Advances in Thermal Energy Storage Materials and Their Applications Towards Zero Energy Buildings: A Critical Review

Advances in thermal energy storage materials and their applications
towards zero energy buildings: A critical review

Jesús Lizana a
Ricardo Chacartegui b
Angela Barrios-Padura a
José Manuel Valverde c, *
a Departamento de Construcciones Arquitectónicas, Universidad de Sevilla, Avda. Reina Mercedes 2, 41012 Seville, Spain
b Departamento de Ingeniería Energética, Universidad de Sevilla, Camino de los Descubrimientos s/n, 41092 Seville, Spain
c Facultad de Física, Universidad de Sevilla, Avda. Reina Mercedes s/n, 41012 Seville, Spain
* Corresponding author. E-mail address: [email protected]
Abstract
Buildings are responsible for one-third of the world’s energy consumption, of which 60% is due to heating and cooling.
To accomplish the low-carbon energy goal in the building sector, thermal energy storage offers a number of benefits by
reducing energy consumption and promoting the use of renewable energy sources. This manuscript reviews recent
advances in the development of thermal energy storage materials for building applications oriented towards zero energy
buildings. Volumetric heat capacity of sensible, latent and thermochemical energy storage materials developed for low-
to-moderate temperature applications are reviewed and assessed with a special focus on their technical characteristics
and development stage. This encompasses most recent publications, international programmes and projects, and
commercially available solutions. Physical, thermodynamic, kinetic and chemical properties are addressed, as well as
costs. Advantages, drawbacks and challenges of the diverse alternatives are discussed. The analysis shows that
solutions with the highest potential for competitive energy efficiency measures are based on latent and sensible energy
storage systems, which present a volumetric thermal energy storage density up to 430 and 250 MJ/m3 respectively. Their
applications in free-cooling ventilation systems, solar energy storage solutions for short and long-term storage periods,
and demand-side management strategies towards the road to zero energy buildings are highlighted as promising, leading
to a reduction of energy consumption of more than 30%. On the other hand, thermochemical energy storage does not
yet show clear advantages for building applications, despite the potentially high energy density (up to 1510 MJ/m3) and
heat availability for long-term storage periods. Currently, there is no available material for thermochemical energy storage
that satisfies all the requirements for building operations. Besides, thermochemical solutions require different tanks and
heat exchangers that should be carefully addressed for small-scale applications. Additional research efforts are needed
to optimise operation conditions, efficiency, costs and system designs.
Keywords: Thermal energy storage, Energy efficiency, Sensible heat storage, Latent heat storage, Thermochemical
storage, Zero energy buildings.
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Nomenclature
𝑐𝑝 specific heat (KJ/kgºC)
CSMP Composite salt in porous matrix
DH District heating
DHW Domestic hot water
DSM Demand-side management
GHG greenhouse gas
ℎ𝑓 latent heat of fusion per unit mass (kJ/kg)
HVAC&R Heating, ventilation, air conditioning and refrigeration
𝑚 mass of heat storage medium (kg)
PCM phase change material
PV photovoltaic
𝑄 quantity of heat stored (MJ)
SHSM sensible heat storage material
T temperature (ºC)
TABS thermally Activated Building system
TES thermal energy storage
TMA thermal mass activation
TSM thermochemical energy storage material
UTES underground thermal energy storage
ZEB zero energy building
Greek letters
α thermal diffusivity (mm2/s)
 thermal conductivity (W/mºC)
𝜌 density (kg/m3)
Subscript
l liquid
s solid
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1. Introduction
The building sector is the largest energy-consuming sector, accounting for over one-third of the final energy consumption
in the world [1]. In the European Union, it is responsible for 40% of the total energy consumption [2] of which heating,
cooling and hot water are responsible for approximately 70% [1]. Currently, around 75% of the primary energy supply for
heating and cooling is based on fossil fuels [3]. In the pathway towards an energy sustainable, efficient, environmentally
friendly and low-carbon building sector, thermal energy storage (TES) offers a great range of opportunities and benefits
to reduce energy consumption and GHG emissions [1,4,5].
TES solutions can be based on sensible, latent or thermochemical energy storage [6] and may be implemented in
buildings through passive and active applications [7,8]. Passive applications allow reducing energy demand in buildings
by means of a higher thermal inertia, decreasing indoor peak-temperature, and improving thermal comfort [4,5]. On the
other hand, active applications allow [1,5]:
i) Reducing the peak load thanks to the supply of stored energy, which reduces the required power capacity of
heating/cooling equipment;
ii) Improving the efficiency of systems by adjusting the operation range (avoiding operations at partial loads and
mitigating intermittent input by frequent start/stop);
iii) Increasing renewable energy contribution, mainly solar and aero-thermal energy, by overcoming the time mismatch
between demand and supply.
Despite the fact that a huge research effort has been carried out on energy storage in recent years [9,10], competitive
TES materials and technologies are being developed slower than expected [11]. An efficient integration of available TES
technologies into the architecture of buildings remain to be technically and commercially developed [8,12]. Nonetheless,
applications are gradually becoming more feasible due to the significant increases of energy prices [13] and regulatory
pressure [2].
This paper provides a critical review of current state-of-the-art TES materials and applications towards Zero Energy
Buildings (ZEBs). Classification and characterisation properties of available sensible, latent and thermochemical TES
materials and their applications are reviewed according to the most recent publications and international programmes
and projects. This encompasses TES materials, technically and commercially developed for low-temperature applications
as required for direct application in buildings: up to 21ºC for cooling applications, between 22ºC and 28ºC for comfort
applications, and over 29ºC for hot water and heating applications. A novel comparison of TES materials is carried out
taking into account volumetric heat capacity instead of mass heat capacity Assessment of the latter is more appropriate
for building applications due to space limitations. Physical, thermodynamic, kinetic and chemical properties of materials
are compared, as well as costs, and current research stages are discussed with the aim of identifying advantages,
drawbacks and challenges for their application and deployment. The results of the review allow the identification of the
most promising TES materials and technologies for building implementation towards ZEBs at different scales (per
dwelling, medium-scale buildings and district networks) with current development levels. This review is also expected to
contribute as a guide for the decision-making process in the development of efficient TES solutions for buildings.
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2. Overview. Classification of Thermal Energy Storage materials and their applications
TES solutions for building applications can be based on sensible, latent or thermochemical energy storage materials.
 Sensible heat storage is the most widely used technique for building applications. It is simply based on increasing
or decreasing the temperature of a high heat capacity storage medium, thus storing and releasing heat [14]. The
average TES capacity of most materials employed is approximately 100 MJ/m3 [6], with water being the most practical
available material having a storage capacity of 250 MJ/m3 for a temperature gradient of 60ºC [15].
 Latent heat storage consists of storing or releasing heat in the storage medium when it undergoes a phase change
(from one physical state to another) [14,16]. Compared to sensible heat storage, phase change materials (PCM) can
store a larger amount of heat in a much shorter temperature range around the phase change temperature. According
to Tatsidjodoung et al. [6], the typical latent heat storage capacity of most materials usable for this end is in the range
300-500 MJ/m3.
 Thermochemical heat storage relies on the use of a source of heat to induce a reversible chemical reaction and/or
sorption process [17,18]. The potential benefits of these storage systems is their rather high energy density
(approximately 1000 MJ/m3 [6]), negligible heat loss, and long-term heat availability [19].
Sensible, latent and thermochemical energy storage materials can be implemented in buildings by means of different
applications. Figure 1 illustrates the relationship between main TES applications and storage methods according to the
classification described in [7,8,16,20,21].
Figure 1. Building applications based on thermal energy storage.
Depending on their characteristics, these applications can be divided into passive and active, ranging from high thermal
inertia conventional solutions in buildings to advanced TES units:
• TES in materials and components of buildings consist of high thermal inertia elements, which improve the
thermal performance of buildings by the attenuation of thermal oscillations in the indoor space. Only sensible heat
storage and latent heat storage are used in passive building applications [7].
• Thermally Activated Building systems (TABS) [21] or Thermal mass activation (TMA) [8] refers to using the
building structure as a TES system through active applications. The operation mode consists of connecting a
construction element of high heat capacity with a thermal energy source. Only sensible heat storage and latent heat
storage are used in these applications.
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• TES components are based on encapsulated PCMs and they are used for improving the environmental
performance of systems, mostly taking advantage of night ventilation, in order to freeze the PCM for cooling purposes
during daytime, absorbing heat gains and mitigating overheating [22]. Thus, it works as a free cooling system by
reducing temperature peaks during daytime. The applications of TES components can be classified into two groups:
PCM applied to ventilation systems for free cooling ventilation, and PCM applied to PV panels for increasing the
electrical yield thanks to a reduction of temperature rise of their surface compared to a system without PCMs [23–
25].
• Small-scale TES units refers to compact storage tanks for heating and cooling applications, which can be based
on the form of sensible, latent or thermochemical storage. This allows increasing the renewable energy use (through
seasonal or daily storage) and/or improving the energy performance of heating, ventilation, air conditioning and
refrigeration (HVAC&R) systems [1,5].
• Large-scale TES systems refer to above-ground large-scale water tanks and underground thermal energy storage
(UTES) systems. Their main applications consist of solar storage in district heating (DH) networks or large-scale
buildings.
The next sections are focused on the characterisation of the best available TES materials for building applications based
on sensible, latent and thermochemical energy storage according to commercial data, most recent publications, and
international programmes and projects. It must be remarked though that for each storage method, the reported studies
use diverse measurement methodologies and test protocols, which are often not defined in detail. Therefore, the solutions
proposed are difficult to compare directly as the differences in measurement methods (e.g., energy density taking into
account stored energy or released energy, measurement conditions of thermal properties, etc.) and operation conditions
(e.g., operation temperatures, flowrate, pressure, operation time, initial-final dehydration levels (%), etc.) have a large
influence on the properties measured [6]. To circumvent this issue, it would be necessary to employ measurement-
standards for energy storage materials and systems.
3. Sensible heat storage materials
3.1. Classification and characterisation parameters.

Sensible heat storage materials (SHSMs) can be either liquid or solid storage materials [26]. The thermodynamic,
physical, chemical and economic parameters of SHSMs are listed in Table 1 [26,27]. Thermal reliability (no change in
thermal properties) and chemical stability (no decomposition or change in chemical composition) after a large number of
thermal cycles, and thermal stability (no degradation or weight loss) at high temperatures should be guaranteed to assure
a long lifetime.
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Table 1. Characterisation parameters of SHSMs.
Thermodynamic Physical Chemical Economic
Specific heat (𝑐𝑝 ) (kJ/kgºC) Density (𝜌) (Kg/m3) No chemical decomposition Available in large quantities
Thermal conductivity () (W/mºC) Volume change (%) Non-corrosive Inexpensive
Thermal diffusivity (α) (mm2/s) Non-poisonous
Thermal effusivity (W√𝑠 /𝑚2 º𝐶) Non-flammable
Thermal expansion coefficient (%) Non-explosive
The amount of energy stored as sensible heat (𝑄) in a given mass of material (𝑚) is given by Eq. 1 [28,29]. Thus, high
specific heat and high density should be pursued to achieve a high volumetric storage capacity (MJ/m3). As a reference
value, the sensible heat storage capacity of water for a temperature difference (𝑇) of 60ºC is 250 MJ/m3.
𝑇𝑓
𝑄 = ∫ 𝑚 𝑐𝑝 𝑑𝑇 (𝑀𝐽) Eq. 1
𝑇𝑖
Charging/discharging periods and power depend on thermal conductivity, exchange flow rate and thermal diffusivity (α),
which provide stratification ability. Thermal diffusivity measures the rate at which the temperature changes within a
substance, and is defined in terms of thermal conductivity, density, and heat capacity according to Eq. 2.

α= (𝑚𝑚2 /𝑠) Eq. 2
𝜌·𝑐𝑝
High thermal stratification allows releasing heat easier, as it allows transferring a low temperature thermal energy source
to the cooler regions in a charged thermal storage medium, and higher quality energy (exergy) is readily available from
the warmer regions of a discharged thermal storage medium [30].
For passive applications, Ståhl [27] analysed the influence of thermal mass on the heating and cooling demands in
buildings, and found that the main influencing parameter on building thermal inertia is the thermal effusivity (Eq. 3), which
characterises the rate at which a material can absorb heat. The higher the thermal effusivity the greater the amount of
heat stored and thus the higher the building energy consumption reduction.
Thermal effusivity = √ · 𝜌 · 𝑐𝑝 (W√𝑠 /𝑚2 𝐾) Eq. 3
Small volume change, availability, low cost and non-toxicity are also important variables to take into consideration.
The main drawbacks of SHSMs are related to their low energy density (owing to space limitation for building applications)
and self-discharge of the system, which can be substantial due to heat losses (particularly for long-period storage) [6].
3.2. Evaluation of available sensible heat storage materials.

Table 2 summarises the properties of main construction materials for sensible heat storage according to [6,15,31,32].
Material cost data was gathered from a number of commercial databases [33–35]. Average volumetric specific heat
capacity data have been calculated according to average parameters of density and specific heat.
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Table 2. Available SHSMs for building applications.
Properties
Average material
Thermal Specific heat Average volumetric
Reference Material cost Type Density
conductivity capacity specific heat
[33–35] (kg/m3)
(W/mºC) (kJ/kgK) capacity (kJ/m3K)
Asan and Sancaktar [32] Asphalt sheet 56 €/m3 Solid 2300 1.2 1.7 3910
Tatsidjodoung et al. [6] Oil 6560 €/m3 Liquid 888 0.14 1.88 1669
Tudela [31] Ceramic brick 36-64 €/m3 Solid 1800 0.73 0.92 1656
Wood 404 €/m3 Solid 450 0.12 1.6 720
Plywood boards 1114 €/m3 Solid 500 0.13 1.6 800
Gypsum (plasterboard) 385 €/m3 Solid 900 0.25 1 900
Gypsum (coating) 78 €/m3 Solid 1000 0.4 1 1000
Oriented strand board 328 €/m3 Solid 600 0.14 1.7 1020
Wood 404 €/m3 Solid 700 0.18 1.6 1120
Oriented strand board 328 €/m3 Solid 900 0.18 1.7 1530
Ceramic tile 1600-3500 €/m3 Solid 2000 1 0.8 1600
Lime mortar 123 €/m3 Solid 1600 0.8 1 1600
Plywood boards 1114 €/m3 Solid 1000 0.24 1.6 1600
Cement bonded particleboard 1309 €/m3 Solid 1200 0.23 1.5 1800
ISO 10456:2007 [15]
Cement mortar 115 €/m3 Solid 1800 1 1 1800
Concrete 76 €/m3 Solid 2000 1.35 1 2000
Sand and gravel 6-8 €/m3 Solid 1700-2200 2 0.910-1.180 2072
Limestone 70-819 €/m3 Solid 1600-2600 0.85-2.3 1 2100
Rock 64-742 €/m3 Solid 2800-1500 3.5-0.85 1 2150
Concrete (high density) 100 €/m3 Solid 2400 2 1 2400
Reinforced concrete (2%) 121 €/m3 Solid 2400 2.5 1 2400
Clay or silt - Solid 1200-1800 1,5 1.670-2.500 3252
Water (80ºC) 1.6 €/m3 Liquid 970 0.67 4.19 4064
Water (40ºC) 1.6 €/m3 Liquid 990 0.63 4.19 4148
Water (10ºC) 1.6 €/m3 Liquid 1000 0.6 4.19 4190
Figure 2 shows the best available SHMs according to their average volumetric specific heat capacity and thermal
diffusivity. The relatively low thermal capacity of the SHSMs is usually balanced by their temperature swing during charge
and release processes (stratification ability).
Figure 2. Common materials for sensible heat storage in building applications.
Regarding solid heat storage materials, the most commonly used ones are rocks, stones, bricks, concrete, dry and wet
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soil, wood, plasterboard, and corkboard [26], which are preferably employed for heating applications. Underground
materials, such as rock, and dry and wet soil, can store heat up to 80ºC with a volumetric storage capacity of
approximately 108 MJ/m3 (ΔT= 50ºC). Concrete can operate in a temperature range from 30 to 70 ºC with a volumetric
storage capacity around 95 MJ/m3 (ΔT= 50ºC). Despite the typically poor heat transfer by conduction between solid
materials, stratification can be maintained over considerable time periods (Figure 2) [6]. Furthermore, underground
solutions show the benefit of using the ground as an insulation medium, as in large-scale underground TES systems.
However, the use of solids is limited by some issues such as reduced energy storage density as compared to water,
relatively high costs of operation and maintenance of the storage units and risks of self-discharge in the long-term.
Regarding liquid storage materials, the most common materials are water or oils, and either pure alcohol or derivatives.
They are widely used for cooling and heating purposes. Water is the best available liquid material employed due to its
high specific heat capacity, availability and low cost [6], with a volumetric storage capacity of 250 MJ/m3 for heating
purposes (ΔT= 60 ºC) and 63 MJ/m3 for cooling applications (ΔT=15 ºC). The main drawbacks are the high investment
cost for liquid storage infrastructures and the risk of leakages.
3.3. Potential building applications based on sensible heat storage towards ZEBs.
Most promising solutions based on sensible heat storage consist of high thermal inertia elements for passive applications,
TABs, small-scale water tanks and large-scale seasonal TES systems.
 High thermal inertia elements based on sensible heat storage have been effectively implemented in buildings to
attenuate indoor temperature fluctuations [36]. Karlsson et al. [37]evaluated the effects of increasing the TES
capacity of building materials through a sensitivity analysis and showed that, for thin internal walls, implementing
materials with high volumetric heat capacity can significantly reduce heat consumption and improve thermal
comfort. In addition, it was reported that high thermal mass can significantly change the power consumption pattern,
which would yield significant benefits. Rempel et al. [38] evaluated different passive applications, such us exposed
mass walls, trombe walls or direct-gain floors, based on different sensible storage materials and design strategies
focused on storing or delivering heat according to the building operating pattern. They demonstrated that despite
passive elements cannot provide the instant heat or cooling as a mechanical system, they are adjustable by varying
the material, thickness and configuration, and therefore can be defined according to users’ requirements and daily
space-heating (or cooling) needs. In addition, peak transmission loads can be reduced in summer and winter
months by increasing the thermal inertia of the building. In intermediate months, cooling and heating energy needs
can be decreased [39]. Al-Sanea et al. [39]investigated the effects of varying amounts of thermal mass of insulated
building walls with same nominal resistance at different locations and demonstrated that wall dynamic resistance
changes according to wall design despite nominal resistance is constant, and it represents actual variations in
transmission loads. Thus, optimizing thermal mass for the same nominal resistance value, leads to higher savings
in yearly transmission loads (about 17% for cooling and 35% for heating). In addition, Al-Sanea et al. showed that,
for a given TES capacity, a wall with outside insulation yields better overall performance than a wall with inside
insulation in applications with continuously operating year-round HVAC systems. However, it should be considered
that there are applications in which adding sensible heat storage would not offer substantial benefits. Karlsson et
al. [37] and Bloomfield and Fisk [40] evaluated the influence of thermal mass on building performance and
concluded that the additional TES capacity of heavy-weight buildings do not offer any substantial improvements.
They also reported that in cases with intermittently heated buildings, high thermal inertia is a clear disadvantage.
 TABs through sensible heat storage have been widely implemented to improve thermal management in buildings.
Kim and Norford [41] evaluated the operation performance of variable speed heat pumps using the building
structure as a TABs to improve power system operation by providing demand-side flexibility in cooling application.
The results showed that the TABs solution achieved smaller operating costs than the convective cooling. In addition,
Arteconi et al. [42] showed that a TABs can undersize the heating and/or cooling system by about 70-80%.
However, a continuous energy demand pattern is required for their effective implementation [8].
 Small-scale water tanks are the most commonly employed sensible TES application in buildings. However, it
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requires a large size for daily-weekly storage, and mainly for seasonal solar energy storage, which increases heat
losses and reduces efficiency. For instance, water volume for covering annual heating needs of an energy efficient
passive house, which is estimated in 6480 MJ [6], is approximately 30-35 m3. On the other hand, a promising
operation mode of small-scale sensible storage in water is based on demand-side management (DSM) applications
[43]. DSM consists of a TES unit linked to a heating or cooling system, such as a heat pump, which takes advantage
of off-peak tariff periods and other sub-optimal times (e.g., better exterior conditions). Renaldi et al. [44] showed
that the integration of water storage and off-peak tariff periods reduces the annual operation cost by around 29%.
 Large-scale seasonal solar energy storage in underground thermal energy storage (UTES) systems based
on water, rock and soil materials is a mature technology that has been implemented and evaluated in many pilot
plants in district heating networks [45–47] such as Drake Landing Solar Community DH system in Okotoks
(Canada), which provides a solar fraction over 90% [48]. Large-scale UTES systems help the integration of solar
thermal energy by storing the energy excess produced in availability periods, thus enhancing the solar contribution
[5,49,50]. Rapantova et al. [51] assessed long-term operation effects in the field of a borehole TES system, showing
that seasonal underground storage can be feasible with a heat recovery of 65%. According to European Large-
Scale Solar Heating Plant Database [52], underground water tanks and borehole TES are the most common
systems in Europe, followed by aquifers and pit TES [52]. However, despite the fact that approximately 5000 thermal
districts have been implemented in Europe [12], providing around 9-10% of the EU’s energy needs [3], large-scale
solar DH networks are just around 3.2% [3,13]. New research is required to demonstrate their economic viability
[53], mainly for warm or mild climates, in order to further cut down investment costs and heat distribution costs [54].
Lizana et al. [55] reported that following specific sizing and design strategies for solar DH systems with BTES in
Mediterranean areas, with high solar thermal energy availability, internal rates of return higher than 9.8% and a
payback period below 10 years could be achieved.
Taking into account all sensible heat storage materials and applications assessed above, it may be concluded that water
and underground materials stand as the most promising on the road to ZEBs due to their high sensible heat storage
capacity and moderate thermal diffusivity. Their application in solar energy storage solutions and demand-side
management strategies yield an efficient reduction of energy consumption in buildings. Furthermore, specific building
designs making use of elements with high thermal inertia can yield significant benefits, albeit specific requirements should
be addressed for their effective application.
4. Latent heat storage materials

This section describes the best available TES materials for building applications based on latent heat storage according
to most recent publications, commercial data and reports from main PCM companies.
4.1. Classification and characterisation parameters.

Solid-liquid PCMs are the most commonly employed solutions in buildings [14]. These PCMs are classified into organic
compounds, inorganic compounds and eutectics mixtures (mixtures between diverse inorganic and/or organic materials)
[56–58]. Each one of these groups can be further categorised into diverse subgroups as shown in Figure 3.
Figure 3. Classification of solid-liquid PCMs.
The thermodynamic, physical, kinetic, chemical and economic parameters of PCMs are listed in Table 3 [14,59,60].
Thermal reliability (no change in thermal properties), chemical stability (no phase segregation or changes in chemical
composition), thermal stability at high temperatures after a large number of thermal cycles (no degradation or weight loss)
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and congruent melting (melting and solidification in a narrow temperature range without subcooling/supercooling) should
be guaranteed to assure applicability and long life-time [14,56,59,61]. According to Harikrishnan et al. [61], stability would
be required for approximately 5000 cycles for around 13-14 years.
Table 3. Characterisation parameters of solid-liquid PCMs.
Thermodynamic Physical Kinetic Chemical Economic
Phase change temperature (ºC) Density (𝜌) (Kg/m3) Rate of nucleation No chemical decomposition Available in large quantities
(phase segregation) b
Latent heat of phase change (ℎ) (kJ/kg) Volume change (%) Not supercooling a Non-corrosive Inexpensive
Specific heat (𝑐𝑝 ) (kJ/kgºC) Non-poisonous
Thermal conductivity () (W/mºC) Non-flammable
Thermal diffusivity (α) (mm2/s) Non-explosive
Thermal effusivity (W√𝑠 /𝑚2 º𝐶)
Thermal expansion coefficient (%)
a Subcooling refers to a liquid existing at a temperature below its normal melting temperature. If that temperature is not reached, PCM will not solidify at all and stored heat will not be released [14].
Not supercooling is achieved through a high rate of nucleation and growth rate of the crystals. Thus, it may be suppressed by introducing a nucleating agent or a “cold finger” in the material [56].
b Phase segregation or separation refers to the conversion of a single-phase system into a multi-phase system (separation of components of a solution).
The total amount of energy stored (𝑄) as latent heat along with the sensible heat stored in each physical state of a mass
of material (𝑚) is given by Eq. 4 [28–30]. High specific heat in each physical state (𝑐𝑝𝑠 and 𝑐𝑝𝑙 ), high density, and high
latent heat of fusion (𝛥ℎ𝑓 ) should be pursued to achieve a high storage density (MJ/m3).
𝑇𝑚 𝑇𝑓
𝑄 = 𝑚 [ (∫𝑇𝑖 𝑐𝑝𝑠 𝑑𝑇 ) + (𝛥ℎ𝑓 )𝑙𝑎𝑡𝑒𝑛𝑡 + (∫𝑇𝑚 𝑐𝑝𝑙 𝑑𝑇 ) ] (𝑀𝐽) Eq. 4
𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒
According to the particular application, the selected material would depend on the suitable phase change temperature.
In addition, the charging/discharging periods and power depend on thermal conductivity, exchange flowrate and thermal
diffusivity. Small volume change, availability, low cost and non-toxicity are also relevant material properties in practice
[57]. Most common drawbacks of PCMs are linked to their high cost, low thermal conductivity, relative large volume
change, flammability, supercooling, corrosiveness, and thermal reliability and stability after undergoing a great number of
thermal cycles [57].
4.2. Assessment of available latent heat storage materials.

Paraffins, salt hydrates and eutectic mixtures are the main PCMs for building applications [57,60]:
 Paraffins are a mixture of pure alkanes obeying the chemical formula CnH2n+2, where 20≤n≤30. They show
favourable properties for building applications, such as negligible supercooling, non-corrosiveness, chemical
stability, no phase segregation and low cost [6,56,62–64]. Their main drawbacks are related to their low volumetric
latent heat storage capacity, low thermal conductivity and flammability [58]. Their average latent heat capacity is
approximately 170 MJ/m3 and the average thermal conductivity is about 0.2 W/mºC [57].
 Salt hydrates are alloys of inorganics salts (AB) and water (H2) with a chemical formula AB·xH2O. They have
relatively high latent heat capacity and thermal conductivity (approximately 350 MJ/m3 and 0.5 W/mºC, respectively)
[57]. Moreover, salt hydrates are cheaper than paraffins [60] and non-flammable [58]. Thus, they show a higher
potential for applicability in buildings [65] albeit with some disadvantages such as their low thermal reliability for
long-operation periods [29], phase segregation, subcooling and corrosiveness [6,58,63,66].
 Eutectics (chemical formula: A compound + B compound) are mixtures of inorganic PCMs (mostly hydrated salts)
and/or organic PCMs. They have a melting temperature below those of the constitutive compounds [60]. In addition,
eutectic alloys present a congruent phase change without phase segregation [6].
Fatty acids, esters and alcohols are usually highly flammable and have low thermal conductivity with diverse levels of
toxicity [29], which limits their application in buildings. Regarding the use of metals in the range of temperatures of interest,
poor availability and very high cost limit their application in buildings despite having a high thermal conductivity [6] and
volumetric fusion heat due to their high density [29].
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Currently, there are more than 250 commercially available PCMs in the temperature range between -10ºC and +120ºC.
They can be obtained from the main existing companies listed in Table 4. Properties of these materials are shown in
Appendix A (Tables A1-8). They are mainly based on paraffins, salt hydrates and eutectic alloys. The average cost of
PCMs is approximately 6 €/kg, ranging from 40€/kg to 3.6€/kg for wholesale orders [67–69].
Table 4. Commercial PCMs and main supplying companies around the world.
Company Country of origin Classification of materials Product ID
Rubitherm GmbH [70] Germany Organic PCMs - Paraffins RT
Inorganic PCMs – Salt hydrates SP
Powder PX
Granules GR
Climator [71] Sweden Salt hydrates ClimSel C
Cristopia Energy Systems [72,73] India and France Air conditioning AC
Industrial refrigeration IN
PCM Energy [74] India Salt hydrates LatestTM
PCM Products Ltd [75] UK Sub Zero Eutectics E
Salt Hydrates S
Organic PCMs A
Salt PCMs H
Solid/Solid PCMs X
BASF - Micronal PCM [76] Germany Powders DS
RGees. savENRG™ [77] USA Inorganic PCMs (hydrated salts) PCM-HS
Organic PCMs PCM-OM
Bio-based PCM (fatty acids) -
Entropy solutions. PureTemp [69] USA Organic PCMs PureTemp
The relationship between the volumetric latent heat density and the melting temperature of commercially available PCMs
in the market is illustrated in Figure 4. Sensible heat storage in water at different temperatures for heating and cooling is
shown as reference (yellow line).
11
*The dashed line corresponds to sensible storage in water as reference material.
Figure 4. Commercially available PCMs for building applications.
12
The volumetric latent heat density of commercially available inorganic materials (blue symbols in Fig. 4) ranges between
150 and 430 MJ/m3. On the other hand, the volumetric latent heat capacity of available organic materials belongs to a
lower range, between 100 and 250 MJ/m3 (red colour marks). Sensible heat storage in water, which can be used as
reference, has a capacity ranging from 63 to 250 MJ/m3 for cooling and heating purposes, respectively.
4.3. Potential building applications based on PCMs towards ZEBs.

Most promising solutions based on latent heat storage consist of passive applications, encapsulated PCM into free-
cooling ventilation systems, and small-scale TES units for solar storage and DSM strategies.
 In passive applications, in order to keep a low weight and size of building components, PCMs are more suitable
than sensible heat storage materials in a reduced temperature range. Ramakrishnan et al. [78] assessed the
performance of building refurbishment through macro-encapsulated PCMs with a melting temperature and
volumetric latent heat capacity of 29 ºC and 51.5 MJ/m3 respectively. Results showed that PCM combined with night
ventilation can effectively reduce the severe discomfort period (discomfort index above 28ºC) by 65% during
extreme heatwave conditions. Mi et al. [79] evaluated the economic performance of PCM passive application in five
different cities of China. The melting temperature was 27ºC and latent heat capacity of approximately 230 kJ/kg.
Test results showed that the energy savings and economic benefits are more prominent for office buildings located
in cold regions, as well as in regions with hot summers and cold winters. In these situations, a static payback period
from 5 to 7 years was achieved. However, at current prices, the PCM investment cannot be recovered in regions
with a relatively moderate climate, with no chilly winters and hot summers. Castell et al. [80] showed energy savings
higher than 15% with macroencapsulated PCM applications in buildings, and Cabeza et al. [81] showed that peak
temperatures can be reduced by approximately 1-2ºC by introducing microencapsulated PCMs into concrete walls.
However, life-cycle assessment evaluation of PCM solutions showed that, although these solutions decrease the
energy consumption during operation, they do not significantly reduce the global impact throughout the lifetime of
buildings [82,83]. Thus, additional research has to be pursued in order to extend the use of PCMs, mainly by
reducing material cost [84] and by achieving higher storage capacity.
 TES components for ventilation systems represent an attractive alternative to air-conducing units. They reduce
overheating during the summer periods by using low night temperatures [8] although solutions can only be
implemented in climate areas where night-day temperature oscillation ranges from 12ºC to 15ºC [22]. Commercial
solutions are available, such as the Cool-Phase systems from Monodraught Ltd (UK Company) [85], based on
macroencapsulated PCMs to regulate indoor temperatures up to ±4ºC and reduce energy consumption by up to
90% according to commercial specifications [86].
 Small-scale TES units based on PCMs allow for higher volumetric heat capacity than sensible heat storage for
solar thermal and DSM strategies [6]. Thus, higher energy and economic benefits can be achieved through more
compact storage solutions. Cui et al. [87] evaluated the performance of a demand management strategy based on
an HVAC system integrated with an active cool TES for commercial buildings. The cool TES unit was designed with
a relatively small scale, up to 6.7% of typical daily cooling load, and was based on a PCM with a melting temperature
of 8ºC and volumetric latent heat capacity of 205.7 MJ/m3. The results showed that cool TES implementation for
shifting peak demand, as well as providing longer duration and larger capacity for demand response, can achieve
a pay-back period of 8.6 years. However, a main challenge for a viable implementation is the high investment
costs. Campos-Celador et al. [67] developed a latent heat storage prototype with a storage volume reduced by
approximately 50% compared with a conventional water tank. Investment cost was around 805€ for 8.5kWh storage
capacity (not including manufacturing and commercial costs). Taking into account that the PCM represented
approximately 75% of the prototype cost, a main challenge for their deployment would be a reduction of the material
cost.
13
By considering all latent heat storage materials and applications assessed, it can be concluded that PCMs based on
hydrated salts are the best choice due to their high volumetric latent heat storage capacity, moderate thermal conductivity
and low-moderate cost. In addition, their applications in free-cooling ventilation systems, solar energy storage solutions,
and demand-side management strategies are in tune with the road to zero energy buildings mainly due to the effective
optimization of the amount of required material and operating conditions. On the other hand, latent heat storage in passive
applications requires specific climate conditions and operating patterns to effectively improve the building thermal
performance.
5. Thermochemical energy storage materials

In this section, the best available TES materials for building applications based on thermochemical energy storage are
analysed from a review of the recent R&D activities, publications and projects.
5.1. Classification and characterisation parameters

Thermochemical energy storage is a wide concept that refers to sorption processes and chemical reactions [17]. A
chemical reaction is characterised by a change in the chemical bonds of the compounds involved in the reaction
(dissociation and recombination) [6]. Energy can be stored through the endothermic reaction and released by the reverse
exothermic reaction, sometimes by adding a catalyst [6]. Sorption storage can be defined as a phenomenon of fixation
or capture of a gas or a vapour by a sorbent substance in a condensed state (solid or liquid) by means of less intense
physical interactions [18]. Sorption processes may have either a thermo-physical or a thermo-chemical nature.
A classification of tested thermochemical storage materials (TSMs) in the literature is illustrated in Figure 5. TSMs are
grouped according to the process involved: physical adsorption (zeolite and silica gel), liquid absorption or chemical
reaction. A separate category consists of composite materials (CSMP) [17,18].
Figure 5. Classification of TSMs for building applications.
Thermal storage sorption processes can be further classified into open or closed systems. Open cycle systems operate
at atmospheric pressure and vapour, as the working fluid is released into the surroundings, which means that only water
processes are used. In contrast, closed cycles operate in isolation from the surrounding environment in closed circuits.
The thermodynamic, physical, kinetic, chemical and economic parameters of TSMs are listed in Table 5. Moreover,
thermal reliability (no change in thermal properties), chemical stability (no change in chemical composition) and thermal
stability at high temperatures (no degradation or weight loss), after a large number of thermal cycles, must be guaranteed
to assure a viable application and long life-time.
Table 5. Characterisation parameters of TSMs.
Thermodynamic Physical Kinetic Chemical Economic
Charging/desorption temperature (ºC) Density (𝜌) Kinetic of reaction (m/s) No chemical decomposition Available in large quantities
Discharging/sorption temperature (ºC) Operating pressure (Pa) Non-corrosive Inexpensive
Heat input (Wh/kg) Degree of sorbate loading (%) Non-poisonous
Heat output (Wh/kg) Volume change (%) Non-flammable
Storage efficiency (Qreleased/Qstored) Non-explosive
Thermal conductivity ()
14
Evolution of output temperature close
to the equilibrium point (ºC)
The total amount of energy stored (𝑄) through thermochemical processes is given by Eq. 5 [30]. High density, high
energy storage density (Wh/kg) and high storage efficiency (Qreleased/Qstored) should be the goals to achieve a high
volumetric storage capacity (MJ/m3).
𝐶1 𝐶2 + 𝐻𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡 ⇒ 𝐶1 + 𝐶2 ⇉ 𝑠𝑡𝑜𝑟𝑎𝑔𝑒 ⇉ 𝐶1 + 𝐶2 ⇒ 𝐶1 𝐶2 + 𝐻𝑒𝑎𝑡 𝑜𝑢𝑡𝑝𝑢𝑡 Eq. 5
According to the particular application, a suitable charging/discharging temperature should firstly be established.
Charging/discharging periods and power depend mainly on operating pressure, reaction kinetics, thermal conductivity
and exchange flowrate. Small volume change, availability, low cost and environmental impact are also important
properties to take into consideration.
The main drawbacks of TSMs are related to their high cost, inappropriate operation temperatures, non-effective discharge
power for building applications, due to slow reaction kinetics and low output temperature close to the equilibrium point,
as well as low/moderate efficiency in storage process [18,84].
5.2. Evaluation of available thermochemical storage materials.

Research and development in thermochemical energy storage remains at an early stage for building applications [6]. The
high cost of materials, poor heat and mass transfer capacity, and system energy density substantially, lower than material
energy density, are the main barriers for deployment [18]. Materials under research for building applications are mainly
focused on solar energy storage solutions for long-term storage [17,88].
Most promising TSMs have been tested through coordinated international programmes and projects [17,18,88]. Some of
these studies are related to Task 32 (2003-2007) [89,90] and Task 42 (2009-2015) [19] in the framework of the Solar
Heating and Cooling Programme of the International Energy Agency (SHC-ECES) [91]. Others are related to European
projects such as HYDES, MODESTORE (2003-2012), MERITS (2007-20013), COMTES (2012-2016) or E-HUB (2010-
2014). Table 6 shows performance results of tested TSMs for building applications. Figure 6 illustrates volumetric storage
capacity and charging/desorption temperatures of reported TSMs. Sensible heat storage in water is shown as reference.
Silica gel 127B and zeolites (4A, 5A, 13X and NaX) have been tested in open and closed physical adsorption cycles.
Silica gel 127B/H2O has been studied in a closed adsorption cycle within the HYDES and MODESTORE projects (2003-
2012). The results showed that the silica gel/water system has to operate with water contents of 3-13%, which hinders
its actual TES capacity. Thus, to achieve a practical seasonal energy storage capacity, large storage volumes are
necessary. Zeolite 13X has been identified as one of the best adsorbents due to its high water uptake, which provides a
high energy storage density. This material has attracted the interest of researchers. Most of the current demonstration
projects are based on zeolite 13X, such as the E-Hub project (2010-2014) or COMTES project (2012-2016). In addition,
novel solid porous materials for adsorption processes have been proposed for TES applications, such as
aluminophosphates (AlPOs), silico-aluminophosphates (SAPOs) and metal-organic frameworks (MOFs). However, their
high production cost is a main barrier for implementation [17].
Liquid materials such as LiCl, NaOH, CaCl2 and LiBr have been tested in closed absorption cycles [19,89,92–94]. These
aqueous absorption materials present higher energy density values than solid adsorption materials, with temperatures in
a proper range for building applications. Also, liquid desiccants can be pumped to be used directly as heat transfer fluid
[95].
Chemical reaction materials such as magnesium sulphate (MgSO4) or calcium chloride (CaCl2), which have a relatively
high energy storage density, have been also tested. However, very slow reaction rates associated with a low temperature
lift in the reactor [96] and low chemical stability after cycling [97] are the main drawbacks. In order to improve chemical
15
storage material properties, and particularly to enhance the reaction rate and heat release, a new family of composite
sorbents, called Composite “salt porous matrix” (CSPM), has been recently proposed [98]. These composite materials
are based on two sorbents: the host matrix (zeolite, silica gel, alumina, expanded vermiculite, aerogel, etc.) with porous
structure and high thermal conductivity to improve the reaction rate and thus the heat release, and an inorganic salt
solution (LiCl, CaCl2, MgCl2, MgSO4, Ca(NO3)2, LiNO3, etc.), placed inside the matrix, which further enhances the energy
storage.
16
Table 6. TSMs reported in the literature for building applications.
Operation conditions TES capacity
Institute/ Type of Density Storage Volumetric
Reference Material Material cost Charge Discharge Storage
Company study (kg/m3) Cycle density storage
(ºC) (ºC) efficiency
(Wh/kg) (MJ/m3)released
Modestore project [89,99] AEE INTEC, Austria Silica gel 127B/H2O 4300 €/m3 EXP Closed 88 70-40 180
SPF [89] SPF, Switzerland Zeolite 13X/ H2O 2-3000 €/m3 a EXP 650 Closed 180 55 648
E-Hub project [97,100] TNO,
Zeolite 5A/ H2O EXP 750 Closed 103 53-36 62.9 170
Solid physical adsorption
Finck et al. [101] Netherlands

COMTES project [102] AEE INTEC, ITW, TH Wildau and
Zeolite 13XBF/ H2O EXP 700 Closed 150 75-47 111 277 b
Helden et al. [103] Vaillant
MonoSorp [89] ITW, Germany Zeolite 4A/Air 2500-2350 €/m3 EXP Open 180 35-10 576
730 180 60-35 131.9 346
Zettl et al. [104] - Zeolite 4A/Air 2500-2350 €/m3 EXP Open
730 230 60-35 147.2 421
180 57 (6h) 0.53 218.75 c
Johannes et al. [105] - Zeolite NaX/Air EXP Open
120 57 (4h) 0.551 148.75 c
E-Hub project [97,100] ECN, Netherlands Zeolite 13X/Air EXP Open 120-160 70-45 93.33
Hauer [106] ZAE Bayern, Germany Zeolite 13X/ H2O PP Open 130-180 65 446
TCA SERC, Sweden 3600 €/m3
LiCl salt/H2O EXP Closed 46-87 30-25 204.67 911
TASK 32 - IEA-SCH [89] (ClimateWell) 6000 €/ton [107]
Liquid absorption
Weber and Dorer [89,92] EMPA, Switzerland NaOH/H2O 250 €/m3 EXP Closed 95-150 70 900
COMTES project [102,108]
Daguenet-Frick [109,110] EMPA, Switzerland NaOH/H2O 3000 €/ton [107] EXP (440 Wh/l)d Closed 95 32.8 or 56 e
Fumey [111]
Quinnell et al. [19,93,95] University of Minnesota, USA CaCl2/H2O 350 €/ton [107] EXP Closed 117-138 - 382-1372
N’Tsoukpoe et al. [94] LOCIE-CNRS, France LiBr/H2O 5000 €/ton [107] EXP Closed 75-90 30-40
TASK 32 - IEA-SCH [89] ECN, the Netherlands MgSO4·7H2O 4870 €/m3 EXP - 150 - 1512
ECN, TNO, and the Eindhoven 25
Chemical
reaction
WAELS project [112] MgSO4·7H2O EXP 1680 Closed 60-275 0.88 1800 c
University 50
E-hub project [97,113]
ECN, the Netherlands MgCl2·6H2O EXP Closed 130 64-50 500 f
Zondag et al. [113]
MCES - Lammak et al. [114] Chiang Ma University, Thailand Na2S-graphite/H2O EXP Closed 80-95 - 2240
SWEAT - Boer et al. [115] ECN, the Netherlands Na2S-cellulose/H2O EXP Closed >83 45-35 0.84 1100
CSPM
Mauran et al. [116] PROMES-CNRS, France SrBr2-ENG/H2O EXP Open 80 35 321 216
Adv. CWS-NT. ITW, Germany
Zeolite 4A-CaCl2/H2O EXP Closed 130 25 1000 900
Combisystem [19,96,117]
a Cost of material is unknown and has been estimated.
b 64% of the theoretical value, mainly due to the relative high residual water vapour content of the zeolite (13%).
c Ratio obtained by means of released energy.
d Experimental energy density of the material without taking efficiency losses into account.
e Discharging temperature in absorber for heating: 32.8ºC (inlet flow at 14ºC). Discharging temperature in absorber for DHW: 56ºC (inlet flow at 25ºC).
f Effective storage density of the material by taking into consideration heat losses in the thermochemical storage process.
17
* The dashed line corresponds to sensible heat storage in water to be taken as reference.
Figure 6. Thermochemical energy storage materials for building applications.
Taking into account all reported TSMs, and despite their high energy density, to date there is no available material that
satisfies all requirements for efficient thermochemical energy storage in the building sector. High cost, low discharge
capacities, variable thermal power over time, and poor thermal stability and reliability through cycling are main challenges
for research.
5.3. Potential building applications based on thermochemical energy storage towards ZEBs.
Today, thermochemical applications for TES are not available as commercial solutions in buildings. Different small-
medium scale heat storage prototypes based on physical sorption and chemical reactions are found in the literature
[17,18,88,118] and in reports from international programmes and projects [19,89,90]. Reported prototypes show
limitations in heat and mass transfer and reaction kinetics, as well as in the extra volume of components required to add
and extract energy from the storage vessel [19], which considerably reduce the volumetric storage capacity, thus
hampering viability for building implementation. Final prototype energy density is often significantly below the material
storage density, usually by more than 50% [18]. Additional efforts are needed to optimise material costs and systems
design.
18
6. Discussion of results. Drawbacks, advantages and challenges
Figure 7 illustrates the ranges of volumetric TES capacity of technically developed and commercially available material
groups.
Water (sensible storage) 0-250

Underground materials (sensible storage) 0-108
Thermal Storage Materials
Concrete (Sensible storage) 0-95

Ice (PCM) 301
Organic PCMs 100-250
Inorganic PCMs 150-430
Solid adsorption TSMs 170-650
Liquid absorption TSMs 900-1370
Chemical reaction TSMs 500-1510
Composite TSMs 215-900
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Volumetric thermal energy storage capacity (MJ/m3)
Figure 7. Comparison of volumetric storage capacity of thermal storage materials reviewed in this work.
Water storage through sensible (liquid) and latent heat (ice) have a volumetric storage capacity of 250 and 301 MJ/m3,
for heating and cooling purposes, respectively. Low cost and wide availability makes this solution highly competitive.
Underground materials, such as rock, and dry and wet soil, have a volumetric storage capacity up to 108 MJ/m3 for
heating applications. Their use allows effective solutions through large-scale UTES systems, since stratification in
underground materials can be maintained over considerable time periods, materials cost is null, and underground
solutions have the benefit of using the ground as insulation.
Organic and inorganic PCMs energy density is in the range 100-430 MJ/m3 for phase change temperatures between -10
and +120ºC. More than 250 materials in this regard are currently available. However, the feasibility of latent heat
applications could be improved if cheaper PCMs were available, as materials represent approximately 75% of system
costs [67].
Thermochemical TES capacity ranges from 170 to 1510 MJ/m3. However, despite this high energy density,
thermochemical-based TES units require additional components such as tanks and heat exchangers, which can reduce
storage density by more than 50% [18]. Solutions require a considerable enlargement of storage systems to increase the
energy density ratio of final units. In addition, the high investment cost of most of the materials successfully tested at the
laboratory scale, from 350 to 3600 €/m3, and further safety requirements, environmental impact, lifetime and compatibility
constrain the application of thermochemical energy solutions in buildings.
Table 7 summarises the main selection criteria, disadvantages, advantages and challenges for each TES method
according to the state-of-the-art reviewed in this work. Thermal, physical, kinetic, chemical and economic parameters for
the selection of appropriate TES materials are proposed. These are average values considering all reported materials to
seek the best possible performance in order to help the technical decision-making process for the design of energy
efficiency applications towards ZEBs.
19
Table 7. Selection criteria, drawbacks, advantages and challenges of TES materials.
TES
Properties Main selection criteria Drawbacks Advantages Challenges
materials
SHSMs Thermal -Specific heat capacity >2000kJ/m3K -High heat losses -Easy stratification -Heat lost reduction
-Thermal conductivity >0.6 W/mºC -Self-discharge -Super insulation of units
-Thermal diffusivity >0.5 mm2/s -Low storage density
Physical -Density >1000 kg/m3 -Huge volumes -Pumpable liquid
Chemical -Compatibility -Long-term stability and
reliability
-Environmentally friendly
Economic -Cost <10 €/m3 -High construction cost -Low cost -Ultra-cheap storage
LHSMs Thermal -Suitable phase change temperature -Low thermal conductivity -High storage density in a -Enhancement of thermal
-Phase change enthalpy >200 kJ/kg -Different heat transfer in each short temperature range conductivity.
-Specific heat capacity in both phases physical state. -Constant operating -Higher thermal reliability.
>2000kJ/m3K -Low thermal stability and temperature
-Thermal conductivity in both phases >0.6 W/mºC reliability
-Thermal reliability >90% after 5000 cycles
Physical -Density > 1000 kg/m3 -Not pumpable -Greater design flexibility -Development of pumpable
-Low density variation -Volume change materials
Kinetic -Not subcooling -Subcooling
-Crystallisation
Chemical -Chemical stability after 5000 cycles -Phase segregation -Higher chemical stability
-Compatibility and security -Toxicity
-Corrosiveness
Economic -Cost <8 €/kg -High cost -Low-cost solutions
TSMs Thermal - Suitable charging/discharging temperature -Poor heat and mass transfer -High storage density - Improvement of thermal
-Volumetric storage capacity > 1000 MJ/m3 property under high-density -Negligible heat losses transfer capacity.
-Thermal transfer capacity condition -Knowledge of material
-Thermal reliability >90% after 5000 cycles -Thermal reliability behaviour under realistic
-Low volumetric storage conditions
capacity of prototypes -Higher storage capacity of
final solutions
Physical -Low operating pressure
Kinetic -Kinetic of reaction
Chemical -Chemical stability after 5000 cycles -Low chemical stability -Higher chemical stability
-Compatibility
Economic -Competitive cost -High cost -Cheap solutions
Following the above selection criteria for most promising solutions on the road to ZEBs , technicians can ensure the
optimum implementation of TES materials for improving the thermal performance and energy management of buildings.
Moreover, the existing drawbacks pointed out for each material group should be addressed from design strategies to
achieve a more effective integration. For instance, heat transfer rate of materials with low thermal conductivity can be
enhanced by using composite materials (metal shavings or metal powder embedded in pure PCM) or by means of
porous graphite matrixes or internal fins. Some critical issues highlighted above should be addressed in future R&D
efforts.
7. Conclusions
This paper reviews, from a critical perspective, recent advances on thermal energy storage materials and their
applications towards zero energy buildings. Thermal energy storage in the form of sensible and latent heat has been
identified as a very attractive strategy for high energy efficiency buildings. A careful assessment of available thermal
energy storage materials leads to the following conclusions:
 Water and underground materials stand as the most convenient materials, due to their high sensible heat storage
capacity and moderate thermal diffusivity. Water has a volumetric storage capacity of 250 MJ/m3 for heating
purposes (ΔT= 60 ºC) and 63 MJ/m3 for cooling applications (ΔT=15 ºC). Underground materials, such as rock or
dry and wet soil, can store approximately 108 MJ/m3 (ΔT= 50ºC). In addition, underground solutions benefit from
20
the insulation of soil, thus thermal energy is stored more efficiently as compared to above-ground solutions. Water
and underground material applications in solar energy storage solutions and demand-side management strategies,
yield an efficient reduction of energy consumption in buildings, leading to savings of over 30%. Nevertheless, these
materials require high storage volumes to meet annual heating demands. In addition, for long-term storage
applications, underground thermal energy storage systems in large-scale solar energy plants are not yet competitive
against fossil fuel systems, and only cover 3.2% of existing European district heating networks. Further research is
required to cut back costs to enhance competitiveness, mainly in areas with high solar availability. In addition, new
advances for heat loss reduction at short and long-term storage should be addressed through better construction
and insulation techniques.
 Today, there are more than 250 commercially available organic and inorganic latent heat storage materials.
Volumetric latent heat storage density of available organic and inorganic materials range from 100 up to 250 MJ/m3
and from 150 up to 430 MJ/m3, respectively. Phase change materials based on hydrated salts are considered as
the best choice due to their high volumetric latent heat storage capacity, moderate thermal conductivity
(approximately 0.6 W/mºC) and low-moderate cost. However, further considerations on long-term stability and
reliability, as well as other issues that may affect safety and feasibility, should be carefully assessed. Their
applications in free-cooling ventilation systems, solar energy storage solutions, and demand-side management
strategies are promising on the road to zero energy buildings with a potential for non-renewable energy consumption
reduction by up 90%. However, PCM cost can represent more than 75% of the system cost, and
charging/discharging periods, which affect the power capacity, are influenced by their low-moderate heat transfer
rates. Further research is needed to reduce investment costs, increase heat transfer rates by improving thermal
conductivity of materials (through new heat transfer enhancement techniques or new composite materials), and to
demonstrate cost-optimal scenarios for their implementation. In addition, new advances to improve thermal
reliability after a large number of thermal cycles (by more than 5000 for a lifespan of approximately 13-14 years)
should be addressed.
 Regarding thermochemical energy storage materials, and in spite of the potentially high energy density achievable
(up to 1510 MJ/m3) and long-term storage ability, there is no available material that satisfies all requirements for a
viable deployment in building applications. The investment cost of most of the materials successfully tested at the
laboratory scale ranges from 350 to 3600 €/m3. In addition, thermochemical solutions require different tanks and
heat exchangers that reduce the effective storage density, typically by more than 50% and increase final costs,
which should be carefully addressed for small-scale applications. Additional research efforts must be pursued to
optimise operation conditions, storage cycle efficiency, material cost and system designs.
Acknowledgments
This work was supported as part of the ClimACT project (SOE1/P3/P0429EU) within the Interreg Sudoe Programme,
funded by European Regional Development Funds. The authors gratefully acknowledge the financial support of the
Spanish Ministry of Education, Culture and Sport via a pre-doctoral contract granted to Francisco Jesús Lizana Moral
(FPU14/06583); and the project “Hybrid thermochemical storage of concentrated solar power” supported by the Spanish
Government Agency Ministerio de Economia y Competitividad and FEDER funds (Contract CTQ2014-52763-C2-2-R).
21
Appendix A. Properties of commercially available PCMs from main existing companies
Table A1. Commercially available PCMs from Rubitherm [70].
Properties (solid/liquid)
Volumetric Latent Volumetric
Company Type Material Melting Thermal Specific heat
Density heat heat of latent heat
temperature conductivity capacity
(kg/m3) capacity fusion capacity
(ºC) (W/mºC) (kJ/kgK)
(kJ/m3K) (kJ/kg) (MJ/m3)
Rubitherm Organic PCMs RT-9 HC -9 880/770 0.2 2 1760 250 220
Rubitherm Organic PCMs RT-4 -4 880/760 0.2 2 1760 180 158
Rubitherm Organic PCMs RT0 0 880/770 0.2 2 1760 175 154
Rubitherm Organic PCMs RT2 HC 2 880/770 0.2 2 1760 200 176
Rubitherm Organic PCMs RT3 HC_1 3 880/770 0.2 2 1760 190 167
Rubitherm Organic PCMs RT69HC 69 940/840 0.2 2 1880 230 216
Rubitherm Organic PCMs RT90 HC 90 950/850 - 2 1900 170 162
Rubitherm Inorganic PCMs SP-21 -21 1300/1200 0.6 2 2600 285 371
Rubitherm Inorganic PCMs SP-13 -13 1250/1150 0.6 2 2500 300 375
Rubitherm Inorganic PCMs SP-7_2 -7 1300/1200 0.6 2 2600 290 377
Rubitherm Inorganic PCMs SP5 5 1350/1400 0.2 2 2700 170 230
Rubitherm Inorganic PCMs SP21 E 21 1500/1400 0.6 2 3000 170 255
Rubitherm Inorganic PCMs SP25 E2 25 1500/1400 0.6 2 3000 180 270
Rubitherm Inorganic PCMs SP29 Eu 29 1550/1500 0.6 2 3100 200 310
Rubitherm Inorganic PCMs SP31 31 1350/1300 - 2 2700 210 284
Rubitherm Powder PX15 15 650 0.2 2 85 55
Rubitherm Powder PX82 82 690 0.1 1.6 105 72
Rubitherm Granules GR42 42 800 0.2 2 55 44
Rubitherm Granules GR82 82 800 0.2 2 55 44
22
Table A2. Commercially available PCMs from Climator [71].
temperatur conductivity capacity*
(kg/m3) capacity* fusion capacity
e (ºC) (W/mºC) (kJ/kgK)
Climator Salt hydrates ClimSel C-21 -21 1100 1.45/0.33 285 314
Climator Salt hydrates ClimSel C-18 -18 1150 2.17/0.56 288 331
Climator Salt hydrates ClimSel C7 7 1400 0.78/0.59 123 172
* Not provided
Table A3. Commercially available PCMs from Cristopia Energy Systems [72,73].
temperatur conductivity* capacity*
Cristopia Energy Systems - IN.15 -15.4 602 277 167
Cristopia Energy Systems - IC.00 0 558 312 174
Cristopia Energy Systems - AC.00 0 560 311 174
Cristopia Energy Systems - AC.27 27 867 185 160
* Not provided
Table A4. Commercially available PCMs from PCM Energy [74].

Volumetri Latent Volumetric
Density c heat heat of latent heat
temperature conductivity capacity
(ºC) (W/mºC) (kJ/kgK)
PCM Energy Hydrated salts LatestTM -50 -50 1300 325 423
PCM Energy Hydrated salts LatestTM 0 0 1000 335 335
PCM Energy Hydrated salts LatestTM 18T 18 1500 175 263
PCM Energy Hydrated salts LatestTM 32S 32 1400 210 294
PCM Energy Hydrated salts LatestTM 89 89 1500/1600 145 218
23
Table A5. Commercially available PCMs from PCM Products Ltd [75].
temperatur conductivity capacity
PCM Products Eutectic PCMs E0 0 1000 0.58 4.186 4186 332 332
PCM Products Eutectic PCMs E-2 -2 1070 0.58 3.8 4066 306 327
PCM Products Eutectic PCMs E-3 -3.7 1060 0.6 3.84 4070 312 331
PCM Products Hydrated salts S117 117 1450 0.7 2.61 3785 160 232
PCM Products Organic PCMs A164* 164 1500 - 2.42 3630 290 435
PCM Products Organic PCMs A155 155 900 0.23 2.2 1980 100 90
PCM Products Organic PCMs A118** 118 1450 - 2.7 3915 340 493
PCM Products Organic PCMs A60H 60 800 0.18 2.15 1720 212 170
24
PCM Products Solid-solid X25 25 1055 0.36 1.63 1720 110 116
Table A6. Commercially available PCMs from BASF (Micronal PCM) [76].
BASF - Micronal PCM Dispersion DS 5000 26 - 45
BASF - Micronal PCM Pulver DS 5001 26 250-350 110 33
* Not provided
Table A7. Commercially available PCMs from RGees. savENRG™ [77].

Rgees Hydrated salts PCM-HS26N -26 1200 205 246
Rgees Hydrated salts PCM-HS22P 22 1540 185 285
Rgees Organic PCMs PCM-OM06P 5.5 735 260 191
Rgees Organic PCMs PCM-OM18P 18 735 260 191
* Not provided
25
Table A8. Commercially available PCMs from Entropy solutions (PureTemp) [69].
PureTemp Organic PCMs PureTemp -37 -37 880 145 128
PureTemp Organic PCMs PureTemp 1 1 1000 301 301
* Not provided
26
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* Corresponding author. E-mail address: [email protected]

Figure 1. Building applications based on thermal energy storage.

3. Sensible heat storage materials

3.1. Classification and characterisation parameters.

Thermal effusivity = √ · 𝜌 · 𝑐𝑝 (W√𝑠 /𝑚2 𝐾) Eq. 3

3.2. Evaluation of available sensible heat storage materials.

Figure 2. Common materials for sensible heat storage in building applications.

4. Latent heat storage materials

4.1. Classification and characterisation parameters.

Figure 3. Classification of solid-liquid PCMs.

4.2. Assessment of available latent heat storage materials.

4.3. Potential building applications based on PCMs towards ZEBs.

5. Thermochemical energy storage materials

5.1. Classification and characterisation parameters

Figure 5. Classification of TSMs for building applications.

𝐶1 𝐶2 + 𝐻𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡 ⇒ 𝐶1 + 𝐶2 ⇉ 𝑠𝑡𝑜𝑟𝑎𝑔𝑒 ⇉ 𝐶1 + 𝐶2 ⇒ 𝐶1 𝐶2 + 𝐻𝑒𝑎𝑡 𝑜𝑢𝑡𝑝𝑢𝑡 Eq. 5

5.2. Evaluation of available thermochemical storage materials.

Finck et al. [101] Netherlands

Water (sensible storage) 0-250

Concrete (Sensible storage) 0-95

Table A4. Commercially available PCMs from PCM Energy [74].

Table A7. Commercially available PCMs from RGees. savENRG™ [77].

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