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Solar Energy Materials & Solar Cells 115 (2013) 114122

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Solar Energy Materials & Solar Cells


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

Selection of materials for high temperature sensible energy storage


S. Khare n, M. Dell'Amico, C. Knight, S. McGarry
CSIRO Energy Technology, 10 Murray Dwyer Circuit, Steel River Estate, Mayeld West, NSW 2304, Australia

art ic l e i nf o a b s t r a c t

Article history: Availability of thermal energy storage systems (TES) is a key to ensuring continuous power supply from
Received 13 November 2012 solar thermal power plants. The application of sensible heat storage (SHS) in solid media is an attractive
Received in revised form economic option, but is dependent on identifying suitable SHS media. Given the growing number of new
11 February 2013
materials available today, nding a suitable material is a time-consuming and difcult process. This paper
Accepted 7 March 2013
Available online 25 April 2013
demonstrates the use of a materials selection software package and identies suitable SHS materials for
high temperature (4 500 1C) TES systems. The environmental performance of some selected materials
Keywords: was also evaluated using the package.
Solar thermal energy Common materials such as alumina, silicon carbide, high temperature concrete, graphite, cast iron
Sensible heat storage materials
and steel were found to be highly suitable for SHS for the duty considered (500750 1C). For cost
Materials selection
comparison, a simple heat exchanger, consisting of a packed bed of the materials (in brick or block form)
heated by an inert gas, was considered. On the basis of equivalent gas phase heat transfer, high alumina
cement concrete blocks had the lowest cost, followed by a common refractory brick at oUS$ 10/kWh
(thermal).
High temperature concretes, such as the high alumina cement-based materials and aluminasilicate
geoploymers, were identied as having potential for SHS media as they are cheap composite materials.
Their thermophysical properties could be optimised for SHS by a suitable choice of aggregates, binders
and additives.
& 2013 Elsevier B.V. All rights reserved.

1. Introduction being directed towards new materials for high temperature SHS
since the traditionally used molten salts are not suitable above
Solar energy is an intermittent energy source, and thermal about 550 1C. Choice of these materials depends on factors such as
energy storage (TES) is necessary for its effective utilisation. Solar their physicochemical properties, heat storage capacity, operating
power technologies, such as linear or parabolic troughs, dishes and temperature, as well as the type of heat transfer uid (HTF) and
power towers, are used to produce high temperature steam for heat exchanger design.
power generation. Integration of TES technology can facilitate Much research work has been carried out on SHS materials and
a continuous generation of power from solar thermal power plants. storage systems in the past and the technology for their utilisation
There are mainly three types of TES systems, sensible heat is well developed [14]. Solid media such as concrete and ceramics
storage (SHS), latent heat storage (LHS) and the thermochemical have been used in packed beds with a suitable HTF to exchange
energy storage. SHS can be achieved using solid or liquid media heat, or in monolithic blocks with embedded heat exchanger
and involves storing energy in a material without phase change in tubes. According to Gil et al. [3], materials such as concrete and
the temperature range of the storage process. LHS systems with ceramics are favoured due to their good thermal and mechanical
solid-liquid transition are considered an alternative to SHS properties and low cost. The German Aerospace Centre (DLR) has
systems, although there are presently no commercial applications. extensively studied the use of concrete and castable ceramics as
SHS systems, such as molten salts, are being used in low heat storage media [57]. These materials have been tested at the
temperature applications at commercial scale and are proven Spanish solar test facility Plataforma Solar de Almeria (PSA) where
technology. There are some advantages for SHS compared to LHS they were used as solid SHS material.
at high temperatures including simplicity of design and construc- It has been reported that upon heating concretes, certain
tion, ease of control and hence lower cost. Currently research is reactions and transformations occur which inuence their
thermophysical properties. The compressive strength decreases
about 20% at 400 1C. Such problems are minimised by addition of
n
Corresponding author. Tel.: +61 2 4960 6169; fax: +61 2 4960 6111. ller material such as steel needles and reinforcement to improve
E-mail address: Sameer.khare@csiro.au (S. Khare). strength [3]. Laing et al. [6] assessed the long term stability of

0927-0248/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.solmat.2013.03.009
S. Khare et al. / Solar Energy Materials & Solar Cells 115 (2013) 114122 115

high temperature concrete storage up to 500 1C for parabolic Table 1


trough solar thermal power plants. There was some initial mass Desirable properties of SHS materials.
loss but this and strength values stabilised over time and through
Properties Desirable characteristics
1900 repeated thermal cycles.
Air and liquid media such as molten salts, water, synthetic oil Thermophysical High energy density (per unit mass or volume), high
and liquid sodium metal have been tested for SHS. From the properties thermal conductivity, high heat capacity, high density,
literature it appears that molten salts have been most widely long term thermal cycling stability
Chemical Long term chemical stability with no chemical
researched for SHS applications [8]. Liquid media facilitate separa- properties decomposition, non-toxic, non-explosive, low corrosion
tion of cold and hot layers depending on uid temperature and a potential or reactivity to HTFs, and compatible with
thermal gradient (thermocline) is set up across the liquid storage materials of construction
tank. This characteristic is utilised for heat storage (charging) and Economic Cheap and abundant materials with low cost of
properties manufacturing into suitable shapes
heat extraction (discharging) respectively. Molten salts as HTF are
Mechanical Good mechanical stability, low coefcient of thermal
commonly used in chemical process industries and have been expansion, high fracture toughness, high compressive
extended to solar thermal power systems. The two most strength
commonly used salts are solar salt and Hitech. Solar salt is a Environmental Low manufacturing energy requirement and CO2
binary mixture (wt%) of 60%NaNO340% KNO3 with a melting footprint

point of 221 1C; whereas, Hitech is a ternary mixture of 40%


NaNO27%NaNO353% KNO3, with a melting point of 142 1C. They Materials selection analysis of this nature has previously been
are non-ammable and non-toxic and are low cost media to store performed by Fernandez et al. [10] to identify suitable materials
thermal energy which are compatible with the operation of steam for low temperature (150200 1C) SHS applications. This paper,
turbines. However, a disadvantage is the relatively high freezing and previous work by Khare et al. [9] for LHS, similarly explores
point of most salts which requires more expensive piping and the methodology for identifying SHS materials for high tempera-
insulation materials, as well as possible heat tracing, to maintain ture applications up to 750 1C.
them in the molten state. A new ternary salt with a freezing point The desirable properties of SHS materials for high temperature
of 133 1C was used in a PSA test facility and ongoing research is storage applications are summarised in Table 1.
directed at developing new salt mixtures with freezing points For SHS in stable solid media, within the operating tempera-
below 100 1C [3]. They are, however, not stable in the high tures, the thermophysical properties of the selected materials are
temperature applications (up to 750 1C) which are of interest here. important. These include specic heat capacity, density, thermal
A recent paper by Khare et al. [9] discussed selection of suitable conductivity, mechanical stability and coefcient of thermal
materials for high temperature LHS applications. This paper expansion. In CES the materials are classied into six basic families
evaluates materials for sensible thermal energy storage in the as metals, polymers, elastomers, glasses, ceramics and hybrids/
range 500750 1C using a similar methodology. Liquids such as composites. Materials with high melting points and service
well known molten nitrate salts are not considered as they cannot temperatures, and high mechanical and chemical stability, were
meet the required temperatures, and liquid metals were consid- considered as a primary requirement. From an initial screening,
ered in Khare et al. [9] in relation to phase change materials. ceramics and metals were identied as being promising for closer
The availability of materials reported in literature is extensive analysisas materials in these family classes would meet the
(4 160,000) [10] and new materials are being developed and specications for desirable properties (Table 1).
added continuously. A database is useful for materials selection Fig. 1, produced by CES, shows a materials properties chart with
and in this paper the CES selector package from Granta Design [11] maximum service temperatures and melting points of numerous
is used to identify engineering materials that are potentially materials from the metals/alloys and ceramics families. The coloured
suitable for SHS on the basis of their bulk physicochemical envelopes show the range of data for given materials, depending on
properties and economics. EcoAudit, a CES tool for assessing the their compositions or physical form. For clarity of presentation, only
environmental credentials of the materials, is also considered in the more common materials are named in Fig. 1.
the selection methodology. From the potential SHS materials Maximum service temperature is dened here as the highest
identied in the selection process a cost comparison is made for temperature at which material can be used in an inert atmosphere
a simple heat exchanger comprising an arrangement of the for an extended period without signicant issues, such as phase
materials as bricks (or blocks of equivalent diameter) in a stacked change, chemical change, excessive creep, loss of strength, or other
column with an inert HTF. primary property for which the material is normally used. For the
application considered here materials for solid state SHS should
have a melting point greater than 750 1C and not undergo any
solid state phase change that might change their strength or
2. Materials selection methodology composition (which could change their thermophysical proper-
ties). Materials like common concretes (e.g. Portland cement) are
Granta Design's CES Selector package [11] is used in the rarely used in applications above 650 1C and can spall or decom-
following for selection of materials suitable for high temperature pose at temperatures as low as 450 1C and hence could not be used
sensible heat storage (up to 750 1C). The design methodology for this application. High alumina cements and concretes using
using CES considers different inputs, such as mechanical and calcium-aluminate cements (refractory concretes) are, however,
thermal properties, costing (amongst other data) and optimises suitable for high temperature applications and are shown in the
the choices for the most suitable outcome. An EcoAudit function- plot. Not shown in the plot (since they are not in the CES database)
ality within the CES package is also used in evaluating the are aluminasilicate or geopolymer concretes which would also
environmental performance of the SHS materials, with regards occupy a position close to the high temperature concretes.
to life cycle energy consumption and carbon dioxide emissions. Although all materials on the plot would be technically acceptable
EcoAudit identies the phases of life of a material, manufacture, for the SHS application here, only the common materials which have
transport and use that carry high demand for energy or acceptable service temperature and melting points are considered
emissions. A white paper on EcoAudit for Industry explains its since exotic materials would obviously be too expensive for large
features [12]. scale thermal storage application. These include graphite, magnesia,
116 S. Khare et al. / Solar Energy Materials & Solar Cells 115 (2013) 114122

Fig. 1. Maximum service temperature vs. melting point (C).

Fig. 2. Maximum service temperature vs. thermal expansion coefcient (microstrain/C).


S. Khare et al. / Solar Energy Materials & Solar Cells 115 (2013) 114122 117

alumina, silicon carbide, high alumina concrete and cement, cast iron compatible (Table 2 lists the thermal expansion of materials
and stainless steel. Navarro et al. [13] have also evaluated low cost considered).
materials derived from mining and metallurgical industries for solid The thermophysical properties of solid SHS media such as
sensible heat storage systems, and compared them using the CES heat capacity, density and thermal conductivity are very important
database. Composite materials of this nature are also considered in considerations. High energy density reduces the storage volume
this paper. required and high thermal conductivity is important for effective
The thermal expansion coefcient of a material is the fraction of heat transfer. From Fig. 3, the common materials previously
material expansion per degree of temperature rise. If the material is to identied such as graphite, silicon carbide, alumina, high alumina
be used with integral heat transfer tubing the materials should have concrete/cement, and ferrous metals can be seen to possess high
similar expansion. For packed beds of materials in tanks with direct energy densities. The thermal conductivity for concrete is, how-
HTF contact, movement of the material during thermal cycling can ever, an order of magnitude below these materials.
cause thermal ratcheting and hence damage to the tank walls from Also included in Fig. 3 is data for geopolymer materials which
increased tensile stresses. were sourced externally (for Zeobond eCrete [14]) and entered
Apart from graphite, all of the common materials considered into the CES database. It has properties close to the high alumina
here have the same order of expansion coefcient. Metals such as concretes and like them is similar in composition. Although not
stainless steel and cast iron, towards the bottom right corner of considered in the literature as a potential SHS, geopolymers, like
Fig. 2, show high volumetric expansion compared to ceramics such refractory concretes, offer the opportunity to make a cheap compo-
as silicon carbide and alumina. High alumina concrete and cement site material. Although the thermal conductivity of the geopolymers
show comparable behaviour to the steels and hence would be shown is low, their properties depend on their composition which
can vary signicantly depending on the aggregate used. This is
also the case for refractory concretes, and is considered further in
this paper in relation to composite materials. Fig. 4 compares the
Table 2
Summary of material properties for the environmental audit.
mechanical properties for different materials.
Fracture toughness is the resistance of materials to crack
Material Specic heat Density Volume expansion propagation, whereas bulk modulus is the volumetric elasticity
solid (J/kg K) (kg/m3) (106/K) of material. The inverse plot for these two properties means
materials closer to the bottom left corner are desirable. Metals
Alumina (99.5%) 800 3960 16.2
Cast iron (BS grade 3D) 540 7800 32.4 such as the stainless steels and cast irons have the highest fracture
High alumina concrete 980 2400 43.5 toughness and bulk modulus with silicon carbide, alumina and
Graphite (pure) 710 2230 23.7 magnesia intermediate compared to graphite and high alumina
Magnesia (hot pressed (HP)) 940 3565 24
concrete and cement. The latter group of materials (upper right
Silicon carbide (HP, Commercial 1040 3210 13.2
purity (CP))
hand side of Fig. 4) might be considered potentially susceptible to
failure on repeated thermal cycling, although experimental work

Fig. 3. Energy density (J/m3C) vs. thermal conductivity (W/mC).


118 S. Khare et al. / Solar Energy Materials & Solar Cells 115 (2013) 114122

Fig. 4. Fracture toughness vs. bulk modulus.

would be needed to verify this. The cost of materials in relation to 3. Environmental factors in material choice
specic heat capacity is shown in Fig. 5.
The cost per unit mass for different bulk materials using CES In addition to their thermal, physiochemical, mechanical and
shows high alumina concrete and cement to be the cheapest, economic properties the choice of SHS materials is inuenced by
while having high specic heat capacity. The dashed lines in the environmental factors. To calculate the environmental footprint
gure signify constant price to specic heat capacity. The ferrous associated with processing, manufacturing, recyclability and/or
metals have lower specic heat capacity but have comparable cost disposal of the SHS materials the CES EcoAudit tool was applied
to alumina (this is also dependent on composition or purity). to the ferrous metals, alumina, high alumina concrete, graphite,
Graphite and SiC have similar cost to, but higher specic heat magnesia and silicon carbide previously identied for their other
capacity than, stainless steel. properties.
From the overall analysis ceramics such as silicon carbide, The tool requires assumptions regarding primary production or
alumina, high alumina concrete and cement and the ferrous manufacturing processes, transport methods, product life and end use
metals cast iron and stainless steel appear to have acceptable to provide a comparison of production/manufacturing, through
combination of properties as SHS materials. Some of these operating and end of life energy and their environmental costs. The
materials, especially refractory concrete, have been identied in end product of the process is bricks (or blocks) of each material, and
literature, as described previously [57]. Of the ferrous metals, thus a casting (metals) or sintering or ring (ceramics) process has
stainless steel, not withstanding its other properties, compared to been included in this analysis.
cast iron was considered to be too expensive and is not considered The environmental impact of the production process is driven
further in the selection process. by a number of key issues and initially the amount of recycled
It should be noted, however, that other considerations for SHS content is important. For this analysis the concrete and metal were
materials should include engineering issues such as corrosion assumed to be made from 50% recycled input, while the remaining
(reactivity) of materials by the HTF used, volumetric expansion materials have no recycled content. The materials are assumed to
and balancing charging and discharging of heat to the working have a lifespan of 20 years and at the end of this life the metal is
uid (such as steam). HTFs for high temperature SHS are more recycled, whilst the remaining materials are reused in products of
likely to be gases since many common liquids in current use are lesser quality or reduced function. The high alumina concrete are
not chemically or physically stable above about 550 1C (e.g. molten sourced in Australia, near the location of end use, while the
salts, hydrocarbon uids) or have high melting points (liquid remaining materials are sourced from China, and hence appro-
metals). The reactivity of cheap gases such as air or CO2 have priate transport methods are selected (e.g. sea, rail or road).
reactivity concerns, for example on a graphite heat storage block, The choice of country also dictates the ecological aspects of the
in which case more expensive inert gases may be required. Also, as electrical energy use. The electrical supply in China is assumed to
in any plant design process, the environmental implications of the be sourced from the available grid, which is made up of 83% fossil
materials used should be considered and this is examined in the fuel, 15% renewable and 2% nuclear. Except for having no nuclear
following section. power, Australia is similar to China in that fossil fuel makes up 92%
S. Khare et al. / Solar Energy Materials & Solar Cells 115 (2013) 114122 119

Fig. 5. Cost per kg vs. specic heat capacity (J/kg.C).

Table 3
Summary of sensible heat stored per kg in the temperature range of 500750 C.

Material Energy stored Energy stored with Mass required for Volume required for
T 250 K (kJ/kg) T 250 K (kWh/kg) 1000 kWh (kg) 1000 kWh (m3)

Alumina (99.5%) 200 0.056 18000 4.5


Cast iron 135 0.038 26700 3.4
High alumina concrete 245 0.068 14700 6.1
Geopolymer 298 0.083 12100 5.1
Graphite 178 0.049 20300 9.1
Magnesia (HP) 235 0.065 15300 4.3
Silicon carbide (HPCP) 260 0.072 13800 4.3

and renewables make up 8% of the grid. Table 2 shows the operational factors, amongst other parameters, but are useful for
summary of relevant properties of materials selected for the comparison.
environmental audit. Using the data from Table 3, Fig. 6 shows the energy consump-
The specic heat and density properties allow calculation of tion associated with the life cycle stages of production of the
total energy stored as sensible heat, within a nominated tempera- prospective heat storage materials on the basis of mass for storage
ture range. The energy storage capacity, Q, of a SHS material with of 1000 kWh thermal energy and with a system high of 750 1C and
specic heat, Cpsolid, heated from T1 to T2, is low of 500 1C. Below 500 1C, steam temperature turbine cycle
efciency is poor but low temperatures are shown for other
Q mCpsolid T 2 T 1 1
potential applications where the Second Law thermodynamic
Eq. (1) is used to calculate the mass, m, of a specic material efciency is not importantsuch as for process steam or heating.
required to store a nominal 1000 kWh (thermal) when heated The total energy consumed at each stage of the life cycle is
from 500 to 750 1C. dominated by the basic material production stage. This stage takes
Table 3 presents the energy stored in each of the materials, and raw and recycled content and consumes energy in order to
the mass and volume required to store 1000 kWh. The mass and manufacture the required material. For the ceramics this step
volume will be the theoretical minimum value, as the calculation accounts for 9698%, with transport most of the remainder.
does not take into consideration practical thermal storage issues For high alumina concrete, the energy required at all stages is
such as charge/discharge conditions, heat losses, and solar eld much less than the other materials as a consequence of little
120 S. Khare et al. / Solar Energy Materials & Solar Cells 115 (2013) 114122

Fig. 6. Environmental analysis for energy consumption (MJ) at each life cycle stage. (HP: hot pressed, CP: commercial purity).

Fig. 7. Environmental analysis for CO2 production (kg) at each life cycle stage.

material processing (mostly quarried aggregate) and local trans- perspective, if the 1000 kWh storage was used every day for 20
port. Due to metals normally being recycled at end of life, they years and that energy was used to generate electricity (in a 30%
have negative potential which means they offset that amount of efcient Rankine steam cycle power plant), 2190 MWh would be
energy in the next production cycle of the material. generated. Using the assumption of 1 kg of CO2 emissions per kWh
The CO2 production at each life cycle stage is shown in Fig. 7. of electricity, 2.2 million kilogrammes of CO2 emissions would be
As would be expected, the CO2 production matches closely with avoided because of the use of solar TES. In environmental terms
the energy consumption. The primary connexion between energy the best materials is high alumina concrete, which displaces more
and CO2 emissions is the electricity mixture of the country of than 1600 times the life cycle emissions. However, even the worst
origin, and the transport method. The two countries involved in performing material, magnesia, still displaces more than 20 times
this analysis are China and Australia, where the electricity mixture its life cycle emissions.
is very similar. The result of this is that the CO2 emissions per unit
of energy are essentially the same with China at 0.178 kg/MJ and
Australia at 0.198 kg/MJ. 4. Sensible heat storage cost
In terms of CO2 production per 1000 kWh (thermal) of storage
the least emissions are clearly favouring the concrete (1300 kg), The cost of storage of thermal energy in the materials identied
with alumina (53,000 kg) and cast iron (42,000 kg). To put this in above (in US$/kWh) can be calculated from their cost and the mass
S. Khare et al. / Solar Energy Materials & Solar Cells 115 (2013) 114122 121

Fig. 8. Cost comparison of thermal storage media in a packed brick heat exchanger arrangement.

required to store the nominal 1 kWh. Here, for comparison, the has been tested up 500 1C by Laing [6]. The high temperature
simple heat exchanger arrangement of bricks of material arranged concrete was made up of blast furnace cement binder, aggregates
in a vessel (such that the heat transfer from an inert gas is of temperature resistant sand and gravel, and polyethylene bres. It
equivalent in each case) is considered. The cost is exclusive of was found to be stable at 500 1C over an extended period of time.
capital or operating and prices of materials were mostly obtained This temperature was the limit of the solar arrangement tested and
from internet sales sites (e.g. alibaba.com). A graph of results over hence higher temperature performance of the concrete was not
the temperature range 400750 1C is shown in Fig. 8. Also investigated. The composition was not detailed but illustrates the
included in Fig. 8 is molten salt and aluminium metal heat storage advantages of concretes in that the various components can be
media and although used molten and in a different heat storage mixed together in an optimal mixture for SHS. For example aggre-
system to the simple gassolid arrangement considered here, can gates can be chosen for heat capacity, binders for thermal conduc-
be compared in terms of material costs only (taken from Ref. [11]). tivity and bres for strength. It may even be possible to use a phase
The latter materials are included for material costs only since change material as aggregate. In summary, there would appear to be
(i) molten salts will not reach the temperatures of interest and opportunities for binder- aggregate-additive composite materials like
(ii) aluminium is a LHS media. high alumina concrete or aluminosilicate geopolymers as cheap high
The lower limit of 400 1C (Fig. 8) represents the maximum temperature SHS media. Experimental work would need to be done,
temperature for parabolic dish systems where refractory concretes however, to optimise the properties of the aggregates or additives to
have been trialled, and molten salts (solar salt) are commercially the composite material with respect to the thermophysical proper-
used, for thermal storage, as in the Andasol trough plants. ties, particularly thermal conductivity.
The molten salt considered, HiTech, is extrapolated to its upper
stability point of about 550 1C whereas the remainder of materials
which have high stability are continued through to 750 1C.
The data for aluminium is taken from Khare et al. [9] and shows 6. Conclusions
the highest cost, apart from across the melting point (661 1C),
where the latent heat effect is signicant. There are advantages of SHS compared to LHS for thermal
Comparable to alumina, the Hitech molten salt media is the energy storage in terms of simplicity of design, construction and
next cheapest material, however, since its operational range is operation (and hence cost). The CES software package has been
limited it is considered only for comparison with the refractory used to identify some common materials for solid state SHS in the
bricks and high alumina concrete. The latter materials are range 500750 1C. Bulk physical properties considered included
considerably cheaper, even compared to the Hitech molten salt, energy density, thermal conductivity and mechanical strength.
and readily available in a variety of compositions and forms. Environmental factors such as embodied energy and GHG emis-
sions in the use of materials was also considered. Suitable
materials included ceramics such as alumina, magnesia, and
5. Composite materials composites such as high alumina concretes, silicon carbide,
graphite and ferrous metals (cast iron and stainless steel). Molten
The materials selection process has identied a number of salts are used commercially in SHS but are unstable above about
common ceramic or refractory materials which are highly cost 600 1C.
competitive, such as magnesia or high alumina concrete, for SHS Using a simple packed bedinert gas heat exchanger based on
media. Normal cement-based concretes have been used for low bricks of the selected materials, a cost comparison was made on
temperature (o420 1C) SHS media and a high temperature concrete the basis of $US/kWh (thermal) of storage. High alumina concrete
122 S. Khare et al. / Solar Energy Materials & Solar Cells 115 (2013) 114122

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