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ASSESSMENT REPORT
Presented to:
May 2013
Prepared by:
SAIC Canada
V08 PUBLIC
STATEMENT OF LIMITATIONS
Warranty:
SAIC Canada makes no representation or warranty with respect to this report other than the
work was undertaken by trained professional and technical staff in accordance with generally
accepted engineering and scientific practices current at the time the work is performed.
(SAIC Canada)
COMPACT THERMAL ENERGY STORAGE TECHNOLOGY ASSESSMENT STUDY CM002478
TABLE OF CONTENTS
Statement of Limitations ............................................................................................................. ii
1 Introduction ......................................................................................................................... 3
2.2.4.4 Liquid and solid materials, fixed bed and agitated bed reactors .....................12
3.1.8 Fraunhofer Institute for Solar Energy FhG-ISE, Freiburg, Germany ..................20
3.1.10 Bavarian Center for Applied Energy Research ZAE Bayern, Munich, Germany .20
3.1.14 TNO, The Netherlands Organisation for Applied Scientific Research ................21
3.1.16 Otto von Guericke University Magdeburg, Institute of Chemistry (ICH), Germany
22
3.2.2 Virginia Polytechnic Institute and State University, Blacksburg, Virginia, USA ...23
th
3.3.3 The 7 Framework Programme of the European Union .....................................27
6 Recommendations .............................................................................................................43
1 INTRODUCTION
SAIC Canada is pleased to have this opportunity to work with the City of Pickering and
Natural Resources Canada to prepare this compact thermal energy storage technology
assessment report for future consideration of R&D potential in this technology area.
Seasonal thermal energy storage has been successfully demonstrated around the
world, including at the Drake Landing Solar Community in Okotoks, Alberta
(www.dlsc.ca). Although successful, to date these demonstration projects have
involved innovative underground thermal energy storage (UTES) technologies that
would appear to have limited application (retrofit) in the existing building stock in
Canada under the current energy price level. Different solutions are needed to address
the challenges of space heating in this country particularly for the vast majority of
Canadians that live and work in existing buildings.
Canada has the ideal climate for the application of seasonal thermal energy storage
technologies. There has been significant effort put towards the research and
development of compact thermal energy storage technologies in Europe with the aim of
eventually developing a product that could be installed in the retrofit market that would
be able to store summer heat and retrieve it for winter use.
The basic principle is simple: a suitable chemical compound is heated to the point
where the chemical dissociates into two (or more) other compounds. When these
compounds are recombined, they re-form the original compound and discharge heat in
the process. The individual compounds can be stored at ambient temperatures for
indefinite periods, without any of the heat energy being lost. The concept is
represented by the diagram (Figure. 1) shown on next page.
The challenges for building space heating in the winter will become more serious
should fossil fuel prices rise significantly in the future. Research efforts in Europe on
compact thermal storage solutions are showing some signs of promise. However,
many technical challenges are still present and commercialization is still some time off
in the future. The solution would have to be appropriately scaled to integrate easily into
the existing heating systems of our buildings and to meet a number of other market
requirements.
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Figure 1: Schematic of thermochemical energy storage. Top: in the charging phase, heat
is provided to the thermochemical material that subsequently splits into its components.
Middle: the two components can be stored separately, virtually without energy loss.
Bottom: if heat is needed again, the two components are brought together and the
reaction generates the heat.[Source: ECN]
The City of Pickering has partnered with Natural Resources Canada to conduct an
assessment of the status of the latest research in the field of compact thermal energy
storage. This assessment will provide valuable input for Canadian researchers and
policy makers to help them gain a better understanding of this emerging concept and
the potential applications in Canada. The specific objective of this study is to assess
the likelihood that an increased research effort in Canada on thermochemical energy
storage (i.e. compact heat storage) would lead to the development of a cost-effective
solution for using solar seasonal energy storage to heat Canadian homes.
Section 2 of this report defines the scope of the reported research work and the range
of technologies being reviewed. The latest research efforts and outcome are
summarized in Section 3. Section 4 captures the current and recent R&D effort in
compact thermal energy storage technologies in Canada. Section 5 is a discussion of
the market opportunities and challenges in Canada for the potential commercialization
of the compact thermal energy storage concept. Included in Section 5 is a list of
technical challenges for the technology towards commercialization. Recommendations
for a possible R&D direction for Canada are included in Section 6.
The authors would like to acknowledge the funding provided by the ecoEnergy
Innovation Initiative and the in-kind support provided by the City of Pickering in making
this study possible.
Work on thermochemical storage materials has been the main focus for the international
research community on compact thermal energy storage. Thermochemical storage also
comprises sorption technologies and therefore some developments in the field of materials and
technologies for sorption heat pumps are also included in the scope of the reported research.
This section also serves as the background material on the compact thermal energy storage
technologies.
The application for the stored thermal energy is to be used for building space heating.
Therefore, the temperature at which the heat has to become available after it is stored is
between 20 and100 degrees C.
Europe and the USA are considered in this section of the report, with possibly some references
to important groups or work elsewhere.
Thermal storage technologies can be subdivided into three classes. These are sensible heat,
latent heat, and sorption and thermochemical heat.
Figure 2: Three graphs of the heat stored in a volume of thermal energy storage material
as a function of the temperature of the material. Left: sensible heat storage; Middle:
latent heat storage; Right: sorption or thermochemical heat storage.
The first class is storage through sensible heat. Here the heat is stored in a material using its
specific heat. This is the oldest and most used technology for storing heat. For temperatures
below 100C water is used mainly as the storage med ium. Water is a very suited storage
material as it has a high specific heat, it is abundantly available and it is non-toxic and cheap.
Water-based heat storage devices range from very small (i.e. domestic boilers) to very large
(i.e. aquifer heat storage systems). For temperatures higher than 100C pressure devices or
steam vessels are needed for water which are very expensive. Therefore, materials other than
water are preferred at these temperatures. For intermediate temperatures up to 400C heat is
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stored in ceramic materials or natural or synthetic oils. At even higher temperatures heat is
mostly stored in concrete, ceramics or molten salts.
The second class is latent heat storage. Here, heat is stored in the phase change of a material,
either from solid to liquid or from liquid to gas. The solid to liquid phase transfer is mostly used.
The typical property of latent heat storage is that heat is stored in a very narrow temperature
range. Consequently, this technology has specific advantages in applications that use heat with
only small temperature differences.
Sorption materials have a tendency to take up vapour of certain other materials, for instance
water vapour. When taking up the vapour the bonding energy of the vapour molecules to the
material structure of the sorption material is released in the form of heat. The temperature at
which this heat is released is proportional to the strength of the bond. When the sorption
material does not change in structure due to the sorption process, it is called adsorption, when
the structure changes it is called absorption. Examples of adsorption materials are silica gel
and zeolites, while lithium bromide and ammonia are often used as absorption materials.
During the charging phase, heat is needed to overcome the (reversible) bonding between the
working fluid molecules and the molecules of the sorption material; thus, in this so-called
desorption phase, the sorption material is dried. When considering the gaseous working fluid, it
is convenient to distinguish between open and closed systems. In open systems, the working
fluid is then released to the environment. In closed systems, the working fluid is condensed, i.e.
the heat of evaporation is released to the environment, in the reverse process step of storage
discharge, heat has to be taken from the environment in order to evaporate the sorbate which is
then adsorbed on the sorption material. The physical principle is shown in the figure below.
Dry Liquid
Storage water
silica gel
This type of storage is called indirect storage, and it is not independent from the environment:
energy has to be released to the environment in charging mode and taken from the
environment in discharging mode.
Adsorption heat storages allow for nearly loss-free heat storage over a long period of time: After
charging, the storage tank can cool down to ambient temperature, but the adsorption enthalpy
stays stored for as long as the two components (sorption material and working fluid) are kept
separate.
The storage densities for silica gel are typically 180 kWh/m3, for synthetic zeolites typically
around 220 kWh/m3.
Figure 4: Examples of zeolite in different shapes and sizes: beads (several mm), pellets
(5-7 mm) and an extruded brick with channels (several centimetres).
Many adsorption materials exist in the market. Almost all of them have been developed for uses
other than heat transformation processes, e.g. gas drying, cleaning and separation. Several
commercial and non-commercial materials have been selected for use in prototype storage
applications. The properties of seven materials are shown below with the aim of presenting
typical representatives for each class of material. Two relatively new developments that are
interesting for heat transformation applications are also included. The data presented here are
based on measurements obtained at the Fraunhofer Institute of Solar Energy Systems ISE.
The zeolites 13X, NaCa 5A, SC Y 1/16 and the silica gels 127B and LE-32 are commercially
available products. The material labeled SWS-1L (selective water sorbent) is a mesoporous
silica gel that has been impregnated with CaCl2 solution. This gives the material an adsorption
characteristic that is a superposition of salt hydration and the adsorption in the silica gel pores.
In applications that use this product, care has to be taken in order to avoid direct contact with
liquid water as some of the salt may be washed out and go into solution leaving the
confinement of the pores which results in a degradation of the adsorption properties.
Functional Adsorption Material (FAM-Z02) is a zeolite based molecular sieve developed by
Mitsubishi Chemical Corporation aimed at the adsorption chiller market.
In the figure below, the differential enthalpy of adsorption of the seven sorption materials
described above is shown as a function of water uptake and for the temperature of 40C.
Integrating this curve from the lowest water content at desorption conditions to the highest
water content achieved at the end of the adsorption process gives the integral heat of
adsorption involved in the ad- or desorption process. It has to be noted that this heat does not
include the sensible heat of the material during the heating process.
As a mode of comparison of the different materials two operation scenarios were chosen for
which the integral heat of adsorption as stated above were calculated. The two operation
conditions are:
In the figure below, the columns are divided into the contribution of the evaporation enthalpy of
the water Hv and the binding enthalpy Hb.
From Figure 6, we can conclude that for all materials, the main contribution to the integral heat
of adsorption is the evaporation enthalpy. Higher contributions of the binding enthalpy come
along with higher desorption temperatures as it is the case for the zeolites. Furthermore, the
adsorbents FAM-ZO2 and SWS-1L show very high integral adsorption enthalpies.
Nevertheless, stability, and corrosion problems have to be taken into account for the SWS
material.
The figure also shows that commercially available adsorbents have relatively low integral heat
of adsorption. This means that the storage density is also quite low. In real applications, there
are additional losses from tanks, pipes and heat exchangers which further reduce the storage
density. Therefore, further materials research is needed to develop materials that offer high
enthalpy of adsorption and high uptake of adsorbents at low desorption temperatures.
Figure 6: Integral energy of adsorption for seven different sorption materials and for two
different operating conditions, from (Hadorn et al. 2005) Thermal energy storage for solar
and low energy buildings
In a chemical reaction, two materials react to form a third new material. In most formation
reactions, heat is released and these are called exothermal reactions. The heat is released at a
certain temperature, depending on the strength of the molecular bonds in the compound. In
principle, the reaction can be reversed. When the compound is heated above the equilibrium
temperature, it is split into the original reaction materials/ components again. In fact, the forward
and backward reactions occur simultaneously and the equilibrium can only be shifted towards
the forward reaction if one of the components is taken out of the reaction volume. This is the
case if one of the original components is a vapour: it vapourises and pushes the reaction
equilibrium forwards.
CHARGE
+ heat +
STORE
DISCHARGE
+ + heat
The temperature levels during the load/unload cycle depend on the materials, i.e. the nature of
the chemical bonds that are involved in the reactions. In general, lower temperature levels bring
about lower reaction enthalpies. The amount of energy that can be stored depends on
temperature and chemical and physical properties like number of bonds per volume,
massdensity, etc.
Even if a lot of potential reactions with a high amount of enthalpy are known from the chemical
industry, a practical thermochemical storage material (TCM) has to fit the conditions of the
desired application. In the case of heating support in the domestic environment these conditions
are: the material has to be reliable, safe, non-toxic, long lasting, inexpensive, and able to be
recycled.
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Examples of thermochemical materials are salt hydrates that react with water vapour, for
instance magnesium sulphate, or oxides of metals, that react with water to form the hydroxide
of the metal, for instance magnesium oxide/hydroxide.
The heat development during the use of heat stored by TCM depends on the kind of material
used, the charging reaction, and the dynamics of the discharge reaction (aggregation) itself. All
parameters involved can hinder the heat development either intended (in case of control) or
unintended (in case of technological limitation).
While a minimum temperature of the heat source is required during the recovery of the TCM as
described above, the situation during discharge is reversed. The higher the desired temperature
during a certain process, the more the reaction-equilibrium is shifted to the starting components
and reaction performance is lower. This reaction-equilibrium limits the usable temperature.
Additional temperature degradation may occur due to thermal losses to the ambient or inside
the reactor (in fixed bed reactors, for example).
As well as chemical reasons there are also technical reasons that can hinder reaction
performance. A prominent example is the hydration reaction of sorption material i.e. the
hydration of salt or zeolite during winter conditions: temperature and power of delivered heat
out of the storage apparatus is strongly dependent on the water content of the supplied air. The
lower the ambient temperature, the lower the vapour content of the supplied air. Optimization of
the materials cannot undergo this general limitation since a certain amount of water vapour is
needed either way. Additional components are required to enhance the vaporization like
borehole heat-exchangers, solar thermal assistance, or others.
Next to the compact storage materials, important system elements are the heat exchanger and,
in some cases, the reactor. These elements determine the power of charging/discharging and
the efficiency of the storage.
With thermochemical materials, not only the heat has to be transferred, but also material has to
be transported from the reaction volume to a storage volume. For this, reactors have to be
developed that provide the boundary conditions for the chemical reaction while exchanging heat
and transporting the original and produced materials to and from the reactor. The geometries
that can be used depend on the phase and structure of the materials. These can be completely
liquid, or solid particles suspended in liquid, or solid particles of various sizes. Especially with
non-liquid materials, reaction technologies have to be adapted from the chemical industry to the
typical situation for domestic-scale or utility-scale.
Below is an example of a possible system using a salt hydrate, for instance magnesium
sulphate or magnesium chloride, to store solar thermal heat for a season.
During the charging phase of a storage system, energy from a heat source is needed to
overcome the bonding between the (solid or liquid) sorption material and the working medium.
The working medium (gaseous) is extracted by thermal energy at typical temperatures and can
be released to the ambient (open systems) or stored (closed systems) in condensed form.
Another distinction can be made if all energy, also from condensation, is stored or condensation
energy is released (Concepts are sometimes named direct storage or indirect storage). After
release, the storage material (sorbent) loses its sensible heat, cools down to ambient
temperature and is stored in a moisture-tight reservoir to preserve the charging state.
For applications of long-term or seasonal storage, in general water is used as the sorbate as it
can be released to the ambient air without environmental problems. The reverse step, the
discharge of the storage, takes place in winter and it is necessary to collect water vapour from
the ambient in open systems for this process. Closed systems would either use parts of the
stored enthalpy to evaporate water (closed-direct storage systems) or thermal energy from the
ambient at low winter temperatures to evaporate water (in closed-indirect storage systems) in a
separate step prior to the adsorption reaction.
The advantage of open and closed-indirect systems is that they can reach in principle higher
energy densities than closed-direct systems. Since thermal power and discharge temperature
strongly depend on the amount of available vapour these systems are more difficult to realize
for practical applications because vapour content of the ambient air and evaporation rates are
low in winter.
2.2.4.4 Liquid and solid materials, fixed bed and agitated bed reactors
Due to the nature of different materials, liquid as well as solid TCMs can be utilized. In liquid or
mixed liquid-solid TCM, heat of dilution and heat of solution can be utilized for storage purposes
while heat of reaction (for fusion and dissociation), heat of absorption, heat of hydration, and
heat of hydrogenation are possible temperature controlled reactions in solids.
Figure 10: Example of prototype bulk reactor (ECN, left) and flow reactor (ITW, right).
The technical principle of the reaction with solids was restricted to fixed bed reactors in the
past. The fixed bed apparatus is relatively simple (tank or container) and heat release is
connected to diffusion and conduction characteristics of the materials. Applications are
therefore restricted to small or low temperature applications. In the case of high temperature
applications, non-granular TCM, or for even larger systems, the concept of a small, controllable
reactor with energy and mass transfer is used. Pumping of liquids or gases as well as
transportation of solids or powders is then part of the reactor concept and technical realization
would be difficult.
The range of possible applications for the purpose of heat storage using thermochemical
reactions is very wide. Starting from temperatures of around 70C (salt-hydrates and
solutions), to typical dissociation processes of hydroxides at around 200-350C, ammonia
dissociation at 400-700C, until around 2000C for solar thermal processes in tower plants (i.e.
for the production of solar fuels).
The amount of stored energy per unit volume is the key indicator for the quality of heat storage.
The energy density of sensible heat storage is limited by the maximum applicable temperature
and the specific heat capacity of the storage material. Water, for example, is able to absorb
about 210kJ per litre or 58 kWh/m3 while being heated from 40 to 90C. Water in a tan k can
store heat when the tank is thermally insulated, and taking into account the space for insulation
realistic energy densities are in the range of 30-40 kWh/m. For example a common buffer-tank
with a volume of 1000 litres and 10 cm of thermal insulation can store 58 kWh and has an
effective volume of 1.6m3 and an energy density of 36kWh/m.
If thermochemical storage (TCS) is compared to water stores, the effective energy density has
to take into account the space for the apparatus, storage for charged and discharged material,
and all other components. Nevertheless TCS systems have not been realized yet, and practical
data is therefore rare. Actual development projects report experimental data of laboratory scale
systems with energy densities that are three times the storage density of water.
There is a distinctive upper limit of the storage density given by the physical constant of the
reaction enthalpy. The reaction enthalpy is the maximum energy that can be transferred during
the reaction. In reality the reaction performance is described by the so called free enthalpy
which is a constant that is always less than the reaction enthalpy and controlled by temperature
and entropy transfer (i.e. the reaction conditions). Further reduction of usable energy amounts
happens due to losses of sensible heat to the ambient and heat exchanger losses between
source and sink. In general, low efficiency during charging is acceptable since charging
happens in (summer) periods with excessive (solar) thermal energy. Energy efficiency and
temperature development during discharge is the main criteria for the applicability of storage
systems.
The lower limit of TCS storage densities in practice is given by heat storage with other
(cheaper) technologies. It was proposed that in order to ensure the competitiveness of TCS
concepts the TCS storage densities need to be in the range of at 4-8 times higher energy
density than water (Weiss et al. 2007).
The selection of a TCM for a certain application depends on the regeneration temperature
levels needed, desired temperature levels of usage, technical requirements like energy
demand, power, number of load cycles during lifetime, technical infrastructure and costs of the
storage materials. Salt solutions, salt hydrates, ammonia, hydroxides, carbonates and metals
are promising candidates for future thermochemical storage applications. Some materials are
subject to intensive research for the purpose of heat storage applications temperature levels
(Bales et al. 2008). Examples of experimental data are given in Table 2. The numbers for
energy density are theoretical values for pure materials under ideal reaction conditions
(thermodynamic equilibrium). Practical values for the energy density have to take into account
the limited efficiency of every sub-process and the additional demand of space for storage
apparatus and technical infrastructure.
Iron Hydroxide Fe(OH)2 FeO+H2O 630 kWh/m 150C (Visscher et al. 2004)
Iron Carbonate FeCO3 FeO+H2O 743 kWh/m 180C (Visscher et al. 2004)
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Calcium Hydroxide Ca(OH)2 CaO+ H2O 1260 kWh/m 550C (Schaube et al. 2009)
Salt hydrates in general are promising candidates for heat storage in the low temperature range
because of their relatively low bonding force of the associated water molecules and
subsequently low dehydration temperatures. Additionally the physical process mechanisms of
salt hydration are very similar to desorption processes in molecular sieves and therefore
combined materials like composites zeolite-salt can be developed.
The hydration reactions of different types of dehydrated salts (MgSO4, CuSO4, Al(SO4)2) have
been investigated. Magnesium-sulphate-monohydrate (MgSO4*H2O) for example, has a high
potential as a chemical storage material (Essen et al. 2009) with the involved condensation heat
of water vapour, a theoretical storage density 633 kWh/m can be obtained. This is about 11
times higher than the storage density of a water store with the same volume (at T = 50 K). In
practical applications, limitations have to be accepted. A material developed on the basis of the
mentioned salt hydrate MgSO4 together with zeolite as a mechanical frame show the capability
to store 166 kWh/m and perform a 25 K temperature lift while hydrated (Hongois et al. 2010).
Nevertheless the utilization of salt hydrates for the purpose of heat storage show material-
related problems:
Structural changes: solid absorption materials undergo structural changes during
absorption (changes in volume, rheological behaviour). This can result in
degradation and failure of the storage material.
Phase change: During the desorption (heating) process the salt can solute in leaking
crystal water (incongruent melting). Salt solutions can cause corrosion and
mechanical damage to the system.
Corrosion: Suitable materials for construction and practical tests of reliability over
long periods (for lifetimes of 20-30 years).
A large number of research institutions are participating in the current IEA Task 42/24 on
compact thermal energy storage. This research network has devoted significant resources
towards the development of this technology thus far. The areas of research covered and the
participating institutions are summarized in the table below. Key contacts at the research
institutions, topics of investigation and their research aims are summarized in this section.
Topics/materials investigated: Seasonal storage, using composite materials (salt hydrate with
zeolite); reactor design and system design.
Project aims, funding: The activities started with the Monosorp project, aiming at designing a
concept for seasonal thermal storage based on sorption materials. This project ran from 2004
to 2008. Then a project was started that was aimed at developing better sorption storage
materials, by combining them with a salt hydrate. This project was nationally funded.
In 2012, ITW will co-operate in the EU funded program COMTES, working on the further
development of the seasonal heat storage, based on composite materials.
Topics/materials investigated: Salt hydrates and composites; bulk reactor design; system
modelling and design.
Project aims, funding: ECN has been working on a long-term R&D program on compact
thermal energy storage since 2003. A large part is funded from their own programming money,
and part through national and international R&D projects. In 2004, a first broad material study
was performed on the possible candidate materials for compact storage at temperatures that
can be provided by solar thermal collectors. Initially, magnesium sulphate was chosen as the
development material. It was found that this material had poor discharging properties and in
2009 a switch was made to magnesium chloride. Recently, work was done to find carrier
materials for the magnesium chloride to prevent it from liquefying when a relatively large
amount of water vapour is taken up. Since 2010, reactor design, engineering and testing work
is being performed on prototype reactors of increasing size.
Project aims, funding: General aim of the work is to develop new materials for thermal energy
storage. Focus is on zeolites and their modification to improve their storage properties. In the
last years, work has been focused on developing synthesis methods for zeolites that provide
better possibilities to form granules of complete zeolite material, without any binder, and on
developing composite materials consisting of zeolites as carrier material and a salt hydrate
impregnated in the zeolite as the active material. The work is performed on national and
international funded projects.
Project aims, funding: The work at EdF was started with the PhD study of Stphanie Hongois
from 2007 to 2011, working on both material and system development. The work is in
collaboration with the University of Lyon. A composite material of zeolite with magnesium
sulphate was investigated, working on the best fraction of salt hydrate in the carrier material.
System simulations were performed.
Project aims, funding: Synthesis of new sorption materials and composites in order to arrive
at better thermal energy storage properties. Funding was through national and international
projects. Project names: a) New micro- and mesoporous materials for sorption, b) New
composites based on mesostructured metal silicate and salt hydrate CaCl2.
Topics/materials investigated: Natural zeolites for seasonal thermal storage, reactor design.
Project aims, funding: In 2012, ASIC will start an Austrian funded project aimed at developing
a prototype seasonal thermal storage with a novel reactor and using natural zeolites as active
storage material. The project has a 3 year duration.
Project aims, funding: The district heating system modelling work is done in a nationally
funded project. In 2012, AIT will start on an EU funded collaborative project SOTHERCO (see
3.3.3)
Project aims, funding: The work is done in the framework of several nationally funded
projects.
Project aims, funding: Work is being done in the internationally funded project Thermal
Battery, with the aim to develop materials and systems to store heat for a cogeneration unit at
intermediate temperatures. The project started in 2011.
3.1.10 Bavarian Center for Applied Energy Research ZAE Bayern, Munich,
Germany
Project aims, funding: The work is being done within national and international projects. A
large part is development work for industry.
Project aims, funding: The work is partly funded by the university and partly from the Dutch
ADEM program (Advanced Dutch Energy Materials).
Project aims, funding: Two consecutive projects are carried out, both nationally funded.
Project aims, funding: Nationally and internationally funded projects and projects for industry.
Project aims, funding: Projects are performed with their own funding. Starting in 2012, TNO
will work in the EU funded project MERIT, of which it is a coordinator.
Project aims, funding: Development in nationally funded projects (Modestore). AEE will
coordinate the EU funded project COMTES, starting in 2012.
Project aims, funding: Funding from the university and from national programs.
Focus of the groups work is on development, synthesis and characterisation of catalysts,
thermo-electric materials, thermal storage materials and other functional materials. Part of the
research is dedicated to material development for thermochemical heat storage, especially
porous materials (zeolites). Recently, work was done on the production of zeolite metal
composites for heating and cooling applications. Several papers were published on the
synthesis of zeolites on substrates. More recent work seems to be focused on improving
material performance through the elimination of binders plus other non-thermal applications
such as thermoelectrics and optics.
Topics/materials investigated: Research in reactor and heat exchanger design for adsorption
storage systems with silica gel or zeolites as a storage medium.
Project aims, funding: The development work was performed through a series of nationally
funded projects. EMPA will start in 2012 with a follow up project, as part of the EU funded
COMTES project.
Project aims, funding: The study was a PhD work of Posern. Funding for a follow-up study
has been applied for.
Note: although this research group is not working with thermochemical technology, it is included
because they specifically aim at seasonal storage of solar thermal energy in a more compact
way.
Project aims, funding: The overall aim of the research is to develop a seasonal heat storage
which will be suitable for solar heating systems, which can fully cover the heat demand of low
energy buildings under Danish conditions. Work was done in nationally funded projects. DTU
will start in 2012 with the EU funded project COMTES.
Topics/materials investigated: Liquid sorption material for heat pump and heat storage, using
crystallisation.
Project aims, funding: Development of the process and technology since 2006. Knowledge
bought by Climatewell and further developed into commercial solar thermally driven
heating/cooling machine with storage possibility.
Project aims, funding: Numerical design tool for thermochemical energy storage systems,
Industry/Internally funded, small projects
The IEA has two programs that have activities on thermal energy storage. These are the Solar
Heating and Cooling (SHC) program and the Energy Conservation through Energy Storage
(ECES) program. They started a joint activity, Task 42/24 on Compact Thermal Energy
Storage: Material Development for System Integration.
Task 42/24 is a worldwide cooperation of institutes, universities and some industries (from over
15 countries including the US, Canada, Japan) with the target to research and develop
- materials
- methods and tools
- standard proposals
- applications
for compact thermal energy storage technologies. The project time frame is 2009 to 2013.
The project leaders (operating agents) are: Wim van Helden (NL) and Andreas Hauer (DE)
Funding: by national funding programs
From the start of Task42/24, there has been a lot of interest from groups all over the
world and there are more than 60 experts from over 40 organisations contributing to the
collaborative work in the Task. As is usual in IEA Tasks, the collaborators both bring in
their own work and collaborate on common Task activities. In the following, a brief
description will be given of some of the development work in the collaborating
organisations and of the work on the Task deliverables.
Cooling
Heating / DHW
Theoretical Limits
Figure 11: IEA SHC/ECES Task 42/24 Scope. [source: IEA Task 42/24]
Theoretical limits
o The materials related work is subdivided into 4 groups: material engineering and
processing, material test and characterisation, numerical modelling and
apparatus and components.
o Within material engineering, the goal is to better understand the principles
underlying the storage characteristics of materials and to use this knowledge to
develop material with improved storage characteristics. Work is done on
improving zeolites and other mesoporous materials, on metal-organic
frameworks, on salt hydrates and on composite materials consisting of zeolites
and salt hydrates. As the performance of the materials is very much dependent
on the storage apparatus and the complete thermal system, the development is
done in close collaboration with the other groups.
o Unlike the present storage materials based on sensible heat storage, the
characteristics of storage materials based on phase change, sorption or
thermochemical principles are not easy to determine. The test and
characterisation working group is developing and testing methods with which the
parameters of a material can be measured accurately and reproducibly. A round
robin test is set up in which a number of storage material samples are tested in
different labs and the results compared. The first comparison already revealed
large differences and led to a better definition of the testing procedure. In a
dedicated workshop, a group of experts performed a number of characterisation
experiments on measurement equipment of different suppliers. This not only
helped to understand the brand-specific testing conditions and sensibilities, but
also served to further train the experts in the characterisation techniques.
o In the numerical methods group, work was done on an overview of the different
numerical simulation methods that are available, on the molecular level as well
as on the grain and system level. At present, the group is gathering measured
data sets from the Task consortium that will be used to validate the numerical
models that are being developed by several of the partners.
o The apparatus and components group has a goal to describe the methods with
which a storage device, composed of storage material, the container and all the
components for heat and mass transfer and control, can be optimally designed.
As a basis, the design methods that are followed by the group partners are
Research and development projects in a broad range of fields is supported by the European
Union in their so-called Framework Programme. At the moment the 7th Framework Programme
is running from 2008 to 2013. Energy is one of the main themes of the programme. Every half
year, calls for proposals in different fields are published. In spring 2011, a call with topics on
Thermal Energy Storage was issued. This led to four large projects on CTES R&D that will start
in the course of 2012. Three projects are aimed at system development and one at material
development. The EU support for these projects is around 12 million Euros.
The projects are: MERIT (led by TNO, The Netherlands), SOTHERCO (led by ESE, Belgium),
COMTES (led by AEE, Austria) and SAM.SSA (on materials development, led by University of
Bordeaux, France).
3.3.4 Germany
The German materials research for Task 42 is co-ordinated by PTJ in Jlich; Basic research
can be funded through the Schwerpunktprogramm of the DFG. In July 2011, a large call for
proposals on storage (electrical and thermal) technologies was issued. The estimated budget
for thermal storage projects is 30 M .
Compared to the R&D effort demonstrated in European countries, the Canadian effort
has been relatively small. However it should be noted that progress has been made in
Canada in this subject area. Furthermore, there is research capacity and expertise to
carry out applied R&D for the potential commercialisation of the compact thermal
energy storage technologies. The main areas of research expertise and capacities are
summarized below.
University of Ottawa (U of O)
Areas of investigation: Thermal energy storage using compact thermal energy storage
materials
Researchers, facilities and laboratory support: Dr. Tezel is a chemical engineer and
has graduate students in the chemical engineering department conducting research at
the graduate level. U of O has laboratory space and expertise in developing laboratory
scale test equipment.
Areas of investigation: thermal energy storage systems analysis and optimization and
mechanical engineering aspects of thermal energy storage integration with building
HVAC systems. In addition, factors affecting system efficiency and performance have
been reviewed and analysed.
Researchers, facilities and laboratory support: laboratory space (bench and fume hood)
is available for lab test work. Research is typically conducted by graduate students and
in partnership with industry.
Accomplishments: Active participation in IEA Annex 34 under the IEA Heat Pump
Programme. Dr. Hosatte completed her PhD studies in chemical heat pump
technologies and had worked with several international leading researchers in this area
in the 90s.
Researchers, facilities and laboratory support: Varenne lab has advanced laboratory
space for materials testing and systems development. Full time researchers are
available to conduct research work.
CANMETEnergy has a well established research group focused on the R&D of solar
thermal technologies for the Canadian market. This research group has championed
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COMPACT THERMAL ENERGY STORAGE TECHNOLOGY ASSESSMENT STUDY CM002478
the technology transfer and implementation of the borehole thermal energy storage
(BTES) technology for the Canadian market.
As an indicative estimate, Canada has over 13 million homes and over 130,000
commercial and institutional buildings as the existing building stock. The market for
new home and building construction is strong in Canada but the new construction is
only a very small fraction (in the order of 1-2% per year) of the existing buildings. The
existing building stock is based mainly on fossil fuel energy source for space heating.
This represents a very large potential for innovative product commercialization utilizing
compact thermal energy storage technologies.
The energy requirement for space heating for an average Canadian home is in the
order of 60% of the total home energy usage. This will present a major challenge for
Canadian homeowners as the cost of fuel increases in the future. For a number of
remote regions using heating oil as the main heat source, the cost of heating oil is
already very high. This is starting to cause financial pressures on some families,
especially those with low and/or fixed incomes.
Figure 12: Canadian Home Average Energy Use. [source: NRCan End-Use Energy
handbook]
In addition, as can be seen from the chart below, over 65% of Canadian homes are
heated by furnace or boilers using a forced-air or hydronic system. Upon further
analysis, one can see the forced-air or hydronic heating systems powered by furnace or
boilers are mainly in the province of Ontario and the Prairie provinces.
The review on compact thermal energy storage technologies reported in earlier sections
shows a preference for technology integration with forced-air or hydronic building
heating systems. This points to the province of Ontario and the Prairie provinces as the
primary markets for potential technology implementation. (See the following two
charts.)
Figure 13: Type of Heating Systems for Canadian Homes. [source: Office of Energy
Efficiency, Energy Use data Handbook Tables]
Figure 14: Canadian Home Heating System Technology. [source: Office of Energy
Efficiency, Energy Use data Handbook Tables]
Approximately 60% of Canadian homes are over 20 years old and the older homes
account for about 70% of our total space heating load. The total space heating and
domestic hot water use for homes is estimated to be approximately 20% of Canadas
total greenhouse gas (GHG) emissions per year. As the types of heating systems
constructed for the home ultimately dictate the type of energy source (fossil fuel in most
cases) used for heat, we are literally stuck with this dependency on fossil fuel for
building operation unless we can develop an alternate method for space heating. As
the age of the buildings and homes increase, this will become a more urgent problem if
our society is serious about the reduction of greenhouse gas emissions.
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Figure 15: Space Heating Usage as a Function of Building Vintage. [source: Office
of Energy Efficiency, Energy Use data Handbook Tables]
It was discussed in Section 1 of this report that Canada has ideal climate conditions for
solar seasonal thermal energy storage. The above observations coupled with the
Canadian climate conditions provide a unique opportunity for the consideration of
alternate building space heating technologies, including compact thermal energy
storage technologies, if proven practical.
1. If a product is available 5-7 years from now, what features would convince you to
include the product in your offerings in the retrofit market?
2. What would you say the challenges and potential barriers might be for the
consumers to accept this new technology?
3. What performance standards or measures you would like to see on the compact
thermal energy storage technology for you to use and communicate with your
customers?
In general the workshop participants expressed a high level of interest about the
technology and its potential application in the Canadian housing market. Many
concerns were also raised and documented. Summaries of the workshop discussions
are presented below under each question.
1. If a product is available 5-7 years from now, what features would convince you to
include the product in your offerings in the retrofit market?
2. What would you say the challenges and potential barriers might be for the
Economics.
Perceived complexity.
Status quo is easy - new technology has to offer very strong benefits for
change.
3. What performance standards or measures you would like to see on the compact
thermal energy storage technology for you to use and communicate with your
customers?
Willing but prefer to start with limited test and reasonable scale.
From this short workshop, it was clear that although the interest expressed by the
stakeholders was high, the workshop participants understood the challenges and
barriers for bringing the compact thermal energy storage technology concept to market
are real and not easily overcome.
As discussed in Section 2, three main types of thermal energy storage have been
referenced:
Sensible heat
Latent heat
The focus of this report is on the third type, sorption or thermochemical heat.
In the past 30 years, there have been several periods in which there was an increased
activity in the research and development of novel thermal storage technologies. The
latest wave started around 2004 and is being carried on by the research groups that
were active in the IEA SHC Task 32 and are active now in its successor, Task 42/24. In
the 8 years since 2004, progress has been made on material development as well as
on system development.
A large portion of the research work has been performed by research institutions in
Germany, Austria, France and the Netherlands. Other participating countries include:
Slovenia, Switzerland, Denmark and the United States of America.
Many adsorption materials exist in the market. Almost all of them have been developed
for uses other than heat transformation processes, e.g. gas drying, cleaning and
separation. Several commercial and non-commercial materials have been selected for
use in prototype storage applications. Test results showed that commercially available
adsorbents have relatively low integral heat of adsorption. This means that the storage
density is also quite low.
Two relatively new developments that are interesting for heat transformation
applications are also included. These two materials are known as SWS-1L and FAM-
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Z02. SWS-1L (selective water sorbent) is a mesoporous silica gel that has been
impregnated with CaCl2 solution. This gives the material an adsorption characteristic
that is a superposition of salt hydration and the adsorption in the silica gel pores. In
applications that use this product, care has to be taken in order to avoid direct contact
with liquid water as some of the salt may be washed out and go into solution, leaving
the confinement of the pores, which results in a degradation of the adsorption
properties. Functional Adsorption Material (FAM-Z02) is a zeolite based molecular
sieve developed by Mitsubishi Chemical Corporation aimed at the adsorption chiller
market.
In laboratory tests, the adsorbents FAM-ZO2 and SWS-1L showed very high integral
adsorption enthalpies. Potentially this could lead to much higher energy storage
density than the commercially available adsorption materials. Nevertheless, stability,
and corrosion problems have to be taken into account for the SWS material.
The range of possible applications for the purpose of heat storage using
thermochemical reactions is very wide. Starting from temperatures of around 70C (salt
hydrates and -solutions), to typical dissociation processes of hydroxides at around 200
350C, ammonia dissociation at 400-700C, up to aro und 2000C for solar thermal
processes in tower plants (i.e. for the production of solar fuels).
Salt hydrates in general are promising candidates for heat storage in the low
temperature range because of the relatively low bonding force of the associated water
molecules and subsequently low dehydration temperatures. Additionally the physical
process mechanisms of salt hydration are very similar to desorption processes in
molecular sieves and therefore combined materials like zeolite-salt composites can be
developed.
In summary we saw the R&D advances in recent years in the following areas:
Materials:
A better understanding of salt hydrate behaviour and properties for heat storage
A good start in the development of numerical methods that can couple the
physics of thermochemical materials on a molecular scale to the dynamic mass
and heat transport behaviour at higher scales
Systems:
The mastering of heat storage systems using liquid sorption materials, including
the crystalline phase
The proof of principle of several salt hydrate based heat storage concepts
The R&D review of the current activities in compact thermal energy storage highlighted
a number of technical challenges facing the development of the compact thermal
energy storage concept. These technical challenges are consistent with the output of
the stakeholder workshop.
In particular, the promise in the potential for higher storage densities in salt hydrates
has attracted many researchers working in this area. However, the utilization of salt
hydrates for the purpose of heat storage has shown a number of material-related
problems:
Phase change: During the desorption (heating) process, the salt can release
solute in leaking crystal water (incongruent melting). Salt solutions can cause
corrosion and mechanical damage to the system.
Sorption materials
Finding new materials with improved properties: higher storage density or more
suitable sorption temperatures. Classes under research are metal-organic
frameworks (MOF) and aluminium-phosphorous oxides (ALPO)
Developing improved techniques for the production of zeolites and other sorption
materials
Thermochemical materials
Finding new materials with higher heat storage density or better reaction
Technology development
Designing reactors suited to the compact TES material used (moist grains,
pellets, etc.)
Canadian industries and the Canadian R&D community have demonstrated strengths in
technical, business and project execution in related areas that will help in developing potential
new solutions and the means to address the technical and process challenges. The following
are examples of Canadian ingenuity and innovation that may be considered as potential assets
to the development of compact thermal energy storage technologies in Canada:
Canada has a strong homebuilding industry supported by R&D in building sciences, net-
zero homes and advanced building mechanical systems (e.g. CanmetENERGY Bells
Corner Campus).
Canada has invested in solar seasonal thermal energy storage and has demonstrated
Canadian ingenuity and technology innovation in the successful completion and
operation of the first solar seasonal thermal energy storage project in North America
(DLSC) and in achieving the highest solar fraction in the world.
Low distribution temperature heating systems have been demonstrated in DLSC homes
and other net-zero homes in Canada, even in extreme cold climates.
Canada has a solid foundation in the development of new codes and standards. For the
possible commercialization of compact thermal energy storage, the supporting technical
standards development will be important. The CSA and other standards organizations
are well suited for tackling new technologies for the Canadian housing industry.
In Section 4 of this report, interested Canadian research groups have the capability of
contributing to the IEA R&D community and adapting new technologies to suit Canadian
requirements.
Based on a limited survey, the areas covered by the existing Canadian research groups
include:
However there was no direct research effort in the development of compact thermal energy
storage materials in Canada. Nonetheless, potential synergy and technology cross-pollination
from other Canadian industries with a material research focus may be possible if explored
further.
Given this possibility and the known technology R&D capacity in Canada in thermal energy
storage, there is no reason to doubt that a concerted Canadian R&D effort in compact thermal
energy storage cannot produce useful R&D outcomes and contribute to the international R&D
effort and the migration of renewable energy technologies into the retrofit building space
heating market.
Based on the foundation of the Canadian technical capacity discussed above, a number of R&D
scenarios are identified and discussed below.
In this scenario, Canada will invest in a range of compact thermal energy storage research,
including the research and development on suitable thermal energy storage materials and join
the existing research institutions in Europe in the development of better materials and systems
for this application. Resources required for this scenario will include materials research
networking from other Canadian industries; investment in testing methods and standards
development as well as the design and development of mechanical thermal energy systems for
potential implementation in homes.
This scenario will cover the research efforts in systems development and participation in the
application of the technology focused on the Canadian market. Canada will leverage the
existing research capability in systems development and mechanical systems and work with
European researchers on compact thermal energy storage for technology application and
commercialization in Canada. Canada will not be involved in the research work in materials
identification and testing and will utilize the research output from the materials research of the
European countries.
This scenario will see the least amount of resource investment in the compact thermal energy
storage technologies. Canadian stakeholders will keep an eye on European research and
development efforts and develop potential partnerships in technology transfer and
commercialization. Once the technology research and development has reached a successful
outcome by European countries, Canada will use the end outcome of the R&D and apply the
technology to the Canadian housing market. Necessary standards can be transferred from
European standards work and adapted for the Canadian market.
Each of the R&D scenarios has its advantages as well as disadvantages. The potential benefits
from the Canadian investment will be commensurate with the level of investment in the
Canadian R&D effort.
For example, in the deep technology scenario, upon the selection and demonstration of an ideal
material, Canada would be able to capitalize on the commercialization of the technology with
full control of the design and implementation for the Canadian market. On the other hand, with
the modest technology adaption scenario, Canada would rely on the research output of the
other countries. Upon the successful development of the technology, Canadian market
stakeholders would have to partner with European technology leaders in the commercialization
of the product in Canada. In such an arrangement, the royalties and a portion of the profit from
commercialization will flow out of Canada.
The most appropriate investment level is not easy to select, especially when research
resources are constrained and the development of compact thermal energy storage
technologies needs to compete with many other priorities and promising innovations. A detailed
discussion on the influencing factors affecting the R&D direction and the potential implications
is outside the scope of this report. However based on the research review conducted and
discussions that took place over the recent months, a recommended process for moving
forward is presented in the next section.
6 RECOMMENDATIONS
Without appropriate and sufficient study on the influencing factors, constraints and potential
benefits of the R&D decision on compact thermal energy storage technology, it is not possible
to arrive at an objective conclusion on the most appropriate R&D scenario for Canada.
However, based on the research output presented in this report, the authors feel the middle
technology development scenario (Scenario 2) is perhaps the best choice. The capacity for
mechanical engineering design, systems analysis and optimization, as well as the strong
foundation in advanced building mechanical systems makes the development of mechanical
systems a natural path to pursue.
The important starting point for this scenario is to partner with European research organizations
with strong materials research experience and with active involvement in the development of
compact thermal energy storage materials. The earlier entry into the development of the
mechanical systems specifically suitable for colder (northern) climates will help position Canada
in a systems development leadership role for potential product commercialization.
It is also recommended that the Canadian government identify Canadian materials experts in
other industries to seek possible synergistic opportunities in materials development. Should a
suitable materials research network be established in Canada, Canada should participate more
actively in the IEA materials research R&D effort and contribute to this critical phase.