SELECTION OF MATERIALS WITH POTENTIAL IN THERMAL ENERGY

STORAGE
A. Ins Fernndez1, Mnica Martnez1, M. Segarra1, Luisa F. Cabeza2
1

Department of Materials Science & Metallurgical Engineering, Universitat de Barcelona, Mart i Franqus
1, 08028 Barcelona (Spain) Phone:+34-934021298, Fax:+34-934035438
2
GREA Innovaci Concurrent
Edifici CREA, Universitat de Lleida, Pere de Cabrera s/n, 25001-Lleida (Spain)
Phone: +34-973 003576, Fax: +34-973 003575
e-mail: lcabeza@diei.udl.cat

ABSTRACT
Thermal energy storage is a technology under investigation from the early 70s. Since then,
numerous new applications have been found and a lot of work has been done to bring this
technology to the market. Nevertheless, the materials used were mostly investigated 30 years
ago, and the research has lead to improve their performance under the different conditions of
the applications. In those years a significant number of new materials have been developed in
many fields other than storage and energy, but a great effort to characterize and classify these
materials has been done. Taking into account that thousands of materials are known and a
great number of new materials are developed every year, the authors use the methodology for
materials selection developed by Prof. Ashby at the Cambridge University to give an
overview of other materials suitable to be used in thermal energy storage. This methodology
is widely used for design purposes, as many different inputs may be considered, such as
thermal properties, mechanical behaviour, price, availability, recyclability, CO2 footprint, etc.
1. INTRODUCTION
Energy storage technologies are a strategic and necessary component for the efficient
utilization of renewable energy sources and energy conservation. Thermal energy storage
(TES) in general has been a main topic in research for the last 30 years, but most researchers
still today feel that one of the weak points of this technology is the material to be used as
storage medium. When one looks at the literature, the same materials described 30 years ago
as potential materials for thermal energy storage [Lane, 1983; Lane, 1986] are the materials
studied today [Zalba et al. 2003; Diner and Rosen, 2002; Mehling and Cabeza, 2008], that is
paraffins, fatty acids and salt hydrates for latent heat storage and molten salts for high
temperature sensible heat storage. When authors try to find new materials, all the research is
based on this type of materials [Bellettre, 1997; Vakilaltojjar, 2001; Esen, 1998].
As thousands of materials are known and are developed every year, the authors believe that
these materials should be looked at, to find out if they are suitable to be used in thermal
energy storage.
In this paper, the methodology for materials selection developed by Prof. Ashby at the
Cambridge University [Ashby, 2005; Ashby et al, 2007] is used with the CES Selector
software, to give an overview of other materials suitable to be used in thermal energy storage.
This methodology is widely used for design purposes as many different inputs may be

considered, such as thermal properties, mechanical behaviour, price, availability,

recyclability, CO2 footprint, etc.
Sensible heat storage materials are defined as a group of materials which undergo no phase
change in the temperature range of the storage process. The ability to store sensible heat for a
given material strongly depends on the value of its energy density, that is the heat capacity per
unit volume or Cp. For a material, to be useful in a TES application, it must be inexpensive
and have good thermal conductivity.
Storage systems based on phase change materials with solid-liquid transition are considered to
be an efficient alternative to sensible thermal storage systems. From an energy efficiency
point of view, PCM storage systems have the advantage that they operate with small
temperature differences between charging and discharging. Furthermore, these storages have
high energy densities compared to sensible heat storages.

2. DESCRIPTION OF THE METHODOLOGY FOR MATERIALS SELECTION

The number of available materials is more than 150,000 with more appearing every year.
Materials scientists classify them in four families: metals and alloys, ceramics and glasses,
polymers and elastomers, and hybrids that include composites and natural materials. Each
family is divided in classes, each of which contains sub-classes containing members. Each
material is characterized by a set of attributes, numeric and non-numeric, that describe its
properties and behaviour.
Browsing or searching in handbooks and databases is useful if we know which material or
process we seek, but they give no comparison or possible relationships between properties of
materials that enable selection. A simple way to compare materials is a bar-chart, were a
certain property is plotted for all the families of materials. The values of most properties of
engineering materials span a total range of many decades and for that reason a logarithmic,
rather than a linear scale is used. Figure 1 shows the specific heat capacity values Cp for a
hundred of the most used engineering materials. From this chart it can be deduced that the
materials with the highest cp are natural and polymeric materials such as natural rubber, or the
thermoplastic copolymer ABS with a Cp value around 2 kJ/kgK. Other composite materials
such as glass fiber reinforced epoxies GFRE and concrete, have Cp values close to 1 kJ/kgK.
The material property charts allows mining the data for patterns. As shown in Figure 2, two
properties are plotted: Specific heat capacity and Density. When this is done it is found that
each family of materials occupies a particular area of the plot, for example polymer foams
near the upper left, a lot of metals and alloys at the lower right, technical ceramics central, and
so on, being each bubble a specific material.
Even at this early stage a selection of materials with certain properties or combinations of
properties can be made. The charts also give a perspective of the materials world, building
knowledge of where certain material families and classes lie in material property space.

Acrylonitrile butadiene styrene (ABS)

2000

Cast magnesium alloys

Specific heat capacity (J/kg.K)

Concrete
1000

Natural Rubber (NR)

Silicon

GFRP, epoxy matrix (isotropic)

500

Medium carbon steel

Tin
200

Figure 1. Bar-chart of Specific heat capacity for a hundred of the most used materials,
obtained with CES Selector

Thermoplastics
Technical ceramics

2000

Specific heat capacity (J/kg.K)

Polymer foams
1000

Ceramic composites

500

200

Metals and alloys

10

100

1000

Density (kg/m^3)

10000

Figure 2. Materials property chart. Specific heat capacity vs. Density.

In order to select the material with the highest performance for a given application, a designled approach strategy is developed. The selection strategy involves four steps: translation,
screening, ranking and documentation. The first step is that of translating the design
requirements into a specification for materials selection. It is followed by a screening step,

where those candidates that do not meet the specifications previously established are rejected.
From a criterion of excellence, the remaining materials are ranked, and finally, more detailed
information about the best material is needed to ensure that the selection is successful. So, the
first of all is to translate the problem to take into account the design requirements that will be
expressed as:
Function of the component for which the material is sought.
List of the constraints it must meet: satisfy limits on thermal or electrical properties
and so forth.
List of objectives, the criteria by which the excellence of choice is to be judged, for
example minimizing cost, minimizing mass, etc.
List of free variables those that the designer is free to change: usually dimensions or
shape, and, of course, the choice of material.
The performance of an engineering component depends on the values of the properties of
materials with which it is made of, but it usually depends not only on one property but on a
combination of two or more expressed as a criteria of excellence, called material index, which
maximizes the performance for a given design and is the result of the translation step.
An example of objective, is to minimize cost. In this case, the cheapest solution that meets all
constraints is the best choice. It is rare that a design has only one objective, and when there
are two objectives to meet, a conflict arises: the choice that minimizes one metric does not
generally minimize the other, and then a compromise must be sought. To reach it we need
some simple ideas drawn from the field of multi-objective optimization, a technique for
reaching a compromise between conflicting objectives. It lends itself to visual presentation in
a way that fits well with methods developed here thus far.
3. CASE STUDY
As case study we will consider materials for sensible thermal energy storage in the range of
temperatures of 150-200 C. To translate design requirements we first identify the function,
which is store thermal energy. The material should meet the following constrains: minimum
service temperature of 150 C, high energy density (or heat capacity per unit volume), good
thermal conductivity (higher than 0.3 W/mK), and good thermal diffusivity. The objectives
for this application are to maximize the energy storage per unit of material cost, and,
additionally, to maximize the thermal diffusivity to minimize the time for energy recovery.
The free variables are the material choice and the dimensions.
A preliminary selection can be made by constructing material property charts and limiting
properties. For example, if we look at the relation of specific heat capacity with the materials
costs, the figure 2 has a new configuration (see Figure 3).
Moreover, we can do a convenient combination of thermal properties and represent it in a
bubble chart. In figure 4 is plotted a material property chart considering energy density (Cp
) vs. thermal conductivity. Thus, if the aim is to look for suitable materials with the
maximum energy density and thermal conductivity above 0.3 W/mK we should focus on the
left upper part of the plot and, among the resulting materials limit the service temperature and
the cost per unit mass.

Thermoplastics

Natural

Specific heat capacity (J/kg.K)

2000

1000

Cement and concrete

500

Ferrous alloys

200

0.1

10

100

Price (EUR/kg)

1000

10000

100000

Figure 3. Specific heat capacity vs. cost per unit mass.

5e6

Energy Density J/m^3K

2e6

1e6

500000

200000

100000

50000

20000

0.1

10

Thermal conductivity (W/m.K)

100

Figure 4. Material property chart with combination of properties. Energy density (Cp ) vs
Thermal conductivity.
A more exhaustive selection can be performed following the selection strategy. First of all, we
translate the objectives into one or more performance equations. So, taking into account that
the thermal energy stored per unit volume can be expressed as:

where is the density of material, Cp its heat capacity and T the temperature interval, and
the cost of a mass m of material with a cost per kg of Cm is:
then the energy stored per unit volume and unit cost is expressed as an objective function:

where V is the volume of material.

If we look at this equation, it can be seen that the objective we want to reach depends on
different variables, some geometrical (volume), other functional (temperature interval), and
other related only to the material properties (Cp/Cm). So, the material with the highest value
for Q is that with the highest value for Cp/Cm, which is defined as the material index.
In order to find the material with the highest material index, we plot both properties on a
chart. Those materials with the same relation Cp/Cm will perform equally well, that is they
give the same value of Q, located under the same line with a slope of 1. Figure 5 shows the
plot of Cp vs. Cm , and the materials with the highest material index are those over the
guideline with a slope of 1. Moreover, as another constraint is a thermal conductivity higher
than 0.3 W/mK, those materials that do not meet this requirement are in grey color in the
plot.

Figure 5. Plot of specific heat capacity versus cost per unit mass.
From Figure 5, different materials are identified: concrete, cast iron, alumina, aluminium
alloys, and several glasses.

We now go one step beyond, and consider the other objective, a diffusivity as high as
possible, but maintaining a high energy storage capacity. So we have another material index,
the diffusivity, calculated from next equation:

where is the thermal conductivity and the density of the material.

To identify those materials that maximize both objectives or minimize their inverse, we plot
one material index in front of the other. Figure 6 shows the cost per unit of thermal energy
stored (that is the inverse of the first material index, which should be minimized) versus the
inverse of the diffusivity. A dotted line is also plotted, which links those materials that cominimize both indices.

Figure 6. Materials that co-minimize both material indices.

From Figure 6, we observe that concretes are the cheapest materials for energy storage, but
their diffusivity is low, thus implying higher times to relay the stored energy. On the other
hand, graphite has a high diffusivity, but it is expensive, while cast iron or aluminium alloys
remain in the middle. The performance indices for those materials are an agreement between
both material indices. Among these materials, an evaluation of service temperature ranges
should be done to have a final/s candidate/s.
4. CONCLUSIONS
A methodology to find potential materials to be used in thermal energy storage is presented
with a case study that evaluates materials for sensible thermal energy storage in the range of
temperatures of 150-200 C. Two materials indices are evaluated, energy stored per unit
volume and unit cost, and diffusivity. The best materials for this application are those that
maximises both indices like graphite, an aluminium alloy, cast irons and concrete.

The proposed methodology allows, combining multiple objectives and restrictions of use, to
evaluate the most used engineering materials for applications in thermal energy storage. Not
only physical properties are considered but others like cost, availability or environmental
aspects such as embodied energy or CO2 footprint may also be taken in consideration to
evaluate a potential material.

ACKNOWLEDGEMENTS
The work was partially funded by the Spanish government (project ENE2008-06687-C0201/CON).

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