attempts have been
applications and have especially high thermal conductivity and made to reduce supercooling in sugar alcohols, by addition of
gravimetric enthalpies of fusion.52 Molten salt eutectics can show seed crystals,61 heterogeneous nucleating agents,55 addition of
better chemical stability than the pure molten salts from which metals,62 and mechanical agitation.63 However, supercooling

Table 3 Structures and properties of some sugar alcohols of interest for use as PCMs in thermal energy storage applications

Compound Tfusa/1C Tcryst/1C DfusHa/J g1 Ref.

118 B10–40 324 54–56

89 40 240 56 and 57

101–106 o30 256 54 and 58

187 115 330 54 and 59

166 120 308 54 and 60

98 o40 166 54 and 61

a
For the stable polymorph at the melting temperature.

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can still be substantial, leading to the situation whereby In further studies using Raman spectroscopy, density func-
thermal energy is stored but cannot be recovered easily. tional theory calculations and small-angle X-ray scattering,65 we
Motivated by an interest in deepening our understanding of determined the size, structure and temperature dependence of
nucleation in hydrogen-bonded materials, we turned to the the clusters of fatty acid molecules in the liquid. The liquid
simpler system of fatty acids. In general, fatty acids nucleate phases of fatty acids show some ordering at all temperatures,
well, with little supercooling, which is another reason why they with, on average, short-range molecular alignment along the
work well as PCMs. However, we found that if liquid saturated long (molecular backbone) axis. Below the threshold tempera-
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fatty acids are heated past a threshold temperature, supercooling ture, the clusters consist of several hundred molecular dimers,
can be induced.64 Fig. 8 shows the situation for octanoic acid and with alkyl chains interdigitated, as shown schematically in
dodecanoic acid. When the high-temperature holding tempera- Fig. 9.65 Above the threshold temperature, the clusters con-
ture is less than about 35 K above the melting point for octanoic tained fewer than 100 molecules. We showed that fatty acid
acid (75 K above for dodecanoic acid), there is little supercooling. clusters in the liquid phase, which predominate in conditions
At higher hold temperatures, supercooling is substantial. Further- in which nucleation is facile and supercooling is minimal,
more, through studies of a fatty acid in an emulsion, which could reduce the nucleation energy barrier and thereby pro-
showed the same threshold to supercooling, we determined mote nucleation by facilitating the creation of critical crystal
that the supercooling is intrinsic to the fatty acid (i.e., nucleation nuclei in fewer additive steps, relative to growth via monomers
is homogeneous), and not an artefact due to heterogeneous or dimers. We explicitly showed that the nucleation barrier in
surfaces.64 fatty acids is lower when the clusters are present.65
We hypothesized that there are fatty acid molecular clusters The insights concerning nucleation and supercooling in
in the liquid structure that usually assist nucleation, but break fatty acids indicate the existence of a high activation energy
apart when the fatty acids are heated above a threshold temperature. for dipolar reorientation of fatty acid molecules, of about
We confirmed this hypothesis through temperature-dependent 50 kJ mol1,64 which is more than 10 times the thermal energy
NMR spin–lattice relaxation times, T1, which showed a available at the melting point (ca. 3 kJ mol1). Therefore it is
change in slope at the threshold temperature, consistent with clear why ‘preorganization’ of the liquid by the presence of
a reduction in number of clusters at the threshold tem- clusters can lead to a very low degree of supercooling in fatty
perature.64 Furthermore, T1 showed hysteresis below the acids under normal circumstances. The rather globular shape
threshold temperature, and restoration of T1 values on sitting of the sugar alcohol molecules (Table 3) and the multitude of
at a temperature just above the melting point, consistent with their possible hydrogen-bonded arrangements predict that,
re-establishment of the clusters.64 Similar hysteresis in dielec- even if clusters exist in sugar alcohols, their molecules are
tric measurement results indicated that the molecular dipoles unlikely to be oriented in such a way that would reduce their
become more mobile on average with heating, and remain so barrier to nucleation. Therefore, homogeneous nucleation of
on cooling.64 sugar alcohols seems highly unlikely, and future efforts should
be placed on heterogeneous nucleation mechanisms.
One further caveat is required concerning use of fatty acids
as PCMs: our studies of clusters and supercooling indicate that
if a fatty acid is heated substantially above its melting point, the

Fig. 9 Schematic of the ordering of fatty acid molecules in clusters (blue)

within the liquid phase of the bulk liquid (orange). The solid circles
represent the hydrogen-bonded linkage between two molecules, to form
dimers with alkyl tails pointing in opposite directions. The clusters, which
would contain 200 to 300 molecules just above the melting point, are
more tightly packed than the bulk, and the alkyl chains of the fatty acid
dimers in clusters are fully interdigitated with their longitudinal neighbours
leading to long-range order. The fatty acids in the bulk liquid are roughly
Fig. 8 Supercooling (= Tfus  Tcryst), where Tcryst is the crystallization aligned along their long axes, and, on average, the alkyl chains of its dimers
temperature, as a function of the high-temperature holding temperature, are half-way inserted between the alkyl chains of its longitudinal neigh-
Thold, relative to the melting temperature, Tfus, for dodecanoic (red data ) bours. For simplicity, alkyl chains are shown as straight lines, but they
and octanoic acid (green data ), with data from ref. 64. would be dynamically disordered. Reprinted with permission from ref. 65.

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liquid can supercool due to the disruption of the nucleation- cost and reduction in GHG emissions driving their possible
promoting clusters. Such supercooling could make it easy to applications.
store thermal energy (on melting) but more difficult to release
that thermal energy unless the operational temperature is very
low. One way to mitigate this problem is to cool the fatty acid 3 Form-stable phase change materials
PCM slowly, allowing time for the clusters to re-establish, 3.1 Background
thereby promoting nucleation and reducing the degree of
Even if a suitable PCM is chosen, two of the most vexing
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supercooling.
problems concerning applications remain. One is the matter
2.5 Commodity materials as PCMs of containment, so that the PCM does not flow away when in its
As mentioned above, fatty acid PCM properties are essentially liquid state. The other concerns the low thermal conductivity
unchanged even when low-grade (and therefore cheaper) mate- of many PCMs, which is especially problematic for organic
rials are used. However, use of commodity materials that melt materials.
at convenient temperatures could offer even further potential The issue of PCM containment can be addressed through
for reduction of cost, and broad accessibility of PCM materials the use of encapsulation, which can be at the macro scale (as in
to consumers. pouches) or micro scale (as in microencapsulation). The
On this basis, we undertook a study of the thermal energy required properties include good mechanical strength and
storage potential of edible oils.66 From these experimental structural stability, high thermal stability, chemical compat-
investigations, we showed that margarine and vegetable short- ibility with the PCM, durability over thousands of melt-freeze
ening are not suitable PCMs due to their low enthalpy of fusion cycles, and high thermal conductivity. With organic contain-
and poor thermal cyclability. ment materials, the thermal conductivity of the containment
However, coconut oil, which consists mostly of fatty acids material generally is not high. Both macro and micro PCM
that are themselves useful PCMs, maintained its melting point containers are used commercially; advantages and disadvan-
(24  1.5 1C) and high enthalpy of fusion (105  11 J g1) over tages of various encapsulation methods are summarized in a
200 melt-freeze cycles, for both refined coconut oil and virgin recent review.72
coconut oil. (Refined is cheaper but has a shorter shelf life. The matter of low thermal conductivity of PCMs can be
Virgin coconut oil has a longer shelf life due to its stabilizers, mitigated somewhat by the addition of higher thermal con-
but this adds to the cost.) ductivity materials to the PCM. Examples of additives include
The coconut oil melting temperature and the low degree of metals, nanomaterials such as graphene and carbon nano-
supercooling of bulk samples makes it especially useful for tubes, and ceramics.73 However, additives can increase the
thermal buffering in buildings in conditions with large diurnal cost, and can settle out over many melt-freeze cycles, and some
temperature swings.67 PCMs require expensive additives at unrealistically high load-
A recent publication has reviewed the properties of bio- ings (e.g., 20%). Furthermore, although many publications
based PCMs,68 showing the wide variety of commodity items claim thermal conductivity enhancements of, for example,
that could potentially serve as PCMs. A life-cycle analysis by the 200%, if the thermal conductivity of the PCM is very low
same authors showed69 that although coconut oil has lower (0.24 W m1 K1 for dodecanoic acid8 would be typical for an
embodied energy than paraffins, the greater thermal energy organic material), a 200% increase to 0.48 W m1 K1 still
storage of paraffins makes their life-time GHG emissions lower results in a low thermal conductivity material.
than coconut oil. However, recycling of ‘waste’ coconut oil can
reduce the environmental impact.68 3.2 Novel form-stable phase change materials
Using approaches similar to those discussed in Section 2.2, Both containment issues and low thermal conductivity can
the literature concerning the relationship between molecular potentially be overcome through the use of composites in
structure (chain length, number and types of functional groups, which the PCM is retained even in its fluid phase, making
polarity, symmetry and isomerism) of vegetable oils and their form-stable phase change materials.
thermal properties as relates to their potential use as PCMs, Composite PCMs can include a wide variety of matrices,
has been critically organized recently.70 The authors concluded including metals, polymers, carbon-based materials, ceramics,
that the flexibility of alkyl chains in vegetable-oil based PCMs with various forms, including foams, aerogels, other porous
places an intrinsic limit on their enthalpies of fusion, which structures and nanostructures, including both synthetic and
could be mitigated by the insertion of multiple polar func- natural components72,74–78 and even magnetically tightened
tional groups or phenyl groups,70 but likely would significantly matrices.79 Many composites made with higher thermal con-
increase costs. ductivity matrix materials show thermal conductivity enhance-
There is potential for additional studies of commodity ment over the PCM contained therein, but, as has been pointed
materials, especially those that would otherwise be considered out recently, characterization of leakage and durability on
to be waste, as phase change materials. One example is spent thermal cycling are still not carried out in many studies.72
coffee grounds, which contain large quantities of fatty acids.71 The material should be referred to as a ‘form-stable’ PCM only
The main concern is stability of thermal properties, with low if there is insignificant leakage of PCM and a stable shape

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(form) after cycling hundreds or thousands of times through From the perspective of phase change materials, high load-
the melting and freezing of the PCM. One of the earliest reports ing of PCM via a simple process is important, to provide
of a form-stable PCM described80 a high-density polyethylene significant thermal storage. Furthermore, the PCM should be
three-dimensional mesh-like structure, containing paraffin held in the pores of the matrix by physical interactions, not
PCM within its pores. The loading was 74% PCM by mass, chemical bonds, to maintain the properties of the bulk PCM
and the composite had the expected proportionally scaled and avoid chemical degradation. Ideally, the PCM should
melting enthalpy change (120 J g1 vs. 160 J g1 for pure remain in the pores even when molten, and even after many
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paraffin) but provided only marginal improvement in heat melt-freeze cycles, to provide form stability. It is challenging to
transfer. It is difficult to achieve both form stability and achieve all these goals, in addition to significant enhancement
thermal conductivity enhancement. However, applications of of thermal conductivity relative to that of the PCM.
successful form-stable phase change materials could include Our investigations of freeze-cast scaffolds impregnated
industrial waste heat recovery, building temperature regula- with PCMs have included many different freeze-cast matrices
tion, solar energy harvesting and storage, and battery thermal (alumina, titania, carbon black, alumina/carbon black, chitosan,
management,81 as well as building energy management82 and carbonized chitosan) with a wide range of PCMs (fatty
electrical energy harvesting.83 acids, polyethylene glycol, paraffins, esters, sugar alcohols, salt
Our contribution to this field has been in the development hydrates).89 In all cases, the PCM loading is simple, with the
of novel composite PCMs, in which the matrix is prepared by a molten PCM pulled into the porous matrix via capillary forces.
freeze-casting method, and then the PCM is drawn into the porous Furthermore, the interaction between the matrix and the PCM
structure by capillary action. The pore structure is critical to hold is purely physical, so the melting point and enthalpy of fusion
the PCM even when molten, allowing for form stability. Further- of the PCM are not significantly influenced by the matrix.89
more, the choice of matrix is key for high PCM loading and/or high The matter of pore morphology in the freeze-cast matrix
thermal conductivity of the resultant composite. requires further explanation. Pure ice crystallizes at atmospheric
In the freeze-cast process, water acts as a fugitive template pressure in a hexagonal structure (space group P63/mmc),90 with
for the matrix structure.84 An aqueous slurry of the matrix- preferential growth along the a-axis, and in the freeze-cast
forming material, usually with some additives, is directionally process this leads to formation of plate-like structures, and
cooled at a rate chosen to form crystals of ice of a controlled results in a lamellar structure within the matrix. However, the
shape and size. After the ice is removed by freeze-drying, the presence of zirconium acetate in the aqueous slurry leads to
matrix is consolidated by sintering. See Fig. 10 for a schematic hexagonal ice pillars due to a switch to preferential ice growth
summary of the process, and Fig. 11 for some of the freeze-cast along the c-axis, and results in vertical, hexagonal (honeycomb)
materials prepared in our lab.85 channels in the freeze-cast matrix. See Fig. 12 for an example
Some of the attributes of the freeze-cast process to form based on Al2O3. We note that the change in structure is generally
PCM matrices include: the control of porosity (by rate of cool- applicable to other matrices, as it relies solely on the growth of
ing, and temperature gradient; choice and concentration of the ice crystals. Other additives also can influence the structures
binders or structuring agents as additives in the slurry, with in more subtle ways.85
morphologies including lamellae or vertical channels, and pore Of the composite phase change materials that we made
volume from moderate to high);86,87 the flexibility of types using the freeze-cast process, those with the alumina matrix
of scaffold materials; the fact that the process is additive have been most thoroughly characterized.89 The motivation
which minimizes material requirements; the use of water as was the use of a commodity item (alumina) and the ability to
the suspension fluid which is far preferable to organic tem- shape the final product, for example by milling, for particular
plates that are later burned out. Applications of freeze-cast applications. A typical product, as shown in Fig. 13, has the
materials, aside from matrices for form-stable PCMs, include honeycomb internal structure (as in Fig. 12(b)). The range of
silver-loaded scaffolds with antibacterial properties, low-cost porosity for alumina scaffolds was 74  7%, with a typical fill
composites with negative thermal expansion, and structures for fraction by volume of PCM of 490% and mass fraction of PCM
dye-sensitized solar cells,88 among many others.84 of about 40%.89 The high density of pure alumina (B4 g cm3)

Fig. 10 Schematic representation of the freeze-cast process. In the first stage, an aqueous slurry is formed. It is then cooled from the bottom, forming
pillars of ice. Next, the ice is removed by freeze drying. In the final step, the remaining matrix is consolidated by sintering. Reprinted with permission from
ref. 85.

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Fig. 13 (a) Freeze-cast alumina scaffold and (b) alumina/dodecanoic acid

form-stable PCM composites. Reproduced with permission from ref. 89.
Fig. 11 (a) Some of the materials freeze-cast in our laboratory. A lamellar
structure is shown in detail in (b) and (c) for Al2O3, and in (d) for PVA.
Reprinted with permission from ref. 85.

Fig. 12 Ice-templated alumina structures showing (a) lamellar structure

from a slurry prepared with no zirconium acetate, and (b) columnar
hexagonal (honeycomb) structure from a slurry prepared with 0.2 M
zirconium acetate. Both scale bars are 250 mm. Reproduced with permis-
sion from ref. 85.

relative to the PCM (typically o1 g cm3) means that the Fig. 14 Thermal conductivity as a function of temperature for two alu-
gravimetric energy storage is considerably less at that porosity mina/dodecanoic acid form-stable PCM composite samples in directions
than for the pure PCM (e.g., 70  7 J g1 for dodecanoic acid in parallel ( ) and perpendicular ( ) to the direction of ice growth
during freeze-casting, i.e., parallel and perpendicular to the hexagonal
alumina, compared with 176  18 J g1 for pure dodecanoic
alumina channels, including experimental uncertainties. The samples had
acid8). However, at this loading the composite was hard an (unfilled) alumina matrix of density 0.85  0.02 (sample 1) and 1.12 
(Vicker’s hardness about the same as silver)89 and there was 0.02 (sample 2) g cm3 with mass fraction of PCM of 43% (sample 1) and
no change in physical form and insignificant loss of mass 39% (sample 2). Although the composite thermal conductivity is much less
(o2%, mostly surface PCM) after 1000 melt-free cycles in a than that of bulk alumina (B20 W m1 K1),91 the thermal conductivity of
pure dodecanoic acid is only 0.24 W m1 K1.8 Thus the thermal con-
glass vial, indicating that these were truly form-stable PCMs.89
ductivities of the alumina form-stable PCM composites represent an 8- to
Furthermore, the thermal conductivity relative to that of the 14-fold enhancement over that of the pure PCM. Reproduced with
pure PCM was enhanced substantially (see Fig. 14), owing to permission from ref. 89.
the high thermal conductivity of alumina,91 which is a signifi-
cant advantage over the pure PCM.
The addition of carbon black into the alumina slurry 10% carbon black. The thermal conductivity was still enhanced
resulted in a freeze-cast alumina – carbon black matrix of lower relative to the PCM, almost identical to that of the composite
density than that of pure alumina (carbon black is less dense with the pure alumina scaffold.89 The pure alumina scaffold had
than alumina), and therefore higher gravimetric loading of the already been optimized somewhat to allow for regular ice growth
PCM (48% compared with 40% for pure alumina), and accord- by use of two particle sizes for the alumina powders in the slurry,
ingly an increase in the gravimetric thermal energy density.89 with the finer particles filling interstices between the coarser
The honeycomb structure was maintained, and the carbon particles while reducing the viscosity of the slurry.92 There is
black was uniformly distributed in the matrix, and the materials further scope to optimize the matrix density to increase porosity
cycled well and were form stable on a glass surface, even at (and gravimetric heat storage) of alumina-based form-stable

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PCMs, while maintaining form stability and high thermal hexagonal structure observed for alumina (Fig. 12) due to
conductivity. greater flexibility of chitosan than alumina. With dodecanoic
Pure carbon black scaffolds also were freeze cast.89 Whether acid in this matrix we were able to achieve even higher PCM
the scaffolds were prepared with PVA binding agent (and loading, B95 mass %, for either the lamellar or columnar
sintered) or with PVA in the slurry (and left unsintered; PVA structure, with partial success in achieving form stability over
held them together), they were fragile and brittle. In both cases, 1000 melt-freeze cycles. However, the thermal conductivity
the pore structure was irregular, and dendritic with PVA as has enhancement was about the same as for chitosan-based com-
been noted with alumina.85 When filled with PCM, the carbon posite PCMs.89
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black composites could be handled more easily. The compo- In our preliminary investigations of titania-based scaffolds,89
sites made with PVA slouched a little but did not collapse over made with only one particle size of anatase titania, which
250 melt-freeze cycles and did not leak PCM on a glass surface. converted to rutile on sintering, the porosity was a little higher
(Without PVA they collapsed completely, indicating insufficient than with alumina (78% compared with 74%). The honeycomb
fusion of carbon particles during sintering.) Mass loading of structure was maintained but with rougher and grainier walls,
dodecanoic acid was 58  4%, i.e. higher than alumina. There likely due to the mono-sized particles not packing as well as for
was a slight (25%) enhancement of thermal conductivity over alumina. As a result, the scaffolds were brittle and crumbled
dodecanoic acid in the composites with PVA; it was likely easily. However, the titania scaffold could be filled with dode-
small because of poor carbon–carbon contacts within the canoic acid PCM, and showed about 3-fold enhancement in
matrix. Graphitic PCM foams (of unspecified mechanical thermal conductivity relative to pure dodecanoic acid. This
properties)93 and porous expanded graphite94 have been enhancement is less than observed for the alumina-based
reported to have even higher thermal conductivities. Therefore, form-stable PCM, but still appreciable considering the poor
it is possible that optimization of ice growth conditions (PVA titania particle packing and the lower thermal conductivity of
concentration and temperature gradient) and sintering condi- rutile compared with alumina (5.6 vs. 20 W m1 K1),91 and on
tions could lead to freeze-cast carbon black matrices that par with many form-stable PCMs with mineral scaffolds.95,96
provide robust, form-stable composite phase change materials Titania-based composite PCMs already have superior properties
with significant thermal conductivity enhancement compared to those based on halloysite nanotubes, a natural aluminosili-
with the PCM. cate material with significant reserves, which can be used as a
Freeze-cast chitosan made very low-density porous materials matrix for form-stable PCMs only if the PCM loading is less
(density about 0.04 g cm3) which had the advantage of very than 50 mass %, and again the thermal conductivity enhance-
high porosity and PCM loading with resultant high DfusH (170  ment is only about a factor of 2, to ca. 0.5 W m1 K1.97 There is
20 J g1 for 94 mass % dodecanoic acid, for example).89 The considerable motivation and scope for further optimization of
morphology of the foam ranged from lamellar to honeycomb (the the titania-PCM composites, for increased robustness and form
latter with zirconium acetate in the slurry). Thermal conductivity stability.
was about twice that of the PCM, but still rather low. However, if
the goal is to achieve a high PCM loading, then chitosan scaffolds 3.3 Prospects for form-stable PCMs
hold promise. Further developments in our approach to freeze-cast PCMs
In an attempt to make a more robust carbon-based compo- could be achieved through additives. For example, it has been
site PCM, we pyrolyzed chitosan foams for the scaffold.89 The shown that the addition of Cu nanoparticles to a porous carbon
microstructure (Fig. 15) was either lamellar (no zirconium matrix, with vacuum impregnated paraffin PCM, gives some-
acetate in the slurry) or columnar pores (zirconium acetate in what higher thermal conductivity than the PCM.98 The loading
the slurry), where the latter were more circular than the of PCMs in chitosan and pyrolyzed chitosan (490 mass %)
is especially promising, and much higher than many carbon-
based composite PCMs.99 This higher loading can allow high
thermal storage capacity, if robustness, form-stability and
thermal conductivity can be enhanced.
Additional matrix materials could be explored by freeze-
casting methods. For example, inspiration could come from
natural materials such as lignin, or delignified wood, or dia-
toms, which have already been used for matrices for composite
PCMs with high PCM loading (up to B90 mass %), although
their thermal conductivities still tend to be low.100
Other methods, such as sol–gel processing, have been used
to prepare shape-stabilized (i.e., form-stable) PCMs, but the
enhancement in thermal conductivity is still low, less than a
Fig. 15 SEM micrographs of carbonized, freeze-cast chitosan (a) grown
with zirconium acetate in the slurry and displaying a columnar (rounded
factor of 2, even if the compressive strength and enthalpy of
honeycomb cellular) structure and (b) grown without zirconium acetate fusion are high.101 If high thermal conductivity is the main
and having a lamellar structure. Reproduced with permission from ref. 89. requirement for a form-stable composite PCM, then freeze-cast

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alumina-based materials are the best bet at present. Furthermore, Our investigations have not been limited to pristine
alumina is robust to high temperatures, opening up the use of chemical systems. Through studies of edible oil products, we
high-temperature form-stable PCMs, e.g. using salts as the PCM. found that coconut oil has considerable potential as a PCM in
One of the main advantages of freeze-cast matrices for warm climates with large diurnal temperature swings, allowing
composite PCMs is the level of control over the porosity direct availability to consumers of useful PCMs.
(including degree of porosity and pore morphology). This To address the seemingly unrelated PCM problems of
control allows infiltration of the PCM at ambient pressure, sample containment and low thermal conductivity, we have
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and, if the pores are small and regular, keeps the PCM in place made form-stable PCMs from freeze-cast matrices. This
by capillary action, even when molten, allowing the composite approach can use commodity materials with little waste, in
to be truly form-stable. Furthermore, pore control can allow an additive process using water as a fugitive template. Some of
efficient filling of the pores (490%). The latter is obviously the resulting composite PCMs are form-stable and machin-
important to increase PCM loading and hence thermal storage able. Others have very high PCM loading and large gravimetric
capacity, but also especially important for enhancement of thermal energy storage values. This process has many adjustable
conductivity. For example, an axial through-pore structure reduces parameters, and further optimization of this approach
tortuosity and enhances heat transfer.102 will provide a wide variety of PCMs suited to a broad range
Overall, the flexibility of the type of material to be freeze cast of applications.
allows for high thermal conductivity matrices for the PCM and Throughout our work, we have promoted the use of careful
resultant high thermal conductivity composites, while main- experimental studies, with well-documented uncertainties,
taining high PCM loading, and attaining form stability over with a goal to advance use of phase change materials. Our
thousands of cycles. The large number of parameters available investigations have included thorough cycling of phase change
for optimization in the freeze-cast approach (including compo- materials, over hundreds or thousands of melt-freeze cycles, as
sition of matrix, additive types and concentrations in the slurry, representative of their use in applications. Such cycling pro-
matrix pore morphology, sintering conditions, PCM composi- vides insights into stability of the physical properties (melting
tion) gives these materials a high degree of promise for thermal point, enthalpy of fusion), chemical stability, and form stability
energy storage applications. and leakage (in the case of composite PCMs), and we recom-
mend extensive cycling for all PCM investigations.
In summary, PCMs have become a key consideration in
4 Conclusions and outlook thermal energy storage technologies and their importance
continues to increase as the implementation of renewable
Phase change materials have an important role to play in (but intermittent) energy sources is growing worldwide. There
energy storage and energy conservation. PCMs are already in is a concomitant increasing demand for passive thermal man-
use in several applications, but novel approaches are required agement materials across different sectors, including build-
to make them more widely applicable, and to satisfy the ings, electronics, textiles, logistics and packaging materials,
extensive suite of criteria (Table 1) required to meet the needs accelerating the research and understanding of the different
of applications. We have reviewed our contributions to this classes of PCMs over the last decade. Our contribution to this
field in the context of their impact. field spans a wide range of research areas including funda-
From a foundational understanding of thermodynamics, we mental understanding of the relationship between molecular
have investigated the relationships between molecular struc- structure and thermodynamic properties of organic PCMs, the
ture and melting properties of organic molecular materials, mechanism of supercooling in organic PCMs, and the develop-
drawing attention to the importance of flexible molecules with ment and characterization of novel form-stable PCM compo-
hydrogen bonding and even numbers of carbons in their alkyl sites and eutectic PCMs. Through our research, we also have
chains, as potential PCMs. Beyond pure organic molecules, we determined best practice methods to characterize and report
have shown that tuning the melting point, especially to lower the thermal properties of PCMs, established an extensive
temperatures, is achievable through eutectics. database of materials that can potentially be used as PCMs,
We have led the way in using life cycle analysis to assess the and tested PCMs in real-life applications including residential
environmental impact and payback period for phase change heating systems and portable electronics.
materials. Life cycle analysis is of fundamental importance
to understanding whether a PCM is merely interesting, or
potentially useful. Author contributions
Through an extensive array of experimental and theoretical
approaches, we have discovered physical processes responsible MAW wrote the original draft of this paper, with SK and JAN
for low supercooling in fatty acids, namely pre-association via reviewing and editing. In the work reviewed herein, MAW led
molecular clusters in the liquid state, which makes nucleation the visualization, funding acquisition, supervision and project
more facile than otherwise. Such fundamental insights have administration. MAW, SK and JAN all contributed to the con-
ramifications in nucleation of PCMs and crystallization of ceptualization, data curation, formal analysis, methodology
many other materials. and validation.

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ChemComm Feature Article

Conflicts of interest 15 A. Joseph, M. Kabbara, D. Groulx, P. Allred and M. A. White,

Characterization and real-time testing of phase change materials
There are no conflicts to declare. for solar thermal energy storage, Int. J. Energy Res., 2016, 40, 61–70.
16 M. Le and G. G. D. Han, Stimuli-Responsive Organic Phase Change
Materials: Molecular Designs and Applications in Energy Storage,
Acc. Chem. Res., 2022, 3, 634–643.
Acknowledgements 17 S. Wu, T. Li, Z.-Y. Zhang, T. Li and R. Wang, Photoswitchable phase
change materials for unconventional thermal energy storage and
upgrade, Matter, 2021, 4, 3385–3399.
The authors gratefully acknowledge their collaborations on 18 W. Fu, X. Yan, Y. Gurumukhi, V. S. Garimella, W. P. King and
Published on 18 January 2024. Downloaded by Dublin City University Library on 10/15/2024 3:11:05 PM.

phase change materials and related research with Professors N. Miljkovic, High power and energy density dynamic phase
D. Groulx (Dalhousie), A. Joseph (NSCC), L. Kreplak (Dalhousie) change materials using pressure-enhanced close contact melting,
Nat. Energy, 2022, 7, 270–280.
and Dr H. Mehling (who we also thank for comments on this 19 S. Kahwaji, M. B. Johnson and M. A. White, Thermal Property
review), and the contributions of former members of our Determination for Phase Change Materials, J. Chem. Thermodyn.,
research group to this topic, especially P. Allred, Dr R. Chen, 2021, 158, 106439.
20 L. Desgrosseilliers, C. A. Whitman, D. Groulx and M. A. White,
Dr J. Conrad, Dr L. Desgrosseilliers, Dr S. Ellis, M. Johnson, and Dodecanoic acid as a promising phase-change material for thermal
Dr C. Whitman. Our studies of phase change materials have energy storage, Appl. Therm. Eng., 2013, 53, 37–41.
been supported by NSERC (Discovery Grant; CREATE Dalhousie 21 S. Kahwaji, M. B. Johnson, A. C. Kheirabadi, D. Groulx and
M. A. White, A Comprehensive Study of Paraffin Phase Change
Research in Energy, Advanced Materials and Sustainability; and Materials for Solar Thermal Energy Storage and Thermal Manage-
NSERC Smart Net-zero Energy Buildings Strategic Research ment Applications, Energy, 2018, 162, 1169–1182.
Network), and by Intel. Our experimental work also was sup- 22 S. Kahwaji and M. A. White, Organic Phase Change Materials for
Thermal Energy Storage: Influence of Molecular Structure on
ported by the Canada Foundation for Innovation, the Atlantic Properties, Molecules, 2021, 26, 6635.
Innovation Fund and other partners that fund the Facilities for 23 J. A. Noël, P. M. Allred and M. A. White, Life Cycle Assessment of
Materials Characterization at Dalhousie University. Two Biologically Produced Phase Change Materials and their
Related Products, Int. J. Life Cycle Anal., 2015, 20, 367–376.
24 C. Fabiani, A. L. Pisello, M. Barbanera and L. F. Cabeza, Palm oil-
based bio-PCM for energy efficient building applications: Multi-
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